JP6953823B2 - Liquid coating device and liquid coating method. - Google Patents

Description

The present invention relates to an apparatus for applying a liquid to a long base material and a method for applying a liquid to a long base material using the apparatus, and more particularly, a roll-shaped long base material is used. Regarding a liquid coating device for unwinding and applying a liquid, a liquid coating device capable of easy maintenance and keeping the inside of the device clean, and as a result, a high-quality silane coupling agent-treated surface can be realized, and a liquid coating method. It is a thing.

Silane coupling agents are widely used at the interface between an inorganic material such as glass and an organic material such as a polymer resin in order to improve the wettability and adhesiveness of the two. The silane coupling agent has a strong adsorptive power to the inorganic material and at the same time tends to cause a self-condensation reaction. Therefore, particles of the condensate are formed in the treatment liquid and the coating liquid, and these particles often cause foreign matter defects on the coating surface and the treatment surface.

In order to solve such a problem, for example, Patent Document 1 discloses a technique of applying a silane coupling agent to a substrate in a vapor phase state. According to such a method, it is possible to realize an extremely thin silane coupling agent layer with low defects. However, in this method, continuous treatment for a long period of time is difficult because the silane coupling agent adheres to every place other than the base material inside the apparatus.

Japanese Unexamined Patent Publication No. 2015-178237

As a result of diligent studies to solve the above problems, the present inventors have made it possible to process a continuous long base material by using a liquid coating apparatus having a specific structure in the liquid coating apparatus, and further low drawbacks. We have found that various silane coupling agent treatments can be performed, and in addition, we have found that the present apparatus and method can be widely applied to all liquid coating methods, and have reached the present invention.

That is, the present invention has the following configuration.
[1] A long base having at least a winding portion of a long base material, a height adjusting roll of the unwinding long base material, a liquid coating mechanism portion, a height adjusting roll of the winding long base material, and a winding portion. A device for applying a liquid to a material, the liquid application mechanism portion has at least an introduction port for introducing a long base material, an outlet for leading out a long base material, and an exhaust port. A liquid coating device for applying a liquid to a long base material, which comprises a housing, a liquid supply unit, and a liquid discharge unit.
[2] The liquid coating apparatus according to [1], further comprising an interleaving paper supply roll and having a function of co-winding a liquid-coated long base material and interleaving paper.
[3] A device for applying a liquid to a long base material having at least a long base material unwinding part having a height adjusting function, a liquid coating mechanism part, and a long base material winding part having a height adjusting function. The pre-liquid coating mechanism unit is a housing having at least an introduction port for introducing a long base material, an outlet for leading out a long base material, and an exhaust port, a liquid supply part, and a liquid. A liquid coating device characterized by consisting of a discharge part.
[4] The liquid coating apparatus according to [3], further comprising an interleaving paper supply roll and having a function of co-winding the liquid-coated long base material and the interleaving paper.
[5] A roll pair close to the outside of the housing is provided at either or both of the long base material introduction port and the long base material outlet of the housing [1] to [4]. The liquid coating device according to any one of.
The roll pair close to the outside of the housing means that the rolls are installed so that the distance between the roll and the housing is 1 mm or less. As a result, leakage of vapor, mist, etc. generated from the coating liquid to the outside of the housing can be minimized.
[6] From [1] to [1], the rolls are arranged so as not to come into direct contact with the liquid coating surface of the long base material on the downstream side of the long base material outlet of the liquid coating mechanism portion. 4] The liquid coating apparatus according to any one of.
[7] Any of [1] to [6], wherein the housing constituting the liquid coating mechanism portion can be divided at a boundary including a long base material introduction hole and a long base material lead-out hole. The liquid coating device according to.
[8] The liquid coating apparatus according to any one of [1] to [7], wherein the liquid coating mechanism unit, the liquid supply unit, and the liquid discharge unit are not directly joined.
Here, "not directly joined" means that they are not integrated by welding, fusion, adhesion, etc., and that they are not fixed by a large number of screws, bolts, or the like. Fixing with thumbscrews, wing nuts, snap locks, etc. is not included in direct joining. Also, joints with 6 or less screws or bolts are not included in direct joints. In short, it means that it can be attached and detached with a relatively simple effort.
[9] A liquid coating method characterized by using the liquid coating apparatus according to the above [1] to [8] to apply a liquid while transporting a long base material having a length of 5 m or more.
[10] The liquid coating method according to [9], wherein the liquid is applied while the long base material is conveyed in a horizontal state in the liquid coating mechanism section.

In the present invention, it is preferable to have the following configuration.
[11] The liquid coating mechanism when the processing amount of the long base material reaches a predetermined integrated coating area or the operating time of the liquid coating apparatus reaches a predetermined time, either of the conditions is satisfied. The liquid application method according to [9] or [10], which comprises dividing and cleaning.
[12] In the liquid coating apparatus or liquid coating method according to any one of [1] to [11], the liquid to be handled contains at least 0.1% by mass or more of a liquid silane coupling agent or a silane coupling agent. [13] The liquid coating apparatus or liquid coating method according to any one of [1] to [11], wherein the solution containing at least 0.1% by mass or more of the run coupling agent is a solvent. Any of [1] to [12], which is a liquid selected from water, a monovalent alcohol having 8 or less carbon atoms, and a divalent alcohol having 4 or less carbon atoms. The liquid coating apparatus or liquid coating method according to.
[14] The liquid coating apparatus according to any one of [1] to [13], wherein the long base material is a long base material made of a polymer film having a thickness of 1 μm or more and 500 μm or less. Or liquid application method.
[15] The liquid coating apparatus according to any one of [1] to [14], wherein a drying zone is provided between the long substrate outlet hole of the liquid coating apparatus and the long substrate winding portion. Or liquid application method.

In the present invention, it is preferable to have the following configuration.
[16] A. Of [1] to [15], wherein a dry cleaning zone is provided between the unwinding portion of the long base material and the introduction hole of the long base material of the liquid coating device by the atmospheric pressure plasma processing device. The liquid coating device or liquid coating method according to any one.
[17] Any of [1] to [16], wherein a dry cleaning zone by a UV ozone treatment device is provided between the long base material unwinding portion and the long base material introduction hole of the liquid coating device. The liquid coating device or liquid coating method described in 1.
[18] Described in any one of [1] to [17], wherein the long base material is a long base material made of a long polymer film having a width of 240 mm or more and a length of 10 m or more. Liquid coating device or liquid coating method.

In the liquid coating apparatus of the present invention, disassembly and cleaning and maintenance of the coating mechanism portion can be performed while the long base material is passed through the apparatus, so that the apparatus can be cleaned with high frequency. Therefore, it has a self-condensation reactivity like a silane coupling agent, and it can be cleaned frequently even in liquid application where gels and foreign substances are easily generated by the reaction. As a result, it is of high quality with few protrusion defects. Liquid application is possible. In the present invention, the process of applying the silane coupling agent treatment liquid to the base by the liquid coating apparatus of the present invention and drying is referred to as silane coupling agent treatment or simply treatment.
In the present invention, the surface of the base material is preferably clean so as not to inhibit the adsorption of the silane coupling agent on the base material. Such cleanliness can be achieved by atmospheric pressure plasma cleaning or UV ozone cleaning.

In the present invention, by using such a treatment method, it is possible to significantly reduce the number of blister defects generated when a silane coupling agent is applied to a long substrate and laminated with an inorganic substrate to prepare a laminate. Become.

Further, according to the present invention, the inorganic substrate of the laminate laminated by the above method and the polymer film surface of the long polymer film are finely processed by using a thin film technique or a printing technique to obtain an electronic device or a MEMS device. A flexible device using the polymer film as a base material can be formed by forming the polymer film and then peeling the polymer film from the inorganic substrate.

In the present invention, if a long polymer film having high heat resistance is used, it is possible to bond the inorganic substrate and the long polymer film without using an adhesive or an adhesive having inferior heat resistance, for example, 180. The functional element can be formed on the long polymer film even when a high temperature such as ° C. or higher is required. In general, semiconductors, dielectrics, and the like can be expected to form higher-performance electronic devices because thin films with better film quality can be obtained when they are formed at high temperatures. Therefore, if the long polymer film laminated substrate of the present invention is used, electronic devices such as dielectric elements, semiconductor elements, MEMS elements, display elements, light emitting elements, photoelectric conversion elements, piezoelectric conversion elements, and thermoelectric conversion elements are long. It is useful for manufacturing flexible electronic devices formed on a polymer film.

FIG. 1 is a schematic view showing an example of the liquid coating apparatus of the present invention. FIG. 2 is a schematic view showing an example of the liquid coating apparatus of the present invention. FIG. 3 is a schematic view showing an example of the liquid coating apparatus of the present invention. FIG. 4 is a schematic view showing an example of the liquid coating apparatus of the present invention.

Hereinafter, the liquid coating apparatus of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing an example of an embodiment of the liquid coating apparatus of the present invention.
The long base material is supplied from the long base material unwinding portion 11, passes through the unwinding long base material height adjusting roll 14, and is guided to the long base material introduction hole 24 of the liquid coating mechanism portion. Here, the liquid coating mechanism unit is composed of a housing 20 having at least an exhaust port 23, a liquid supply unit 21, and a liquid discharge unit 22. The long polymer film guided into the housing is liquid-coated, wound from the long base material lead-out hole 25, passed through the height adjusting roll 15 of the long base material, and preferably supplied from the interleaving paper supply roll 13. It is wound up by the long base material winding unit 12 together with the interleaving paper.

FIG. 2 is a schematic view showing an example of an embodiment of the liquid coating apparatus of the present invention. In this example, the long base material unwinding portion 11 and the long base material winding portion 12 each have their own height adjusting functions without using the height adjusting roll.

FIG. 3 is a schematic view showing an example of an embodiment of the liquid coating device of the present invention. In this example, a pair of sealing rolls 16 are installed in close proximity to the long base material introduction hole of the liquid coating mechanism and the action of deriving the long base material, which is caused by the liquid to be applied from the housing of the liquid coating mechanism. Prevents the leakage of steam, gas, mist, etc. to the outside world.

FIG. 4 is a schematic view showing an example of an embodiment of the liquid coating device of the present invention. In this example, a pressure reducing container 31 having a pressure reducing hole 32 is further provided on the outside of the device configuration corresponding to FIG. 2, and leakage of vapor, gas, mist, etc. due to the liquid to be applied to the outside world from the liquid coating mechanism unit. To prevent.

In the present invention, a drying step can be provided after deriving the long polymer film from the liquid coating mechanism portion to obtain a method for producing a long base material treated with a silane coupling agent. For drying, air drying with clean air, heat drying, drying with infrared heating, or the like can be used, and a plurality of drying methods can be used in combination.
When a long polymer film is used as the base material in the present invention, the water content of the long polymer film is preferably 0.3% by mass or less, more preferably 0.15% by mass or less, still more preferably 0. It is preferable to dry until it becomes .08% by mass or less. If more water remains on the long polymer film than necessary, blister defects are likely to occur. Controlling the water content is particularly important when an aramid film, a polyimide film, or a polyamide-imide film is used as the long polymer film.

In the present invention, it is preferable to dry-clean the long polymer film with the atmospheric pressure plasma processing apparatus and then introduce it into the liquid coating mechanism of the present invention. In the present invention, it is preferable to dry-clean the substrate with a UV ozone irradiation device and then apply the liquid. Here, the UV ozone treatment device is a treatment device that irradiates the base material with ultraviolet rays having a wavelength of 300 nm or less in the atmosphere and at the same time exposes the base material to ozone generated in the vicinity of the UV light source.

In the present invention, after the substrate is wet-cleaned, the liquid can be applied by the apparatus of the present invention. Here, wet cleaning means cleaning the base material with a liquid cleaning solvent, and as the cleaning solvent, a cleaning solvent containing a generally known surfactant, a cleaning solvent mainly composed of an organic solvent, water and alcohol are used. Main component cleaning solvent, alkaline aqueous cleaning solvent, alkali metal hydroxide or carbonate-containing cleaning solvent, ammonia or urea-containing cleaning solvent, primary ammonium salt-containing cleaning solvent, secondary ammonium A cleaning solvent containing a salt, a cleaning solvent containing a tertiary ammonium salt, a cleaning solvent containing a quaternary ammonium salt, and the like can be used. The concentration of alkali metal ions or ammonium ions contained in the cleaning solvent is preferably 0.02 to 8.0% by mass.

In the present invention, at least a part of the base material can be subjected to atmospheric pressure plasma treatment or UV ozone irradiation treatment after the silane coupling agent solution is applied and dried by applying the liquid of the present invention to the base material. In particular, when the base material is a sheet, a film, a plate, or a substrate, the post-treatment is effective when it is desired to make a difference between the front and back treatments.

In the present invention, the silane coupling agent treatment using the liquid coating method is performed on an inorganic substrate or a long polymer film as a base material, or both an inorganic substrate and a long polymer film, and the inorganic substrate and the long polymer are subjected to the treatment. By laminating the film, it is possible to obtain a laminate of a long polymer film and an inorganic substrate having few defects.

Examples of the inorganic substrate of the present invention include a glass substrate, a ceramic plate, a semiconductor wafer, a metal plate, and the like. Further, a composite substrate in which two or more types selected from a glass substrate, a ceramic plate, a semiconductor wafer, and a metal plate are laminated can also be used. Further exemplifying a composite in which one or more materials selected from glass, ceramics and metals are powder-dispersed in other inorganic or organic materials. Further, a substrate material having a fiber reinforced composite structure in which one or more fibrous substances selected from glass, ceramics and metals are compounded in another inorganic material or an organic material can be exemplified.

The long polymer film in the present invention refers to a polyester film such as PET, PEN, PBT, a polyamide film, a polyimide film, a polyimide benzothiazole film, a polyimide benzoxazole film, a polyimide benzoimidazole film, a polybenzoxazole film, and a polyether sulfone. A film, a polyamideimide film, a polyethylene film, a polypropylene film, a polyvinyl chloride film, a polyvinylidene chloride film and the like can be used.
In the present invention, a sheet-shaped long polymer film having an area of 0.1 square meter or more can be used. Further, in the present invention, a long polymer film in the form of a long film having a width of 240 mm or more and a length of 10 m or more can be used. Using a large-area base material is superior in terms of productivity. However, on the other hand, if the area is large, defects are likely to occur stochastically, and the yield of the product is difficult to increase. However, in the treatment method of the present invention, since the frequency of occurrence of defects is very low, a large-area base material can be effectively used.

In the present invention, flexible glass can be used as a long base material. Here, the flexible glass is a thin glass having a thickness of 5 μm or more and 200 μm or less, has flexibility like a polymer film, and can be wound into a roll. As the flexible glass, flexible glass in which a polymer film is bonded to one side may be used for safety such as handleability and anti-scattering property when broken.

In the present invention, a silane coupling treatment liquid can be used as the coating liquid. The silane coupling agent treatment liquid in the present invention is a solution containing a liquid silane coupling agent or silane coupling agent in an amount of 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 2% by mass or more. Is.
In the present invention, it is preferable to adjust the temperature of the silane coupling agent treatment liquid to -18 ° C. or higher and 40 ° C. or lower so that the silane coupling agent is brought into contact with the substrate. The temperature of the silane coupling agent treatment liquid is preferably −15 ° C. or higher, more preferably −10 ° C. or higher, and even more preferably −5 ° C. or higher. The upper limit of the temperature of the silane coupling agent treatment liquid is preferably 33 ° C. or lower. 24 ° C. or lower is still more preferable, and 18 ° C. or lower is even more preferable.
When the temperature exceeds a predetermined range, the activity of the silane coupling agent increases, the condensation reaction of the silane coupling agent proceeds in the treatment liquid, and agglomerates are likely to occur, and when the condensation proceeds, the concentration of silanol groups increases. The lowering coupling effect is reduced. It is preferable that the water content is low from the viewpoint of chemical activity, but if the temperature is lower than zero, it becomes difficult to use pure water as a solvent. In this case, an alcohol-based solvent can be used, or a mixed solvent containing water can be used by lowering the freezing point of the solvent. Of course, a plurality of solvents other than water may be used alone or in combination.

Examples of the silane coupling agent that can be used in the present invention include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-. 2- (Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyl Trichlorsilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Glysidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Ethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyl Triethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanuppropyltriethoxysilane, tris- (3) -Trimethoxysilylpropyl) isocyanurate, chloromethylphenetyltrimethoxysilane, chloromethyltrimethoxysilane, aminophenyltrimethoxysilane, aminophenetyltrimethoxysilane, aminophenylaminomethylphenetyltrimethoxysilane, hexamethyldisilazane, etc. Be done.

In addition to the above, silane coupling agents that can be used in the present invention include n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, and diacetoxydimethylsilane. Ethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dodecyllichlorosilane, dodecyltrimethoxylane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltrichlorosilane , N-octyltriethoxysilane, n-octyltrimethoxysilane, triethoxyethylsilane, triethoxymethylsilane, trimethoxymethylsilane, trimethoxyphenylsilane, pentyltriethoxysilane, pentyllichlorosilane, triacetoxymethylsilane, trichloro Hexylsilane, trichloromethylsilane, trichlorooctadecylsilane, trichloropropylsilane, trichlorotetradecylsilane, trimethoxypropylsilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, trichlorovinylsilane , Triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, trichloro-2-cyanoethylsilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, Etc. can also be used.

Further, other alkoxylans such as tetramethoxysilane and tetraethoxysilane may be appropriately added to the silane coupling agent. Further, the reaction is slightly carried out by adding mixing and heating operations, including the case where other alkoxylans such as tetramethoxysilane and tetraethoxysilane are appropriately added to the silane coupling agent, and the case where the silane coupling agent is not added. You may use it after proceeding.

Among such silane coupling agents, the silane coupling agent preferably used in the present invention is preferably a silane coupling agent having a chemical structure having one silicon atom per molecule.
In the present invention, particularly preferable silane coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2. -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, aminophenyl Examples thereof include trimethoxysilane, aminophenyl trimethoxysilane, and aminophenyl aminomethylphenyl trimethoxysilane. When particularly high heat resistance is required in the process, it is desirable to connect Si and an amino group with an aromatic group.
In the present invention, a phosphorus-based coupling agent, a titanate-based coupling agent, or the like may be used in combination, if necessary.

The solvent of the silane coupling agent solution in the present invention is preferably at least one liquid selected from water, a monohydric alcohol having 8 or less carbon atoms, and a divalent alcohol having 4 or less carbon atoms. stomach. More preferably, it is one or more solvents selected from methanol, ethanol, normal propanol, isopropanol, butanol, ethylene glycol, propylene glycol, and water. In the present invention, a mixed solvent composed of two or more kinds of solvents can be used. In the present invention, it is preferable to use a mixed solvent of water and alcohol, a mixed solvent of water and ethylene glycol or propylene glycol, and a mixed solvent of water, an alcohol having 3 or less carbon atoms, and a diol having 3 or less carbon atoms.

The laminate using the long polymer film and the base material obtained by the silane coupling agent treatment of the present invention has extremely few blister defects and can be usefully used as a substrate for an electronic device having a fine structure. Can be done. In the present invention, a polyimide film is used as one of the base materials of the laminate, and at least one of the polyimide film and the inorganic substrate is treated with a silane coupling agent to form a laminate, and after forming an electronic device or the like on the polyimide film. By peeling the polyimide film and the inorganic substrate, a flexible electronic device using the polyimide film as a substrate can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The evaluation method of the physical properties in the following examples is as follows.

<Adhesive strength>
The adhesive strength (180 degree peel strength) between the inorganic substrate of the laminate and the polymer film (polyimide film) was measured under the following conditions according to the 180 degree peeling method described in JIS C6471.
Device name: "Autograph (registered trademark) AG-IS" manufactured by Shimadzu Corporation
Measurement temperature: Room temperature Peeling speed: 50 mm / min Atmosphere: Atmosphere Measurement sample width: 10 mm
The measurement was carried out immediately after the laminate was prepared and after the heat treatment at 500 ° C. for 10 minutes in the inert oven. The number of measurements was N = 5, and the average value was calculated.

<Number of foreign substances>
By observing the surface treated with the silane coupling agent under a microscope, the number of foreign substances having a size of 30 μm or more was counted and converted into the number per square meter.
<Number of blister>
The number of blisters having a diameter of 0.2 mm or more in the laminated body was counted and converted into the number per square meter. A blister is a type of defect in which a gap is formed between a long polymer film and an inorganic substrate, and is sometimes called a float, a bubble, a bubble, or the like.
<Moisture content of long polymer film>
The long polymer film after the drying treatment was cut into 100 mm × 100 mm, the initial mass W0 was measured, and then the mass Wh after heat treatment at 200 ° C. for 10 minutes was measured.
Moisture content (mass%) = 100 x (W0-Wh) / W0
The water content was determined in.

<Example / Comparative example>
As a silane coupling agent, a silane coupling agent diluted solution obtained by diluting 3-aminopropyltrimethoxysilane (“KBE-603” manufactured by Shin-Etsu Chemical Co., Ltd.) with isopropanol (IPA) to 1.0% by mass was prepared as a treatment solution. ..
Using a polyimide film, which is a long polymer film, and flexible glass (with a single-sided protective film) (manufactured by Nippon Denki Glass Co., Ltd.) with a thickness of 50 μm as the base material, the equipment and treatment liquid (coating liquid) shown in Table 1 are used. Depending on the conditions, a silane coupling agent-treated film using the liquid coating apparatus of the present invention was obtained. The water content of the obtained silane coupling agent-treated film was measured, and the results are shown in Table 1.
During the coating experiment, the housing of the liquid coating mechanism was divided and removed every 20 square meters in which the total treatment area (coating area) of the film substrate was integrated, and the film was washed with high-pressure water.

From the obtained silane coupling agent-treated film, a rectangle of 360 mm x 460 mm was cut and placed on a glass substrate (370 mm x 470 mm) subjected to UV ozone treatment so as to be 5 mm away from the periphery, and a laminator (manufactured by Climb Products Co., Ltd.). Temporary laminating was performed using SE650nH) to obtain a temporary laminating laminate. The laminating conditions were a processing substrate side temperature of 100 ° C., a roll pressure of 5 kg / cm2 at the time of laminating, and a roll speed of 5 mm / sec. The polyimide film after the temporary lamination was not peeled off by the weight of the film itself, but the adhesiveness was such that it could be easily peeled off when the edge of the film was scratched. Then, the obtained temporary laminate laminate was placed in a clean oven, heated at 200 ° C. for 30 minutes, and then allowed to cool to room temperature to obtain a laminate of a long polymer film (polyimide film) and a glass substrate. .. The same operation was performed to obtain 5 laminated bodies, the number of blister was counted for all the laminated bodies, converted per square meter to obtain the blister density, and the results are shown in Table 1.

Hereinafter, experiments were sequentially carried out according to the base material, the treatment device, and the conditions shown in Table 1, and the characteristics of the obtained base material were evaluated. The results are shown in Table 1.
The meanings of the abbreviations in Table 1 are as follows.
Polyimide film 1: XENOMAX-F38LR manufactured by Toyobo Co., Ltd.
Polyimide film 2: UPILEX 25S manufactured by Ube Industries, Ltd.
Flexible glass (with single-sided protective film): Made by Nippon Electric Glass Co., Ltd.

SCA: Silane Coupling Agent KBM-603: 3-Aminopropyltrimethoxysilane ("KBM-603" manufactured by Shin-Etsu Chemical Co., Ltd.)
KBE-903: 3-aminopropyltrimethoxysilane ("KBE-903" manufactured by Shin-Etsu Chemical Co., Ltd.)
IPA: Isopropanol ETOH: Ethanol MEOH: Methanol Water / MEOH: Water to methanol = 50/50 (mass ratio) mixed solvent Laminated base material: Base material on the other side to be laminated to the treated base material Glass plate: manufactured by Corning Co., Ltd. Substrate glass for liquid crystal display PI film: Polyethylene film 1

<Application example>
Using the laminates obtained in Examples and Comparative Examples, a tungsten film (thickness 75 nm) was formed on the polyimide film by the vacuum deposition method by the following steps, and an insulating film was further formed without being exposed to the atmosphere. A silicon oxide film (thickness: 150 nm) was laminated and formed. Next, a silicon oxide film (thickness 100 nm) to be a base insulating film was formed by a plasma CVD method, and an amorphous silicon film (thickness 54 nm) was laminated and formed without being exposed to the atmosphere.

Next, the hydrogen element of the amorphous silicon film was removed to promote crystallization, and a heat treatment at 510 ° C. was performed for 10 minutes to form a polysilicon film.
A TFT element was manufactured using the portion of the obtained polysilicon film in the easily peelable portion. First, a polysilicon thin film is patterned to form a silicon region having a predetermined shape, and as appropriate, a gate insulating film is formed, a gate electrode is formed, a source region or a drain region is formed by doping the active region, and an interlayer insulating film is formed. , The source electrode and the drain electrode were formed, and the activation treatment was performed to prepare an array of P-channel TFTs using polysilicon.
A long polymer film part is burnt off with a UV-YAG laser along the inside of the outer circumference of the TFT array by about 0.5 mm, and peeled off from the end of the cut by using a blade on a thin razor to scoop up the flexible TFT. Obtained an array. The peeling was possible with a very small force, and it was possible to peel without damaging the TFT. The obtained flexible TFT array did not show any deterioration in performance even when wound around a round bar having a diameter of 10 mm, and maintained good ON / OFF characteristics.

The liquid coating apparatus of the present invention is particularly suitable for coating a silane coupling agent in a silane coupling agent treatment, and can perform high-quality treatment with a small amount of foreign matter. When this liquid coating device is applied to the production of flexible electronic devices, it is possible to produce electronic devices in high yield, which greatly contributes to the industrial world.
Further, in the present invention, a long polymer film and a long flexible glass can be used as the base material. In the liquid coating apparatus of the present invention, electronic devices such as dielectric elements, semiconductor elements, MEMS elements, display elements, light emitting elements, photoelectric conversion elements, piezoelectric conversion elements, thermoelectric conversion elements, etc. are mounted on a long polymer film or flexible glass. It can be usefully used in the process of forming on top.

11 Long base material unwinding part 12 Long base material winding part 13 Insert paper supply roll 14 Unwinding long base material height adjustment roll 15 Winding long base material height adjustment roll 16 Sealing roll 20 Body 21 Liquid supply part 22 Liquid discharge part 23 Exhaust port 24 Long base material introduction hole 25 Long base material outlet hole 31 Decompression container 32 Decompression hole

Claims (10)

Liquid on a long base material having at least a long base material unwinding part, an unwinding long base material height adjusting roll, a liquid coating mechanism part, a winding long base material height adjusting roll, and a winding part The liquid coating mechanism is a housing having at least an introduction port for introducing a long base material, an outlet for leading out a long base material, and an exhaust port. , the liquid supply unit, Ri Do from the liquid discharge portion, a liquid coating apparatus for applying a liquid to the elongate base material in which the liquid is featuring a silane coupling agent der Rukoto. The liquid coating apparatus according to claim 1, further comprising an interleaving paper supply roll and having a function of co-winding the liquid-coated long base material and the interleaving paper. A device for applying a liquid to a long base material having at least a long base material unwinding part having a height adjusting function, a liquid coating mechanism part, and a long base material winding part having a height adjusting function. The liquid coating mechanism unit is composed of a housing having at least an introduction port for introducing a long base material, an outlet for leading out a long base material, and an exhaust port, a liquid supply part, and a liquid discharge part. Ri, liquid coating device in which the liquid is featuring a silane coupling agent der Rukoto. The liquid coating apparatus according to claim 3, further comprising an interleaving paper supply roll and having a function of co-winding the liquid-coated long base material and the interleaving paper. Any of claims 1 to 4, wherein either or both of the long base material introduction port and the long base material outlet of the housing have a sealing roll pair close to the outside of the housing. The liquid coating device described in Crab. Claims 1 to 4 are characterized in that the rolls are arranged so as not to come into direct contact with the liquid coating surface of the long base material on the downstream side of the long base material outlet of the liquid coating mechanism portion. The liquid coating apparatus according to any one. The invention according to any one of claims 1 to 6, wherein the housing constituting the liquid coating mechanism portion can be divided at a boundary including a long base material introduction hole and a long base material lead-out hole. Liquid coating device. The liquid coating apparatus according to any one of claims 1 to 7, wherein the liquid coating mechanism unit, the liquid supply unit, and the liquid discharge unit are not directly joined. A liquid coating method using the liquid coating apparatus according to any one of claims 1 to 8, wherein the liquid is coated while conveying a long base material having a length of 5 m or more. The liquid coating method according to claim 9, wherein a liquid is applied while the long base material is conveyed in a state of being kept horizontal in the liquid coating mechanism section.

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