Coating agent for lift-off process and method for producing laminate

Abstract

To provide a coating agent for a lift-off process including a pattern formation step that does not need exposure to light, the coating agent being excellent in fine line reproducibility, immersion cleanability, printability and stability over time.SOLUTION: A coating agent for a lift-off process including a pattern formation step that does not need exposure to light includes an aqueous resin having acidic groups and inorganic fine particles. A laminate having a coating layer of 1 μm thickness formed on a substrate using the coating agent is treated under the following conditions, and the residual rate of the coating layer, expressed by the following (formula 1) is less than 80 mass%. (Treatment conditions) the laminate is immersed in ion-exchanged water at 40°C for 10 minutes, and then dried in an oven at 80°C for 1 minute. (Formula 1) the residual rate of coating layer (mass%)=(the mass of the coating layer after the treatment) / (the mass of the coating layer before the treatment)×100.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a coating agent for a lift-off process and a method for manufacturing a laminate.

[0002] Conventionally, as one of the methods for forming a fine-patterned electrode layer on a base material of an electronic component such as a semiconductor or a solar cell panel, a lift-off method or a photolithography method has been mainly adopted. However, from the viewpoint of improving productivity, the lift-off method (lift-off process) that does not require an etching process has attracted attention.

[0003] The lift-off process generally includes: (1) forming a resist layer by attaching a photoresist film or applying a photoresist solution on a base material; (2) exposing the resist layer using a photomask; (3) removing the unnecessary resist layer using a developer to form a resist pattern; (4) forming an electrode layer on the base material and on the resist layer by sputtering or evaporation; and (5) finally removing the resist pattern to form a patterned electrode layer. However, this method still requires a large number of man-hours and has become a bottleneck in the production of semiconductors and solar cell panels, and further improvement in production efficiency is required. For improving productivity, in the step (1) above, a process has also been developed to form a resist layer patterned by printing and not including the steps (2) and (3) above, and this process is also included in the lift-off process. Specifically, (1’) forming a resist film (resist pattern) patterned without exposure by gravure printing or the like on a base material; (2’) forming an electrode layer on the base material and on the resist layer by sputtering or evaporation; and (3’) finally removing the resist pattern to form a patterned electrode layer.

[0004] In Patent Document 1, a method has been proposed in which, instead of the resist film formed in (1) to (3) of the above lift-off process, a coating agent containing hydroxypropyl cellulose is pattern-coated by gravure printing. In Patent Document 2, a method has been proposed in which, instead of the resist film formed in (1) to (3) of the above lift-off process, a coating agent containing hydroxypropyl cellulose and inorganic fine particles is pattern-coated by silk screen printing. However, the coating agents containing hydroxypropyl cellulose described in Patent Documents 1 and 2 do not have a resin having an acidic group and have low solubility in water, so there is a concern that they cannot be sufficiently removed when washed with water.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention relates to a coating agent for a lift-off process including a pattern formation step not depending on exposure, which is excellent in fine line reproducibility, immersion washability, printability, and stability over time.

[0007] As a result of intensive studies on the above problems, the present inventor has found that the above problems can be solved by using the packaging material described below, and has thus completed the present invention.

[0008] That is, the present invention relates to the following [1] to

[13] .

[0009] [1] A coating agent for a lift-off process including a pattern formation step not depending on exposure, the coating agent containing an aqueous resin having an acidic group and inorganic fine particles.

[0010] [2] The coating agent according to [1], which is a laminate having a coating layer with a film thickness of 1 μm formed using the coating agent on a substrate and processed under the following conditions, and the residual ratio of the coating layer represented by the following (Formula 1) is less than 80% by mass. (Processing conditions) The laminate is immersed in ion-exchanged water at 40°C for 10 minutes and then dried in an oven at 80°C for 1 minute. (Formula 1) Residual ratio of coating layer (% by mass) = (mass of coating layer after treatment) / (mass of coating layer before treatment) × 100

[0011] [3] The coating agent according to [1] or [2], wherein the aqueous resin having an acidic group is a polyvinyl alcohol-based resin (A) having an acidic group.

[0012] [4] Furthermore, the coating agent according to any one of [1] to [3], which contains an aqueous resin having no acidic group.

[0013] [5] The coating agent according to [4], wherein the mass ratio of the aqueous resin having an acidic group to the aqueous resin having no acidic group is 9:1 to 1:9.

[0014] [6] The coating agent according to any one of [1] to [5], wherein the inorganic fine particles are at least one selected from the group consisting of calcium carbonate, barium sulfate, magnesium carbonate, silica, titanium oxide, talc, montmorillonite, kaolin, and mica.

[0015] [7] The coating agent according to any one of [1] to [6], wherein the average particle diameter of the inorganic fine particles by the laser scattering method is 5 μm or less.

[0016] [8] The coating agent according to any one of [1] to [7], wherein the mass ratio of the aqueous resin having an acidic group to the inorganic fine particles is 1:0.2 to 1:3.

[0017] [9] Furthermore, the coating agent according to any one of [1] to [8], which further contains an alcohol-based organic solvent.

[0018]

[10] The coating agent according to [9], wherein the alcohol-based organic solvent is at least one selected from the group consisting of methanol, ethanol, isopropanol, and n-propanol.

[0019]

[11] The coating agent according to any one of [1] to

[10] , wherein the viscosity at 25 °C and a solid content of 18% by mass, measured in accordance with JIS K 7117-1, is 20 to 500 mPa·s.

[0020]

[12] The coating agent according to any one of [1] to

[11] , wherein the pH of the extracted water of the inorganic fine particles is 7.5 to 14.0.

[0021]

[13] A step of printing a lift-off coating agent containing an aqueous resin having an acidic group and inorganic fine particles on a part of a substrate to form a patterned coating layer without exposure; A step of obtaining a laminate (C) having a coating layer and an electrode layer on the substrate by forming an electrode layer on the substrate and on the coating layer; A step of obtaining a laminate (D) having a patterned electrode layer on the substrate by immersing the laminate (C) having a coating layer and an electrode layer on the substrate in a coating layer removing solution to remove the coating layer. A method for manufacturing a laminate, comprising:

Advantages of the Invention

[0022] The present invention enables the provision of a coating agent for a lift-off process including a pattern formation process that is excellent in fine line reproducibility, immersion cleanability, printability, and stability over time without exposure.

Brief Description of the Drawings

[0023]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0024] Hereinafter, embodiments of the present invention will be described in detail. However, the description of the described embodiments or requirements is an example of the embodiments of the present invention, and the present invention is not limited to these contents unless it exceeds the gist.

[0025] <Coating Agent for Lift-Off Process> The coating agent of the present invention contains an aqueous resin having an acidic group and inorganic fine particles, and is characterized by being used for a lift-off process including a pattern formation step not depending on exposure. In a general lift-off process, the method for forming a patterned resist film is not limited. However, the "lift-off process" in the present invention means that a coating layer (resist film) made of the coating agent can be removed to form a layer having a patterned electrode layer. Specifically, a process of forming and removing a patterned resist film using a known printing method such as gravure printing can be mentioned. In the present invention, by forming a patterned resist film without exposure, an exposure step in forming the patterned resist film is unnecessary, which is a process different from the known technologies where the exposure step is essential. The present invention is a coating agent for a lift-off process including a pattern formation step not depending on exposure. The method includes printing the coating agent of the present invention on a part of a substrate to form a patterned coating layer, and forming an electrode layer on the substrate and on the coating layer to obtain a laminate (C) having a coating layer and an electrode layer on the substrate. It is preferably used in a step of immersing in a coating layer removing solution to remove the coating layer and the electrode layer to obtain a laminate (D) having a patterned electrode layer on the substrate.

[0026] As described above, the lift-off process including a pattern formation step not depending on exposure in the present invention is a process of patterning a release layer such as a resist using a known printing method such as gravure printing, then forming a film of an electrode material, and peeling off the release layer such as a resist to form an electrode. Note that there are other names for the lift-off process, such as the sealite process and sealite processing, but they are the same process. The lift-off process including a pattern formation process not relying on exposure, for example, gravure prints the coating agent of the present invention at the locations on the base material where the electrode layer is unnecessary to form a pattern coating layer (Fig. 1), and then, an electrode layer is formed by a method such as sputtering using an electrode material such as indium tin oxide on the base material and on the pattern coating layer (Fig. 2), and finally, the process includes removing the pattern coating layer using a coating layer removing liquid described later. Thereby, the electrode layer can be formed only at necessary locations (Fig. 3). Note that the fine line reproducibility which is the problem of the present invention evaluates the presence or absence of disconnection of the fine lines of the finally obtained electrode layer, and by using the coating agent of the present invention, the above-described pattern coating layer can be formed with high precision, so that disconnection of the electrode layer can be suppressed. The coating agent of the present invention can be used in a lift-off process including a pattern formation process not relying on exposure, and for example, it is preferably used to form a fine patterned electrode layer on a base material of an electronic component used in the manufacture of a semiconductor or a solar cell panel.

[0027] The viscosity of the coating agent of the present invention measured according to JIS K7117-1 at 25°C and a solid content of 18 mass% is preferably 20 to 450 mPa·s, more preferably 100 to 300 mPa·s, and even more preferably 200 to 280 mPa·s. When the viscosity of the coating agent at 25°C and a solid content of 18 mass% is within the above range, viscosity adjustment can be performed while maintaining the necessary solid content during viscosity adjustment for printing with a diluting solvent, etc., so that fine line reproducibility, printing suitability, and stability over time become good. Also, from the viewpoint of the appropriate viscosity for gravure printing and flexographic printing capable of high-speed printing, the viscosity at 25°C and a solid content of 10% is preferably 20 to 200 mPa·s, and more preferably 50 to 150 mPa·s. When the viscosity of the coating agent at 25°C and a solid content of 10 mass% is within the above range, fine line reproducibility and printing suitability become good.

[0028] Since the coating agent of the present invention contains an aqueous resin having an acidic group and inorganic fine particles, the acidic group of the aqueous resin is adsorbed on the surface of the inorganic fine particles, forming a highly stable inorganic fine particle dispersion. Therefore, it has viscoelasticity suitable for high-speed printing and high solubility in water. In addition, since the inorganic fine particle dispersion has viscoelasticity suitable for high-speed printing, a highly precise pattern coating layer can be formed, thereby suppressing disconnection of the electrode layer. Therefore, excellent fine line reproducibility, immersion cleanability, and stability over time can be realized. However, the above effects are based on scientific considerations, and the present invention is not limited to those having such effects only.

[0029] For the above reasons, the coating agent of the present invention is suitable for printing at a printing speed of, for example, 10 m / min or more, and is also suitable for high-speed printing at 50 m / min or more, 100 m / min or more, or 120 m / min or more. The coating agent of the present invention can exhibit excellent fine line reproducibility particularly in high-speed printing with a printing speed of 120 m / min or more in gravure printing, which is highly productive.

[0030] <aqueous resin having an acidic group> The coating agent of the present invention contains an aqueous resin having an acidic group. The aqueous resin is a resin miscible with an aqueous solvent described later and is soluble in an aqueous coating layer removing liquid. It has. The acidic group preferably has an adsorption ability to inorganic fine particles, and known acidic groups such as a sulfonic acid group, a carboxyl group, and a phenolic hydroxyl group can be used. Among them, a carboxyl group is preferable.

[0031] Examples of the resin skeleton of the aqueous resin having an acidic group include polyvinyl alcohol-based resins, acrylic resins, styrene-acrylic resins, styrene-maleic acid resins, urethane resins, polylactic acid resins, resol-type phenol resins, methylolated urea resins, methylolated melamine resins, polyethylene oxides, polyacrylamides, polysaccharide-based resins, and modified resins thereof. These aqueous resins having an acidic group can be used alone or in combination of two or more. Among these, it is preferably at least one selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, and polysaccharide-based resins, more preferably a polyvinyl alcohol-based resin and / or a polysaccharide-based resin, and still more preferably a polyvinyl alcohol-based resin. The polysaccharide-based resin may be a compound in which two or more known monosaccharides are bonded, and examples thereof include cellulose-based resins, pullulan, starch, agarose, and gum arabic. It is preferably at least one selected from the group consisting of cellulose-based resins, pullulan, and starch. In the case of a resin skeleton having no acidic group, acid modification can be performed by a known method to impart an acidic group.

[0032] From the viewpoints of fine line reproducibility, immersion cleaning property, printing suitability, and stability over time, the content of the aqueous resin having an acidic group is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, and still more preferably 3 to 8% by mass in 100% by mass of the coating agent.

[0033] <Polyvinyl alcohol-based resin (A)> As described above, the aqueous resin having an acidic group is preferably a polyvinyl alcohol-based resin (A) having an acidic group. The polyvinyl alcohol-based resin (A) may be any resin having the above-mentioned acidic group and vinyl alcohol units, and may further be an ethylene vinyl alcohol resin containing a structural unit derived from ethylene.

[0034] The degree of polymerization of the polyvinyl alcohol-based resin (A) is preferably from 100 to 3,000, more preferably from 500 to 2,400. When the degree of polymerization of the polyvinyl alcohol-based resin (A) is within the above range, the dipping cleanability, fine line reproducibility, printing suitability, and stability over time are good.

[0035] The content of the structural unit derived from ethylene in the polyvinyl alcohol-based resin (A) is preferably from 1 to 40 mol%, more preferably from 3 to 20 mol%, and still more preferably from 5 to 15 mol%. When the content of the structural unit derived from ethylene is within the above range, the dipping cleanability and stability over time are good.

[0036] As the polyvinyl alcohol-based resin (A), a crosslinked one with a crosslinking agent can be used. Examples of the crosslinking agent used include known crosslinking agents such as isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, oxazoline-based crosslinking agents, and silane coupling-based crosslinking agents. Oxazoline-based crosslinking agents and / or silane coupling-based crosslinking agents are preferred.

[0037] The saponification degree of the polyvinyl alcohol-based resin (A) is represented by the following (Formula 2) and is preferably 80 mol% or more, more preferably 90 mol%, and still more preferably 95 mol%. When the saponification degree of the polyvinyl alcohol-based resin (A) is within the above range, the dipping cleanability and stability over time are good. (Formula 2) Saponification degree: (number of hydroxyl groups) / {(number of hydroxyl groups)+(number of acetate groups)}×100 [mol%]

[0038] Examples of commercially available products of the polyvinyl alcohol-based resin (A) include, for example, Kuraray Poval 25-88KL (manufactured by Kuraray Co., Ltd., itaconic acid-modified polyvinyl alcohol resin), 6-77KL (manufactured by Kuraray Co., Ltd., acid-modified polyvinyl alcohol resin), Gosenex L-3266, and CKS-50 (manufactured by Mitsubishi Chemical Corporation, sulfonic acid-modified polyvinyl alcohol resin).

[0039] <aqueous resin having no acidic group> The coating agent of the present invention preferably further contains an aqueous resin having no acidic group. Examples of the aqueous resin having no acidic group include polyvinyl alcohol-based resins, acrylic resins, styrene-acrylic resins, styrene-maleic acid resins, urethane resins, polylactic acid resins, polysaccharide-based resins, and modified resins thereof. These hydrophilic resins can be used alone or in combination of two or more. Among these, it is preferable to contain a polyvinyl alcohol-based resin.

[0040] From the viewpoints of fine line reproducibility, printability, and immersion cleaning property, the content of the aqueous resin having no acidic group is preferably 0.1 to 30% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 8% by mass in 100% by mass of the coating agent.

[0041] When the coating agent of the present invention contains both an aqueous resin having an acidic group and an aqueous resin having no acidic group, the total content of the aqueous resin having an acidic group and the aqueous resin having no acidic group is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 5 to 15% by mass in 100% by mass of the coating agent from the viewpoints of fine line reproducibility, immersion cleaning property, printability, and stability over time.

[0042] When the coating agent of the present invention contains both an aqueous resin having an acidic group and an aqueous resin having no acidic group, the mass ratio of the aqueous resin having an acidic group to the aqueous resin having no acidic group is preferably 9:1 to 1:9, and more preferably 7:3 to 3:7. When the above mass ratio is within the above range, fine line reproducibility, immersion cleaning property, printability, and stability over time are good.

[0043] <Polyvinyl alcohol-based resin (B)> As described above, it is also preferable that the coating agent of the present invention contains, in addition to the aqueous resin having an acidic group, a polyvinyl alcohol-based resin (B) having no acidic group. The polyvinyl alcohol-based resin (B) may be any resin that does not have an acidic group and has vinyl alcohol units, and may further contain structural units derived from ethylene. Regarding the preferred embodiments of the degree of polymerization, crosslinking, and saponification degree of the polyvinyl alcohol-based resin (B), the description of the <polyvinyl alcohol-based resin (A)> above can be incorporated by reference.

[0044] The polyvinyl alcohol-based resin (B) preferably contains structural units derived from ethylene. The content of the structural units derived from ethylene in the polyvinyl alcohol-based resin (B) is preferably 1 to 40 mol%, more preferably 3 to 20 mol%, and still more preferably 5 to 15 mol%. When the content of the structural units derived from ethylene is within the above range, the immersion cleaning property and the stability over time are good.

[0045] <Inorganic fine particles> The coating agent of the present invention contains inorganic fine particles. Examples of the inorganic fine particles include titanium oxide, zinc oxide, zinc sulfide, chromium oxide, aluminum particles, mica, bronze powder, chromite, lead yellow, cadmium yellow, cadmium red, ultramarine blue, dark blue, red iron oxide, iron black, silica, barium sulfate, mica, montmorillonite, kaolin clay, talc, calcium carbonate, magnesium carbonate, etc. It is preferably at least one selected from the group consisting of calcium carbonate, barium sulfate, magnesium carbonate, silica, titanium oxide, talc, montmorillonite, kaolin, and mica, and more preferably calcium carbonate. Calcium carbonate is suitable because it has a small specific gravity and is difficult to settle, which improves the stability of the coating agent, and there is little increase in the viscosity of the coating agent due to the oil absorption amount and shape. ーmillion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, dark blue, red iron oxide, iron black, silica, barium sulfate, mica, montmorillonite, kaolin clay, talc, calcium carbonate, magnesium carbonate, etc. are mentioned, and it is preferably at least one selected from the group consisting of calcium carbonate, barium sulfate, magnesium carbonate, silica, titanium oxide, talc, montmorillonite, kaolin, and mica, and more preferably calcium carbonate. Calcium carbonate is suitable because it has a small specific gravity and is difficult to settle, which improves the stability of the coating agent, and there is little increase in the viscosity of the coating agent due to the oil absorption amount and shape.

[0046] The average particle diameter measured by the laser scattering method of the inorganic fine particles is preferably 5 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.5 μm or less, and most preferably 0.01 to 0.1 μm. When the average particle diameter by the laser scattering measurement method of the inorganic fine particles is within the above range, the fine line reproducibility, printability, and stability over time are improved.

[0047] The pH of the extracted water of the inorganic fine particles is preferably neutral to alkaline, preferably 7.5 to 14, more preferably 7.8 to 12, and still more preferably 8.0 to 9.0. Particularly when it is alkaline, the acidic groups of the aqueous resin are likely to adsorb, so the fine line reproducibility, immersion cleaning property, and stability over time are improved. The pH of the extracted water of the inorganic fine particles is determined by mixing 5 parts of the inorganic fine particles and 100 parts of ion-exchanged water, boiling for 5 minutes, stirring for 30 minutes, and then measuring the pH of the supernatant water with a pH meter in accordance with JIS Z 8802.

[0048] The specific surface area of the inorganic fine particles is preferably 10 to 100 m 2 / g, and more preferably 10 to 80 m 2 / g. When the specific surface area of the inorganic fine particles is within the above range, the fine line reproducibility, printability, and stability over time are improved.

[0049] The shape of the inorganic fine particles may be a known shape such as spherical, square, cubic, or layered, but from the viewpoint of dispersibility, it is preferably spherical. When the inorganic fine particles are spherical, the fine line reproducibility, immersion cleaning property, printability, and stability over time are improved.

[0050] <Calcium carbonate> As calcium carbonate, there are natural calcium carbonate (heavy calcium carbonate) and synthetic calcium carbonate (light calcium carbonate). Natural calcium carbonate is produced directly from limestone, and can be produced, for example, by mechanically pulverizing and classifying limestone raw stones. Synthetic calcium carbonate is produced from calcium hydroxide, and can be produced, for example, by reacting calcium hydroxide with carbon dioxide gas. As calcium carbonate, those surface-treated with fatty acids, resin acids, silane coupling agents, etc. can also be used.

[0051] The content of the inorganic fine particles in the coating agent is preferably 3 to 20% by mass, more preferably 5 to 15% by mass, in 100% by mass of the coating agent. When the content of the inorganic particles is within the above range, the fine line reproducibility, dipping washability, printing suitability, and stability over time are improved.

[0052] The mass ratio of the aqueous resin having an acidic group to the inorganic fine particles is preferably 1:0.2 to 1:3, more preferably 1:0.8 to 1:2. When the mass ratio of the aqueous resin having an acidic group to the inorganic fine particles is within the above range, the fine line reproducibility, dipping washability, printing suitability, and stability over time are improved.

[0053] <Aqueous solvent> The coating agent of the present invention preferably contains an aqueous solvent. The main component of the aqueous solvent is preferably water, but in addition to water, a water-soluble organic solvent can be used. Specifically, depending on the printing conditions (speed, plate depth, design, drying temperature), an alcohol-based organic solvent, a glycol-based organic solvent, etc. can be contained. Among them, from the viewpoints of fine line reproducibility, printing suitability, and stability over time, it is preferable to contain an alcohol-based organic solvent. Here, in the present invention, the main component being water means that the content of water is the highest in the aqueous solvent. Also, the water-soluble organic solvent refers to a substance that is liquid at 25°C and has a solubility in water at 25°C of 1% by mass or more.

[0054] From the viewpoints of fine line reproducibility, printing suitability, and stability over time, the content of the aqueous solvent is preferably 50 to 95% by mass, more preferably 70 to 90% by mass, in 100% by mass of the coating agent.

[0055] The water content is preferably 70 to 100% by mass, more preferably 85 to 95% by mass, in 100% by mass of the aqueous solvent, from the viewpoints of fine line reproducibility, printability, and stability over time.

[0056] The content of water-soluble organic solvents such as alcohol-based organic solvents and glycol-based organic solvents is preferably 0.1 to 30% by mass, more preferably 1 to 15% by mass, in 100% by mass of the coating agent, from the viewpoints of stability over time, printability, and fine line reproducibility.

[0057] Examples of the alcohol-based organic solvent include methanol, ethanol, n-propanol, isopropanol, isobutanol, normal butanol, tertiary butanol, hexanol, octanol, decanol, etc. In the case of a coating method by gravure printing or flexographic printing, at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol is preferable, and n-propanol is more preferable in terms of stability.

[0058] When the aqueous solvent contains water and an alcohol-based organic solvent, the mass ratio of water to the alcohol-based organic solvent is preferably 70:30 to 97:3, more preferably 85:15 to 95:5, from the viewpoints of stability over time, printability, and fine line reproducibility.

[0059] Examples of the glycol-based organic solvent include acetylene diol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monooctyl ether, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, dibutyl glycol, and the like. Among these, at least one selected from the group consisting of diethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monopropyl ether is preferred, and propylene glycol and / or propylene glycol monopropyl ether is more preferred. These water-soluble organic solvents may be used alone or in combination of two or more. is preferred, and propylene glycol and / or propylene glycol monopropyl ether is more preferred. These water-soluble organic solvents may be used alone or in combination of two or more.

[0060] When the aqueous solvent contains water and a glycol-based organic solvent, the mass ratio of water to the glycol-based organic solvent is preferably from 100:10 to 100:0.2, more preferably from 100:5 to 100:0.2. When the mass ratio of water to the glycol-based organic solvent is within the above range, the fine line reproducibility, printability, and stability over time are improved.

[0061] <Additive> The coating agent of the present invention can contain known additives such as isocyanate compounds, silane coupling agents, dispersants, stabilizers, viscosity modifiers, colorants, etc., as long as the effects of the present invention are not impaired.

[0062] <Method for producing coating agent for lift-off process> The coating agent of the present invention can be produced, for example, by mixing an aqueous resin having an acidic group, inorganic fine particles, and, if necessary, an aqueous solvent, etc., dispersing the inorganic fine particles using a dispersing machine, and then mixing various additives, organic solvents, etc. into the obtained dispersion. As the dispersing machine, generally used ones such as a roller mill, ball mill, pebble mill, attritor, and sand mill can be used.

[0063] <Formation of coating layer> The coating agent of the present invention can be coated on a substrate and the volatile components can be removed to form a coating layer. The coating method is preferably printing, and examples of the printing method include conventionally known methods such as gravure printing method, flexographic printing method, dipping method, roll coating method, screen printing method, spray method, etc. Among them, the gravure printing method and / or flexographic printing method are preferred, and the gravure printing method is more preferred. That is, the coating agent of the present invention is preferably for gravure printing or flexographic printing, and more preferably for gravure printing.

[0064] The coating agent is diluted with a diluting solvent to a viscosity and concentration suitable for, for example, gravure printing, and is supplied to each printing unit alone or in admixture and applied. Thereafter, a coating layer can be obtained by fixing the coating film by drying with an oven or the like. The thickness of the coating layer is preferably from 0.1 μm to 10 μm, more preferably from 0.2 to 5 μm, still more preferably from 0.3 to 3 μm, and particularly preferably from 0.6 to 2 μm. The printing speed is not particularly limited, but from the viewpoint of productivity, it is preferably from 10 to 300 m / min, more preferably from 50 to 200 m / min, and still more preferably from 80 to 150 m / min.

[0065] <Gravure printing> (Gravure plate) The gravure plate is a metal cylinder. As a method for forming the cells of the gravure plate, there are an engraving method and an etching method (photoresist coating - exposure - development - etching), and in terms of making the contour of the coating layer sharp, the etching method capable of forming cells along the edge of the image is preferred. Further, in the etching method, the accuracy of the cells can be increased by increasing the resolution during exposure. As a plate-making apparatus, for example, the laser automatic plate-making system FXIII manufactured by Shin K Laboratories Co., Ltd. (laser drawing resolution: 3200 dpi in the longitudinal direction of the surface / 12800 dpi in the circumferential direction) or the laser plate-making apparatus / electronic engraving machine DIGILAS5000 manufactured by MDC Co., Ltd. It is preferable to use the laser plate-making apparatus / electronic engraving machine DIGILAS5000 manufactured by MDC Co., Ltd., and it is more preferable to use the laser plate-making apparatus / electronic engraving machine DIGILAS5000 manufactured by MDC Co., Ltd.

[0066] The line number, which is a parameter corresponding to the resolution during printing, is preferably from 200 to 350 lines / inch. When the line number is 200 / inch or more, the edge shape of the printed portion becomes good, and the fine line reproducibility tends to improve. When the line number is 350 / inch or less, the cell opening becomes large, and the ink transfer becomes good, and the fine line reproducibility tends to improve.

[0067] The plate depth, which is a parameter for controlling the amount of ink transfer, is preferably 15 to 25 μm. When the plate depth is 15 μm or more, the streaks on the coating layer can be suppressed, so the fine line reproducibility tends to improve. When the plate depth is 25 μm or less, the coating amount of the coating agent becomes an appropriate amount, so the bleeding of the coating layer can be suppressed and the fine line reproducibility tends to improve. Further, by setting the plate depth to 25 μm or less, the coating agent application amount can be reduced, so the drying energy can also be reduced, and the printing speed, that is, the productivity can be improved.

[0068] In the case of water-based ink with slow drying or polyester film with good wet spreading, the pattern line width of the printed matter tends to be wider than the plate pattern line width due to the wet spreading of the coating agent on the film. In that case, from the viewpoint of suppressing the bleeding due to the wet spreading of the coating layer, the ratio of the plate pattern line width to the target pattern line width (plate pattern line width / target pattern line width) is preferably 75 to 90%, more preferably 77 to 85%. When the plate pattern line width / target pattern line width is within the above range, the fine line reproducibility is good.

[0069] (Printing press) In a gravure printing press, one printing unit is equipped with the above gravure plate and doctor blade. There are a number of printing units, and printing units corresponding to organic solvent-based printing ink and pattern ink can be set, and each unit has an oven drying unit. Printing is performed by rotation and is a roll-fed printing method. The type of plate and the type of doctor blade are appropriately selected, and those corresponding to the specifications can be selected.

[0070] <Method for manufacturing a laminate (D) having a patterned electrode layer on a substrate> The method for manufacturing a laminate having a patterned electrode layer on a substrate using the coating agent for the lift-off process of the present invention is characterized by the following steps. (1) Print a lift-off coating agent containing an aqueous resin having an acidic group and inorganic fine particles on a part of the substrate to form a patterned coating layer without exposure. (2) By forming an electrode layer on the substrate and on the coating layer, obtain a laminate (C) having a coating layer and an electrode layer on the substrate. (3) Immerse the laminate (C) having a coating layer and an electrode layer on the substrate in a coating layer removing solution to remove the coating layer and the electrode layer formed on the coating layer.

[0071] <Usage example> The laminate (D) having a patterned electrode layer on the substrate can be used as a part for forming a semiconductor, a solar cell panel, etc. For example, it can be used as "substrate / transparent conductive film (-)" in the laminated structure example of a perovskite solar cell "substrate / transparent conductive film (-) / metal oxide layer / perovskite / hole transport layer / electrode (+)".

[0072] <Substrate> The substrate is not particularly limited. In recent years, in the applications of next-generation solar cells that are overheating in the development towards realizing a decarbonized society, it is particularly preferable to use a lightweight and flexible plastic film as the substrate. As the plastic film, a polyester film, a polyimide film, etc. are preferable for weather resistance. As the polyester film, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN) are preferably cited. In order to give the laminate a water vapor barrier property, the substrate itself may have a barrier layer such as a transparent vapor deposition layer of an inorganic oxide. Further, the substrate may be subjected to surface treatment such as corona treatment and frame treatment for imparting easy adhesiveness for printing and post-processing, or may have a coat layer.

[0073] <Electrode layer> The electrode layer can be formed by depositing a conductor on a substrate by a dry process such as vapor deposition or sputtering. Among these, it is preferably formed by sputtering, which is excellent for forming a large-area film suitable for mass production. Examples of the conductor include metals such as Al, Ti, Pb, Ni, Cu, Ag, Au, Cr, Sn, and In, and oxides such as ITO, Al2O3, and SiO2. In particular, for the application of next-generation solar cells, ITO, which is a transparent electrode and Pb-free, is suitable.

[0074] <Method for removing coating layer> The coating layer is exposed to a coating layer removal liquid by an appropriate method. For example, the coating layer removal liquid is spray-coated onto the conductor covering the coating layer, or the coating layer and the conductor covering it are immersed in the coating layer removal liquid, so that the coating layer is exposed to the coating layer removal liquid. As the method for removing the coating layer, immersion in the coating layer removal liquid is preferred.

[0075] <Coating layer removal liquid> From the perspective of environmental response such as facilitating waste liquid treatment, it is preferable to use water as the coating layer removal liquid. Further, as the coating layer removal liquid, a mixed liquid containing a water-soluble organic solvent can also be used. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, 2-propanol, and 1,2-propanediol; glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl cellosolve, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, butyl cellosolve, ethylene glycol monoisobutyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and dipropylene glycol monomethyl ether; and cyclohexanone. Also, it is also preferable that the coating layer removing liquid contains at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant. When using the mixed solution of the above solvents, the water content in the mixed solution is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more in 100% by mass of the mixed solution. When the water content in the mixed solution is within the above range, the fine line reproducibility tends to improve.

[0076] <Residual ratio of coating layer> The residual ratio of the coating layer in the present invention is a value represented by the following (Formula 1) after treating a laminate formed by applying a coating agent on a substrate to form a coating layer with a film thickness of 1 μm under the following conditions. The residual ratio of the coating layer is preferably less than 80% by mass, more preferably less than 50% by mass, still more preferably less than 10% by mass, and particularly preferably less than 5% by mass. When the residual ratio of the coating layer is within the above range, during immersion cleaning, the removal rate of the coating layer and the unnecessary electrode layer portion improves, so the fine line reproducibility tends to improve. (Treatment conditions) The laminate is immersed in ion-exchanged water at 40°C for 10 minutes and then dried in an oven at 80°C for 1 minute. (Formula 1) Residual ratio of coating layer (% by mass) = (Mass of coating layer after treatment) / (Mass of coating layer before treatment) × 100

[0077] In an embodiment of the coating agent of the present invention that satisfies the requirement for the residual ratio of the coating layer represented by the above (Formula 1), the aqueous resin having an acidic group preferably has a sulfonic acid group, a carboxyl group, or a phenolic hydroxyl group as the acidic group. As the resin skeleton of the aqueous resin having an acidic group, for example, a polyvinyl alcohol-based resin (A), an acrylic resin, a styrene-acrylic resin, a styrene-maleic acid resin, a urethane resin, a polylactic acid resin, a resol-type phenolic resin, a methylolated urea resin, a methylolated melamine resin, polyethylene oxide, polyacrylamide, a polysaccharide-based resin, and modified resins thereof are preferable. By using the resin having the above acidic group and resin skeleton, the solubility in the coating agent removing liquid is improved, and thus the tendency to satisfy the residual ratio of the coating layer is enhanced. Further, the inorganic fine particles are preferably at least one selected from the group consisting of calcium carbonate, barium sulfate, magnesium carbonate, silica, titanium oxide, talc, montmorillonite, kaolin, and mica, and the shape of the inorganic fine particles is preferably spherical. When the inorganic fine particles are in the above-described embodiment, the dispersibility of the inorganic fine particle dispersion formed by the resin having an acidic group and the inorganic fine particles is improved, and the solubility in water becomes good, so that the tendency to satisfy the residual ratio of the coating layer is enhanced.

[0078] The content of the aqueous resin having an acidic group in the coating agent is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, and still more preferably 3 to 8% by mass in 100% by mass of the coating agent. Furthermore, the content of the inorganic fine particles in the coating agent is preferably 3 to 20% by mass in 100% by mass of the coating agent, and the mass ratio of the aqueous resin having an acidic group to the inorganic fine particles is preferably 1:0.2 to 1:3. Since the solubility in a solvent such as water is improved when the inorganic fine particles are in a state dispersed by the aqueous resin having an acidic group, when the content of the aqueous resin having an acidic group in the coating agent and the mass ratio of the aqueous resin having an acidic group to the inorganic fine particles are within the above ranges, the tendency to satisfy the residual ratio of the coating layer is enhanced.

[0079] The coating agent of the present invention preferably further contains an aqueous resin having no acidic group, and the aqueous resin is preferably a polyvinyl alcohol resin (B). The polyvinyl alcohol resin (B) preferably contains a structural unit derived from ethylene. The content of the structural unit derived from ethylene in the polyvinyl alcohol resin (B) is preferably 1 to 40 mol%, more preferably 3 to 20 mol%, and still more preferably 5 to 15 mol%. When the aqueous resin dries, it tends to exhibit the property of being difficult to dissolve in water due to hydrogen bonding. Therefore, by using a combination of resins having different structures, the hydrogen bonding force decreases, and the tendency to satisfy the residual rate of the coating layer increases. In particular, by using a polyvinyl alcohol resin (B) containing a structural unit derived from ethylene as the aqueous resin having no acidic group, the total amount of hydroxyl groups in the coating layer decreases, and the tendency to satisfy the residual rate of the coating layer further increases.

[0080] The content of the aqueous resin having no acidic group is preferably 0.1 to 30% by mass, particularly preferably 2 to 8% by mass in 100% by mass of the coating agent. The mass ratio of the aqueous resin having an acidic group to the aqueous resin having no acidic group is preferably 9:1 to 1:9, particularly preferably 7:3 to 3:7. When the content of the aqueous resin having no acidic group and the mass ratio of the aqueous resin having an acidic group to the aqueous resin having no acidic group are within the above ranges, the balance between the hydrogen bonding force and the dispersibility of the inorganic fine particles becomes good, and the tendency to satisfy the residual rate of the coating layer increases.

Examples

[0081] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the present invention, parts and % represent parts by mass and % by mass unless otherwise noted.

[0082] <Measurement Method of pH of Extracted Water of Inorganic Fine Particles> 5 parts of inorganic fine particles and 100 parts of ion-exchanged water were mixed and heated at 100 °C for 5 minutes. Then, after cooling to room temperature, ion-exchanged water was added so that the total amount of the inorganic fine particles and the ion-exchanged water became 105 parts. After stirring, pH measurement was carried out using a multi pH meter (manufactured by AS ONE Corporation) in accordance with JIS Z 8802.

[0083] <Viscosity measurement> The viscosity of the coating agent was measured under the following conditions using a Viscometer TUB-10 manufactured by Toki Sangyo Co., Ltd. in accordance with JIS K 7117-1. When the solid content concentration was low, the lid of the storage container of the coating agent was opened and left standing to volatilize the solvent to adjust the solid content. 《Measurement conditions》 · Rotor: M1 · Rotation speed: 6 rpm · Liquid temperature: 25 °C · Solid content at the time of viscosity measurement before dilution: 18 mass% · Solid content at the time of viscosity measurement after dilution: 10 mass%

[0084] <Measurement of weight average molecular weight> The weight average molecular weight was determined as the converted molecular weight using polyethylene glycol as a standard substance. The measuring instrument was a GPC device: Shodex GPC-401 manufactured by Showa Denko KK, the column was Shodex OHpak LB-805 manufactured by Showa Denko KK, and the detector was RI (differential refractometer). The eluent used was a 0.1 N aqueous solution of NaNO3, and the measurement was carried out at a column temperature of 35 °C and a flow rate of 3 mL / min.

[0085] <Preparation of resin solution> (Preparation Example 1) Resin solution V01 12 parts of polyvinyl alcohol-based resin PVA1 and 88 parts of ion-exchanged water were heated with stirring, and heating and stirring were continued at 90 °C for 1 hour. Then, heating was stopped and stirring was continued until the temperature returned to normal temperature to obtain resin solution V01.

[0086] (Preparation Examples 2 to 6) Resin solutions V02 to V06 Resin solutions V02 to V06 were obtained in the same manner as in Preparation Example 1, except that the raw materials and compounding ratios described in Table 1 were changed. The properties of the raw materials used in Preparation Examples 1 to 6 are as follows. · Polyvinyl alcohol-based resin PVA1: Itaconic acid-modified polyvinyl alcohol, degree of polymerization = 1800, viscosity (20 °C, 4% aqueous solution) = 25 mPa·s, saponification degree = 88%, solid content 100% · Polyvinyl alcohol-based resin PVA2: Sulfonic acid-modified polyvinyl alcohol, degree of polymerization = 300, viscosity (20 °C, 4% aqueous solution) = 2.5 mPa·s, saponification degree = 98%, solid content 100% · Polyvinyl alcohol-based resin PVA3: Ethylene vinyl alcohol resin, ethylene content: 8 mol%, degree of polymerization = 400, viscosity (20 °C, 4% aqueous solution) = 4 mPa·s, saponification degree = 98%, solid content 100% · Polyvinyl alcohol-based PVA4: Manufactured by Kuraray Co., Ltd., Poval 28-98, unmodified polyvinyl alcohol, degree of polymerization = 1700, viscosity (20 °C, 4% aqueous solution) = 28 mPa·s, saponification degree = 98%, solid content 100% · Cellulose-based resin CE1: Manufactured by Daicel Corporation, CMC Daicel #2200, carboxymethyl cellulose, viscosity (25 °C, 1% aqueous solution) = 2200 mPa·s, solid content 100% · Cellulose-based resin CE2: Manufactured by Nippon Soda Co., Ltd., HPC-SL, hydroxypropyl cellulose, viscosity (25 °C, 10% aqueous solution) = 150 mPa·s, solid content 100%

[0087]

Table 1

[0088] <Manufacture of Coating Agent for Lift-Off Process> (Example 1) Coating Agent C1 for Lift-Off Process 75.0 parts of resin solution V01, 9.0 parts of calcium carbonate, 8.0 parts of ion-exchanged water, and 8.0 parts of n-propyl alcohol were mixed and dispersed with a bead mill for 20 minutes to obtain a coating agent C1 for the lift-off process.

[0089] (Examples 2 to 29, Comparative Examples 1 and 2) Coating Agents C2 to 31 for Lift-off Process Except for changing the raw materials and compounding ratios described in Table 2, Coating Agents C2 to 31 for lift-off process were obtained in the same manner as in Example 1. The properties of the raw materials used are as follows. The pH is the pH of the respective extracted water. · Calcium carbonate CA1: Manufactured by Shiraishi Calcium Co., Ltd., Homocal D, synthetic calcium carbonate, average particle size 0.08 μm, pH 8.6, solid content 100% · Calcium carbonate CA2: Average particle size 0.3 μm, pH 8 · Calcium carbonate CA3: Average particle size 1.5 μm, pH 9 · Calcium carbonate CA4: Average particle size 4.5 μm, pH 8.9 · Silica: Manufactured by Fuji Silysia Chemical Ltd., Silicia 310, gel method silica, average particle size 1.7 μm, pH 7.5 · Barium sulfate: Manufactured by Sakai Chemical Industry Co., Ltd., Variess B31, precipitated barium sulfate, average particle size 0.3 μm, pH 7 · Montmorillonite: Manufactured by Kunimine Industries Co., Ltd., Kunipia F, swelling montmorillonite, particle aspect ratio 500, particle thickness 1 μm, average particle size 0.5 μm, pH 8 to 8.5 · Titanium oxide: Manufactured by Tayca Corporation, Titannix JR-808, average particle size 2.3 μm, pH 7.7 · Mica: Average particle size 6 μm, aspect ratio 100, specific surface area 9m 2 / g, pH 8 · Kaolin: Average particle size 1.2 μm, aspect ratio 100, specific surface area 10m 2 / g, pH 6 · Talc: Manufactured by Specialty Minerals, AlBACAR5970, average particle size 1.9 μm, pH 8

[0090] <Manufacture of Laminate Using Coating Agent of Example 1> For the coating agent C1 for the lift-off process, a diluting solvent (water / n-propyl alcohol = 92 / 8) was added so that the solid content of the coating agent became 10%, and they were stirred and mixed. Then, using a gravure printing machine equipped with a gravure plate (cell formation method: etching method, laser plate-making apparatus D1: laser plate-making apparatus and electronic engraving machine DIGILAS5000 manufactured by MDC, line count 300 lines / inch, plate depth 20 μm, plate pattern line width / target pattern line width: 90%) having fine line stripe patterns with line widths of 20 μm, 50 μm, 100 μm, and 200 μm and a plate depth of 20 μm on the corona-treated surface of a corona-treated biaxially stretched polyester film (PET film) with a thickness of 50 μm, the diluted coating agent C1 for the lift-off process was printed under the conditions of a printing speed of 120 m / min and an in-line oven at 80°C to form a coating layer, and an intermediate laminate having fine line patterns with line widths of 20 μm, 50 μm, 100 μm, and 200 μm formed by the coating agent for the lift-off process was obtained. On the fine line pattern printing surface of the intermediate laminate formed by the coating agent for the lift-off process and on the substrate without the pattern, using the SPC series manufactured by Canon Anelva Corporation, under the conditions of a degree of vacuum of 10 -4 Pa and an applied voltage of 5.1 kV, ITO was deposited by sputtering to form a transparent electrode layer with a thickness of 0.4 μm, and a laminate was obtained. The laminate has constituent parts of substrate / coating layer / electrode layer and constituent parts of substrate / electrode layer.

[0091] <Manufacture of laminates using the coating agents of Examples 2 to 29, Comparative Examples 1 and 2> Except for using the coating agent for the lift-off process and the diluting solvent shown in Table 2, laminates were produced in the same manner as <Manufacture of laminates using the coating agent of Example 1>.

[0092] <Manufacture of laminates of Examples 30 to 43> Except for using the coating agent for the lift-off process and the plate shown in Table 3, laminates were produced in the same manner as <Manufacture of laminates using the coating agent of Example 1>. The plate-making apparatuses used are as follows. · Laser plate-making device D1: DIGILAS5000 manufactured by MDC · Laser plate-making device D2: HelioKlischograph K500 G4 manufactured by HelioGraph Japan · Laser plate-making device D3: newFXIII manufactured by Sink Laboratory

[0093] <Evaluation of Coating Agent and Laminate> The obtained coating agent and laminate were evaluated as follows. The results are shown in Tables 2 and 3.

[0094] <Dip Washability> The obtained laminate was cut into pieces of 10 mm × 50 mm, immersed in ion-exchanged water at 40 °C for 10 minutes, then dried in an oven at 80 °C for 1 minute, and the residual rate (mass %) of the coating layer before and after washing was determined and evaluated according to the following formula 1. AA to C are at the practical level. When the coating agent of the present invention is used in the lift-off process, in order to achieve high productivity, the removal of the coating layer is preferably only by immersion in ion-exchanged water. Therefore, in the dip washability test of the present invention, only immersion in ion-exchanged water was performed. As a conventional washability test, a test method of removing the coating layer by applying pressure with water flow or the like is known. However, the dip washability of the present invention is different from the conventional washability test in that no pressure such as water flow is applied, and it is a strict test method that requires higher solubility in the cleaning liquid. (Formula 1) Residual rate of coating layer (mass %) = (mass of coating layer after treatment) / (mass of coating layer before treatment) × 100 AA: Residual rate of coating layer (mass %) is less than 5 mass % A: Residual rate of coating layer (mass %) is 5 mass % or more and less than 10 mass % B: Residual rate of coating layer (mass %) is 10 mass % or more and less than 50 mass % C: Residual rate of coating layer (mass %) is 50 mass % or more and less than 80 mass % D: Residual rate of coating layer (mass %) is 80 mass % or more

[0095] <Thin line reproducibility> After the immersion cleaning property test of the obtained laminate, the thin line stripe pattern part was visually observed and evaluated according to the following criteria. AA to C are at the practical level. AA: There is no disconnection in all stripe pattern parts. A: There is a disconnection in the 20 μm thin line stripe pattern part, but there is no disconnection in the 50 μm, 100 μm, and 200 μm thin line stripe pattern parts. B: There is a disconnection in the 50 μm thin line stripe pattern part, but there is no disconnection in the 100 μm and 200 μm thin line stripe pattern parts. C: There is a disconnection in the 100 μm thin line stripe pattern part, but there is no disconnection in the 200 μm thin line stripe pattern part. D: There is a disconnection in the 200 μm stripe pattern part.

[0096] <Stability over time> The coating agent for the lift-off process was filled into a 225 g mayonnaise bottle (body diameter 62 mm / total length 109 mm), and the layer separation after 7 days at 40 °C was confirmed and evaluated according to the following criteria. The length in each criterion is the length of the layer measured when viewing the mayonnaise bottle horizontally. A to C are at the practical level. A: There is no layer separation. B: There is layer separation, and a separation layer less than 10 mm occurs. C: There is layer separation, and a separation layer of 10 mm or more and less than 20 mm occurs. D: There is layer separation, and a separation layer of 20 mm or more occurs.

[0097] <Printing suitability> The coating agent for the lift-off process diluted with the diluting solvent shown in Table 2 was put into the printing ink container of the printing machine. After rotating the plate under the conditions of a printing speed of 120 m / min for 60 minutes, the colored area of the non-image part on the plate was visually evaluated, and the printing suitability was evaluated according to the following criteria. Examples 1 to 29, Comparative Examples 1 and 2 used the plate of D1, and Examples 30 to 45 used the plates shown in Table 3. A to C are at the practical level. A: There is no coloring in the non-image part. B: There is coloring in the non-image part, and the colored area is less than 5 area %. C: There is coloring in the non-image area, and the colored area is 5 area% or more and less than 30 area%. D: There is coloring in the non-image area, and the colored area is 30 area% or more.

[0098]

Table 2

[0099]

Table 2

[0100]

Table 3

[0101] From the above results, in Comparative Example 1, since it does not contain an aqueous resin having an acidic group, the fine line reproducibility, immersion cleaning property, printing suitability, and stability over time were poor. In Comparative Example 2, since it does not contain inorganic fine particles, the fine line reproducibility and immersion cleaning property were poor. On the other hand, in the examples, since it contains an aqueous resin having an acidic group and inorganic fine particles, the fine line reproducibility, immersion cleaning property, printing suitability, and stability over time were good.

Claims

1. A coating agent for a lift-off process including a pattern formation process not relying on exposure, The coating agent contains an aqueous resin having an acidic group and inorganic fine particles.

2. The coating agent according to Claim 1, wherein the residual ratio of the coating layer represented by the following (Formula 1) after treating a laminate having a coating layer with a thickness of 1 μm formed on a substrate using the coating agent under the following conditions is less than 80% by mass. (Treatment conditions) The laminate is immersed in ion-exchanged water at 40°C for 10 minutes and then dried in an oven at 80°C for 1 minute. (Formula 1) Residual ratio of the coating layer (% by mass) = (mass of the coating layer after treatment) / (mass of the coating layer before treatment) × 100

3. The coating agent according to Claim 1 or 2, wherein the aqueous resin having an acidic group is a polyvinyl alcohol-based resin (A) having an acidic group.

4. The coating agent according to Claim 1 or 2, further containing an aqueous resin having no acidic group.

5. The coating agent according to Claim 4, wherein the mass ratio of the aqueous resin having an acidic group to the aqueous resin having no acidic group is 9:1 to 1:

9.

6. The coating agent according to Claim 1 or 2, wherein the inorganic fine particles are at least one selected from the group consisting of calcium carbonate, barium sulfate, magnesium carbonate, silica, titanium oxide, talc, montmorillonite, kaolin, and mica.

7. The coating agent according to Claim 1 or 2, wherein the average particle diameter of the inorganic fine particles by the laser scattering method is 5 μm or less.

8. The coating agent according to Claim 1 or 2, wherein the mass ratio of the aqueous resin having an acidic group to the inorganic fine particles is 1:0.2 to 1:

3.

9. The coating agent according to Claim 1 or 2, further containing an alcohol-based organic solvent.

10. The coating agent according to Claim 9, wherein the alcohol-based organic solvent is at least one selected from the group consisting of methanol, ethanol, isopropanol, and n-propanol.

11. The coating agent according to Claim 1 or 2, wherein the viscosity at 25°C and a solid content of 18% by mass measured according to JIS K 7117-1 is 20 to 450 mPa·s.

12. The coating agent according to Claim 1 or 2, wherein the pH of the extracted water of the inorganic fine particles is 7.5 to 14.

0.

13. A step of printing a lift-off coating agent containing an aqueous resin having an acidic group and inorganic fine particles on a part of a substrate to form a patterned coating layer without exposure; A step of obtaining a laminate (C) having a coating layer and an electrode layer on the substrate by forming an electrode layer on the substrate and on the coating layer; A step of obtaining a laminate (D) having a patterned electrode layer on the substrate by immersing the laminate (C) having the coating layer and the electrode layer on the substrate in a coating layer removing liquid to remove the coating layer. A method for manufacturing a laminate, comprising the steps.

Images