Method for manufacturing coating agents and laminates

Abstract

This invention provides a coating agent for a lift-off process that includes a pattern formation step without using photolithography, enabling high-speed printing and offering excellent fine line reproduction and coating layer removal capabilities. [Solution] The present invention relates to a coating agent for a lift-off process that includes a pattern formation step without using photolithography, wherein the coating agent comprises an aqueous resin and water, and contains 50 to 95% by mass of water in 100% by mass of the coating agent, and has a viscosity at 25°C of 50 mPa·s or more and less than 45,000 mPa·s, as measured according to JIS K 7117-1.

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a coating agent and a laminate.

Background Art

[0002] Conventionally, as a method for forming an electrode layer with a fine pattern on a substrate of an electronic component such as a semiconductor or a solar cell panel, a lift-off method or a photolithography method has been used. Among these, 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 (1) forms a resist layer by attaching a photoresist film or applying a photoresist solution on a substrate. Next, (2) the resist layer is exposed using a photomask. Next, (3) an unnecessary resist layer is removed using a developer to form a resist pattern. Next, (4) an electrode layer is formed on the substrate and on the resist layer by sputtering or vapor deposition. Next, (5) the resist pattern can be removed to form an electrode pattern. However, this method has a large number of steps and has become a bottleneck in the production of semiconductors, solar cell panels, and the like.

[0004] Therefore, in order to improve productivity, in the step (1) above, a process has been developed that forms a resist layer patterned by printing and does not include the steps (2) and (3) above.

[0005] Patent Document 1 discloses a method for patterning a metal oxide film including a step of pattern-printing a water-soluble resin on a synthetic resin film, a step of vapor-depositing a metal oxide on the entire pattern-printed surface of the synthetic resin film, and a step of washing the synthetic resin film with water to simultaneously remove the water-soluble pattern-printed portion and the metal oxide film vapor-deposited on its surface layer.

[0006] Patent Document 2 discloses a resist agent for the lift-off method used to form a resist film on a substrate when forming a conductive pattern on the substrate by the lift-off method, which contains hydroxyalkylcellulose in a proportion of 8 to 25% by mass.

[0007] Patent Document 3 discloses a method for manufacturing a substrate for a touch panel, which includes the steps of forming a transparent electrode on a transparent substrate and forming a metal electrode on the transparent substrate that conducts to the transparent electrode, wherein at least one of the transparent electrode and the metal electrode is formed by a lift-off method using a water-soluble resist agent containing at least one of a water-soluble polyester and hydroxyalkylcellulose. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2002-200833 [Patent Document 2] Japanese Patent Publication No. 2013-258215 [Patent Document 3] Japanese Patent Publication No. 2013-257669 [Overview of the project] [Problems that the invention aims to solve]

[0009] The technology disclosed in Patent Document 1 had problems such as difficulty in removing the pattern by washing with water and poor formability when forming fine line printed patterns. Specifically, the technology disclosed in Patent Document 1 uses a water-soluble resin solution prepared by dissolving 3 parts by weight of hydroxypropyl cellulose in 97 parts by weight of isopropyl alcohol to print patterns. In this technology, the water-soluble resin is fixed to the film on the surface of the substrate while the isopropyl alcohol evaporates in a short time, so the pattern printed area formed in this way tends to have reduced resolubility in water.

[0010] The technologies disclosed in Patent Documents 2 and 3 provide resists suitable for screen printing. Such resists have a limited water content to suit screen printing. Furthermore, the viscosity of the resist is also high to suit screen printing. In this technology, because moisture is difficult to remove from the resist film on the surface of the substrate, drying is performed at high temperature and for a certain period of time after printing the resist onto the substrate. The resist film formed in this way tends to have reduced resolubility in water, and when the resist film dissolves in water, its viscosity increases again, causing the resist film to easily remain on the substrate and affecting the reproduction of fine lines. Moreover, high-viscosity resists are not suitable for high-speed printing, and the drying time after printing is also long, making it difficult to speed up pattern formation.

[0011] This disclosure relates to a coating agent for a lift-off process that includes a pattern formation step without using photolithography, which enables high-speed printing and has excellent fine line reproducibility and coating layer removal properties, and to a method for manufacturing a laminate using the same. [Means for solving the problem]

[0012] One example of an embodiment of the present disclosure relates to a coating agent for a lift-off process that includes a pattern formation step that does not use photolithography, wherein the coating agent comprises an aqueous resin and water, and contains 50 to 95% by mass of water in 100% by mass of the coating agent, and has a viscosity at 25°C of 50 mPa·s or more and less than 45,000 mPa·s, as measured according to JIS K 7117-1.

[0013] Another example of embodiments of the present disclosure relates to a coating agent for a lift-off process that includes a pattern formation step that does not use a photolithography method, wherein the coating agent is used in a state diluted with a diluent solvent, the coating agent comprising an aqueous resin and water, and being at least one selected from the group consisting of gravure printing, flexographic printing and inkjet printing, having a viscosity at 25°C of 50 mPa·s or more and less than 2000 mPa·s as measured according to JIS K 7117-1, containing 50 to 95% by mass of water in 100% by mass of the coating agent in the state diluted with the diluent solvent, and having a viscosity at 25°C of 50 mPa·s or more and 500 mPa·s or less as measured according to JIS K 7117-1.

[0014] Further embodiments of the present disclosure relate to a method for manufacturing a laminate, comprising the steps of: printing a coating agent onto a substrate to form a patterned coating layer without using photolithography; forming a conductive film on the substrate on which the coating layer is formed; and contacting the substrate on which the conductive film is formed with a coating layer removal liquid to remove the coating layer and form a conductive pattern, wherein the coating agent comprises an aqueous resin and water, with 50 to 95% by mass of water per 100% by mass of the coating agent, and having a viscosity at 25°C of 50 mPa·s or more and less than 45,000 mPa·s as measured according to JIS K 7117-1. [Effects of the Invention]

[0015] This disclosure makes it possible to provide a coating agent for a lift-off process that includes a pattern formation step without using photolithography, enabling high-speed printing and offering excellent fine line reproducibility and coating layer removal properties, as well as a method for manufacturing a laminate using the same. [Brief explanation of the drawing]

[0016] [Figure 1]This is an image diagram showing a state in which a coating agent is printed on a substrate to form a pattern coating layer in a lift-off process. [Figure 2] This is an image diagram showing a state in which a conductive film is formed on the substrate and the pattern coating layer shown in FIG. 1 in a lift-off process. [Figure 3] This is an image diagram showing a state in which a conductive film is formed on a substrate by removing the pattern coating layer shown in FIG. 2 using a coating layer removing liquid in a lift-off process. [Figure 4] This is a schematic cross-sectional view for explaining one embodiment of a printing system.

Embodiments for Carrying Out the Invention

[0017] Hereinafter, embodiments of the present disclosure will be described in detail. However, the description of the described embodiments or requirements is an example of the embodiments of the present disclosure, and the present disclosure can be modified within the range that can solve the problems.

[0018] <<Coating Agent>> One embodiment of the coating agent of the present disclosure is a coating agent for a lift-off process including a pattern forming step that does not use a photolithography method. The coating agent contains an aqueous resin and water, contains 50 to 95% by mass of water in 100% by mass of the coating agent, and has a viscosity at 25 °C measured according to JIS K 7117-1 of 50 mPa·s or more and less than 45000 mPa·s. Note that the coating agent may be referred to as ink in descriptions such as printing (coating). Also, the coating layer may be referred to as a printed matter or the like.

[0019] In the present disclosure, the viscosity of the coating agent is the viscosity at 25 °C measured according to JIS K7117-1. The viscosity of the coating agent can be specifically measured according to the method described in the examples.

[0020] In some embodiments, the coating agent can be used in a lift-off process that includes a pattern formation step that does not use photolithography. In this disclosure, the “lift-off process” is a step of removing a coating layer (resist film) made of the coating agent and forming a conductive pattern. The “lift-off process” is a process of forming and removing a resist film pattern using a known printing method such as gravure printing. In this disclosure, since the resist film pattern can be formed by printing, a photolithography step is unnecessary, and it is a process that differs from known technologies in which a photolithography step is essential.

[0021] An example of a lift-off process including a pattern formation step will be explained using Figures 1 to 3. The lift-off process including a pattern formation step includes, for example, forming a pattern coating layer 2 by gravure printing the coating agent of this disclosure onto areas on the substrate 1 where a conductive film 3 is not desired (Figure 1), then forming a conductive film 3 on the substrate 1 and the pattern coating layer 2 using a conductive material such as indium tin oxide by sputtering or the like (Figure 2), and finally removing the pattern coating layer 2 using a coating layer removal liquid described later. This allows the conductive film 3 to be formed only where necessary (Figure 3). In the following description, the coating layer removal liquid will also be simply referred to as the removal liquid.

[0022] Furthermore, the fine-line reproducibility evaluates whether or not there are any breaks in the fine lines of the final conductive pattern. By using the coating agent of this disclosure, the patterned coating layer described above can be formed with high precision, thereby suppressing breaks in the conductive pattern.

[0023] The coating agent can be used in lift-off processes that include a pattern formation step that forms a pattern without using photolithography. For example, it is preferably used to form fine conductive patterns on a substrate of an electronic component used in the manufacture of semiconductors or solar panels.

[0024] A laminate having a conductive pattern on a substrate can be used as part of a semiconductor or solar panel, for example, as the "substrate / transparent conductive film (-)" in a laminate configuration example of a perovskite solar cell: "substrate / transparent conductive film (-) / metal oxide layer / perovskite / hole transport layer / electrode (+)". It can also be used as a component in a battery management system such as an automotive battery.

[0025] The effects of using a coating agent in some embodiments are described below, but these effects are based on scientific considerations, and this disclosure is not limited to embodiments that produce such effects.

[0026] The coating agent contains 50-95% water per 100% by mass of the coating agent. When the coating agent is printed onto the substrate, the water-based resin adheres to the substrate along with the water, and the water-based resin forms a coating film on the surface of the substrate, with an excess of water present. In this process, the water-based resin coating film is formed while being contained in water, so hydrophilic parts are oriented on the surface of the coating film. A conductive film is then formed on top of the coating layer formed in this way, and when the coating layer is removed later, it can be quickly dissolved or peeled off using a removal solution.

[0027] The coating agent contains 50-95% water per 100% by mass of the coating agent. On the surface of the substrate, the water evaporates while encapsulating the water-based resin, forming a coating film. During this process, sufficient water is contained within the water-based resin, and as this contained water evaporates, tiny channels are formed that lead from the outside to the inside of the coating film. These channels allow the removal solution to easily penetrate into the interior of the coating layer when the dried coating layer is removed with a removal solution, increasing the dissolution rate of the coating layer and enabling rapid removal of the coating layer.

[0028] Water is preferably present in an amount of 50% by mass or more, 70% by mass or more, or 80% by mass or more, per 100% by mass of the coating agent. Within these ranges, the aqueous resin is incorporated into the water on the surface of the substrate to form a coating layer, so that the coating layer can be quickly removed with a removal solution after the conductive film has been formed. For example, the amount of water may be 50-95% by mass, 70-90% by mass or 75-85% by mass, per 100% by mass of the coating agent.

[0029] The coating agent has a viscosity of 50 mPa·s or more and less than 45,000 mPa·s, allowing it to be printed on substrates using various printing methods. Furthermore, because the coating agent has a viscosity of less than 45,000 mPa·s, it exhibits excellent printability even in high-speed printing. Such a coating agent can be applied to high-speed printing, such as roll-to-roll printing.

[0030] Since the coating agent has a viscosity of 50 mPa·s or more and less than 45,000 mPa·s, the aqueous resin on the surface of the substrate can easily contain water, orienting hydrophilic parts on the surface of the coating layer and improving the removal of the coating layer by the removal solution. Furthermore, within this viscosity range, the aqueous resin on the surface of the substrate can contain a sufficient amount of water, and when this contained water evaporates, minute channels are easily formed in the coating film, further improving the removal of the coating layer by the removal solution.

[0031] From the viewpoint of enabling high-speed printing, the viscosity of the coating agent should be 40,000 mPa·s or less, 30,000 mPa·s or less, or 15,000 mPa·s or less. Within these ranges, the aqueous resin will be sufficiently fixed to the substrate surface while water is contained within it. Furthermore, on the surface of the substrate, water can easily evaporate from the inside to the outside of the coating film, forming tiny channels.

[0032] The viscosity of the coating agent is not particularly limited, but is preferably 50 mPa·s or higher, 100 mPa·s or higher, or 150 mPa·s or higher, depending on the printing method. Within these ranges, the wetting spread of the aqueous resin and water on the surface of the substrate is suppressed, making it easier to maintain a state where water contains the aqueous resin on the surface of the substrate. In addition, it becomes easier to form a coating film on the surface of the substrate with the aqueous resin containing a sufficient amount of water. For example, the viscosity of the coating agent may be 50 mPa·s to 40,000 mPa·s, 100 mPa·s to 30,000 mPa·s, or 150 mPa·s to 15,000 mPa·s.

[0033] The viscosity of the coating agent is preferably such that the viscosity when printed on the substrate meets the above range. From the viewpoint of adjusting viscosity, the non-volatile content of the coating agent when printed on the substrate is preferably 5-30% by mass, 8-20% by mass, or 10-15% by mass. In this disclosure, the non-volatile content is the mass of the coating layer formed by printing the coating agent on the substrate and drying it.

[0034] The coating agent can be printed using various printing methods, and preferably at least one selected from the group consisting of gravure printing, flexographic printing, waterless offset printing, rotary screen printing, and inkjet printing.

[0035] When the coating agent is selected from the group consisting of those for gravure printing, flexographic printing, and inkjet printing, the viscosity is preferably 50 mPa·s or more and less than 2000 mPa·s, more preferably 70 mPa·s or more and 1000 mPa·s or less, even more preferably 100 mPa·s or more and 500 mPa·s or less, and particularly preferably 150 mPa·s or more and 200 mPa·s or less. Within these ranges, it is possible to provide a coating agent that is suitable for gravure printing, flexographic printing, and inkjet printing, respectively, while maintaining a state in which water contains the aqueous resin on the surface of the substrate, and furthermore, easily forming minute channels in the coating layer. Furthermore, within these ranges, it is possible to provide a coating agent suitable for high-speed printing such as roll-to-roll in each printing method.

[0036] When the coating agent is selected from the group consisting of waterless offset printing and rotary screen printing, the viscosity is preferably 2000 mPa·s or more and less than 45000 mPa·s, more preferably 5000 mPa·s or more and 40000 mPa·s or less, even more preferably 7000 mPa·s or more and 30000 mPa·s or less, and particularly preferably 10000 mPa·s or more and 20000 mPa·s or less. Within these ranges, it is possible to provide a coating agent that is suitable for waterless offset printing and rotary screen printing, respectively, while maintaining a state in which water contains the aqueous resin on the surface of the substrate, and furthermore, easily forming minute channels in the coating layer. Furthermore, within these ranges, it is possible to provide a coating agent suitable for high-speed printing such as roll-to-roll in each printing method.

[0037] The coating layer can be removed using water alone, a mixture of water and a water-soluble organic solvent, or an aqueous medium such as alkaline water (by adding alkali to these). Since the coating agent contains an aqueous resin and water, and the water content and viscosity are specified, sufficient coating layer removal can be obtained even when using an aqueous medium as the removal solution. Furthermore, the coating layer can be removed by spraying, running water, immersion, etc., using the removal solution. By using a coating agent with high coating layer removal properties, sufficient immersion cleaning can be obtained even at low water pressure or without water pressure when immersing the substrate after the conductive film has been formed in the removal solution.

[0038] <Water-based resin> The coating agent contains an aqueous resin. The aqueous resin is a resin that is soluble in an aqueous medium, and preferably a resin that is soluble in an aqueous removal solution. For example, the aqueous resin may be a resin that is miscible with an aqueous medium, preferably water, as described later.

[0039] The aqueous resin may contain an aqueous resin having a polar structure. Examples of aqueous resins having a polar structure include aqueous resins having polar groups and aqueous resins having polar moieties in the resin skeleton. Polar groups and polar moieties include, for example, one or more selected from the group consisting of acid groups, hydroxyl groups, ether bonds, ester bonds, urethane bonds, amino groups, and amide groups. The resin skeleton is preferably one of the aqueous resins having acidic groups described later. For example, at least one selected from the group consisting of polyvinyl alcohol resins, acrylic resins, urethane resins, polysaccharide resins, casein, polyether resins, polyester resins, polyethyleneimine resins, polyallylamine resins, and polyvinylpyrrolidone resins. Among these, one or more selected from the group consisting of polyvinyl alcohol resins, acrylic resins, urethane resins, casein, polyether resins, polyethyleneimine resins, polyallylamine resins, and polyvinylpyrrolidone resins is preferred. Aqueous resins with a polar structure are less prone to gelation and maintain an appropriate viscosity range when designing coating agents suitable for high-speed printing. This allows for high-resolution printing of coating layer patterns and further enhances the fine-line reproducibility of conductive films. Examples of polysaccharide resins include cellulose resins and water-soluble polysaccharides. Examples of cellulose resins include carboxymethylcellulose and hydroxypropylcellulose. In one embodiment, a cellulose resin may not be used as the main component. Therefore, the cellulose resin may be present in amounts of 5% by mass or less, 1% by mass or less, or 0.1% by mass or less per 100% by mass of the coating agent, and may be substantially absent.

[0040] <Water-based resin containing acidic groups> In some embodiments, the aqueous resin is preferably an aqueous resin having acidic groups, and a combination of an aqueous resin having acidic groups and an aqueous resin not having acidic groups may be used. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phenolic hydroxyl groups. Among these, carboxyl groups are preferred. The presence of acidic groups in the aqueous resin makes it easier for hydrophilic parts to orient themselves further to the surface of the coating layer. If the coating agent further contains particles or colorants, the aqueous resin having acidic groups has the ability to adsorb to the particles or colorants, thus contributing to the dispersibility of the particles or colorants. The acid value of the aqueous resin having acidic groups is preferably 5 to 200 mgKOH / g, and more preferably 30 to 150 mgKOH / g. When the acid value of the aqueous resin having acidic groups is within the above range, fine line reproducibility and immersion washability are further improved. In this disclosure, the acid value of the aqueous resin is the acid value (mgKOH / g) measured in accordance with the potentiometric titration method of JIS K 0070.

[0041] Examples of aqueous resin skeletons having acidic groups include polyvinyl alcohol resins, acrylic resins, styrene-acrylic resins, styrene-maleic acid resins, urethane resins, polylactic acid resins, resol-type phenolic resins, methylolated urea resins, methylolated melamine resins, polyethylene oxide, polyacrylamide, polysaccharide resins, and modified resins thereof. These aqueous resins having acidic groups can be used individually or in combination of two or more. Among the above, one or more selected from the group consisting of polyvinyl alcohol resins, acrylic resins, and polysaccharide resins (excluding cellulose resins) are preferred, polyvinyl alcohol resins and / or polysaccharide resins (excluding cellulose resins) are more preferred, and polyvinyl alcohol resins are even more preferred.

[0042] The polysaccharide resin can be any compound in which two or more known monosaccharides are bonded together, such as cellulose resins, pullulan, starch, agarose, and gum arabic. Among these, one or more selected from the group consisting of pullulan and starch are preferred.

[0043] Furthermore, in the case of resin skeletons that do not have acidic groups, acidic groups can be imparted by acid modification using known methods.

[0044] <Polyvinyl alcohol-based resin (A)> 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. The polyvinyl alcohol resin (A) may also be an ethylene vinyl alcohol resin that further contains structural units derived from ethylene.

[0045] The degree of polymerization of the polyvinyl alcohol-based resin (A) is preferably 100 to 3,000, and more preferably 500 to 2,400. When the degree of polymerization of the polyvinyl alcohol-based resin (A) is within the above range, the immersion washability, fine line reproducibility, high-speed printing suitability, and long-term stability are further improved.

[0046] When the polyvinyl alcohol-based resin (A) contains ethylene-derived structural units, the content of ethylene-derived structural units in the polyvinyl alcohol-based resin (A) is preferably 1 to 40 mol%, more preferably 3 to 20 mol%, and even more preferably 5 to 15 mol%. When the content of ethylene-derived structural units is within the above range, the immersion washability and long-term stability are further improved.

[0047] The polyvinyl alcohol-based resin (A) can be a resin crosslinked with a crosslinking agent. Examples of known crosslinking agents include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, oxazoline-based crosslinking agents, and silane coupling-based crosslinking agents. Among these, oxazoline-based crosslinking agents and silane coupling-based crosslinking agents are preferred.

[0048] The degree of saponification of the polyvinyl alcohol-based resin (A) is expressed by the following formula (Formula 2), and is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more. When the degree of saponification of the polyvinyl alcohol-based resin (A) is within the above range, the immersion washability and long-term stability are further improved. (Equation 2) Degree of saponification: (Number of hydroxyl groups) / {(Number of hydroxyl groups) + (Number of acetate groups)} × 100 [mol%]

[0049] Polyvinyl alcohol-based resin (A) is, for example, carboxylic acid-modified polyvinyl alcohol, specifically itaconic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and the like.

[0050] Examples of commercially available polyvinyl alcohol-based resins (A) include 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).

[0051] <Water-based resin without acidic groups> In some embodiments, the coating agent may include an aqueous resin that does not have acidic groups. The aqueous resin that does not have acidic groups may be used alone or in combination with an aqueous resin that has acidic groups. Examples of aqueous resins that do not have acidic groups 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. The aqueous resins can be used alone or in combination of two or more. Among the above, it is preferable to include a polyvinyl alcohol-based resin.

[0052] <Polyvinyl alcohol-based resin (B)> In some embodiments, the coating agent may also preferably include a polyvinyl alcohol-based resin (B) that does not have acidic groups. This polyvinyl alcohol-based resin (B) that does not have acidic groups is preferably included in the coating agent together with an aqueous resin that has acidic groups. The polyvinyl alcohol-based resin (B) may be any resin that does not have acidic groups and has vinyl alcohol units, and may further contain ethylene-derived structural units. For example, it may be an ethylene vinyl alcohol resin. Preferred embodiments regarding the degree of polymerization, crosslinking, and saponification of the polyvinyl alcohol-based resin (B) can be found by referring to the description of <Polyvinyl alcohol-based resin (A)> above.

[0053] The polyvinyl alcohol-based resin (B) preferably contains ethylene-derived structural units, and the content of ethylene-derived structural units in the polyvinyl alcohol-based resin (B) is preferably 1 to 40 mol%, more preferably 3 to 20 mol%, and even more preferably 5 to 15 mol%. When the content of ethylene-derived structural units is within the above range, the immersion washability and long-term stability are further improved.

[0054] In some embodiments, the total content of the aqueous resin is preferably 10 to 80% by mass, more preferably 25 to 70% by mass, and even more preferably 40 to 60% by mass, based on 100% by mass of the non-volatile content of the coating agent, from the viewpoint of fine line reproducibility, immersion washability, suitability for high-speed printing, and stability over time. A total content of 20% by mass or less, 18% by mass or less, or 15% by mass or less can further improve washability with water. Furthermore, a low viscosity coating agent makes it easier to obtain viscoelasticity suitable for high-speed printing.

[0055] The total content of the aqueous resin is preferably 0.1 to 30% by mass, more preferably 1 to 15% by mass, and even more preferably 2 to 8% by mass, based on 100% by mass of the coating agent.

[0056] When using an aqueous resin having an acidic group, the content of the aqueous resin having an acidic group is preferably 3 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 30% by mass, based on 100% by mass of the nonvolatile content of the coating agent, from the viewpoint of fine line reproducibility, immersion washability, suitability for high-speed printing, and stability over time.

[0057] When using an aqueous resin that does not contain acidic groups, the content of the aqueous resin that does not contain acidic groups is preferably 3 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 30% by mass, based on 100% by mass of the nonvolatile content of the coating agent, from the viewpoint of fine line reproducibility, suitability for high-speed printing, and ease of immersion cleaning.

[0058] In some embodiments, when the coating agent includes an aqueous resin having an acidic group and an aqueous resin not having an acidic group, the mass ratio of the aqueous resin having an acidic group to the aqueous resin not having an acidic group is preferably 9:1 to 1:9, and more preferably 7:3 to 3:7. When the mass ratio is within the above range, fine line reproducibility, immersion washability, suitability for high-speed printing, and stability over time are good.

[0059] <Particles and colorants> In some embodiments, the coating agent may further contain at least one selected from the group consisting of particles and colorants. This can further improve the removeability of the coating layer, particularly its water-based removeability, and further improve the fine line reproducibility. In addition to the removeability of the coating layer, colorants can be included in the coating agent for quality control purposes, such as visually confirming the formation of the coating layer.

[0060] The colorant may include at least one selected from the group consisting of organic pigments, inorganic pigments, and dyes. The particles may include resin particles. The resin particles may be colored resin particles or uncolored resin particles. Colored resin particles may be used as organic pigments. The particles and colorants may be used individually or in combination of two or more. From the viewpoint of viscoelasticity of a coating agent suitable for high-speed printing, organic pigments and inorganic pigments are preferred, and inorganic pigments are more preferred.

[0061] The average particle diameter (number-average diameter) in the volume-based particle size distribution measured by laser diffraction and scattering of particles and colorants is preferably 5 μm or less, more preferably 2 μm or less, even more preferably 1 μm or less, particularly preferably 0.5 μm or less, and even more preferably 0.01 to 0.1 μm. When the average particle diameter of particles and colorants measured by laser diffraction and scattering is within the above range, fine line reproducibility, suitability for high-speed printing, and stability over time are improved.

[0062] The specific surface area of ​​the particles and colorants is 10 to 100 m². 2 / g is preferred, 10-80m 2 / g is more preferable. When the specific surface area of ​​the particles and colorants is within the above range, fine line reproducibility, suitability for high-speed printing, and stability over time are improved.

[0063] The particle and colorant shapes can be known shapes such as spherical, square, cubic, or layered. Among these, spherical is preferred from the viewpoint of dispersibility. When the particles are spherical, fine line reproducibility, immersion washability, suitability for high-speed printing, and stability over time are improved.

[0064] <Organic pigments> The following are specific examples of organic pigments, indicated by their color index numbers. Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2 , 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 2 Examples include 50, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, etc.

[0065] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0066] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0067] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc.

[0068] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118 Examples include 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, etc.

[0069] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73.

[0070] Examples of cyan coloring compositions include blue pigments such as CI Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, and 81.

[0071] Examples of magenta colored compositions include purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, and 81.

[0072] <Inorganic pigments> Inorganic pigments include metal particles, metal oxide particles, metal carbonate particles, metal sulfide particles, non-metal oxide particles, mineral particles, and carbon black. Examples of inorganic pigments include calcium carbonate, titanium dioxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black. These pigments may be surface-treated with resins or the like.

[0073] <Inorganic fine particles> In some embodiments, it is preferable to include inorganic fine particles as one embodiment of the inorganic pigment. The inorganic fine particles are preferably particles that are finely ground to a degree that they can be dispersed in the coating agent. The inorganic fine particles may have an average particle diameter of 5 μm or less, 2 μm or less, 1 μm or less, 0.5 μm or less, or 0.1 μm or less in the volume-based particle size distribution measured by laser diffraction-scattering.

[0074] Examples of inorganic fine particles include metal fine particles, alloy fine particles, and inorganic compound fine particles. The inorganic fine particles may be inorganic compound fine particles and may contain at least one selected from the group consisting of inorganic oxide fine particles, inorganic carbonate fine particles, inorganic sulfate fine particles, and mineral fine particles. Examples of inorganic fine particles include titanium dioxide, zinc oxide, zinc sulfide chromium oxide, aluminum particles, mica, bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine, Prussian blue, red iron oxide, yellow iron oxide, iron black, silica, barium sulfate, mica, montmorillonite, kaolin clay, talc, calcium carbonate, magnesium carbonate, etc. At least one selected from the group consisting of calcium carbonate, barium sulfate, magnesium carbonate, silica, titanium dioxide, talc, montmorillonite, kaolin, and mica is preferred, and calcium carbonate is more preferred. The specific gravity of the inorganic fine particles is preferably 1.5 to 6, 2 to 4, or 2.4 to 2.7 from the viewpoint of suppressing sedimentation in the coating agent. Calcium carbonate is preferable because its low specific gravity makes it less likely to settle, thus improving the stability of the coating agent, and also because it causes less increase in viscosity of the coating agent due to its oil absorption and shape.

[0075] The pH of the extract water for inorganic fine particles is preferably neutral to alkaline, preferably 7.5 to 14, more preferably 7.8 to 12, and even more preferably 8.0 to 9.0. In particular, if the pH is alkaline, the acidic groups of the aqueous resin are easily adsorbed, which improves the fine wire reproducibility, immersion washing ability, and stability over time. The pH of the extract water for inorganic fine particles can be determined by mixing 5 parts inorganic fine particles with 100 parts 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.

[0076] <Calcium carbonate> Calcium carbonate can be produced in two forms: natural calcium carbonate (heavy calcium carbonate) and synthetic calcium carbonate (light calcium carbonate). Natural calcium carbonate is produced directly from limestone, for example, by mechanically crushing and classifying raw limestone. Synthetic calcium carbonate is produced from calcium hydroxide, for example, by reacting calcium hydroxide with carbon dioxide. Calcium carbonate that has been further surface-treated with fatty acids, resin acids, silane coupling agents, etc., can also be used.

[0077] <Resin particles> Examples of resin particles include amino resin particles, (meth)acrylic resin particles, styrene-acrylic copolymer resin particles, urethane resin particles, polyethylene terephthalate (PET) resin particles, silicone resin particles, polycarbonate resin particles, polyethylene particles, and polystyrene resin particles. Among amino resin particles, benzoguanamine-based resin particles such as melamine resin particles, melamine-benzoguanamine resin particles, and formaldehyde-benzoguanamine resin particles are preferred. Among these, amino resin particles, urethane resin particles, (meth)acrylic particles, and polyethylene resin particles are particularly preferred, as these resin particles have a high affinity for aqueous resins, which tends to improve washability, printability, and long-term stability.

[0078] The resin particles may be used in a dispersed state in a liquid medium such as an aqueous dispersion. The resin particles may be used individually or in combination of two or more types.

[0079] Commercially available urethane resin particles include, for example, cross-linked urethane beads such as Art Pearl C-1000 transparent and Art Pearl MM-120T (manufactured by Negami Kogyo Co., Ltd.).

[0080] Examples of commercially available melamine resin particles include Epostor SS, Epostor S, Epostor FS, Epostor S6, and Epostor S12 (manufactured by Nippon Shokubai Co., Ltd.). An example of a commercially available melamine-benzoguanamine resin particle is Epostor M30 (manufactured by Nippon Shokubai Co., Ltd.).

[0081] Examples of commercially available acrylic resin particles include Epostor MA1002, Epostor MA1004 (manufactured by Nippon Shokubai Co., Ltd.), Toughtick FH-S005 (manufactured by Toyobo Co., Ltd.), Chemisnow MX-80H3wT, MX-150, MX-180TA, MX-300, and MX-500 (manufactured by Soken Chemical Co., Ltd.).

[0082] Examples of commercially available polyethylene resin particles include ChemiPearl W100, ChemiPearl W300, and ChemiPearl W500 (manufactured by Mitsui Chemicals, Inc.).

[0083] <dye> Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Also included are derivatives of dyes and lake pigments, which are dyes that have been transformed into lakes.

[0084] The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), and quinoneimine dyes (oxazine dyes). Examples include dyes such as thiazine dyes, azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes.

[0085] When particles, colorants, or combinations thereof are used, the total content of these in the coating agent may be 3 to 90% by mass of 100% by mass of the nonvolatile content of the coating agent. When inorganic pigments, organic pigments, resin particles, or combinations thereof are used, the total content of these in the coating agent is preferably 10 to 90% by mass, more preferably 25 to 80% by mass, and even more preferably 45 to 75% by mass, of 100% by mass of the nonvolatile content of the coating agent. When dyes are used, the dye content in the coating agent is preferably 3 to 70% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 25% by mass, of 100% by mass of the nonvolatile content of the coating agent. When these content levels are within the above ranges, fine line reproducibility, immersion washability, suitability for high-speed printing, aging stability, and fine line visibility are improved. Improved aging stability of the coating agent allows for higher-resolution printing of the coating agent pattern, thus further improving the fine line reproducibility of conductive patterns.

[0086] When particles, colorants, or combinations thereof are used, the total content of these in the coating agent is preferably 3 to 20% by mass, and more preferably 5 to 15% by mass, based on 100% by mass of the coating agent. When these content levels are within the above range, fine line reproducibility, immersion washability, suitability for high-speed printing, and stability over time are improved.

[0087] Dispersants can be used to improve the dispersibility of particles or colorants. Examples of dispersants include surfactants and resin dispersants. Among these, resin-type dispersants are particularly useful. Preferred structures for resin-type dispersants are AB block polymers, comb polymers, and graft polymers. Examples of resin types for resin-type dispersants include acrylic resins, styrene-acrylic resins, and polyester resins. Resin-type dispersants preferably contain one or more acidic groups and amino groups, depending on the polarity of the particles or colorants. The content of the dispersant is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the total of the particles and colorants.

[0088] The mass ratio of the aqueous resin to the total mass of particles, colorants, or combinations thereof is preferably 1:0.01 to 1:3, more preferably 1:0.05 to 1:2, and even more preferably 1:0.1 to 1:1. When these mass ratios are within the above ranges, fine line reproducibility, immersion washability, suitability for high-speed printing, stability over time, and fine line visibility are further improved.

[0089] The coating agent preferably contains an aqueous resin having an acidic group and inorganic fine particles. In this case, the mass ratio of the aqueous resin having an acidic group to the inorganic fine particles is preferably 1:0.2 to 1:3, and 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, fine line reproducibility, immersion cleaning ability, suitability for high-speed printing, and stability over time are improved.

[0090] <Aqueous medium> In some embodiments, the coating agent may contain water and a water-soluble organic solvent as an aqueous medium. Depending on the printing method and printing conditions (speed, plate depth, design, drying temperature), the water-soluble organic solvent may include alcohol-based organic solvents, glycol-based organic solvents, etc. Among these, it is preferable to include an alcohol-based organic solvent from the viewpoint of fine line reproducibility, suitability for high-speed printing, and stability over time. In this disclosure, a water-soluble organic solvent refers to a solvent that is liquid at 25°C and has a solubility of 1 part by mass or more in 100 parts by mass of water at 25°C.

[0091] The total amount of water and water-soluble organic solvent is preferably 50 to 95% by mass, and more preferably 70 to 90% by mass, of 100% by mass of the coating agent, from the viewpoint of fine line reproducibility, suitability for high-speed printing, and stability over time.

[0092] From the viewpoint of fine line reproducibility, suitability for high-speed printing, and stability over time, the water content is preferably 70 to 100% by mass, and more preferably 85 to 95% by mass, of 100% by mass of the aqueous medium.

[0093] 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, and more preferably 1 to 15% by mass, per 100% by mass of the coating agent, from the viewpoint of long-term stability, suitability for high-speed printing, and fine line reproduction.

[0094] Examples of the above-mentioned alcohol-based organic solvents include methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, tertiary-butanol, hexanol, octanol, and decanol. In the case of coating methods using gravure printing or flexographic printing, at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol is preferred, with n-propanol being even more preferred in terms of long-term stability.

[0095] When the aqueous medium 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, and more preferably 85:15 to 95:5, from the viewpoint of long-term stability, suitability for high-speed printing, and fine line reproduction.

[0096] Examples of the glycol-based organic solvents mentioned above include acetylenediol, 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, dipyrropylene 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, and dibutyl glycol. 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. The water-soluble organic solvent may be used alone or in combination of two or more.

[0097] When the aqueous medium contains water and a glycol-based organic solvent, the mass ratio of water to the glycol-based organic solvent is preferably 100:10 to 100:0.2, and more preferably 100:5 to 100:0.2. When the mass ratio of water to the glycol-based organic solvent is within the above range, fine line reproducibility, suitability for high-speed printing, and stability over time are improved.

[0098] <Additives> In some embodiments, the coating agent may contain known additives such as isocyanate compounds, silane coupling agents, dispersants, stabilizers, viscosity modifiers, and colorants, to the extent that they do not impair the effects of the present disclosure.

[0099] <Alkaline-removable coating agent> Another embodiment of the coating agent is an alkaline peelable coating agent that uses Al-Ali water as the removal solution. Alkaline peelable coating agents are particularly useful in lift-off processes that form patterns without using photolithography, for example, when using substrates from which the coating layer is difficult to remove with water alone.

[0100] The alkali-removable coating agent may contain an alkali-soluble resin and water. The alkali-removable coating agent may be the same as or different from the coating agent described above. The alkali-soluble resin may be a resin having an acidic group, and preferably a resin having one or more acidic groups selected from the group consisting of sulfonic acid groups and carboxyl groups.

[0101] The alkali-soluble resins can be, for example, polyvinyl alcohol, urethane resin, styrene-acrylic resin, styrene (anhydrous) maleic acid resin, acrylic resin, acrylamide resin, or acrylic / acrylamide copolymer resin. From the viewpoint of fine line reproducibility and removeability, urethane resin, acrylic resin, styrene-acrylic resin, and styrene (anhydrous) maleic acid resin are preferred.

[0102] The acid value of the alkali-soluble resin is preferably 30 to 200 mg KOH / g, and more preferably 60 to 150 mg KOH / g. When the resin has an appropriate acid value, the coating layer removal performance is improved. The content of the alkali-soluble resin is preferably 1 to 95% by mass, and more preferably 5 to 80% by mass, of 100% by mass of the non-volatile content of the alkali-removable coating agent.

[0103] The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 200,000, and more preferably 3,000 to 150,000. When the resin has an appropriate Mw, it can achieve a high degree of both fine-wire formation and alkali-release properties. Note that Mw is the molecular weight on a polystyrene basis, measured by gel permeation chromatography.

[0104] The alkali-removable coating agent may further contain at least one selected from the group consisting of particles and colorants. Specifically, one or more particles and colorants can be selected from those included in the coating agent described above. The mass ratio of alkali-soluble resin to particles and colorants, and their respective contents in the coating agent, may be the same as those of the coating agent described above. The alkali-removable coating agent may contain any additives in any proportion, similar to the coating agent described above.

[0105] <Method of manufacturing coating agent> In some embodiments, the coating agent can be manufactured by mixing, for example, an aqueous resin, water, and optionally particles, a colorant, a water-soluble organic solvent, dispersing the colorant using a disperser, and then mixing various additives and organic solvents into the resulting dispersion. Commonly used dispersers such as roller mills, ball mills, pebble mills, attritors, and sand mills can be used.

[0106] <Residual rate of the coating layer> In this disclosure, the residual rate of the coating layer is the value represented by the following formula (Formula 1) after processing a laminate formed by applying a coating agent to a substrate to create a coating layer with a thickness of 1 μm under the following conditions. In some embodiments, the residual rate of the coating layer formed using the coating agent is preferably less than 80% by mass, more preferably less than 50% by mass, even more preferably less than 10% by mass, and particularly preferably less than 5% by mass. When the residual rate of the coating layer is within the above range, the removal rate of the coating layer and unwanted conductive film portions is improved during immersion cleaning, which tends to improve fine line reproducibility. (Processing conditions) The laminate was immersed in deionized water at 40°C for 10 minutes, then dried in an oven at 80°C for 1 minute. (Equation 1) Residual rate of the coating layer (mass %) = (mass of the coating layer after treatment) / (mass of the coating layer before treatment) × 100

[0107] A coating agent that satisfies the requirements for the residual rate of the coating layer represented by the above formula (Formula 1) comprises an aqueous resin and water, and preferably contains 50 to 95% by mass of water in 100% by mass of the coating agent. In this case, the aqueous resin is preferably an aqueous resin having an acidic group. The coating agent further preferably contains particles and a colorant, and more preferably contains inorganic fine particles.

[0108] <Other examples of coating agents> Another example of embodiments of this disclosure relates to a coating agent for a lift-off process that includes a pattern formation step that does not use photolithography, wherein the coating agent is used in a state diluted with a diluent solvent, the coating agent comprising an aqueous resin and water, and being at least one selected from the group consisting of gravure printing, flexographic printing, and inkjet printing, having a viscosity at 25°C of 50 mPa·s or more and less than 2000 mPa·s as measured according to JIS K 7117-1, containing 50 to 95% by mass of water in 100% by mass of the coating agent in the state diluted with the diluent solvent, and having a viscosity at 25°C of 50 mPa·s or more and 500 mPa·s or less as measured according to JIS K 7117-1.

[0109] In this example, the coating agent before dilution with the diluent solvent is also referred to as the undiluted coating agent, and the coating agent after dilution with the diluent solvent is also referred to as the diluted coating agent. The undiluted coating agent contains the components at a high concentration. The undiluted coating agent should ideally be provided in a state where it has been stored from the time of manufacture until before printing. The diluted coating agent is diluted with the diluent solvent to suit the printing conditions and printing method. The diluted coating agent should ideally be provided with the diluent solvent added when printing the coating agent.

[0110] The viscosity of the coating agent before dilution is preferably 50 mPa·s or more and less than 2000 mPa·s. The viscosity of the coating agent before dilution is preferably 50 mPa·s or more, 150 mPa·s or more, 180 mPa·s or more, or 200 mPa·s or more. Within these ranges, aggregation or sedimentation of each component can be suppressed under storage conditions, and the storage stability of the coating agent before dilution can be further improved. The viscosity of the coating agent before dilution is preferably less than 2000 mPa·s, 1000 mPa·s or less, 700 mPa·s or less, or 500 mPa·s or less. Within these ranges, when diluting with a diluting solvent, the compatibility between the coating agent before dilution and the diluting solvent can be increased, and the component uniformity of the diluted coating agent can be further improved. In addition, increasing the water content of the diluted coating agent can further improve compatibility with the diluting solvent and the component uniformity of the resulting diluted coating agent. For example, the viscosity of the coating agent before dilution may be 50 mPa·s or more but less than 2000 mPa·s, 150 mPa·s or more but 1000 mPa·s or less, 180 mPa·s or more but 700 mPa·s or less, or 200 mPa·s or more but 500 mPa·s or less.

[0111] From the viewpoint of adjusting viscosity, the non-volatile content of the pre-diluted coating agent when printed on the substrate is preferably 10-50% by mass, 15-30% by mass, or 18-25% by mass. In this disclosure, the non-volatile content is the mass of the coating layer formed by printing the coating agent on the substrate and drying it.

[0112] The pre-dilution coating agent contains an aqueous resin and water, and may further contain particles, colorants, and optional additives. The components contained in the pre-dilution coating agent can be the same as those of the coating agent described above. The pre-dilution coating agent should contain each component such that, after dilution with a diluting solvent, the diluted coating agent has the same components and their proportions as the coating agent described above.

[0113] The pre-dilution coating agent may contain, for example, 50-90% by mass, 70-85% by mass, or 75-80% by mass of water per 100% by mass of the coating agent. The pre-dilution coating agent may contain 0.1-40% by mass, 1-25% by mass, or 2-18% by mass of aqueous resin per 100% by mass of the coating agent. If particles, colorants, or combinations thereof are included, the pre-dilution coating agent may contain a total of 3-30% by mass, 5-25% by mass, or 7-15% by mass of these per 100% by mass of the coating agent.

[0114] The diluent is preferably an aqueous medium. The aqueous medium may include water, a water-soluble organic solvent, or a combination thereof. The water-soluble organic solvent can be selected from one or more of the water-soluble organic solvents contained in the coating agent described above.

[0115] The diluent preferably contains one or more aqueous media from among those contained in the pre-dilution coating agent to be diluted. Furthermore, if the pre-dilution coating agent contains two or more aqueous media, the diluent preferably uses the same two or more aqueous media as those contained in the pre-dilution coating agent, in the same mass ratio.

[0116] In the diluted coating agent, the water content and viscosity are preferably the same as those of the coating agent suitable for at least one type selected from the group consisting of gravure printing, flexographic printing, and inkjet printing, as described above.

[0117] <<Manufacturing method for laminates>> One embodiment of the present disclosure relates to a method for manufacturing a laminate, comprising the steps of: printing a coating agent onto a substrate to form a patterned coating layer without using photolithography; forming a conductive film on the substrate on which the coating layer is formed; and contacting the substrate on which the conductive film is formed with a coating layer removal liquid to remove the coating layer and form a conductive pattern. In this manufacturing method, the coating agent described above can be used as the coating agent.

[0118] The following describes a method for manufacturing a laminate according to several embodiments. In some embodiments, the method for manufacturing the laminate is characterized by the following steps. In these methods for manufacturing the laminate, the coating agent contains an aqueous resin and water, and the water content and viscosity are preferably within the range described above. Details of the coating agent are as described above. (1) A step of printing a coating agent onto a substrate to form a patterned coating layer without using photolithography. (2) A step of forming a conductive film on a substrate on which a coating layer has been formed. (3) A step of bringing a substrate on which a conductive film has been formed into contact with a removal solution to remove the coating layer and form a conductive pattern.

[0119] The coating agent contains an aqueous resin and water, and since the water content and viscosity are specified, the removal of the coating layer by the removal solution is enhanced, and together with the formation of a highly detailed patterned coating layer, fine line reproducibility of the conductive film can be obtained. In preferred examples, the coating agent may further contain particles, colorants, or a combination thereof. The coating agent may also contain a resin having a polar structure as the aqueous resin. With these coating agents, the aqueous resin is incorporated into the water while the coating film is formed on the surface of the substrate, so hydrophilic parts are more easily oriented on the surface of the coating layer. Furthermore, the aqueous resin contains water while the coating film is formed on the surface of the substrate, and minute channels are more easily formed in the coating layer due to the evaporation of water. When removing such a coating layer with a removal solution, the coating layer can be quickly dissolved or peeled off even when using an aqueous medium, thus further improving fine line reproducibility. However, the above effects are based on scientific considerations, and this disclosure is not limited to embodiments that exhibit these effects.

[0120] <Base material> The substrate is not limited as long as it can form a coating layer and a conductive pattern. For example, in applications of next-generation solar cells, which have seen a surge in development in recent years toward realizing a decarbonized society, it is preferable to use a lightweight and flexible plastic film as the substrate. As plastic films, polyester films, polyimide films, polyamide films, and polyphenylene ethers (including polystyrene-modified ones) are preferred for their weather resistance. Examples of polyester films include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). To provide the laminate with water vapor barrier properties, the substrate itself may have a barrier layer such as a transparent vapor-deposited inorganic oxide layer, or a hard coat layer to prevent scratching. Furthermore, the substrate may have surface treatments such as corona treatment or flame treatment to provide easy adhesion for printing and post-processing, and may also have a coating layer.

[0121] <Formation of the coating layer> A patterned coating layer can be formed by printing a coating agent onto a substrate. For example, a coating agent can be applied to a substrate, and volatile components can be removed to form the coating layer. Printing is preferred as the coating method. The printing method is preferably at least one selected from the group consisting of gravure printing, flexographic printing, waterless offset printing, inkjet printing, and rotary screen printing. Among these, at least one selected from the group consisting of gravure printing, flexographic printing, waterless offset printing, and inkjet printing is preferred. Plate printing methods such as gravure printing, flexographic printing, waterless offset printing, and rotary screen printing enable high-speed printing and are suitable for roll-to-roll printing using a rotary printing press. Plate printing allows for high-speed printing of multiple conductive patterns of the same shape in succession. Digital printing such as inkjet printing also enables high-speed printing by high-speed transport of the substrate and is suitable for roll-to-roll printing. Among these, gravure printing and flexographic printing are particularly preferred, and gravure printing is even more preferred.

[0122] The coating agent is printed onto the substrate using various printing methods, and then the coating layer is obtained by fixing the film through drying in an oven or the like.

[0123] The thickness of the coating layer is preferably 0.1 μm to 10 μm, more preferably 0.2 to 5 μm, even more preferably 0.3 to 3 μm, and particularly preferably 0.6 to 2 μm. When the thickness of the coating layer is within the above range, fine line reproducibility, washability, and fine line visibility tend to improve. From the viewpoint of productivity, the printing speed is preferably 10 to 300 m / min, more preferably 50 to 200 m / min, and even more preferably 80 to 150 m / min.

[0124] In this disclosure, the method for measuring the thickness of the coating layer involves sampling a 5mm x 25mm sample from a laminate having a patterned coating layer on a substrate, fixing it in a vise between plastic plates, creating a smooth cross-section using a retratome REM-710 (Yamato Koki Kogyo Co., Ltd.), measuring the surface at 10 locations using a laser microscope VK-9700 (Keyence Corporation), and calculating the average value of these measurements to obtain the thickness of the coating layer.

[0125] In the process of printing the coating layer, volatile components such as solvents may be removed by drying the substrate after printing the coating agent. The drying temperature is preferably 70 to 120°C, and the drying time is preferably 0.1 to 10 seconds, more preferably 1 to 5 seconds. The airflow during drying is preferably 40 m / min or more. As the drying apparatus, a known continuous processing oven or an in-line oven attached to the printing press can be used, and it is preferable to use an in-line oven attached to the printing press.

[0126] Gravure printing (Gravure version) Gravure plates are cylindrical and made of metal. There are two methods for forming the cells of a gravure plate: engraving and etching (photosensitive film coating - exposure - development - etching). Etching is preferred because it allows cells to be formed along the edges of the image, resulting in sharper contours of the coating layer. Furthermore, the etching method allows for increased cell precision by improving the resolution during exposure. For plate-making equipment, it is preferable to use, for example, the Sync Laboratory FXIII laser automatic plate-making system (laser drawing resolution: 3200 dpi in the longitudinal direction / 12800 dpi in the circumferential direction) or the MDC DIGILAS5000 laser plate-making equipment / electronic engraving machine, and more preferably the MDC DIGILAS5000. In yet another example of the etching method, cells of the gravure plate may be formed by photosensitive film coating - laser irradiation - etching. For such plate-making equipment, for example, the MDC DIGILAS5000 can be used.

[0127] The line screen frequency, a parameter equivalent to the printing resolution, is preferably 200 to 350 lines / inch. When the line screen frequency is 200 / inch or higher, the edge shape of the printed area tends to be better, which improves the reproduction and visibility of fine lines. When the line screen frequency is 350 / inch or lower, the cell openings become larger, which improves ink transfer, which also tends to improve the reproduction and visibility of fine lines.

[0128] The plate depth, a parameter that controls the amount of ink transferred, is preferably 10 to 25 μm. When the plate depth is 15 μm or more, streaking of the coating layer can be suppressed, which tends to improve fine line reproducibility and fine line visibility. When the plate depth is 25 μm or less, the amount of coating agent applied is appropriate, which suppresses bleeding of the coating layer, which tends to improve fine line reproducibility and fine line visibility. In addition, by setting the plate depth to 25 μm or less, the amount of coating agent applied can be reduced, which also reduces drying energy and improves printing speed, i.e., productivity. Furthermore, it is preferable that the plate has island patterns and, in addition to island patterns, printing frame processing, and when the line width of the frame processing is within the above range, fine line reproducibility and fine line visibility tend to improve.

[0129] In the case of water-based inks with slow drying times or polyester films with good wetting and spreading properties, the pattern line width of the printed material tends to be wider than the plate pattern line width due to the coating agent wetting and spreading on the film. In such cases, from the viewpoint of suppressing bleeding due to the wetting and 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 75-90%, and more preferably 77-85%. When the plate pattern line width / target pattern line width is within the above range, fine line reproduction and fine line visibility are good.

[0130] (Gravure printing machine) In a gravure printing press, each printing unit is equipped with the above-mentioned gravure plate and doctor blade. There are multiple printing units, and typically, printing units corresponding to organic solvent-based printing inks and pattern inks can be configured, and each unit has an oven drying unit. Printing is performed by rotary printing using a roll printing method. The type of plate and doctor blade can be selected as appropriate, according to the specifications. In some embodiments, a coating layer pattern can be printed using a printing unit on the upstream side in the transport direction, and a conductive film can be formed using a conductive film forming unit on the downstream side in the transport direction.

[0131] <Flexographic printing> (Flexographic version) Flexographic plates used in flexographic printing include photosensitive resin plates that utilize ultraviolet curing or elastomer plates that use a direct laser engraving method. From the viewpoint of fine line reproduction and fine line visibility, regardless of the method of forming the image portion of the flexographic plate, a screening screen count of 75 lines / inch or higher is preferred. Photosensitive resin plates are preferred for obtaining high-definition printed materials. Photosensitive resin plates include liquid plates, which form a relief by curing a fluid liquid resin, and solid plates, which form a relief by exposing and curing a sheet-like solid resin and removing unwanted parts with a development process. Furthermore, solid plates have various development processes, including solvent-developed types that use organic solvents, water-developed types that use aqueous developer instead of organic solvents, and thermal-developed types that absorb uncured parts with a nonwoven fabric by applying heat. Among these, the water-developed type is preferred because it produces a high-definition plate with less swelling. For processing the flexographic plate, a microcell and flat top are preferred. Microcell processing involves adding fine patterns to the printing plate to improve transferability and suppress unevenness and margins. Flat top processing blocks oxygen during exposure, resulting in a flat surface. Compared to round top processing, it tends to reduce dot gain during long runs, distributes pressure for increased plate durability, allows for kiss-touch printing, and minimizes the appearance of raised edges. The sleeves and cushioning tapes used to attach the printing plate can be selected as desired.

[0132] (Flexographic printing press) In a flexographic printing press, the anilox roller first receives the coating agent from the coating agent tank, and then the ink is transferred to the flexographic plate. The flexographic plate has the design to be printed embossed on it, and ink remains only on the design area. As the substrate passes between the impression cylinder and the flexographic plate, the design is transferred onto the substrate. The anilox roller has a fine cell structure, which allows for a uniform supply of the coating agent to the plate. Flexographic printing presses used in the flexographic printing method include CI-type multi-color flexographic printing presses and unit-type multi-color flexographic printing presses, and ink supply methods include the chamber method and the two-roll method. Anilox rolls used in the flexographic printing method can be cell-engraved ceramic anilox rolls, chrome-plated anilox rolls, etc. To obtain printed materials with excellent dot reproduction, anilox rolls with a line screen count of 5 times or more, preferably 6 times or more, the line screen count of the printing plate used during printing are used. For example, if the screen resolution is 75 lpi, an anilox roll of 375 lpi or higher is required, and if the screen resolution is 150 lpi, an anilox roll of 750 lpi or higher is required. Regarding the anilox roll capacity, from the perspective of fine line reproducibility and fine line visibility, it should be 1-8 cc / m². 2 Capacity, preferably 2-6 cc / m³ 2 This is an anilox roll.

[0133] <Waterless offset printing> (Waterless offset printing version) The waterless offset printing plate has a thin silicone layer on its surface. This silicone layer prevents the coating agent from adhering to the non-image areas. Beneath the silicone layer is an exposable polymer layer, which is the area where the image is formed. During plate making, this polymer layer is exposed to form the image area. The silicone layer and polymer layer are provided on an aluminum substrate, thereby providing a stable structure and durability. From the viewpoint of fine line reproduction and fine line visibility, the resolution of the waterless offset printing plate is preferably 300 dots / inch or higher, more preferably 1000 dots / inch or higher, and even more preferably 2000 dots / inch or higher.

[0134] (Waterless offset printing press) In a waterless offset printing press, all components except the printing plate can be the same as those used in conventional offset printing presses. For example, a coating agent is transferred to the plate via an ink roller, and only the image portion receives the coating agent, which is then transferred to the substrate in a later process. The image is transferred from the coated plate to a rubber cylinder called a blanket cylinder, and finally the ink is transferred from the blanket cylinder to the substrate. A web printing system is preferred for waterless offset printing presses, and a web printing system with a drying oven is more preferred.

[0135] <Screen Printing> (Screen print version) In screen printing, a design is transferred to a mesh material called a screen, which can then be used as a printing plate. Typically, synthetic fibers such as nylon or polyester, or metal materials, are used for the screen material. The screen has areas that the coating agent can pass through and areas that it cannot. The design can be printed by pressing the coating agent onto the substrate through the mesh. Low-density mesh is used in normal screen printing, but for high-definition printing, a higher-density mesh (more fibers and finer) is used, and a mesh count of 200 or more is preferable from the viewpoint of fine line reproduction and fine line visibility.

[0136] (Screen printing machine) A screen printing apparatus supplies a coating agent onto a screen and uses a squeegee to spread the coating agent evenly. This allows the coating agent to pass through the openings in the screen and be transferred to the substrate. Among screen printing apparatuses, rotary screen printing is preferred from the viewpoint of productivity. Rotary screen printing uses a cylindrical screen. The coating agent is supplied into the screen, and as the screen rotates, the coating agent is pushed out from the mesh portion by the squeegee and transferred to the substrate.

[0137] <Inkjet printing> In inkjet printing, two main technologies, the piezoelectric method or the thermal method, are used to eject the coating agent from the nozzle. The higher the nozzle density, the more ink drops can be accurately placed at once. Therefore, from the viewpoint of fine line reproduction and fine line visibility, a nozzle density of dots / inch or higher is preferable, 300 dots / inch is more preferable, and 600 dots / inch or higher is even preferable. Also, the smaller the nozzle diameter, the finer the drops that are formed. Therefore, from the viewpoint of fine line reproduction and fine line visibility, a nozzle diameter of 10 to 30 μm is preferable, and 15 to 20 μm is more preferable.

[0138] <Formation of conductive film> Conductive films can be formed by depositing a conductor onto a substrate using dry methods such as vapor deposition and sputtering. Among these methods, sputtering is preferred as it is excellent for depositing large-area films suitable for mass production. Examples of conductors include metals such as Al, Ti, Pb, Ni, Cu, Ag, Au, Cr, Sn, and In, and oxides such as ITO, FTO (fluorine-doped tin oxide), IZO, Al2O3, and SiO2. For applications in next-generation solar cells, ITO is particularly preferred because it is a transparent electrode and Pb-free. Conductive films can also be formed by laminating foil-shaped conductive films.

[0139] The conductive film may be formed using a roll-to-roll method. For example, in a rotary printing press, a printing unit may be provided on the upstream side in the transport direction to print the pattern of the coating layer, and a sputtering unit or deposition unit may be provided on the downstream side in the transport direction to form the conductive film. Since the conductive film only needs to be formed uniformly on the substrate and the coating layer, a high-resolution printing method is not required, and it is preferable to form it by sputtering, vacuum deposition, ion plating, or CVD (chemical vapor deposition).

[0140] The thickness of the conductive film is preferably 0.01 μm to 100 μm, more preferably 0.05 to 50 μm, and even more preferably 0.1 to 10 μm. From the viewpoint of coating layer removalability, the thickness of the conductive film is preferably 0.01 μm or more, and less than 10 μm, less than 5 μm, less than 1 μm, or less than 0.4 μm.

[0141] The thickness of the conductive film and the thickness of the coating layer preferably satisfy the following formula. When this formula is satisfied, the area of ​​the side surface of the pattern coating layer that is not covered by the conductive film increases, which tends to improve cleaning performance as the cleaning solution penetrates the coating layer more easily. Formula: Thickness of conductive film [μm] < Thickness of coating layer [μm]

[0142] For example, if the thickness of the coating layer is 100%, the thickness of the conductive film should be 0.1% or more, and preferably less than 100%, less than 50%, less than 10%, or less than 4%.

[0143] In this disclosure, the method for measuring the thickness of a conductive film involves sampling a 5 mm x 25 mm sample from a laminate having a pattern coating layer and a conductive film on a substrate, fixing it in a vise between plastic plates, creating a smooth cross-section using a retratem REM-710 (Yamato Koki Kogyo Co., Ltd.), measuring 10 locations where the conductive film is present using an electron microscope JSM-7800 (manufactured by JEOL Ltd.), and calculating the average value of these measurements to obtain the thickness of the conductive film.

[0144] <Removal of the coating layer> The coating layer is brought into contact with the removal solution by an appropriate method. For example, the coating layer may be sprayed onto the conductor covering the coating layer, the fluid of the removal solution may be flowed onto the surface of the conductor covering the coating layer, or the coating layer and the conductor covering it may be immersed in the removal solution. Immersion in the removal solution is preferred as the method for removing the coating layer.

[0145] The coating layer may be removed in-line after the conductive film is formed, or the substrate after the conductive film has been formed, which has been wound into a roll, may be unwound again. Removing the coating layer in-line after the conductive film is formed tends to improve fine-line reproducibility because the pressure applied during winding is eliminated. In addition, there is the advantage that blocking of the coating layer does not occur.

[0146] <Coating layer removal solution> As the removal solution, it is preferable to use water from an environmental perspective, such as facilitating wastewater treatment. Furthermore, while water may be used alone as the removal solution, a mixed solution containing a water-soluble organic solvent can also be used. Examples of water-soluble organic solvents 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.

[0147] Furthermore, the removal solution preferably contains at least one selected from the group consisting of nonionic surfactants, anionic surfactants, and cationic surfactants. When using a mixture of the above solvents, the water content in the mixture is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on 100% by mass of the mixture. When the water content in the mixture is within the above range, the fine line reproducibility tends to improve.

[0148] Another embodiment of the removal solution is a lift-off process that forms a pattern without using photolithography. For example, when using a substrate from which the coating layer is difficult to remove with water alone, alkaline water can be used as the removal solution. Examples of alkaline water include aqueous solutions of inorganic bases such as potassium hydroxide and sodium hydroxide. The concentration of the alkaline water is not limited as long as the coating layer can be removed, but it is preferably 0.01 to 1% by mass, and more preferably 0.02 to 0.5% by mass. A surfactant can be used in combination with the alkaline water.

[0149] <Roll-to-roll method> In some embodiments, the method for manufacturing the laminate may involve performing the coating layer formation step and the conductive film formation step, respectively, using a roll-to-roll method. In one example of the roll-to-roll method, a long substrate is wound into a roll, the substrate is continuously conveyed, a coating agent is printed on it, and after optional drying, the substrate is wound up to obtain a roll-shaped substrate with the coating layer formed. Next, the obtained roll-shaped substrate with the coating layer formed is further continuously conveyed to form a conductive film, and after optional drying, the substrate is wound up to obtain a roll-shaped substrate with the conductive film formed. Next, the roll-shaped substrate with the conductive film formed is further continuously conveyed to contact with a removal liquid to form a conductive pattern, and after optional drying, the substrate is wound up to obtain a roll-shaped substrate with the conductive pattern formed. In this example, roll winding is performed after each step of forming the coating layer, forming the conductive film, and removing the coating layer. However, roll winding may be performed after the processes from forming the coating layer to forming the conductive film are carried out continuously, or after the processes from forming the coating layer to removing the coating layer are carried out continuously, or roll winding may be performed after forming the coating layer, and then roll winding may be performed after the processes from forming the conductive film to removing the coating layer are carried out continuously. In other examples, the roll-shaped substrate may be cut into individual sheets before removing the coating layer, or the roll-shaped substrate may be cut into individual sheets after removing the coating layer.

[0150] According to some embodiments, the formation of both the coating layer and the conductive film can be performed using a roll-to-roll method, enabling high-speed pattern formation of the conductive film. The coating agent contains an aqueous resin and water, and the water content and viscosity are specified, providing viscoelasticity suitable for high-speed printing, allowing for the formation of a highly detailed patterned coating layer even with a roll-to-roll method. Furthermore, because fine line reproducibility of the coating layer pattern is achieved, even when the conductive film is subsequently formed using a roll-to-roll method, the reproducibility of the conductive pattern can be improved during the subsequent removal of the coating layer. Note that the manufacturing method of the laminate in this embodiment includes not only high-speed printing but also low-speed printing.

[0151] In some embodiments, the printing speed of the coating agent in a roll-to-roll method is preferably, for example, 10 m / min or more. High-speed printing of 25 m / min or more, 50 m / min or more, 100 m / min or more, or 120 m / min or more is also preferred. Furthermore, printing speeds of 300 m / min or less, 250 m / min or less, 200 m / min or less, or 180 m / min or less are also preferred. In some embodiments, the coating agent can exhibit excellent fine line reproduction even in high-speed printing of 120 m / min or more in gravure printing, which is particularly productive.

[0152] An example of a printing system will be described below with reference to the drawings. Figure 4 is a schematic cross-sectional view showing an example of a printing system. The printing system comprises, in order from the direction in which the substrate is transported, a substrate supply unit 10, a coating agent printing unit 20, a conductive film forming unit 30, and a substrate discharge unit 40. The substrate supply unit 10 houses a substrate roll 101 in which a long substrate 102 is wound into a roll shape, and continuously supplies the substrate 102 from the substrate roll 101. The substrate discharge unit 40 houses a substrate roll 401 in which a long substrate 104 is wound into a roll shape after printing.

[0153] The coating agent printing unit 20 is a rotary printing press that performs gravure printing on a long substrate 102. The coating agent printing unit 20 comprises a gravure cylinder 21a, an impression cylinder 21b, an ink pan 21c, and a doctor blade 21d. A pattern-shaped plate is formed on the outer surface of the gravure cylinder 21a, and the gravure cylinder 21a is pressurized by the impression cylinder 21b via the substrate 101, and the coating agent is contained in the ink pan 21c. As the gravure cylinder 21a rotates, the coating agent is carried from the ink pan 21c to the gravure cylinder 21a, the thickness of the coating agent is adjusted by the doctor blade 21d, and the coating agent is transferred to the substrate 102 by the pressure from the impression cylinder 21b to perform printing. After printing, the substrate may be dried in the drying unit 22.

[0154] The conductive film forming unit 30 receives a substrate on which a patterned coating layer has been formed, and uniformly forms a conductive film on the substrate and the coating layer. For example, the conductive film can be formed by sputtering 31.

[0155] The substrate on which the conductive film has been formed is wound up in the substrate discharge section 40. The substrate roll 401 after the conductive film has been formed is then used in a coating layer removal section (not shown). In the coating layer removal section, the removal liquid may be brought into contact with the long substrate while it is being transported, or the long substrate may be cut into sheets before being brought into contact with the removal liquid. Furthermore, the printing system is not limited to the illustrated example. For example, the coating layer printing section 20, the conductive film forming section 30, and the coating layer removal section may be performed continuously in a roll-to-roll manner, or each process may be performed in a roll-to-roll manner, wound up, and the wound substrate may be used in the next process.

[0156] <Example of an embodiment> Some examples of embodiments of this disclosure are given below. This disclosure is not limited to the following. <1> A coating agent for a lift-off process that includes a pattern formation step without using photolithography, wherein the coating agent comprises an aqueous resin and water, and contains 50 to 95% by mass of water in 100% by mass of the coating agent, and has a viscosity at 25°C of 50 mPa·s or more and less than 45,000 mPa·s, as measured according to JIS K 7117-1.

[0157] <2> Further comprising at least one selected from the group consisting of particles and colorants, <1> The coating agent described above.

[0158] <3> The coloring agent comprises at least one selected from the group consisting of organic pigments, inorganic pigments, and dyes. <2> The coating agent described above.

[0159] <4> The average particle size of the colorant and the particles determined by laser diffraction and scattering is 5 μm or less. <2> or <3> The coating agent described above.

[0160] <5> The aqueous resin includes an aqueous resin having a polar structure. <1> from <4> A coating agent as described in any of the following.

[0161] <6> The acid value of the aqueous resin is 5 to 200 mg KOH / g. <5> The coating agent described above.

[0162] <7> The coating agent is at least one selected from the group consisting of those for gravure printing, flexographic printing, waterless offset printing, rotary screen printing, and inkjet printing. <1> from <6> A coating agent as described in any of the following.

[0163] <8> The coating agent is at least one selected from the group consisting of those for gravure printing, flexographic printing, and inkjet printing, and has a viscosity at 25°C measured according to JIS K 7117-1 of 50 mPa·s or more and less than 2000 mPa·s. <1> from <6> A coating agent as described in any of the following.

[0164] <9> The coating agent is at least one selected from the group consisting of those for waterless offset printing and those for rotary screen printing, and has a viscosity at 25°C measured according to JIS K 7117-1 of 2000 mPa·s or more and less than 45000 mPa·s. <1> from <6> A coating agent as described in any of the following.

[0165] <10> A coating agent for a lift-off process that includes a pattern formation step that does not use a photolithography method, wherein the coating agent is used in a state diluted with a diluent solvent, the coating agent comprising an aqueous resin and water, and being at least one selected from the group consisting of gravure printing, flexographic printing, and inkjet printing, having a viscosity at 25°C of 50 mPa·s or more and less than 2000 mPa·s as measured according to JIS K 7117-1, containing 50 to 95% by mass of water in 100% by mass of the coating agent in the state diluted with the diluent solvent, and having a viscosity at 25°C of 50 mPa·s or more and 500 mPa·s or less as measured according to JIS K 7117-1, as described above.

[0166] <11> A method for manufacturing a laminate, comprising the steps of: printing a coating agent onto a substrate to form a patterned coating layer without using photolithography; forming a conductive film on the substrate on which the coating layer is formed; and contacting the substrate on which the conductive film is formed with a coating layer removal liquid to remove the coating layer and form a conductive pattern, wherein the coating agent contains an aqueous resin and water, with 50 to 95% by mass of water per 100% by mass of the coating agent, and having a viscosity at 25°C of 50 mPa·s or more and less than 45,000 mPa·s as measured according to JIS K 7117-1.

[0167] <12> The process of forming the patterned coating layer is carried out by a printing method selected from the group consisting of gravure printing, flexographic printing, waterless offset printing, rotary screen printing, and inkjet printing. <11> A method for manufacturing the laminate described above. [Examples]

[0168] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples. In this disclosure, parts and % refer to parts by mass and mass%, respectively, unless otherwise noted. In the table, NV means non-volatile content. In the table, a blank space indicates that the component has not been added.

[0169] <Method for measuring the pH of water extracted from inorganic fine particles> Five parts of inorganic fine particles and 100 parts of deionized water were mixed and heated at 100°C for 5 minutes. After cooling to room temperature, deionized water was added until the total volume of inorganic fine particles and deionized water reached 105 parts. After stirring, the pH was measured using a multi-pH meter (manufactured by AS ONE Corporation) in accordance with JIS Z 8802.

[0170] <Viscosity measurement> The viscosity of the coating agent was measured in accordance with JIS K 7117-1 using a Viscometer TUB-10 manufactured by Toki Sangyo Co., Ltd. under the following conditions. If the non-volatile content concentration was low, the non-volatile content was adjusted by opening the lid of the coating agent storage container and allowing the solvent to evaporate. Measurement conditions • Rotor: M1 • Rotation speed: 6 rpm • Liquid temperature: 25℃

[0171] <Weight average molecular weight measurement> The weight-average molecular weight was determined as the converted molecular weight using polystyrene as the standard substance. The measuring instrument used was a GPC instrument: Showa Denko Corporation Shodex GPC-401, column: Showa Denko Corporation Shodex OHpak LB-805, and detector: RI (differential refractometer). A 0.1 N NaNO3 aqueous solution was used as the eluent, and the measurement was performed at a column temperature of 35°C and a flow rate of 3 mL / min.

[0172] <Average particle size> The average particle diameter is the average particle diameter in the volume-based particle size distribution measured by laser diffraction and scattering, and is measured using the Microtrac-Bell MT-3300EX II instrument.

[0173] <Preparation of resin solution> (Preparation example 1) Resin solution V01 Twelve parts of polyvinyl alcohol resin PVA1 and eighty parts of deionized water were heated while stirring at 90°C for one hour. After that, heating was stopped, and stirring was continued until it returned to room temperature to obtain resin solution V01.

[0174] (Preparation Examples 2-6) Resin Solutions V02-14 Resin solutions V02 to V14 were obtained using the same method as in Preparation Example 1, except that the raw materials and mixing ratios listed in Table 1 were changed. The properties of the raw materials used in Preparation Examples 1 to 14 are as follows.

[0175] Polyvinyl alcohol resin PVA1: Itaconic acid-modified polyvinyl alcohol, degree of polymerization = 1800, viscosity (20℃, 4% aqueous solution) = 25 mPa·s, degree of saponification = 88%, non-volatile content 100%, acid value = 80.7 mgKOH / g Polyvinyl alcohol resin PVA2: Sulfonic acid-modified polyvinyl alcohol, degree of polymerization = 300, viscosity (20℃, 4% aqueous solution) = 2.5 mPa·s, degree of saponification = 98%, non-volatile content 100%, acid value = 80.2 mg KOH / g Polyvinyl alcohol resin PVA3: Ethylene vinyl alcohol resin, ethylene content: 8 mol%, degree of polymerization = 400, viscosity (20℃, 4% aqueous solution) = 4 mPa·s, degree of saponification = 98%, non-volatile content 100% • Polyvinyl alcohol resin PVA4: Manufactured by Kuraray Co., Ltd., POVAL 28-98, unmodified polyvinyl alcohol, degree of polymerization = 1700, viscosity (20℃, 4% aqueous solution) = 28 mPa·s, degree of saponification = 98%, non-volatile content 100% • Hydroxypropyl cellulose resin HPC1: Manufactured by Nippon Soda Co., Ltd., HPC-SL, viscosity (25℃, 10% aqueous solution) = 150 mPa·s, non-volatile content 100% • Hydroxypropyl cellulose resin HPC2: Manufactured by Nippon Soda Co., Ltd., HPC-SSL, viscosity (25℃, 10% aqueous solution) = 30 mPa·s, non-volatile content 100% • Rotary screen printing: Manufactured by NagaseViita, rotary screen printing, 100% non-volatile content. • Styrene-acrylic resin: Hyros X QL-1358 (manufactured by Seikoh PMC, solids content 24.3%, acid value 190 mg KOH / g) • Polyacrylamide resin: Arakawa Chemical Industries, Ltd., Polystrom 705, non-volatile content 10% • Polyethyleneimine resin: Manufactured by Nippon Shokubai Co., Ltd., Epomin P-1000, non-volatile content 30% • Polyester resin: PLUS COAT Z221, manufactured by Go-o Chemical Industry Co., Ltd., a polyester resin containing SO4Na groups, acid value less than 5 mgKOH / g, non-volatile content 20%)

[0176] (Synthesis Example 1) Synthesis of carboxyl group-containing urethane resin A 2000 ml four-necked flask equipped with a reflux condenser, dropping funnel, gas inlet tube, stirrer, and thermometer was charged with 52.3 parts of polytetramethylene glycol with a number average molecular weight of 2000, 25 parts of polyethylene glycol with a number average molecular weight of 2000, 13 parts of dimethylolbutanoic acid, 8 parts of bis(2-hydroxypropyl)aniline, and 1.7 parts of 1,4-cyclohexanedimethanol. The flask was then purged with dry nitrogen and heated to 100°C. Under stirring, 41.3 parts of isophorone diisocyanate were added dropwise over 20 minutes, and the temperature was gradually increased to 140°C (NCO / 0H = 0.95). After reacting for a further 30 minutes, 750 parts of distilled water containing 8.9 parts of 28% aqueous ammonia were added while cooling to obtain a carboxyl group-containing urethane resin with a non-volatile content of 25% (weight-average molecular weight approximately 40,000, glass transition temperature -91°C, acid value 34.8 mg KOH / g, hydroxyl value = 11.1 mg KOH / g).

[0177] (Synthesis Example 2) Synthesis of Oil-Based Urethane Resin 120.6 parts of ethyl acetate, 153.7 parts of a polyester polyol with a number average molecular weight of 2,000 (hereinafter referred to as "MPD / AdA 2000"), which is a condensate of 3-methyl-1,5-pentanediol (MPD) and adipic acid (AdA), 27.9 parts of a polyester polyol with a number average molecular weight of 5,000 (hereinafter referred to as "MPD / AdA 5000"), which is a condensate of 3-methyl-1,5-pentanediol (MPD) and adipic acid (AdA), 12.4 parts of polypropylene glycol with a number average molecular weight of 700 (hereinafter referred to as "PPG 700"), 35.0 parts of polypropylene glycol with a number average molecular weight of 2,000 (hereinafter referred to as "PPG 2000"), and 52.3 parts of isophorone diisocyanate (hereinafter referred to as "IPDI") were mixed and reacted at 90°C for 5 hours under a nitrogen atmosphere to obtain a urethane prepolymer of terminal isocyanates. Next, 279.6 parts of isopropanol, 299.7 parts of ethyl acetate, 2.1 parts of iminobispropylamine (hereinafter "IBPA"), and 16.6 parts of isophoronediamine (hereinafter "IPDA") were stirred and mixed, and the resulting urethane prepolymer of terminal isocyanates was gradually added at 40°C. The mixture was reacted at 80°C for 1 hour to obtain a solution of oily urethane resin with a non-volatile content of 30% by mass, a urea bond concentration of 0.78 mmol / g, an amine value of 1.3 mg KOH / g, and a mass-average molecular weight of 36100.

[0178] [Table 1]

[0179] <Manufacturing of coating agents> (Manufacturing Example 1) Coating Agent C1 75.0 parts of resin solution V01, 9.0 parts of calcium carbonate, 8.0 parts of deionized water, and 8.0 parts of n-propyl alcohol were mixed and dispersed in a bead mill for 20 minutes to obtain coating agent C1.

[0180] (Manufacturing Examples 2-29, Comparative Manufacturing Examples 1-6) Coating agents C2-29, CC1-6 The coating agent was obtained using the same method as in Production Example 1, except that the raw materials and mixing ratios listed in Table 2 were changed. The properties of the raw materials used are as follows. The pH is the pH of the extracted water.

[0181] • Calcium carbonate CA1: Manufactured by Shiraishi Calcium Co., Ltd., Homocal D, synthetic calcium carbonate, average particle size 0.08 μm, pH 8.6, 100% non-volatile content. Calcium carbonate (CA2): Average particle size 0.3 μm, pH 8 Calcium carbonate (CA3): Average particle size 0.7 μm, pH 8.3 Calcium carbonate (CA4): Average particle size 0.8 μm, pH 8.5 Calcium carbonate (CA5): Average particle size 1.5 μm, pH 9 Calcium carbonate (CA6): Average particle size 4.5 μm, pH 8.9 • Silica S1: Manufactured by Fuji Silysia Chemical Co., Ltd., Silysia 310, gel-processed silica, average particle size 1.7 μm, pH 7.5 • Silica S2: Aerosil 200, manufactured by Aerosil, average particle size 0.2 μm Barium sulfate: Manufactured by Sakai Chemical Industry Co., Ltd., Variace 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 diameter 0.5 μm, pH 8~8.5 • Carbon Black: Made by Columbia Carbon, Raven 420P • Copper phthalocyanine: Toyo Color Co., Ltd., LIONOL BLUE FG7400-G, Pigment Blue 15:4 • Azo pigment: Toyo Color Co., Ltd., LIONOL RED 5620, Pigment Red 146, insoluble azo pigment • Nigrosine-based black dyes: WATER BLACK R-455, CIAcid BLACK2, manufactured by Orient Chemical Industries Co., Ltd. • Azo dye: Water Black 256L, manufactured by Orient Chemical Industries, Ltd., water-soluble disazo dye • Amino resin microparticles: Manufactured by Nippon Shokubai Co., Ltd., Epostor MS, benzoguanamine resin microparticles, average particle size 2 μm, non-volatile content 100% • Polyethylene resin particles: Manufactured by Mitsui Chemicals, ChemiPearl W500, average particle size 2.5 μm, non-volatile content 40%

[0182] <Example 1> To 100 parts of coating agent C1, 80 parts of diluent solvent (water / n-propyl alcohol = 92 / 8) were added and stirred. A gravure printing press equipped with a gravure plate with a plate depth of 20 μm and fine line stripe patterns of line widths of 20 μm, 50 μm, 100 μm, and 200 μm (cell formation method: etching method, laser plate making device D1: MDC laser plate making device / electronic engraving machine DIGILAS5000, line count 300 lines / inch, plate depth 20 μm, plate pattern line width / target pattern line width: 90%) was used to print a diluted coating agent C1 onto a PET film (Toyobo Co., Ltd., Cosmoshine A4160, thickness 50 μm) unwound from a printed roll. Under conditions of a printing speed of 150 m / min and an in-line oven of 80°C, a coating layer was formed by printing with a diluted coating agent C1, thereby obtaining a first intermediate laminate having fine line patterns of line widths of 20 μm, 50 μm, 100 μm, and 200 μm. These processes were carried out using a roll-to-roll method.

[0183] On the surface of the first intermediate laminate with a fine line pattern printed using a coating agent, and on a substrate without a pattern, the film was formed at a pressure of 0.37 Pa and an input power density of 3.3 W / cm². 2 The substrate was adjusted, and under the introduction of argon and oxygen gas (argon:oxygen = 95:5), ITO containing 95% by mass of indium oxide and 5% by mass of tin oxide was sputtered to form a conductive film with an average thickness of 0.02 μm, obtaining a second intermediate laminate. This laminate consists of a substrate / coating layer / conductive film component and a substrate / conductive film component, and these processes were carried out using a roll-to-roll method.

[0184] The second intermediate laminate was brought into contact with 40°C water in a cleaning layer for 3 minutes to remove the pattern coating layer and the conductive film located on the pattern coating layer, and then dried by air blowing to obtain a laminate. This laminate has a substrate / conductive film component, and these processes were carried out using a roll-to-roll method.

[0185] <Examples 2-44, 47-73, Comparative Examples 1-6> Laminates were prepared in the same manner as in Example 1, except that the coating agents, printing conditions, substrates, conductive films, and cleaning methods shown in Table 2 were changed. The substrates used are as follows. Coating agents C28-29 and CC3-5 were used without dilution.

[0186] • Polyimide 1: Kapton H, manufactured by Toray DuPont, 25 μm thick • Polyimide 2: Manufactured by AS ONE Corporation, polyimide film PI, thickness 25 μm • PEN: Toyobo Co., Ltd., Theonex Q51, 50 μm thickness

[0187] <Example 45> On a PET film (Toyobo Co., Ltd., Cosmoshine A4160, 50 μm thick) unwound from a printing roll, a flexographic plate (Milacron FLEXCELNXH digital flexographic plate, 1.14 mm thick, 150 lines / inch) with fine line stripe patterns of 20 μm, 50 μm, 100 μm, and 200 μm line widths was printed, along with an anilox roll (900 lpi 3 cc / m²). 2 Using a flexographic printing press (MIRAFLEXCM) equipped with ), the coating agent C23 was printed under conditions of a printing speed of 150 m / min and an in-line oven at 80°C to form a coating layer, and a first intermediate laminate having fine line patterns with line widths of 20 μm, 50 μm, 100 μm, and 200 μm due to the coating agent was obtained. These processes were carried out using a roll-to-roll method. The subsequent conductive film formation process and cleaning process were carried out in the same manner as in Example 1.

[0188] <Example 46> A coating layer was formed on a PET film (Toyobo Co., Ltd., Cosmoshine A4160, 50 μm thick) unwound from a printed roll using a Mitsubishi BT2-800 NEO offset web printing press (Mitsubishi Heavy Industries, Ltd.) equipped with a CTP plate (Toray Industries, Inc., resolution 2000 dots / inch) having fine line stripe patterns with line widths of 20 μm, 50 μm, 100 μm, and 200 μm. The coating agent C24 was printed at a printing speed of 150 m / min and an in-line oven at 80°C to obtain a first intermediate laminate having fine line patterns with line widths of 20 μm, 50 μm, 100 μm, and 200 μm due to the coating agent. These processes were carried out using a roll-to-roll method. The subsequent conductive film formation and cleaning processes were carried out in the same manner as in Example 1.

[0189] <Evaluation of coatings and laminates> The obtained coating agents and laminates were evaluated as follows. The results are shown in Tables 2 to 4.

[0190] <Suitable for high-speed printing (gravure printing)> For coating agents C1-C27, CC1-3, and CC5-6, after dilution with the diluting solvents listed in Table 2, the agents were placed in the printing ink containers of the printing press. Under conditions of a printing speed of 150 m / min for 60 minutes, the colored area of ​​the non-image portion on the plate after rotation was visually evaluated, and the suitability for high-speed printing was assessed according to the following criteria. Grades A-C represent practical levels.

[0191] A: There is no coloring in the non-image areas. B: There is coloring in the non-image area, and the colored area is less than 5% of the total area. C: Non-image areas are colored, with a colored area of ​​5% or more but less than 30%. D: There is coloring in the non-image area, and the colored area is 30% or more.

[0192] <Suitable for high-speed printing (flexographic printing)> Coating agent C28 was printed onto PET film using a flexographic printing press (MIRAFLEXCM), then the press was run idle for 30 minutes. After the idle period ended, the PET film was printed again, and the unevenness of the print was visually evaluated. Grades A to C represent practical levels.

[0193] A: There are absolutely no printing inconsistencies. B: Slight printing inconsistencies are noticeable. C: Printing inconsistencies are observed. D: Printing inconsistencies are very noticeable.

[0194] <Suitable for high-speed printing (waterless offset printing)> Coating agents C29 and CC4 were added to the printing ink containers of a printing press, and printed onto PET film using a Mitsubishi BT2-800 NEO offset web printing press (manufactured by Mitsubishi Heavy Industries, Ltd.). The degree of background contamination (ink adhesion to non-image areas) was visually evaluated. Grades A to C represent practical levels.

[0195] A: No soiling was observed. B: Slight soiling is visible. C: Some staining is visible on the surface. D: Significant soiling is visible.

[0196] <Stability over time> The coating agent was filled into a 225g mayonnaise jar (body diameter 62mm / total length 109mm), and phase separation was observed after 7 days at 40°C. The following criteria were used for evaluation. The length for each criterion is the length of the layer measured when viewing the mayonnaise jar from the horizontal. Grades A to C represent practical levels.

[0197] A: There is no phase separation. B: Phase separation occurs, and a separation layer less than 10 mm thick is generated. C: Phase separation occurs, resulting in a separation layer between 10mm and 20mm in thickness. D: Phase separation occurs, and a separation layer of 20 mm or more is generated.

[0198] <Fine line reproducibility> The fine-line stripe pattern portion of the resulting laminate was visually observed and evaluated according to the following criteria. AA to C represent practical levels.

[0199] AA: There are no breaks in any of the stripe pattern sections. A: There are breaks in the 20μm fine-line stripe pattern section, but there are no breaks in the 50μm, 100μm, and 200μm fine-line stripe pattern sections. B: There are breaks in the 50μm fine-line stripe pattern section, but there are no breaks in the 100μm fine-line and 200μm fine-line stripe pattern sections. C: There is a break in the 100μm fine line stripe pattern, but there is no break in the 200μm fine line stripe pattern. D: There is a break in the 200μm stripe pattern.

[0200] <Cleaning properties> The residual rate (mass %) of the coating layer before and after cleaning was calculated and evaluated using Equation 1 below, based on the mass of the obtained laminate and the second intermediate laminate before cleaning. AA to C represent practical levels. When the coating agent of this disclosure is used in a lift-off process, in order to achieve high productivity, it is preferable to remove the coating layer only by immersion in water or alkaline water. Therefore, the cleanability test of this disclosure is limited to contact with water or alkaline water. Conventional cleanability tests are known to remove the coating layer by applying pressure with a water flow or the like. However, the immersion cleanability test of this disclosure differs from conventional cleanability tests in that it does not apply pressure with a water flow or the like, and is a rigorous test method that requires higher solubility in the cleaning solution. (Formula 1) Coating layer residue rate (mass %) = (mass of coating layer after cleaning) / (mass of coating layer before cleaning) × 100

[0201] AA: The residual rate (by mass) of the coating layer is less than 5% by mass. A: The residual rate (mass%) of the coating layer is 5% or more and less than 10% by mass. B: The residual rate (mass%) of the coating layer is 10% or more and less than 50% by mass. C: The residual rate (by mass) of the coating layer is 50% by mass or more and less than 80% by mass. D: The residual rate (mass%) of the coating layer is 80% by mass or more.

[0202] [Table 2]

[0203] [Table 2]

[0204] [Table 2]

[0205] [Table 3]

[0206] [Table 3]

[0207] [Table 3]

[0208] [Table 3]

[0209] While this disclosure has been described with reference to some of the embodiments described above, this disclosure is not limited to those embodiments. Various modifications can be made to the structure and details of this disclosure within the scope of this disclosure. [Explanation of symbols]

[0210] 1. Substrate, 2. Pattern coating layer, 3. Conductive film, 4. Laminate 10 Substrate supply unit 10, 20 Coating agent printing unit, 30 Conductive film forming unit, 40 Substrate discharge unit 101 Substrate rolls 101, 102 Substrates 102, 401 Substrate rolls after printing

Claims

1. A coating agent for a lift-off process that includes a pattern formation step that does not use photolithography, The coating agent comprises at least one selected from the group consisting of aqueous resin, water, and particles and colorants. The coating agent contains 50 to 95% by mass of the water in 100% by mass. The coating agent is for gravure printing or flexographic printing. The viscosity at 25°C, measured according to JIS K 7117-1, is 50 mPa·s or more and less than 2000 mPa·s. The aqueous resin comprises one or more selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, urethane resins, and polyethyleneimine resins. A coating agent comprising 10 to 80% by mass of one or more aqueous resins selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, urethane resins, and polyethyleneimine resins, based on 100% by mass of the non-volatile content of the coating agent.

2. The coating agent according to claim 1, wherein the coloring agent comprises at least one selected from the group consisting of organic pigments, inorganic pigments, and dyes.

3. The coating agent according to claim 1 or 2, wherein the average particle diameter of the colorant and the particles, determined by laser diffraction and scattering, is 5 μm or less.

4. The coating agent according to claim 1 or 2, wherein the aqueous resin comprises an aqueous resin having a polar structure.

5. The coating agent according to claim 4, wherein the acid value of the aqueous resin is 5 to 200 mg KOH / g.

6. A coating agent for a lift-off process that includes a pattern formation step that does not use photolithography, The coating agent comprises at least one selected from the group consisting of aqueous resin, water, and particles and colorants. The coating agent contains 50 to 95% by mass of the water in 100% by mass. The coating agent is for waterless offset printing or rotary screen printing. The viscosity at 25°C, measured according to JIS K 7117-1, is 2000 mPa·s or more and less than 45000 mPa·s. The aqueous resin comprises one or more selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, urethane resins, and polyethyleneimine resins. A coating agent comprising 10 to 80% by mass of one or more aqueous resins selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, urethane resins, and polyethyleneimine resins, based on 100% by mass of the non-volatile content of the coating agent.

7. A coating agent for a lift-off process that includes a pattern formation step that does not use photolithography, wherein the coating agent is used in a state diluted with a diluent solvent, The coating agent comprises at least one selected from the group consisting of aqueous resin, water, and particles and colorants. The coating agent is for gravure printing or flexographic printing. The viscosity at 25°C, measured according to JIS K 7117-1, is 50 mPa·s or more and less than 2000 mPa·s. The aqueous resin comprises one or more selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, urethane resins, and polyethyleneimine resins. The coating agent contains 10 to 80% by mass of one or more aqueous resins selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, urethane resins, and polyethyleneimine resins, based on 100% by mass of the non-volatile content of the coating agent. In the state diluted with the aforementioned diluent, the coating agent contains 50 to 95% by mass of the water in 100% by mass. The coating agent, when diluted with the aforementioned diluent, has a viscosity at 25°C measured according to JIS K 7117-1, which is 50 mPa·s or more and 500 mPa·s or less.

8. A process of printing a coating agent onto a substrate to form a patterned coating layer without using photolithography. A step of forming a conductive film on a substrate on which the coating layer has been formed, and The process includes bringing the substrate on which the conductive film is formed into contact with a coating layer removal solution to remove the coating layer and form a conductive pattern, The coating agent comprises at least one selected from the group consisting of aqueous resin, water, and particles and colorants. The coating agent contains 50 to 95% by mass of the water in 100% by mass. When the process of forming the aforementioned patterned coating layer is carried out by gravure printing or flexographic printing, the viscosity at 25°C, measured according to JIS K 7117-1, is 50 mPa·s or more and less than 2000 mPa·s. When the process of forming the patterned coating layer is performed by waterless offset printing or rotary screen printing, the viscosity at 25°C, measured according to JIS K 7117-1, is 2000 mPa·s or more and less than 45000 mPa·s. The aqueous resin comprises one or more selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, urethane resins, and polyethyleneimine resins. A method for producing a laminate, comprising: one or more aqueous resins selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, urethane resins, and polyethyleneimine resins, in an amount of 10 to 80% by mass of the non-volatile content of the coating agent.

Images