JP6897337B2 - Wet treatment equipment, silane coupling agent treatment method and surface treatment sample production method - Google Patents

Description

The present invention relates to a wet treatment apparatus useful for precision coating of a silane coupling agent, a silane coupling agent treatment method using the apparatus, and a method for producing a surface-treated sample using the treatment method.

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 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 vapor phase state. According to such a method, it is possible to realize an extremely thin silane coupling agent layer with low defects. However, with this method, continuous treatment for a long period of time is difficult because the silane coupling agent adheres to every part other than the sample 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 found that the silane coupling agent treatment can be performed continuously and with low defects by arranging the treatment steps according to a specific sequence in the wet treatment apparatus. , The present invention has been reached.

That is, the present invention has the following configuration.
[1] A wet processing apparatus having at least the following steps.
(1) First step of applying the treatment liquid to the sample by at least one means selected from shower coat, brush coat and dip coat (2) At least one selected from shower coat, brush coat and dip coat Second step of cleaning the sample with the cleaning solution by the means of (3) Third step of removing the cleaning solution from the sample with an air knife [2] In the first step using the wet treatment apparatus according to the above [1]. A method for treating a silane coupling agent, which comprises applying a coating liquid containing at least a silane coupling agent to a sample, and then applying a cleaning liquid containing no silane coupling agent in the second step.
[3] A method for treating a silane coupling agent, which comprises performing the treatment according to the above [2] after dry washing the sample with an atmospheric pressure plasma treatment apparatus.
[4] A method for treating a silane coupling agent, which comprises performing the treatment according to the above [2] after dry washing the sample with a UV ozone irradiation device.
[5] The sample is subjected to the silane coupling agent treatment according to any one of [2] to [4] above, and then at least a part of the sample is subjected to atmospheric pressure plasma treatment or UV ozone irradiation treatment. Silane coupling agent treatment method.
[6] The method for treating a silane coupling agent according to any one of [2] to [5], wherein the sample is a polymer film.
[7] A method for producing a surface-treated sample, which comprises performing a silane coupling agent treatment method by the treatment method according to any one of claims 2 to 6.

In the present invention, it is preferable to further have the following configuration.
[8] A method for producing a surface-treated polymer film, which comprises performing a silane coupling agent treatment method by the treatment method according to the above [6].
[9] The silane coupling agent treatment method according to any one of [2] to [6], wherein the polymer film is in the form of a sheet having an area of 0.1 square meter or more, and the above. The method for producing a surface-treated polymer film according to [8].
[10] The silane coupling agent treatment method according to any one of [2] to [7] above, wherein the polymer film is a long film having a width of 240 mm or more and a length of 10 m or more. The method for producing a surface-treated polymer film according to the above [8].

In the present invention, it is preferable to further have the following configuration.
[11] A wet processing apparatus having at least the following steps.
(1) First step of applying the treatment liquid to the sample by at least one means selected from shower coating, brush coating, and dip coating (4) Fourth step of removing excess treatment liquid with an air knife (2) ) Second step of cleaning the sample with a cleaning solution by at least one means selected from shower coating, brush coating, and dip coating (3) Third step of removing the cleaning solution from the sample with an air knife.

According to the present invention, in the first step, the silane coupling agent is adsorbed on the sample surface by bringing the sample into contact with the treatment liquid containing the silane coupling agent, and then the excess treatment liquid is removed with an air knife, and then the sample. By contacting the sample with a cleaning solution that does not contain a silane coupling agent (for example, pure water, alcohol, a mixture thereof, etc.) and removing the silane coupling agent that has not been adsorbed on the sample, it is extremely thin, close to a monolayer. A treated film can be formed. At the same time, since the condensate has a weak interaction with the sample surface, it is easily removed from the sample surface when the unnecessary liquid is removed and when it comes into contact with the cleaning liquid. As a result, it is possible to realize a thin film that is extremely thin and has low defects.
In the present invention, at least one means selected from a shower coat, a brush coat, and a dip coat can be used as a means for bringing the sample into contact with the treatment liquid or the cleaning liquid. These processes are relatively simple, and it is possible to divert existing equipment.
In the present invention, the surface of the sample is preferably clean so as not to inhibit the adsorption of the silane coupling agent on the sample in the treatment liquid. Such cleanliness can be achieved by atmospheric pressure plasma cleaning or UV ozone cleaning.

In the present invention, a polymer film or an inorganic substrate is used as a sample, and by using such a treatment method, a silane coupling agent treatment is performed on the surface of at least one of the samples, and the other sample is laminated on the treated surface. By doing so, a laminate of the polymer film and the inorganic substrate can be obtained, and the number of blister defects generated at that time can be significantly reduced.
The present invention can be applied to either a sheet-shaped polymer film or a long roll-shaped polymer film. When a polymer film is used as a sample, it can be bonded to an untreated inorganic substrate or an inorganic substrate subjected to the same treatment, and a polymer film laminate having extremely few defects such as blister can be obtained. it can.

Further, according to the present invention, the inorganic substrate laminated by the above method and the polymer film surface of the polymer film are microfabricated by using a thin film technique or a printing technique to form an electronic device or a MEMS device, and then high. By peeling the molecular film together with the inorganic substrate, a flexible device using the polymer film as a base material can be formed.

In the present invention, if a polymer film having high heat resistance is used, the inorganic substrate and the polymer film can be bonded to each other without using an adhesive or an adhesive having inferior heat resistance, for example, at a high temperature of 180 ° C. or higher. The functional element can be formed on the polymer film even when the above 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 polymer film laminate 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 can be placed on the polymer film. It is useful for manufacturing flexible electronic devices formed in.

(First step)
The first step is a step of applying the treatment liquid to the sample by at least one means selected from shower coating, brush coating, and dip coating. In this step, it is preferable to use a sufficient amount of the treatment liquid until at least the entire sample is wetted by the treatment liquid.
The shower coat is also called a spray coat, and is a treatment method in which a treatment liquid is sprayed onto a sample in the form of a shower or a spray.
The brush coat is a device that preferably uses a rotating cylindrical brush and sprinkles the treatment liquid while operating the brush so that the treatment liquid adheres evenly to the sample surface. At that time, if the brush comes into direct contact with the sample, the sample may be scratched. Therefore, it is preferable to keep the brush at a distance that does not touch the sample. The distance between the brush and the sample is preferably 1 mm or more and 50 mm.
A dip coat is a processing device that literally immerses a sample in a processing solution.

(4th step)
The fourth step is placed between the first step and the second step as needed. In the fourth step, the excess treatment liquid on the sample surface is removed by the air knife. However, it is preferable that the excess treatment liquid is removed in this step to the extent that the treatment liquid is not completely dried.

(Second step)
In the second step, the cleaning liquid is applied to the sample by at least one means selected from shower coating, brush coating, and dip coating, and the sample is washed. The cleaning liquid does not contain a silane coupling agent, and the cleaning liquid is pure water or an organic solvent containing the solvent of the silane coupling agent used in the treatment liquid, preferably a silane coupling agent from the treatment liquid. It is preferable that the component is obtained by removing the above. In the second step, substantially all of the silane coupling agent that could not be adsorbed on the sample surface was removed, and the silane coupling agent molecules adsorbed on the sample surface between the first step and the second step were removed on the sample surface. Only remains.

(Third step)
In the third step, the cleaning liquid is removed from the substrate by an air knife. The third step may also serve as a drying step.

(Fifth step)
In the present invention, a drying treatment unit can be preferably provided as a fifth step. For drying, air drying with clean air or heat drying may be used in combination.

In the present invention, it is preferable to dry-clean the sample with an atmospheric pressure plasma treatment apparatus and then perform the wet treatment of the present invention. In the present invention, it is preferable that the sample is dry-washed with a UV ozone irradiation device and then wet-treated. Here, the UV ozone treatment device is a treatment device that irradiates a sample with ultraviolet rays having a wavelength of 300 nm or less in the atmosphere and at the same time exposes the sample to ozone generated in the vicinity of a UV light source.

In the present invention, the wet treatment of the present invention can be performed after the sample is wet-washed. Here, wet cleaning means cleaning a sample with a liquid cleaning solution, and the cleaning solution includes a cleaning solution containing a generally known surfactant, a cleaning solution mainly composed of an organic solvent, and a cleaning solution containing water and alcohol as main components. , Aqueous cleaning solution showing alkalinity, cleaning solution containing alkali metal hydroxide or carbonate, cleaning solution containing ammonia or urea, cleaning solution containing primary ammonium salt, cleaning solution containing secondary ammonium salt, tertiary ammonium salt A cleaning solution containing a quaternary ammonium salt, a cleaning solution containing a quaternary ammonium salt, or the like can be used. The concentration of alkali metal ions or ammonium ions contained in the cleaning liquid is preferably 0.02 to 8.0% by mass.

In the present invention, after the sample is treated with the silane coupling agent by the wet treatment of the present invention, at least a part of the sample can be subjected to atmospheric pressure plasma treatment or UV ozone irradiation treatment. In particular, when the sample is in the form of a sheet, a film, a plate, or a substrate, the post-treatment is effective when it is desired to make a difference in the front and back treatments.

When a polymer film is used as a sample in the present invention, the water content of the polymer film is 0.3% by mass or less, preferably 0.12% by mass or less, and more preferably 0.08% by mass or less. It is preferable to dry it. If more water remains on the polymer film than necessary, blister defects are likely to occur.

In the present invention, a silane coupling agent treatment using such a wet treatment method is performed on both an inorganic substrate or a polymer film, or both an inorganic substrate and a polymer film as a sample, and the inorganic substrate and the polymer film are laminated. It is possible to obtain a laminate of a 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 complex 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 polymer film in the present invention includes polyester films such as PET, PEN, and PBT, polyamide films, polyimide films, polyimide benzothiazole films, polyimide benzoxazole films, polyimide benzoimidazole films, polybenzoxazole films, and polyether sulfone films. Polyamidoimide film, polyethylene film, polypropylene film, polyvinyl chloride film, polyvinylidene chloride film and the like can be used.
In the present invention, a sheet-shaped polymer film having an area of 0.1 square meter or more can be used. Further, in the present invention, a 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 sample is superior 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, the frequency of occurrence of defects is very low, so that a large-area sample can be effectively used.

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 Trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Glycydoxypropyltriethoxysilane, 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-isocyanoxidetriethoxysilane, 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 they are 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 silane coupling agent in the present invention can be applied with water, a solution of a solvent such as methanol, ethanol propanyl, MEK, acetone, dioxane, butanol, or a stock solution.

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 following examples are examples in which a polymer film and an inorganic substrate (glass substrate) are used as samples. 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 blisters>
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. The blister is a drawback of a type in which a gap is generated between the polymer film and the inorganic substrate, and is sometimes called a float, a bubble, a bubble, or the like.
<Moisture content of polymer film>
The 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.

<Processing example 1: Comparative example>
As a silane coupling agent, a silane coupling agent diluted solution obtained by diluting 3-aminopropyltriethoxysilane (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.) with pure water to 1.0% by mass was prepared as a treatment solution.
As a sample, a polyimide film having an effective size of 360 mm × 460 mm, which was fixed with a stainless steel frame around the periphery, was used.
First, as the first step, the treatment liquid was applied to the sample using a shower coater. Then, in the second step, the treatment liquid was blown off with an air knife and dried as it was at 120 ° C. for 15 minutes to obtain a silane coupling agent-treated film A. The water content of the silane coupling agent-treated film A was 0.11% by mass.

<Processing Example 2: Example 1>
As a silane coupling agent, a silane coupling agent diluted solution obtained by diluting 3-aminopropyltriethoxysilane (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.) with pure water to 1.0% by mass was prepared as a treatment solution.
As a sample, a polyimide film having an effective size of 360 mm × 460 mm, which was fixed with a stainless steel frame around the periphery, was used.
Before performing the wet treatment, as a pretreatment, the sample is shower-washed with a cleaning solution obtained by diluting the cleaning agent "Semi-clean RPG-1" manufactured by Yokohama Oil & Fat Industry Co., Ltd. with water to 5%, rinsed with deionized water, and then rinsed. The wet treatment of the present invention was carried out without going through a drying step. Since "Semi-clean RPG-1" contains 4 to 5% by mass of potassium hydroxide, the potassium hydroxide concentration of the cleaning liquid is 0.2 to 0.25% by mass.
Next, as a first step, the treatment liquid was applied to the sample using a shower coater. Next, in the 4th step, the treatment liquid is blown off with an air knife (without drying), and immediately after that (within 3 seconds), pure water is showered as a cleaning liquid in the 2nd step, and then in the 3rd step, pure water is blown with an air knife. Was dried in a drying zone at 80 ° C. for about 60 seconds, and then dried in a clean dry oven at 120 ° C. for 15 minutes to obtain a silane coupling agent-treated film B. The water content of the silane coupling agent-treated film B was 0.07% by mass.

<Processing Example 3: Example 2>
In Treatment Example 2, the first step and the second step were changed to a rotating brush coater, and the same operation was performed except that the fourth step was omitted, to obtain a silane coupling agent-treated film C. The water content of the silane coupling agent-treated film C was 0.06% by mass.
The clearance between the rotating brush and the sample was set to 5 mm so that the brush did not come into direct contact with the surface of the sample.

<Processing Example 4: Example 3>
In Treatment Example 2, the same operation was carried out except that the first step and the second step were changed to dip coaters to obtain a silane coupling agent-treated film D. The water content of the silane coupling agent-treated film D was 0.07% by mass.

The number of foreign substances on the surfaces of the silane coupling agent-treated films A, B, C, and D was counted and converted per square meter. The number of foreign substances in the treated film A was 1862 per square meter. (248 pieces per 360 mm × 460 mm. The treated film B was 15 pieces / square meter, the treated film C was 38 pieces / square meter, and the treated film D was 8 pieces / square meter.

Next, the obtained silane coupling agent-treated film was cut out from the frame and placed on a UV ozone-treated glass substrate (370 mm × 470 mm) so as to be 5 mm away from the surroundings, and a laminator (SE650nH manufactured by Climb Products Co., Ltd.) was placed. Temporarily laminated using the product to obtain a temporary laminated 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 laminated 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 polymer film (polyimide film) and a glass substrate. The laminate obtained from the silane coupling agent-treated film A was designated as AA, and the laminate obtained from B, C, and D was designated as BB, CC, and DD, respectively.

The number of blister was counted in the obtained laminate of the polymer film and the glass substrate, and the peel strength of the polymer film was measured. As a result, 2065 blister per square meter was confirmed in the laminate AA. On the other hand, in the laminated body BB, the number was 15 per square meter, the number of CC was 38, and the number of DD was 8. For BB, CC and DD, the blisters matched the number of foreign objects. On the other hand, in AA, the number of blisters increased from the number of foreign substances, suggesting that the number of foreign substances or protrusions increased with the passage of time. It is presumed that this is because the thickness of the silane coupling agent layer is thin and not controlled, so that the condensation of the silane coupling agent proceeds and foreign matter is generated on the substrate.

The initial adhesive strength between the polymer film and the inorganic substrate (within 5 hours from the production of the laminate) and the adhesive strength after heat treatment at 500 ° C. for 10 minutes in an inert oven are AA: initial 0.85 N / cm, after heat treatment 1 .54 N / cm
BB: Initial 0.23 N / cm, after heat treatment 0.25 N / cm
CC: Initial 0.26 N / cm, after heat treatment 0.27 N / cm
DD: Initial 0.25 N / cm, after heat treatment 0.26 N / cm
Met.

<Processing Example 5: Example 4>
Using a glass substrate having a size of 370 mm × 470 mm and a thickness of 0.7 mm as a sample, the pretreatment and the wet treatment of the present invention were carried out in the same manner as in Treatment Example 2 to obtain a silane coupling agent glass substrate E.
Next, the obtained silane coupling agent-treated glass substrate E and a 360 mm × 460 mm polyimide film (moisture content: 0.05% by mass) subjected to UV ozone treatment after drying in a clean oven at 150 ° C. for 10 minutes were attached to the glass substrate. A temporary laminate laminated body was obtained by arranging the particles 5 mm away from the periphery and temporarily laminating them using a laminator (SE650nH manufactured by Climb Products Co., Ltd.). 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 EE of a polymer film (polyimide film) and a glass substrate.
In the obtained laminate EE, the defects of blister are 15 per square meter, and the adhesive strength between the film and the glass substrate is EE: initial 0.18 N / cm, after heat treatment 2.1 N / cm.
Met.

<Application example>
Using the laminate D obtained in the examples, a thin film transistor ray having a bottom gate type structure was produced on a polyimide film by the following steps.
The entire surface side of the polymer film of the laminate was first cleaned by atmospheric pressure plasma treatment. Then, a 100 nm gas barrier film made of SiON was formed by using a reactive sputtering method. Next, an aluminum layer having a thickness of 80 nm was formed by a sputtering method, and a gate wiring and a gate electrode were formed by a photolithography method. Subsequently, an epoxy resin-based gate insulating film (thickness 80 nm) was formed using a slit die coater. Further, a Cr layer of 5 nm and a gold layer of 40 nm were formed by a sputtering method, and a source electrode and a drain electrode were formed by a photolithography method. In addition, an epoxy resin to be an insulating layer and a dam layer is applied using a slit die coater, and a dam layer having a thickness of 250 nm for a semiconductor layer including a source electrode and a drain electrode is formed by ablation with a UV-YAG laser. A circular shape having a diameter of 100 μm was formed, and a via was formed at the same time as a connection point with the upper electrode. Then, polythiophene, which is an organic semiconductor, was applied into the dam by an inkjet printing method, silver paste was embedded in the via portion, and aluminum wiring was further formed as an upper electrode to form a thin film transistor ray having 640 × 480 pixels.

The obtained thin film transistor ray is used as a backplane, and an electrophoretic display medium is superposed on the front plane to form a display element. Was peeled off from the inorganic substrate to obtain a flexible electrophoretic display.
The obtained flexible electrophoresis element showed good display performance, and it was confirmed that all pixels were driven. Further, the obtained flexible electrophoresis element did not show any deterioration in performance even when wound around a round bar having a diameter of 5 mm.

The wet treatment apparatus of the present invention can form a high-quality treatment film with few foreign substances, especially in the treatment of a silane coupling agent. When this wet processing 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.

Claims (7)

A wet processing apparatus characterized by having at least the following steps.
(1) A first step of applying a treatment liquid to a sample by at least one means selected from a shower coat, a brush coat, and a dip coat.
The first treatment liquid is a solution of water, methanol, ethanol, propanol, MEK, acetone, dioxane or butanol of a silane coupling agent, or a stock solution of a silane coupling agent, and the sample is a polymer film or an inorganic substrate. Step (2) A second step of washing a sample with a washing solution by at least one means selected from shower coating, brush coating, and dip coating .
Second step in which the cleaning solution is water, methanol, ethanol, propanol, MEK, acetone, dioxane or butanol (3) Third step of removing the cleaning solution from the sample with an air knife.
(4) A fourth step that is placed between the first step and the second step and removes excess treatment liquid on the sample surface with an air knife. Using the wet treatment apparatus according to claim 1, a coating liquid containing at least a silane coupling agent is applied to a sample in the first step, and a cleaning liquid containing no silane coupling agent is applied in the second step. A method for treating a silane coupling agent. A method for treating a silane coupling agent, which comprises performing the treatment according to claim 2 after dry washing the sample with an atmospheric pressure plasma treatment apparatus. A method for treating a silane coupling agent, which comprises performing the treatment according to claim 2 after the sample is dry-washed with a UV ozone irradiation device. Silane coupling, which comprises subjecting the sample to the silane coupling agent treatment according to any one of claims 2 to 4, and then subjecting at least a part of the sample to atmospheric pressure plasma treatment or UV ozone irradiation treatment. Agent treatment method. The silane coupling agent treatment method according to any one of claims 2 to 5, wherein the sample is a polymer film. A method for producing a surface-treated sample, which comprises performing the silane coupling agent treatment method by the treatment method according to any one of claims 2 to 6.