JP2019005675A - Liquid coating apparatus and liquid coating method. - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid coating apparatus for obtaining a high-quality silane coupling agent-treated substrate with few foreign substances, and a liquid coating method using the apparatus. SOLUTION: An unwinding part 11 of a long base material, a height adjusting roll 14 of an unwinding long base material, a liquid coating mechanism part, a height adjusting roll 15 of a winding long base material, and a winding part 12 are provided. A device for applying a liquid to at least a long base material, wherein the liquid application mechanism unit has an introduction port 24 for introducing the long base material and an outlet 25 for leading out the long base material. A liquid coating device for applying a liquid to a long base material including a housing 20 having at least an exhaust port 23, a liquid supply section 21, and a liquid discharge section 22, and a silane coupling agent using the device. A method of applying a silane coupling agent, which comprises applying and drying. [Selection diagram] Fig. 1

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 specifically, a roll-shaped long base material. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for unwinding and applying a liquid, and relates to a liquid applying apparatus and a liquid applying method that can easily maintain and clean the inside of the apparatus, and as a result, can realize a high-quality silane coupling agent treated surface Is.

  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 adhesion between the two. Silane coupling agents have a strong adsorptive power to inorganic materials and at the same time tend to cause self-condensation reactions. For this reason, condensate particles are formed in the treatment liquid and the coating liquid, and these particles often cause foreign matter defects on the coated surface and the treated 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 gas phase state. According to this method, it is said that an extremely thin silane coupling agent layer can be realized with low defects. However, in this method, since the silane coupling agent adheres to every place other than the base material inside the apparatus, continuous treatment over a long time is difficult.

JP-A-2015-178237

  As a result of intensive studies to solve the above-mentioned problems, the present inventors can process a continuous long base material by using a liquid coating apparatus having a specific structure in the liquid coating apparatus, and further have low defects. In addition, the present inventors have found that the silane coupling agent treatment can be performed, and in addition, have found that the present apparatus and method can be widely applied to all liquid application methods.

That is, the present invention has the following configuration.
[1] A long base having at least an unwinding portion of a long base material, a height adjusting roll of the unwinding long base material, a liquid application mechanism portion, a height adjusting roll of the long winding base material, and a winding portion. An apparatus for applying a liquid to a material, wherein the liquid application mechanism unit has at least an introduction port for introducing a long substrate, a discharge port for deriving the long substrate, and an exhaust port. A liquid application apparatus for applying a liquid to a long base material comprising a casing, a liquid supply part, and a liquid discharge part.
[2] The liquid coating apparatus according to [1], further including a slip sheet supply roll and having a function of winding the liquid-coated long base material and the slip sheet together.
[3] An apparatus 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 application mechanism part, and a long base material winding part having a height adjusting function The pre-liquid application mechanism unit includes a housing having at least an introduction port for introducing a long substrate, a discharge port for deriving the long substrate, and an exhaust port, a liquid supply unit, a liquid A liquid applicator characterized by comprising a discharge unit.
[4] The liquid coating apparatus according to [3], further including a slip paper supply roll and having a function of co-winding the liquid-coated long base material and the slip sheet.
[5] [1] to [4], characterized in that either or both of the long base material introduction port and the long base material outlet port of the housing have a roll pair close to the outside of the housing. The liquid coating apparatus according to any one of the above.
Here, the pair of rolls close to the outside of the casing means that the gap between the roll and the casing is set to be 1 mm or less. Thereby, it is possible to minimize leakage of steam, mist and the like generated from the coating liquid to the outside of the housing.
[6] From [1] to [1], the roll is disposed so as not to directly contact the liquid application surface of the long base material on the downstream side of the long base material outlet of the liquid application mechanism. 4] The liquid coating apparatus according to any one of the above.
[7] Any one of [1] to [6], wherein the casing constituting the liquid application mechanism section can be divided at a boundary including a long base material introduction hole and a long base material lead hole. The liquid coating apparatus according to 1.
[8] The liquid application apparatus according to any one of [1] to [7], wherein the liquid application 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, bonding, or the like, and are not fixed by a large number of screws, bolts, or the like. Fixing with a wing screw, wing nut, patchon lock, etc. is not included in direct joining. In addition, the joining in which the number of screws or bolts is 6 or less is not included in the direct joining. In short, it means that it can be detached with a relatively simple work.
[9] A liquid application method using the liquid application apparatus according to any one of [1] to [8], wherein the liquid is applied while a long substrate having a length of 5 m or more is conveyed.
[10] The liquid application method according to [9], wherein the liquid is applied while the long base material is transported in a state of being kept horizontal in the liquid application mechanism.

The present invention preferably further has the following configuration.
[11] The liquid application mechanism when the processing amount of the long base material reaches a predetermined integrated application area, or the operation time of the liquid application apparatus reaches a predetermined time, or satisfies any of the conditions. The liquid application method according to [9] or [10], wherein the cleaning is performed by dividing the liquid.
[12] In the liquid coating apparatus or the 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. The liquid coating apparatus or the liquid coating method according to any one of [1] to [11], wherein the solution containing at least 0.1% by mass of the run coupling agent is a solvent. Any one of [1] to [12], wherein the liquid is at least one liquid selected from water, monohydric alcohols having 8 or less carbon atoms, and dihydric alcohols having 4 or less carbon atoms A liquid coating apparatus or a liquid coating method according to claim 1.
[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 to 500 μm. 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 base material outlet hole of the liquid coating apparatus and the long base material winding portion. Or liquid application method.

The present invention preferably further has the following configuration.
[16] From [1] to [15], characterized in that a dry cleaning zone is provided by an atmospheric pressure plasma treatment apparatus between the long base material unwinding portion and the long base material introduction hole of the liquid coating apparatus. The liquid coating apparatus or liquid coating method according to any one of the above.
[17] Any one 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 apparatus. A liquid coating apparatus or a liquid coating method according to claim 1.
[18] 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 application apparatus or liquid application method.

In the liquid coating apparatus of the present invention, since the disassembly cleaning and maintenance of the coating mechanism can be performed while the long base material is kept away from the apparatus, the apparatus can be cleaned frequently. For this reason, it has high self-condensation reactivity like a silane coupling agent, and can be cleaned frequently even in liquid applications where gels and foreign substances are easily generated by the reaction. Liquid application is possible. In the present invention, a process in which a silane coupling agent treatment liquid is applied to a base by the liquid coating apparatus of the present invention and dried is referred to as silane coupling agent treatment or simply treatment.
In the present invention, the surface of the substrate is preferably clean so as not to inhibit adsorption of the silane coupling agent to the substrate. Such cleanliness can be realized by atmospheric pressure plasma cleaning or UV ozone cleaning.

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

  Furthermore, according to the present invention, an electronic device or a MEMS device is obtained by performing fine processing using a thin film technique or a printing technique on the inorganic substrate of the laminate and the polymer film surface of the long polymer film laminated by the above method. By forming and then peeling together with the polymer film from the inorganic substrate, a flexible device based on the polymer film can be formed.

  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 pressure-sensitive adhesive having poor heat resistance. Even when a high temperature such as ° C. or higher is required, a functional element can be formed on a long polymer film. In general, semiconductors, dielectrics, and the like can be expected to form higher-performance electronic devices because a thin film with better film quality is obtained when formed at a high temperature. Accordingly, when 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, thermoelectric conversion elements are long. This is useful for manufacturing flexible electronic devices formed on polymer films.

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 section 11 and guided to the long base material introduction hole 24 of the liquid application mechanism section through the unwinding long base material height adjusting roll 14. Here, the liquid application mechanism unit includes at least a casing 20 having an exhaust port 23, a liquid supply unit 21, and a liquid discharge unit 22. The long polymer film introduced into the casing is applied with a liquid, and is taken up from the long base material outlet hole 25, passed through the height adjusting roll 15 of the long base material, and preferably supplied from the slip paper supply roll 13. Together with the interleaving paper, it is wound up by the long base material winding unit 12.

  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 part 11 and the long base material winding part 12 each independently have a height adjusting function without using a height adjusting roll.

  FIG. 3 is a schematic view showing an example of an aspect of the liquid coating apparatus of the present invention. In this example, a pair of sealing rolls 16 are installed in the vicinity of the long base material introduction hole of the liquid application mechanism portion and the long base material lead-out action, respectively, resulting from the liquid to be applied from the casing of the liquid application mechanism portion. Prevent leakage of steam, gas, mist, etc. to the outside world.

  FIG. 4 is a schematic view showing an example of an aspect of the liquid coating apparatus of the present invention. In this example, a decompression vessel 31 having a decompression hole 32 is further provided outside the apparatus configuration corresponding to FIG. 2, and leakage of vapor, gas, mist, and the like caused by the liquid to be applied to the outside from the liquid application mechanism unit. To prevent.

In this invention, a drying process can be provided after derivation | leading-out from the liquid application | coating mechanism part of a long polymer film, and it can be set as the manufacturing method of a silane coupling agent process long base material. Drying uses air drying with clean air, heat drying, drying by infrared heating, or the like, and a plurality of drying methods can be used in combination.
In the present invention, when a long polymer film is used as the substrate, the water content of the long polymer film is preferably 0.3% by mass or less, more preferably 0.15% by mass or less, and still more preferably 0. It is preferable to dry until it becomes 0.08 mass% or less. If moisture remains in the long polymer film more than necessary, blister defects are likely to occur. Control of moisture content is particularly important when an aramid film, polyimide film, or polyamideimide film is used as the long polymer film.

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

  In the present invention, the liquid can be applied by the apparatus of the present invention after wet cleaning of the substrate. Here, wet cleaning means that the substrate is cleaned with a liquid cleaning solvent. 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. Cleaning solvent containing main component, aqueous cleaning solvent showing alkalinity, cleaning solvent containing alkali metal hydroxide or carbonate, cleaning solvent containing ammonia or urea, cleaning solvent containing primary ammonium salt, secondary ammonium A washing solvent containing a salt, a washing solvent containing a tertiary ammonium salt, a washing 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, after applying and drying the silane coupling agent solution on the base material by the liquid application of the present invention, at least a part of the base material can be subjected to atmospheric pressure plasma treatment or UV ozone irradiation treatment. In particular, when the base material is in the form of a sheet, film, plate, or substrate, post-processing is effective when it is desired to make a difference between the front and back processing.

  In the present invention, the silane coupling agent treatment using such a liquid coating method is performed on an inorganic substrate or a long polymer film, or both an inorganic substrate and a long polymer film as a base material. By laminating the film, a laminate of a long polymer film and an inorganic substrate with few defects can be obtained.

  Examples of the inorganic substrate of the present invention include a glass substrate, a ceramic plate, a semiconductor wafer, and a metal plate. A composite substrate in which two or more selected from a glass substrate, a ceramic plate, a semiconductor wafer, and a metal plate are laminated can also be used. Furthermore, a composite in which one or more materials selected from glass, ceramic, and metal are dispersed in powder form in other inorganic or organic materials can be exemplified. Further examples include a substrate material having a fiber-reinforced composite structure in which one or more kinds of fibrous materials selected from glass, ceramic, and metal are combined in another inorganic material or an organic material.

The long polymer film in the present invention is a polyester film such as PET, PEN, PBT, polyamide film, polyimide film, polyimide benzothiazole film, polyimide benzoxazole film, polyimide benzimidazole film, polybenzoxazole film, polyethersulfone. A film, a polyamideimide film, a polyethylene film, a polypropylene film, a polyvinyl chloride film, a polyvinylidene chloride film, or the like can be used.
In the present invention, a sheet-like long polymer film having an area of 0.1 square meters or more can be used. 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. The use of a large-area substrate is advantageous in terms of productivity. 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 substrate can be used effectively.

  In the present invention, flexible glass can be used as the long substrate. Here, the flexible glass is a thin glass having a thickness of 5 μm or more and 200 μm or less, and has flexibility such as a polymer film and can be wound in a roll shape. As flexible glass, you may use the flexible glass which bonded the polymer film on the single side | surface for safety, such as handling property and the prevention of scattering at the time of a crack.

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 a silane coupling agent in an amount of 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 2% by mass or more. It is.
In this invention, it is preferable to adjust the temperature of a silane coupling agent processing liquid to -18 degreeC or more and 40 degrees C or less, and to make it contact with a base material. The temperature of the silane coupling agent treatment liquid is preferably −15 ° C. or higher, more preferably −10 ° C. or higher, and still 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 more preferable, and 18 ° C. or lower is still 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. Lowering coupling effect is reduced. From the viewpoint of chemical activity, the lower one is preferable, but if it is below 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 with the freezing point of the solvent lowered. 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, 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 Trichlorosilane, vinyltrimethoxysilane, vinylto Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p -Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3- Lolopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, tris- (3-trimethoxysilylpropyl) Examples include isocyanurate, chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, aminophenyltrimethoxysilane, aminophenethyltrimethoxysilane, aminophenylaminomethylphenethyltrimethoxysilane, and hexamethyldisilazane.

  In addition to the above, the silane coupling agent that can be used in the present invention includes n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, di-silane. Ethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltrichlorosilane , N-octyltriethoxysilane, n-octyltrimethoxysilane, triethoxyethylsilane, triethoxymethylsilane Trimethoxymethylsilane, trimethoxyphenylsilane, pentyltriethoxysilane, pentyltrichlorosilane, triacetoxymethylsilane, trichlorohexylsilane, 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) Chirushiran, 3-glycidyloxypropyltrimethoxysilane, and the like may also be used.

  Further, other alkoxysilanes such as tetramethoxysilane and tetraethoxysilane may be appropriately added to the silane coupling agent. In addition, when other alkoxylanes such as tetramethoxysilane, tetraethoxysilane, etc. are added to the silane coupling agent as appropriate or not, mixing and heating operations are added to slightly react. It may be used after it has been advanced.

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 of the coupling agent.
In the present invention, particularly preferred 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 Trimethoxysilane, aminophenethyltrimethoxysilane Emissions, such as aminophenyl aminomethyl phenethyltrimethoxysilane the like. In the case where particularly high heat resistance is required in the process, it is desirable to use an aromatic group between Si and an amino group.
In the present invention, if necessary, a phosphorus coupling agent, a titanate coupling agent, or the like may be used in combination.

  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 dihydric alcohol having 4 or less carbon atoms. Yes. More preferably, the solvent 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, 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 treatment with the silane coupling agent of the present invention has an extremely small number of blister defects and is useful as a substrate for an electronic device having a fine structure. Can do. 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 an electronic device or the like is formed on the polyimide film By peeling the polyimide film and the inorganic substrate, a flexible electronic device using the polyimide film as the substrate can be obtained.

    EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. The physical property evaluation methods in the following examples are 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 in accordance with the 180 degree peel 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
Note that the measurement was performed immediately after the laminate was manufactured and after heat treatment at 500 ° C. for 10 minutes in an inert oven. The number of measurements was N = 5, and the average value was obtained.

<Number of foreign objects>
The number of foreign matters of 30 μm or more was counted by microscopic observation of the silane coupling agent treated surface and converted into the number per square meter.
<Number of blisters>
The number of blisters with a diameter of 0.2 mm or more in the laminate was counted and converted to 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 referred to as “uki”, “bubble”, or “bubble”.
<Water content of long polymer film>
The long polymer film after the drying treatment is cut into 100 mm × 100 mm, the initial mass W0 is measured, and then the mass Wh after heat treatment at 200 ° C. for 10 minutes is measured.
Moisture content (mass%) = 100 × (W0−Wh) / W0
The water content was determined at

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

  A 360 mm × 460 mm rectangle was cut from the obtained silane coupling agent-treated film, and placed on a glass substrate (370 mm × 470 mm) subjected to UV ozone treatment so as to be separated from the surroundings by 5 mm. SE650nH) was temporarily laminated to obtain a temporary laminated laminate. Lamination conditions were a processing substrate side temperature of 100 ° C., a roll pressure of 5 kg / cm 2 during lamination, and a roll speed of 5 mm / sec. The polyimide film after temporary lamination did not peel off due to its own weight, but had such adhesiveness that it was easily peeled off when the film edge was scratched. Thereafter, the obtained temporary laminate laminate was put 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 laminates, and the number of blisters for all laminates was counted, converted to per square meter, and set as the blister density. The results are shown in Table 1.

Hereinafter, experiments were sequentially performed using the base material, processing apparatus, and 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 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): manufactured 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: Mixed solvent of water / methanol = 50/50 (mass ratio) Laminate base material: Substrate on the other side laminated to the treated base material Glass plate: manufactured by Corning Substrate glass for liquid crystal displays PI film: Polyimide film 1

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

Subsequently, a hydrogen element in the amorphous silicon film was removed to promote crystallization, and a heat treatment at 510 ° C. was performed for 10 minutes in order to form a polysilicon film.
A TFT element was fabricated using a portion in the easily peelable portion of the obtained polysilicon film. First, a polysilicon thin film is patterned to form a silicon region having a predetermined shape, and 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, an interlayer insulating film , Formation of source and drain electrodes, and activation treatment were performed to fabricate an array of P-channel TFTs using polysilicon.
A flexible TFT with a UV-YAG laser that burns out a long polymer film along the inner periphery of the TFT array, and then scoops it off from the end of the cut using a thin razor blade. An array was obtained. Peeling was possible with extremely little force, and peeling was possible without damaging the TFT. Even when the obtained flexible TFT array was wound around a 10 mmφ round bar, the performance was not deteriorated, and good ON / OFF characteristics were maintained.

The liquid coating apparatus of the present invention is particularly suitable for silane coupling agent application in silane coupling agent treatment, and can perform high-quality treatment with less foreign matter. When this liquid coating apparatus is applied to the production of flexible electronic devices, it is possible to produce electronic devices with a high yield, and the contribution to the industry is great.
Further, in the present invention, a long polymer film and a long flexible glass can be used as the substrate. The liquid coating apparatus according to the present invention includes an electronic device such as a dielectric element, a semiconductor element, a MEMS element, a display element, a light emitting element, a photoelectric conversion element, a piezoelectric conversion element, and a thermoelectric conversion element on a long polymer film or a flexible glass. Useful in the process of forming above.

DESCRIPTION OF SYMBOLS 11 Long base material unwinding part 12 Long base material winding part 13 Interleaf supply roll 14 Height adjustment roll of unwinding long base material 15 Height adjusting roll of winding long base material 16 Sealing roll 20 Housing 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 Depressurization container 32 Decompression hole

Claims (10)

  The long base material unwinding part, the unwinding long base material height adjusting roll, the liquid application mechanism part, the winding long base material height adjusting roll, the long base material having at least the winding part is liquid The liquid application mechanism unit includes a housing having at least an introduction port for introducing a long substrate, a discharge port for deriving the long substrate, and an exhaust port. A liquid application apparatus for applying a liquid to a long base material comprising a liquid supply unit and a liquid discharge unit.   The liquid coating apparatus according to claim 1, further comprising a slip sheet supply roll and having a function of co-winding the liquid-coated long base material and the slip sheet.   An apparatus for applying a liquid to a long base material having at least a long base material unwinding section having a height adjusting function, a liquid application mechanism section, and a long base material winding section having a height adjusting function. The liquid application mechanism unit includes a casing having at least an introduction port for introducing a long base material, a lead-out port for deriving the long base material, and an exhaust port, a liquid supply unit, and a liquid discharge unit. A liquid applicator characterized by this.   The liquid coating apparatus according to claim 3, further comprising a slip paper supply roll, and having a function of co-winding the liquid-coated long base material and the slip sheet. ,
Either of the long base material introduction port of the said housing | casing, a long base material outlet port, or both have the sealing roll pair which adjoins the housing | casing outer side. A liquid coating apparatus according to claim 1.   5. The roll according to claim 1, wherein the roll is disposed so as not to directly contact the liquid application surface of the long base material on the downstream side of the long base material outlet of the liquid application mechanism portion. The liquid coating apparatus according to any one of the above.   The case which comprises the said liquid application | coating mechanism part can be divided | segmented in the boundary containing a elongate base material introduction hole and a elongate base material extraction hole, The claim 1 characterized by the above-mentioned. Liquid applicator.   The liquid application apparatus according to any one of claims 1 to 7, wherein the liquid application mechanism unit, the liquid supply unit, and the liquid discharge unit are not directly joined to each other.   A liquid application method using the liquid application apparatus according to claim 1, wherein the liquid is applied while conveying a long substrate having a length of 5 m or more.   The liquid application method according to claim 9, wherein the liquid is applied while the long base material is transported in a state of being kept horizontal in the liquid application mechanism unit.