CN116323836A - Film-forming composition, film, circuit sheet, and sensor sheet - Google Patents
Film-forming composition, film, circuit sheet, and sensor sheet Download PDFInfo
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- CN116323836A CN116323836A CN202280006496.6A CN202280006496A CN116323836A CN 116323836 A CN116323836 A CN 116323836A CN 202280006496 A CN202280006496 A CN 202280006496A CN 116323836 A CN116323836 A CN 116323836A
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- forming composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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Abstract
The protective film which protects the circuit wiring or the sensor electrode of the circuit sheet or the sensor sheet can be formed in a thin film and has excellent protective performance for the circuit wiring or the sensor electrode, and a film forming composition for forming the protective film can be obtained. The coating film-forming composition contains a cycloolefin polymer, a physical property regulator and a solvent. The coating film is composed of the coating film forming composition.
Description
Technical Field
The present invention relates to a film that can be used as a protective layer or the like of a circuit sheet, a film-forming composition for forming the film, and a circuit sheet and a sensor sheet each having the film.
Background
The wires arranged in the circuit sheet or the sensor electrodes arranged in the sensor sheet are formed of silver paste containing silver or transparent conductive polymer called PEDOT/PSS. In order to protect these wires and sensor electrodes from breakage, corrosion, and the like, a protective layer having high transparency is provided on the surface of the circuit sheet or the sensor sheet.
However, silver paste or transparent conductive polymer is liable to be degraded by water vapor, ultraviolet rays, or the like, and is liable to be vulcanized by sulfur gas or the like. Therefore, it is desirable that the protective layer has properties that make these phenomena difficult to generate. The technique of coating a wire with a protective layer is described in, for example, japanese patent No. 6167103 (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6167103
Disclosure of Invention
Problems to be solved by the invention
The thin film and improved protection performance of the protective layer are required in response to the demands for light weight and low cost of the circuit sheet or the sensor sheet.
Means for solving the problems
One embodiment of the present invention is a film-forming composition comprising a cycloolefin polymer, a physical property adjuster, and a solvent. According to one embodiment of the present invention, since the cycloolefin polymer is contained, a film excellent in transparency and firmness can be formed. Further, since the coating film-forming composition contains a physical property adjuster, the coating film-forming composition can form a coating film having improved Printability (Printability) and quality. Further, since the coating film-forming composition contains a solvent, a coating film can be formed by a method such as printing.
In one embodiment of the present invention, the cycloolefin polymer is a cycloolefin ring-opening polymer or a copolymer of cycloolefins and olefins. According to one embodiment of the present invention, since the cycloolefin polymer is a cycloolefin ring-opening polymer or a copolymer of cycloolefin and olefin, the film-forming composition can form a film excellent in transparency and firmness.
In the film-forming composition according to one embodiment of the present invention, the cycloolefin polymer has a polar group in a ring. According to an embodiment of the present invention, the cycloolefin polymer is easily dissolved in a solvent having high polarity. Further, as the physical property adjuster, a substance having high polarity can be contained in a high concentration in the film-forming composition.
In one embodiment of the present invention, the composition for forming a coating film is at least one of a printability improving agent and a coating film quality improving agent.
According to one aspect of the present invention, at least one of printability and film quality of the film-forming composition can be improved.
The composition for forming a coating film according to an embodiment of the present invention contains 0.1 to 30% by volume of the physical property regulator.
According to one aspect of the present invention, since the physical property adjuster is contained in an amount of 0.1 to 30% by volume, the possibility of deterioration in printability and deterioration in coating quality can be avoided.
In the film-forming composition according to one embodiment of the present invention, the physical property adjuster has a polar group selected from a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, a nitro group, a sulfo group, an ester group, an amide group, and a halogen group.
According to one aspect of the present invention, the physical property adjuster has a polar group selected from a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, a nitro group, a sulfo group, an ester group, an amide group, and a halogen group, and therefore, adhesion, adhesiveness, and miscibility with respect to an object to be coated can be improved.
In the film-forming composition according to one embodiment of the present invention, the physical property adjuster has a reactive functional group selected from an epoxy group, a methacrylic group, a vinyl group, a mercapto group, and an amino group.
According to one aspect of the present invention, the physical property adjuster has a reactive functional group selected from an epoxy group, a methacrylic group, a vinyl group, a mercapto group, and an amino group, and therefore, the adhesion of the film-forming composition to a substrate sheet, a circuit wiring, or the like to be coated can be improved.
The coating film according to one embodiment of the present invention is composed of the above-mentioned arbitrary coating film-forming composition.
According to one aspect of the present invention, a film having excellent transparency, firmness, and film quality can be realized.
One embodiment of the present invention is a circuit sheet comprising a base sheet, a circuit wiring, and a protective layer formed of a film formed of the arbitrary film-forming composition.
According to one aspect of the present invention, since the coating film composed of the arbitrary coating film forming composition is used as the protective layer, it is possible to form a circuit sheet excellent in protection of the circuit wiring sandwiched between the base sheet and the protective layer.
The circuit sheet according to one embodiment of the present invention has a three-dimensional shape having a curved surface.
According to one aspect of the present invention, since the circuit sheet has a three-dimensional shape having a curved surface, the circuit sheet can be formed along a space where the circuit sheet is applied, and the degree of freedom in designing an apparatus using the circuit sheet can be increased.
One aspect of the present invention is a sensor sheet comprising a base sheet, a circuit wiring, a sensor electrode, and a protective layer formed of a film formed of the arbitrary film-forming composition.
According to one aspect of the present invention, since the sensor sheet has a coating film composed of the arbitrary coating film forming composition as a protective layer, it is possible to form a sensor sheet excellent in protection of a circuit wiring and a sensor electrode interposed between the base sheet and the protective layer.
The sensor sheet according to one embodiment of the present invention has a three-dimensional shape having a curved surface.
According to one aspect of the present invention, since the sensor sheet has a three-dimensional shape having a curved surface, the sensor sheet can be formed along a space where the sensor sheet is applied, and the degree of freedom in designing an apparatus using the sensor sheet can be enlarged.
Effects of the invention
According to one aspect of the present invention, a film-forming composition having printability can be provided.
According to one aspect of the present invention, a coating film having excellent protective performance can be provided.
According to one aspect of the present invention, a circuit sheet or a sensor sheet having a coating film excellent in protective performance can be provided.
Drawings
Fig. 1A and 1B are schematic views of a circuit sheet according to an embodiment of the present invention, wherein fig. 1A is a front view and fig. 1B is a plan view.
Fig. 2A and 2B are schematic views of a sensor sheet according to an embodiment of the present invention, where fig. 2A is a front view and fig. 2B is a plan view.
Fig. 3A and 3B are schematic views of a sensor sheet according to another embodiment of the present invention, wherein fig. 3A is a cross-sectional view taken along line iii a-iii a of fig. 3B, and fig. 3B is a top view.
Detailed Description
An example of an embodiment of the present invention will be described below with reference to the drawings. The following description of the embodiments and embodiments does not unduly limit the content of the present invention described in the claims, and all the components described in the embodiments are not essential to the solving means of the present invention.
The description of "first" and "second" in the present specification and claims is for distinguishing between different components, and is not intended to indicate a particular order or advantage or disadvantage. In the respective embodiments, members that achieve the same effects by common structures are denoted by the same reference numerals, and overlapping descriptions thereof are omitted.
Coating film-forming composition
The coating film-forming composition described in this embodiment is applied to a base sheet such as a circuit sheet or a sensor sheet, and is used for a protective layer for protecting circuit wiring (wires) or sensor electrodes, and the like, and has high transparency and high protective performance of a coating object. The coating film-forming composition contains a cycloolefin polymer, a physical property regulator and a solvent. Hereinafter, the components of the film-forming composition will be described.
Cycloolefin polymer: when the cycloolefin polymer is dissolved in a solvent, the cohesive force Gao Re tends to be drawn as a coating liquid such as a printing ink, and generally has poor printability. In addition, the adhesion to a resin film such as PET as a base sheet is weak, and the peeling is easy. Therefore, although a cycloolefin polymer is used as a preformed sheet, it is difficult to say that it is a binder resin suitable for printing and the like, and is a resin that is difficult to use as a coating liquid. However, since the cycloolefin polymer is amorphous, the transparency is high and the birefringence is low. Further, since the resin has an alicyclic structure, the resin has a high glass transition point Tg and is excellent in heat resistance and strength. Further, since the resin has a hydrocarbon structure having few polar groups, the resin has low hygroscopicity and excellent light resistance and chemical resistance. Therefore, the present inventors studied what treatment is performed on the cycloolefin polymer to use as a binder resin for a coating material.
The cycloolefin polymer is a polymer having an alicyclic structure in the polymer main chain, and a COP resin, a COC resin, or the like obtained by polymerizing cycloolefin can be exemplified. The COP resin is a cyclic olefin ring-opening polymer or a hydrogenated product thereof, and examples thereof include norbornene, tetracyclododecene (Tetracyclododecene), derivatives thereof, and the like. The COC resin is a cyclic olefin polymer which is a copolymer of a cyclic olefin and an olefin, and examples thereof include a copolymer in which a cyclopentyl residue or a substituted cyclopentyl residue is inserted into a molecular chain by polymerizing a cyclic olefin such as norbornene, tetracyclododecene or a derivative thereof with ethylene or propylene.
The cycloolefin as a raw material of the cycloolefin polymer may be a monocyclic one or a polycyclic one. In addition, the thermoplastic norbornene resin or thermoplastic tetracyclododecene resin is excellent in adhesion to a base sheet or a circuit wiring, and is preferably obtained by drying and curing without requiring high-temperature heating at the time of film formation of the film-forming composition. Examples of the thermoplastic norbornene resin include a ring-opened polymer of a norbornene monomer, a hydrogenated product thereof, an addition polymer of a norbornene monomer and an olefin, and the like. Examples of the thermoplastic tetracyclododecene resin include a ring-opened polymer of a tetracyclododecene monomer, a hydrogenated product thereof, an addition polymer of a tetracyclododecene monomer, and an addition polymer of a tetracyclododecene monomer and an olefin.
As described above, the hydrocarbon structure having few polar groups reduces hygroscopicity. However, as the cycloolefin polymer, a substance having a polar group in the ring is preferably used from the viewpoint of improving the adhesion, the adhesiveness and the miscibility. Such a cycloolefin polymer having a polar group is preferable in that the type and the amount of the compatible physical property regulator are increased, because the solubility of the cycloolefin polymer in a solvent having a high polarity, for example, ethyl acetate, butyl acetate, or the like is good. The cycloolefin polymer may have a functional group such as a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, a nitro group, a sulfo group, an ester group, an amide group, or the like. When the coating film-forming composition has a reactive functional group such as an epoxy group, a methacrylic group, a vinyl group, a mercapto group, or an amino group, adhesion of the coating film-forming composition to a substrate sheet to be coated, a circuit wiring, or the like can be improved.
Examples of commercially available products of cycloolefin polymers include Zeonex (Zeonex, registered trademark; manufactured by japan rayleigh), zeonor (registered trademark; manufactured by japan rayleigh), arton (registered trademark; manufactured by JSR), and the like as COP resins. Examples of the COC resin include Apel (registered trademark), topas (registered trademark), and the like manufactured by treasured plastics.
The cycloolefin polymer is blended in an amount of 5 to 70% by volume, preferably 35 to 60% by volume, in the film-forming composition. If the blending amount of the cycloolefin polymer in the film-forming composition is less than 5% by volume, it becomes difficult to form a desired thickness. If the blending amount exceeds 70% by volume, the viscosity becomes too high, and the printability becomes poor. When the amount is 35 to 60% by volume, the film-forming composition has suitable printability.
Solvent: the solvent can be used to dissolve or disperse the cycloolefin polymer and impart a proper viscosity to the dissolved product or the dispersed product, thereby realizing a mixed composition suitable for the properties of the coating liquid. Examples of such solvents include organic solvents such as hydrocarbons, aromatics, ethers, and ketones, and more specifically, pentane, hexane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1, 2-dimethylcyclohexane, cyclohexene, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, cyclohexanone, methylethylketone, methylisobutylketone (MIBK), isophorone, and the like. For COP resins or COC resins having polar groups in the molecular chain such as a cyclic ring, ethyl acetate, butyl acetate, hexyl acetate, dihydroterpinyl acetate and the like can be used as the ester solvent. A solvent having a high boiling point is preferable in terms of improving printability.
The amount of the solvent to be blended is the remainder other than the cycloolefin polymer and the physical property adjuster, and the amount to be blended may be approximately 25 to 90% by volume, preferably 35 to 60% by volume, of the coating film-forming composition. If the amount of the solvent blended in the film-forming composition is less than 25% by volume, the nonvolatile component becomes excessive, and the printability is deteriorated. If the blending amount exceeds 90% by volume, the nonvolatile components are too small, and it is difficult to form a desired thickness. When the amount is 35 to 60% by volume, the film-forming composition has suitable printability.
Physical property regulator: the physical property adjuster is a substance which is contained in a liquid substance in which a cycloolefin polymer is dissolved or dispersed and imparts a property to the liquid substance which cannot be obtained by only dissolving or dispersing the polymer. The cycloolefin polymer can be used as a binder resin for coating materials such as printing inks by adding a physical property adjuster to the cycloolefin polymer in addition to dissolving or dispersing the cycloolefin polymer in a solvent.
Among the physical property modifiers, examples of the printability improving material that improves printability include a viscosity modifier such as a plasticizer that adjusts viscosity, a thixotropic property imparting agent that imparts thixotropic properties, a foam inhibitor such as a foam suppressor that suppresses foaming during printing, a stringing inhibitor that suppresses stringing, a wettability improving agent that prevents shrinkage on a print substrate and prevents uneven printing and the occurrence of a mottled pattern, a cutting improving agent that enables continuous printing, a coating stabilizer such as a silane coupling agent, a polymerization inhibitor, or an antioxidant that stabilizes the properties of a film-forming composition, and the like.
Among the physical property modifiers, a film quality improving agent that improves the quality of a film may be exemplified as a smoothing agent that improves the surface smoothness when the film is formed from the viewpoint of improving the quality of the film itself. Further, from the viewpoint of protecting the quality of the conductive portion coated inside by the coating film functioning as a protective layer, examples thereof include a moisture resistance improver for improving moisture resistance, a vulcanization resistance improver for improving vulcanization resistance, a gas barrier property improver for suppressing gas permeability such as oxygen, a heat resistance improver for improving heat resistance, a light resistance improver for preventing discoloration, an ultraviolet inhibitor for suppressing ultraviolet ray permeability, an adhesion improver for improving adhesion to a base sheet, and the like. Among them, from the viewpoint of acting as a protective layer, a moisture resistance improver, a vulcanization resistance improver, a gas barrier property improver, a heat resistance improver, a light resistance improver, or an ultraviolet inhibitor is a weather resistance improver. In addition, they may also be referred to as names that exhibit barrier properties improving agents in one functional aspect.
Examples of the physical property adjusting agent include petroleum hydrocarbons such as aromatic hydrocarbons, paraffin hydrocarbons, and naphthenes; or polyolefin such as polyethylene, polypropylene, polybutene, liquid polyisobutylene, liquid polybutene, hydrogenated liquid polyisoprene, and derivatives thereof; petrolatum (Petrolatum), petroleum asphalt, and the like. Alternatively, other physical property modifiers include polyolefins such as maleic anhydride-modified polypropylene modified with an acid such as a halogenated or carboxylic acid such as maleic acid. These are printability improvers, and also film quality improvers such as weather resistance improvers. These may be used in an amount of 1 or 2 or more.
The physical property adjusting agent having a polar group such as a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, a nitro group, a sulfo group, an ester group, an amide group, or a halogen group is an adhesion improving agent that contributes to improving adhesion of the coating film forming composition to a substrate sheet, a circuit wiring, or the like, which is a coating object. The physical property modifier having a reactive functional group such as an epoxy group, a methacrylic group, a vinyl group, a mercapto group, or an amino group contributes to improving the adhesion of the coating film-forming composition to a substrate sheet to be coated, a circuit wiring, or the like.
The functional filler such as titanium oxide or zinc oxide functions as a moisture resistance improver that suppresses the permeability of water vapor, an ultraviolet inhibitor that suppresses the permeability of ultraviolet light, a vulcanization resistance improver that suppresses the gas permeability of sulfur gas, a film quality improver such as a gas barrier property improver, or the like. Further, the composition can also function as a printability-improving agent such as a viscosity-adjusting agent, a foaming inhibitor, or a thixotropic agent.
The amount of the physical property regulator to be blended is 0.1 to 30% by volume, preferably 0.5 to 25% by volume, more preferably 3 to 20% by volume, based on the film-forming composition. The amount of the physical property adjuster to be blended is one embodiment, preferably 0.1 to 15% by volume, and 3 to 10% by volume, in the film-forming composition. If the amount of the physical property adjuster is less than 0.1% by volume, printability may be deteriorated, and if the amount exceeds 30% by volume, the quality of the coating film may be deteriorated. When the amount is 3 to 20% by volume, the ink composition has suitable printability and can form a film of good quality.
Preparation of a film-Forming composition: the coating film-forming composition is prepared by dissolving or dispersing the cycloolefin polymer in a solvent, and adding and mixing the cycloolefin polymer with a physical property regulator. The viscosity of the obtained coating film-forming composition is preferably 1 to 300 Pa.s as measured using a rotational viscometer at a rotational speed of 10rpm and at 25 ℃. If the viscosity of the coating film-forming composition is less than 1pa·s, the shape retention of the patterned circuit wiring may be reduced. If the viscosity exceeds 300pa·s, clogging is likely to occur in screen printing, which is a typical coating method, for example, and productivity may be lowered.
The film-forming composition described above has a moderate viscosity and printability with respect to the base sheet. In addition, the coating film forming composition is less likely to cause pinholes or the like during coating such as printing, and a smooth coating film can be formed. In addition, if the film-forming composition solidifies, a film which can be of high quality as a protective layer is formed.
Formation of a coating: the coating film-forming composition is applied to a base sheet made of a resin film or the like by screen printing or the like, and is cured to form a coating film, thereby functioning as a protective layer for the base sheet. The protective layer may be a film having high transparency, and the average light transmittance of the protective layer in the visible light range of 400nm to 800nm may be preferably 80% or more, and more preferably 85% or more, depending on the characteristics of the cycloolefin polymer. The coating method can use, in addition to screen printing, spray coating, coater printing, transfer printing, dipping, or the like.
The thickness of the coating film as a protective layer for protecting the circuit wiring or the sensor electrode may be 0.5 to 50 μm, preferably 3 to 30 μm, and more preferably 6 to 8 μm. The reason for this is that the thickness of the coating film as the protective layer can be made to exceed 10 μm and the film can be formed, but the film is contrary to the requirement for thinning. If the thickness of the coating film is smaller than 3 μm, the protection of the circuit wiring or the sensor electrode becomes sparse. Further, the thickness can be increased by laminating the cover films. This makes it possible to thicken the coating film to about 100 μm.
According to the film, the moisture resistance, light resistance, and vulcanizing resistance are excellent, and the film has low reactivity and solvent barrier property with respect to a drug, and the film itself does not bleed out due to low volatility. Further, the coating film has non-migration property and non-resin erosion property to other members attached to the surface of the coating film, and is less in contamination to these other members.
< Circuit sheet >)
Fig. 1A and 1B are a front view and a plan view, respectively, showing an embodiment of a protective layer formed of a film-forming composition. In the circuit sheet 10 shown in these figures, a film-forming composition is applied as a protective layer 13 so as to cover the wires 12 provided on the base sheet 11, and in these figures, only one wire 12 forming a circuit is schematically shown. In the drawings, the layer structure is shown to be thicker than the lateral width for the purpose of easy understanding, and therefore the lateral-to-longitudinal ratio is different from that in practice.
A base material sheet: as the base material sheet 11 which is a base material of the circuit sheet, a resin film having transparency is preferably used. Examples of such resin films include polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, polycarbonate (PC) resin, methacrylic acid (PMMA) resin, polypropylene (PP) resin, polyurethane (PU) resin, polyamide (PA) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, triacetyl cellulose (TAC) resin, cyclic Olefin Polymer (COP), and the like. As the base sheet 11, a coating film composed of the coating film forming composition may be used as the base sheet 11. Alternatively, the base sheet 11 may be provided with a primer layer, a surface protective layer, an antistatic topcoat layer, or the like for improving adhesion to the wire 12 or the protective layer 13, or a material subjected to surface treatment such as corona treatment, plasma treatment, or ultraviolet irradiation treatment may be used. Preferably, the primer coating is a layer having high adhesion to the substrate sheet. Examples thereof include a coating layer containing a resin such as urethane, polyester, acrylic, vinyl acetate, vinyl chloride, styrene-acrylic, acrylic-silica gel, and styrene-butadiene, and a coating layer containing an emulsion of these resins.
Circuit wiring: in fig. 1A and 1B, for convenience of explanation, only one wire 12 is shown as a wire 12 constituting a circuit wiring, and generally, such a wire 12 is arranged in a pattern on a base sheet 11 to form a circuit (circuit wiring network). As a material of the conductive wire 12, a conductive paste or a conductive ink containing a powder of a highly conductive metal such as copper, aluminum, silver, or an alloy containing these metals can be exemplified. Among these metals and alloys, silver wiring mainly using silver is preferable because of high conductivity and less oxidation than copper. The lead 12 may be a wire using a graphite powder, a carbon powder such as a carbon fiber or a carbon black, or a wire made of a material obtained by mixing these materials with a metal.
In addition to printing, the circuit wiring may be formed by providing a conductive portion on the base sheet 11 by metal vapor deposition, and then generating a circuit pattern by etching or the like. In the case of metal deposition, metals such as copper, aluminum, nickel, chromium, zinc, and gold can be used. Among them, copper is preferable because copper has low resistance and low cost.
The circuit sheet 10 is manufactured by printing and forming circuit wiring (wires 12) at predetermined positions on a transparent resin film as the base sheet 11. Then, a film-forming composition is applied thereon, and cured to form the protective layer 13. Thus, the circuit sheet 10 can be obtained. The cycloolefin polymer or the physical property adjuster can react with the base film even when the reactive functional group is contained therein.
Sensor sheet >, sensor sheet
Fig. 2A is a front view and fig. 2B is a plan view showing another embodiment of a protective layer of a film made of the film-forming composition. The sensor sheet 20 such as the capacitive sensor sheet shown in these figures is a sheet in which a film-forming composition is applied as the protective layer 13 so as to cover the lead wires 22 and the sensor electrodes 24 provided on the base sheet 21. Here, for convenience, only one sensor electrode 24 is shown, and the sensor sheet 20 having the circuit wiring and the sensor electrode 24 will be described as an example.
Sensor electrode: the base sheet 21 or the lead 22 as the base of the sensor sheet 20 is the same as that used for the circuit sheet 10. The sensor electrode 24 may be formed of a conductive paste, a conductive ink, a metal vapor deposited film, or the like, which form a circuit wiring, or may be formed of a conductive polymer having transparency. When a material having high transparency is used, the sensor position can be made to emit light by transmitting back illumination light.
Examples of the transparent conductive polymer include polythiophene, polypyrrole, polyaniline, polyparaphenylene, and polyacetylene. Specifically, PEDOT/PSS (poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) and the like can be exemplified. As the transparent conductive polymer, commercially available printing ink of paint type can be used. Alternatively, the sensor electrode 24 may be made of a conductive paste or a conductive ink containing a material having high transparency, such as metal nanoparticles, e.g., silver nanoparticles, carbon nanoparticles, or Indium Tin Oxide (ITO) powder.
With respect to the production of the sensor sheet 20, circuit wiring (lead 22) and sensor electrodes 24 are printed and formed at predetermined positions on a transparent resin film as the base sheet 21. Then, a film-forming composition is applied thereon, and the solvent is evaporated and cured to form the protective layer 23. Thus, the sensor sheet 20 can be obtained.
Sensor sheet (2) >
Other embodiments of the sensor sheet 30 are shown in front view in fig. 3A and in top view in fig. 3B, respectively. The sensor sheet 30 shown in these drawings is similar to the sensor sheet 20 described above in that the circuit wiring (the lead wire 32) and the sensor electrode 34 on the base sheet 31 are covered with the protective layer 33 formed by applying the film-forming composition. However, the sensor sheet 30 of the present embodiment is different in terms of being formed into a three-dimensional shape. The raw materials and the like of the respective members are the same.
The formation of the sensor sheet 30 may be performed by a method of forming the circuit wiring (the lead wire 32) and the sensor electrode 34 on the substrate sheet 31 formed in a three-dimensional shape by printing, vapor deposition, or the like, in addition to a method of forming the circuit wiring (the lead wire 32) and the sensor electrode 34 on the substrate sheet 31 formed in a flat plate shape and then thermally deforming the same as the sensor sheet 20. When the base sheet 31 is thermally deformed in a later step, it is preferable that the glass transition point Tg of the cycloolefin polymer contained in the film-forming composition as the protective layer 33 is close to the glass transition point Tg of the base sheet 31. Since the closer the temperature of the glass transition point Tg is, the more the deformation degree of the base sheet 31 and the protective layer 33 is the same, the less likely to be distorted, deformed, broken, or the like.
Sensor sheet (3) >
The sensor sheet may be a sheet coated with a protective layer after being formed into a three-dimensional shape. The protective layer can be provided by applying the film-forming composition to the stereoscopic surface using a spray coating method or the like.
Further, those skilled in the art will readily appreciate that many modifications are possible without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are included in the scope of the present invention. For example, in the specification or the drawings, a term described at least once together with a different term having a broader meaning or a synonymous meaning may be replaced by the different term at any position of the specification or the drawings. The configuration of the embodiment is not limited to that described in the above embodiment, and various modifications can be made.
Examples
Next, the present invention will be further described based on examples (comparative examples). Coating film-forming compositions obtained by mixing the materials shown in the following tables were prepared as samples 1 to 12. Further, a conductive film having a thickness of 0.5 μm and formed of PEDOT/PSS (trade name; organic EL-P3145, manufactured by AGFA Co.) and a conductive wire having a thickness of 10 μm and formed of silver paste (trade name; FA-323, manufactured by Teng Co.) were formed in parallel on the surface of a base sheet, and thereafter, a composition for forming any of the coating films 1 to 12 was applied to the surface of the base sheet on which these conductive film and conductive wire were formed, at a thickness of 8. Mu.m, to thereby produce a test circuit sheet on which the conductive film and conductive wire were coated. However, exposed positions (exposed portions) of the conductive film are provided at both ends of the conductive film, and the conductive film is not provided for measuring the resistance value. The test circuit sheets obtained were labeled with the same sample numbers as the applied coating film-forming composition.
TABLE 1
TABLE 2
In table 1, "COC" represents a cycloolefin copolymer (trade name; APL6509T, manufactured by mitsunobu chemical company, tg80 ℃), "COP1" represents a cycloolefin polymer (trade name; zeonor 1020R, manufactured by japan rayleigh chemical company, tg102 ℃) and a COP resin having no polar group in the ring, "COP2" represents a cycloolefin polymer (trade name; ARTON F4520, manufactured by JSR corporation, tg164 ℃) and a COP resin having a polar group in the ring, "acrylic" represents an acrylic resin coating (trade name; ALON S-1017, manufactured by east asia chemical company, tg95 ℃) and "urethane" represents a polyurethane resin coating (trade name; take lac WS-5100, manufactured by mitsunobu chemical company, tg120 ℃). In addition, when the polarity of COP2, COP1, acrylic acid, and urethane is compared, and the polarity of acrylic acid and urethane is high, if the polarity is "high", the polarity of COP2 is medium, which means "medium", and the polarity of COP1 and COC is low, which means "low". In addition, since the amount of the solvent to be dispensed was adjusted so that the total of the materials and the solvent of each sample reached 100% by volume, the column "concentration (vol%)" of the solvent was denoted as "remaining".
< various experiments >)
For each of the above samples, various tests described below were performed.
(printability 1) viscosity since printability was evaluated from the viewpoint of viscosity, the viscosity of each sample was observed. The results are shown in the column "viscosity" of Table 1. In table 1, "a" represents viscosity in a range in which screen printing can be performed without problem. "B" represents a viscosity slightly higher, and although screen printing is possible, the printing speed cannot be increased, and mass production is difficult. "C" represents a viscosity that cannot be printed due to high viscosity.
(printability 2) air bubbles: since printability was evaluated from the degree of generation of bubbles in the coating film, it was observed whether bubbles were generated in the coating film of each of the samples. The results are shown in the column "bubble" in Table 1. In table 1, "a" shows that no bubbles were generated. "B" shows that a minute amount of bubbles are generated. "C" shows that a large number of bubbles are generated.
(film quality 1) transmittance: since the film quality was evaluated from the transparency of the film, the film-forming composition of each sample was applied to a PET film to form a film having a thickness of 8 to 25 μm. Then, the parallel light transmittance of the film at a wavelength of 200 to 800nm was measured using a spectrophotometer (manufactured by Shimadzu corporation, "UV-1600 PC").
(film quality 2) adhesion: since the film quality was evaluated from the viewpoint of adhesion to the base sheet, adhesion test was performed on each of the above-mentioned samples. More specifically, the test results were classified into 6 stages by the cross-cut method based on JISK5600-5-6 (ISO 2409).
The results are shown in the column "adhesion" of table 1. In table 1, the numbers 0 to 5 are the classification of test results obtained by the cross-cut method, 0 is no peeling, and 5 is a large peeling of 35% or more. If it is 0 or 1, the adhesion is considered to be good.
In table 1, samples 3 and 6 are "2", samples 1, 4 and 5 are "1", sample 2 is "3", and the other samples are "0".
(film quality 3A) moisture resistance a: since the film quality was evaluated from the viewpoint of moisture resistance, moisture resistance test was performed on each of the above-mentioned samples. More specifically, the test circuit sheets of each sample were left under an environment having a humidity of 85% and a temperature of 85 ℃ for 250 hours, 500 hours, 750 hours, and 1000 hours, and the moisture resistance was evaluated based on the change in resistance value of the conductive film due to the transparent conductive polymer after each time. The humidity resistance test observed from this resistance change was referred to as "humidity resistance a".
The resistance value was measured from the exposed portions at both ends of the conductive film formed of the transparent conductive polymer using a resistance meter (tester).
As a result, it was observed that the resistance value increased very slowly after 250 hours, for samples 4, 5, 7, 8 and 11 and 12, and the resistance value after 1000 hours was 1.2 times that before being placed under the humidity, 1.1 times for sample 4, 2.6 times for sample 7, 2.2 times for sample 8, 1.1 times for sample 11, 1.1 times for sample 12, and approximately 1.1 to 1.2 times for COP1 resin, and 1.1 to 2.6 times for COP2 resin. On the other hand, sample 9 was 20.0 times and sample 10 was 10.5 times.
(film quality 3B) moisture resistance B: for each sample under the same conditions as in the above-mentioned moisture resistance test, the color tone of the conductive film of the transparent conductive polymer was observed, and the moisture resistance was evaluated based on the change in the color tone, unlike the moisture resistance a test for measuring the resistance value. The humidity resistance test observed from this change in color tone was referred to as "humidity resistance B".
The color change of the conductive film was evaluated based on an index defined as the distance between coordinates in the CIE1976L x a x b x color space, based on JIS Z8781-4 as a reference. The color difference can be obtained by using, for example, a hand-held spectrocolorimeter ("JX 777" manufactured by Kagaku COLOR TECHNO SYSTEM) or a color colorimeter ("CR-400" manufactured by Konikoku Meida Co.). The samples before and after the test were judged to be preferable in that the difference in color Δe was 13 or less, which is a range in which it was difficult to distinguish the difference in color by the naked eye, and the difference in color Δe was 6.5 or less, which is more preferable.
In the moisture resistance B test, for sample 4 and sample 5, a change was observed after 500 hours passed, and after 1000 hours, the Δe change for sample 4 was 3.97, the Δe change for sample 5 was 3.60, the Δe change for sample 7 was 3.00, and the Δe change for sample 8 was 3.00. On the other hand, the Δe of sample 9 was 15.00, and the Δe of sample 10 was 7.72. In addition, Δe of sample 11 and sample 12 was 4.00.
(film quality 4A) weather resistance a: since the film quality was evaluated from the viewpoint of weather resistance, the test circuit sheets of the respective samples were subjected to a thermal cycle test. More specifically, each test circuit sheet was placed in a constant temperature and humidity tank having a temperature set range of-40 ℃ to +85 ℃, a temperature rise rate of 3 ℃/min, and a temperature reduction rate of 2 ℃/min. Then, weather resistance was evaluated based on the change in resistance value of the conductive film of the transparent conductive polymer after 1000 hours had elapsed. The weather resistance test observed from this resistance change was regarded as "weather resistance A".
As a result, the resistance after the test was 0.9 times that before the thermal cycle test, for each of samples 4, 5, 7 and 8. On the other hand, sample 9 was 1.5 times and sample 10 was 2.0 times. Sample 11 and sample 12 were 1.4 times as large.
(film quality 4B) weather resistance B: for each sample under the same conditions as in the above-mentioned thermal cycle test, unlike the weather resistance a test in which the resistance value was measured, the hue of the conductive film of the transparent conductive polymer was observed, and weather resistance was evaluated based on the change in hue. The weather resistance test observed from this change in color tone was regarded as "weather resistance B".
As a result, for Δe after the test, Δe of sample 4 was 1.02, Δe of sample 5 was 0.65, Δe of sample 7 was 1.10, and Δe of sample 8 was 0.80. On the other hand, Δe of sample 9 was 2.55, and Δe of sample 10 was 3.00. Further, Δe of sample 11 and sample 12 was 2.00.
(film quality 5) vulcanization resistance: since the film quality was evaluated from the viewpoint of the vulcanization resistance, the vulcanization resistance test was performed. More specifically, each test circuit sheet was placed in a closed space in which sulfur powder was placed, and left in a saturated sulfur vapor atmosphere at 85 ℃ for 250 hours. Then, the condition of the silver paste wire after 250 hours was observed by visual observation and resistance measurement.
As a result of the vulcanization resistance test, samples 1, 4, 5, 7, 8, and 10 were still low in resistance value, and were not broken. In addition, samples 11 and 12 were still low in resistance, and were not broken. Sample 9 was evaluated as broken line at a position where blackening occurred over the entire width of the wire, and the resistance value exceeded 2mΩ of the displayable value of the tester.
< study >
Based on the results of the respective experiments, the following studies were performed.
(printability 1) viscosity: all samples were evaluated above "B" and all samples were screen printed in terms of viscosity. When examined carefully, it was found that by adding a polyolefin such as liquid polybutene to the COP1 resin, and further adding a functional filler such as titanium oxide or zinc oxide, the printability in terms of viscosity was improved. From this, it is found that not only polyolefin such as liquid polybutene but also functional filler such as titanium oxide or zinc oxide becomes a viscosity adjuster, and the viscosity can be adjusted to an appropriate viscosity. Further, it is known that the COP resin is excellent in viscosity suitability as compared with the COC resin.
Further, it is found from the samples 11 and 12 that the blending amount of the maleic anhydride-modified polypropylene was increased to 10% by volume and 20% by volume, respectively, and the evaluation of the viscosity was "a", and the polyolefin such as the maleic anhydride-modified polypropylene was not adversely affected in printability, and was added at a high concentration.
(printability 2) air bubbles: sample 2 and sample 6, which do not contain a functional filler such as titanium oxide or zinc oxide, generate bubbles, and thus it is found that the functional filler acts as a foaming inhibitor and improves printability. Further, it is found from comparison of sample 2 and sample 3 that since polybutene is contained, the viscosity and the bubble are improved, and polybutene becomes a printability improver. Similarly, it is found from comparison of sample 6 and sample 11 or comparison of sample 6 and sample 12 that since polyolefin such as maleic anhydride-modified polypropylene is contained, the air bubbles are improved, and such polyolefin becomes a foaming inhibitor.
(film quality 1) transmittance: regarding the transmittance at 550nm, the coating film of sample 3 containing no filler was 87%, and the coating film of sample 10 made of only urethane resin was 82%. The transmittance of the PET film alone was 89.2%, and comparing the above transmittance, it was found that the COP resin had a higher transmittance than the urethane resin. Further, the waveform of the transmittance of the film of sample 2 made of only COP resin was substantially identical to the waveform of the transmittance of the PET film, and it was found that the COP resin had a high visible light transmittance close to that of the PET resin, without containing the physical property adjuster. As is clear from comparison of the COC resin and the COP resin, the value of sample 1 was higher than that of sample 4, and the COC resin had a higher transmittance than that of the COP resin.
On the other hand, the transmittance of comparative samples 6 to 8 was substantially the same in the visible light range of 550nm, and the transmittance of samples 7 and 8 was lower than that of sample 6 in the ultraviolet light range of 350nm, and the reason for this was that the functional fillers not contained in sample 6 were contained in samples 7 and 8, and therefore the functional fillers of titanium oxide or zinc oxide reflected ultraviolet light and did not transmit it. In addition, the transmittance of sample 6, sample 11 and sample 12 was compared, and it was slightly observed that the transmittance of sample 11 and sample 12 was lower in the visible light range of 550nm than that of sample 6, and also the transmittance was lower in the ultraviolet light range of 350nm than that of sample 6. As a result, since the samples 11 and 12 contain the polyolefin such as the maleic anhydride-modified polypropylene not contained in the sample 6, the polyolefin reflects ultraviolet rays but does not transmit the same, and it is found that the polyolefin also functions as an ultraviolet inhibitor. It was also found from a comparison between sample 2 and sample 3 that polybutene also functions as an ultraviolet inhibitor.
(film quality 2) adhesion: in comparison with the samples 2 and 6, the samples 2 containing no physical property adjuster and using COP1 resin with low polarity had poor adhesion, whereas the samples 6 containing no physical property adjuster and using COP2 resin with medium polarity had slightly improved adhesion. From this, from the viewpoint of adhesion, it is preferable to use a COP resin having a polarity which is medium in polarity.
It is also clear from comparison of sample 2 and sample 3 using COP resins of the same polarity that sample 3 containing polybutene has higher adhesion than sample 2 containing no polybutene, and polyolefin such as polybutene functions as an adhesion improver.
Further, it was found that the samples 4 and 5 having the functional filler were excellent in adhesion as compared with the sample 3 containing no functional filler, and thus the functional filler also functioned as an adhesion improver. As is clear from the comparison of samples 6 to 8, the adhesion properties can be significantly improved by the inclusion of the functional filler.
It is also evident from comparison of samples 6, 11 and 12 that the adhesion of the samples to which the maleic anhydride-modified polypropylene was added was improved, and that the polyolefin other than polybutene also functions as an adhesion improver.
(film quality 3) moisture resistance: the resistance values of samples 9 and 10 were significantly increased, while Δe was also significantly changed, and the changes in the resistance values and color tones of samples 4 and 5, samples 7 and 8, samples 11 and 12 were suppressed, so that it was found that the moisture resistance of samples 4 and 5, samples 7 and 8, samples 11 and 12 was excellent. From the results, it was found that polyolefin such as polybutene and maleic anhydride-modified polypropylene or functional filler functions as a moisture resistance improver, and the quality of the film is improved.
(film quality 4) weather resistance: in the weather resistance a test, after the 1000-hour test was completed, the resistance values of the conductive films of samples 4 and 5 and samples 7 and 8 were changed to 0.9 times, while sample 9 was 1.5 times and sample 10 was 2.0 times. In the weather resistance B test, after the 1000-hour test, the change Δe of the color tone of the conductive film was 0.65 to 1.10 in samples 4 and 5 and samples 7 and 8, while sample 9 was 2.55 and sample 10 was 3.00. From the results, it was found that samples 4, 5 and samples 7 and 8 were more excellent in weather resistance than samples 9 and 10, and polyolefin such as polybutene or functional filler was used as a weather resistance improver to improve the quality of the film.
In addition, the resistance value change of the conductive film in the weather resistance a test was 1.4 times for each of the samples 11 and 12, and the color tone change Δe of the conductive film in the weather resistance B test was 2.00. From these results, it is found that although weather resistance is not as excellent as that of sample 7 or sample 8, weather resistance is excellent as that of sample 9 or sample 10, and maleic anhydride-modified polypropylene also functions as a weather resistance improver to improve the quality of the film.
(film quality 5) vulcanization resistance: from the results of the vulcanization resistance test, it was found that vulcanization was not accelerated in samples 4 and 5 and samples 7 and 8, and samples 11 and 12, and that the vulcanization resistance was increased. From these results, it was found that polyolefin such as polybutene and maleic anhydride-modified polypropylene or functional filler functions as a vulcanization resistance improver and improves the quality of the film.
[ PREPARATION METHOD ]: as is clear from a comparison between sample 2 and sample 3, the printability and adhesion were improved by adding polybutene to the COP resin. From this, it was found that although it is somewhat difficult to improve the adhesion, it is possible to form a coating film from the coating film forming composition even with a COP1 resin having low polarity because of its printability.
Similarly, it is found from comparison of sample 6 and sample 11 that the printability and adhesion are improved by adding maleic anhydride-modified polypropylene to the COP resin. From this, it was found that even with the COP2 resin having low polarity, a coating film can be formed from the coating film forming composition.
Description of the reference numerals
10 circuit sheet, 20 sensor sheet, 30 sensor sheet.
Claims (12)
1. A composition for forming a coating film, which comprises a cycloolefin polymer, a physical property regulator and a solvent.
2. The composition for forming a coating film according to claim 1, wherein the cycloolefin polymer is a cycloolefin ring-opening polymer or a copolymer of cycloolefin and olefin.
3. The film-forming composition according to claim 1 or 2, wherein the cycloolefin polymer has a polar group on a ring.
4. The composition according to any one of claims 1 to 3, wherein the physical property adjuster is at least one of a printability improving agent and a film quality improving agent.
5. The composition according to any one of claims 1 to 4, wherein the composition contains 0.1 to 30% by volume of the physical property adjuster.
6. The composition according to any one of claims 1 to 5, wherein the physical property adjuster has a polar group selected from a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, a nitro group, a sulfo group, an ester group, an amide group, and a halogen group.
7. The composition according to any one of claims 1 to 6, wherein the physical property adjuster has a reactive functional group selected from an epoxy group, a methacrylic group, a vinyl group, a mercapto group, and an amino group.
8. A coating film comprising the coating film-forming composition according to any one of claims 1 to 7.
9. A circuit sheet comprising a base sheet, a circuit wiring, and a protective layer comprising a film comprising the film-forming composition according to any one of claims 1 to 7.
10. The circuit sheet of claim 9, wherein the circuit sheet is a three-dimensional shape having a curved surface.
11. A sensor sheet comprising a base sheet, a circuit wiring, a sensor electrode, and a protective layer comprising a film formed from the film-forming composition according to any one of claims 1 to 7.
12. The sensor sheet of claim 11, wherein the sensor sheet is a three-dimensional shape having a curved surface.
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| JP2021-060988 | 2021-03-31 | ||
| JP2021060988 | 2021-03-31 | ||
| PCT/JP2022/015387 WO2022210690A1 (en) | 2021-03-31 | 2022-03-29 | Film forming composition, film, circuit sheet, and sensor sheet |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19509173A1 (en) * | 1994-03-14 | 1995-09-21 | Nippon Zeon Co | Mass from a cycloolefin resin containing epoxy groups |
| JP2001354896A (en) * | 2001-04-27 | 2001-12-25 | Nippon Zeon Co Ltd | Thermoplastic norbornane-based resin coating agent and method for forming coating layer |
| JP2006253573A (en) * | 2005-03-14 | 2006-09-21 | Fuji Photo Film Co Ltd | Insulating film and its production method, and electronic device employing it |
| JP2007084764A (en) * | 2005-09-26 | 2007-04-05 | Jsr Corp | Coating material and method for producing the same |
| CN108778722A (en) * | 2016-03-04 | 2018-11-09 | 琳得科株式会社 | Protective film formation composite sheet |
| CN111566173A (en) * | 2018-02-13 | 2020-08-21 | 株式会社艾迪科 | Coating composition, method for curing the composition, barrier film, and method for producing cured product |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3230250B2 (en) * | 1991-08-13 | 2001-11-19 | 日本ゼオン株式会社 | Thermoplastic norbornene-based resin coating agent and coating layer forming method |
| JP3588498B2 (en) * | 1994-03-14 | 2004-11-10 | 日本ゼオン株式会社 | Cyclic olefin resin composition having epoxy group and insulating material using the resin composition |
-
2022
- 2022-03-29 JP JP2023511366A patent/JPWO2022210690A1/ja active Pending
- 2022-03-29 WO PCT/JP2022/015387 patent/WO2022210690A1/en active Application Filing
- 2022-03-29 CN CN202280006496.6A patent/CN116323836A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19509173A1 (en) * | 1994-03-14 | 1995-09-21 | Nippon Zeon Co | Mass from a cycloolefin resin containing epoxy groups |
| JP2001354896A (en) * | 2001-04-27 | 2001-12-25 | Nippon Zeon Co Ltd | Thermoplastic norbornane-based resin coating agent and method for forming coating layer |
| JP2006253573A (en) * | 2005-03-14 | 2006-09-21 | Fuji Photo Film Co Ltd | Insulating film and its production method, and electronic device employing it |
| JP2007084764A (en) * | 2005-09-26 | 2007-04-05 | Jsr Corp | Coating material and method for producing the same |
| CN108778722A (en) * | 2016-03-04 | 2018-11-09 | 琳得科株式会社 | Protective film formation composite sheet |
| CN111566173A (en) * | 2018-02-13 | 2020-08-21 | 株式会社艾迪科 | Coating composition, method for curing the composition, barrier film, and method for producing cured product |
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| JPWO2022210690A1 (en) | 2022-10-06 |
| WO2022210690A1 (en) | 2022-10-06 |
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