JP6946751B2 - Silane coupling agent treatment method, silane coupling agent treatment base material manufacturing method, and laminate manufacturing method - Google Patents

Description

The present invention relates to a silane coupling agent treatment method for realizing a high-quality treated surface, a method for producing a silane coupling agent-treated substrate using the silane coupling agent treatment method, and further obtained by the production method. The present invention relates to a method for producing a laminate using a silane coupling agent-treated substrate. Such a laminate is preferably useful as a processing device for manufacturing a flexible electronic device.

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, 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 perform continuous treatment by processing in a wet processing apparatus according to a specific sequence, and further, it is possible to perform silane coupling agent treatment with low drawbacks. And arrived at the present invention.

That is, the present invention has the following configuration.
[1] A cleaning solvent that does not substantially contain a silane coupling agent after the base material is brought into contact with a silane coupling agent treatment liquid at -18 ° C. or higher and 40 ° C. or lower for a time of 1 second or longer and 10 minutes or shorter. A method for treating a silane coupling agent, which comprises contacting the silane for 3 seconds or more and 10 minutes or less.
[2] The silane coupling according to [1], wherein the silane coupling agent treatment liquid is a liquid silane coupling agent or a solution containing at least 0.1% by mass or more of the silane coupling agent. Agent treatment method.
[3] The cleaning solvent is 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 [1]. Alternatively, the method for treating a silane coupling agent according to [2].
[4] The method for treating a silane coupling agent according to any one of [1] to [3], wherein the base material is a polymer film having a thickness of 1 μm or more and 500 μm or less.
[5] A silane coupling agent-treated base material, which comprises a base material drying step after the base material is treated with the silane coupling agent according to any one of [1] to [4]. Manufacturing method.
[6] A silane coupling agent-treated base material, which comprises a base material drying step after the base material is treated with the silane coupling agent according to any one of [1] to [4]. Manufacturing method.
[7] A method for producing a laminate by laminating a silane coupling agent-treated substrate obtained by the production method according to claim 7 and another substrate.

In the present invention, it is preferable to have the following configuration.
[8] The silane coupling agent treatment method, which comprises performing the treatment according to any one of [1] to [4] after dry cleaning the base material with an atmospheric pressure plasma treatment apparatus, and [6]. The method for producing a silane coupling agent-treated base material according to the above, and the method for producing a laminate according to [7].
[9] The method for treating a silane coupling agent, which comprises performing the treatment according to any one of [1] to [4] after the base material is dry-cleaned with a UV ozone irradiation device, and [6]. The method for producing a silane coupling agent-treated substrate and the method for producing a laminate according to [7].
[10] After performing the silane coupling agent treatment on the base material, which comprises performing the treatment according to any one of [1] to [4], at least a part of the base material is subjected to atmospheric pressure plasma treatment or UV. A silane coupling agent treatment method characterized by performing ozone irradiation treatment.
[11] The silane coupling agent treatment method according to any one of [1] to [4], wherein the polymer film is in the form of a sheet having an area of 0.1 square meter or more, and [6]. ] The method for producing a silane coupling agent-treated substrate, and the method for producing a laminate according to [7].
[12] The silane coupling agent treatment method according to any one of [1] to [4], wherein the polymer film is a long film having a width of 240 mm or more and a length of 10 m or more, and [12]. 6] The method for producing a silane coupling agent-treated substrate, and [7] a method for producing a laminate.
[13] A polyimide film is used as the polymer film, and after the silane coupling agent treatment using the silane coupling agent treatment method according to any one of [1] to [4], the water content is 0.3 mass by mass. The method for producing a silane coupling agent-treated substrate according to [6], and the method for producing a laminate according to [7], which comprises a step of drying with Suma reaching%.
[14] The silane coupling agent-treated base material according to [13], wherein the polyimide film as the polymer film is cleaned with a cleaning agent containing potassium hydroxide before being treated with a silane coupling agent. A manufacturing method and a method for manufacturing a laminate according to [7].
[15] The silane coupling agent-treated film treated by the treatment method according to any one of [1] to [4] above and the inorganic substrate cleaned with a cleaning agent containing potassium hydroxide are laminated. A method for producing a laminate having a blister defect number of 15 pieces / square meter.

According to the present invention, in the step of bringing the base material into contact with the silane coupling agent treatment liquid, the silane coupling agent is adsorbed on the surface of the base material, and then the excess silane not adsorbed on the base material by contacting with the washing solvent. By removing the coupling agent, a thin treated film that is extremely close to a monomolecular film can be formed. At the same time, the condensate of the silane coupling agent has a weak interaction with the surface of the substrate, so that it is easily removed from the surface of the substrate upon contact with the cleaning solvent. As a result, it is possible to realize a white curtain that is extremely thin and has low defects.
In the present invention, at least one means selected from shower coat, brush coat, sponge coat, dip coat and spin coat can be preferably used as a means for bringing the substrate into contact with the silane coupling treatment liquid or the cleaning solvent. .. These processes are relatively simple, and it is possible to divert existing equipment.
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 that occur when a silane coupling agent is applied to a polymer film or an inorganic substrate and the two are laminated to form a laminate. It becomes.

Further, according to the present invention, an electronic device or a MEMS device is formed by finely processing the inorganic substrate of the laminate laminated by the above method and the polymer film surface of the polymer film using thin film technology or printing technology. After that, the polymer film is peeled off from the inorganic substrate to form a flexible device using the polymer film as a base material.

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 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 can be placed on the polymer film. It is useful for manufacturing flexible electronic devices formed in.

The first step of the present invention is a step of bringing a silane coupling agent treatment liquid (hereinafter, simply referred to as a treatment liquid) into contact with a substrate. In this step, it is preferable to use a sufficient amount of the treatment liquid until at least the entire base material becomes wet with the treatment liquid.
In the present invention, the means for bringing the treatment liquid into contact with the base material is not particularly limited, but at least one means selected from a shower coat, a brush coat, a sponge coat, a dip coat, and a spin coat can be preferably used.
The shower coat is also called a spray coat, and is a treatment method in which a treatment liquid is sprayed onto a base material in a shower-like or spray-like manner.
The brush coat is a device that preferably uses a rotating cylindrical brush and sprinkles the treatment liquid on the brush so that the treatment liquid adheres evenly to the surface of the base material. At that time, if the brush comes into direct contact with the base material, the base material may be scratched. Therefore, it is preferable to keep the brush at a distance that does not touch the base material. The distance between the brush and the base material is preferably 1 mm or more and 50 mm. Sponge coating is a method that uses a sponge roll or the like instead of a brush.
A dip coat is a treatment device that literally immerses a base material in a treatment liquid.

The second step of the present invention is a step of bringing the cleaning solvent into contact with the base material. In the second step, the cleaning solvent is applied to the substrate by at least one means preferably selected from shower coat, brush coat, dip coat, sponge coat and spin coat, and excess silane coupling agent from the substrate. Is removed. The cleaning solvent does not contain a silane coupling agent, and the cleaning solvent is pure water or an organic solvent containing the solvent of the silane coupling agent used in the treatment liquid, preferably a silane cup from the treatment liquid. It is preferably a component from which the ring agent has been removed. In the second step, substantially all of the silane coupling agent that could not be adsorbed on the surface of the base material was removed, and the silane cup adsorbed on the surface of the base material between the first step and the second step on the surface of the base material. Only the ring agent molecule remains.
The cleaning solvent 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. 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.

In the present invention, a drying step may be provided after the silane coupling agent treatment of the present invention to provide a method for producing a silane coupling agent-treated film. 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 polymer film is used as the base material in the present invention, the water content of the polymer film is preferably 0.3% by mass or less, more preferably 0.15% by mass or less, still more preferably 0.08% by mass. It is preferable to dry until the following. If more water remains on the 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 polymer film.

In the present invention, it is preferable to dry-clean the substrate with an atmospheric pressure plasma treatment apparatus and then perform the wet treatment of the present invention. In the present invention, it is preferable to dry-clean the substrate with a UV ozone irradiation device and then perform wet treatment. 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, the wet treatment of the present invention can be performed after the substrate is wet-cleaned. 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, after the silane coupling agent treatment is applied to the base material by the wet treatment 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 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, a silane coupling agent treatment using such a wet treatment method is performed on an inorganic substrate or a polymer film as a base material, or both an inorganic substrate and a polymer film, 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 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 materials selected from glass, ceramics, and metals are composited 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 film or sheet having a thickness of 1 μm or more and 500 μm or less can be used. In the present invention, the preferable film thickness is 4 μm or more and 260 μm or less, preferably 7 μm or more and 130 μm or less, and more preferably 12 μm or more and 80 μm or less.
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 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.

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 aminophenylaminomethylphenyl 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 laminate using the base material obtained by the silane coupling agent treatment of the present invention has an extremely small number of blister defects and can be usefully used as a substrate for an electronic device having a fine structure. 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 following examples are examples in which a polymer film and an inorganic substrate (glass substrate) are used as the base material. 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. The blister is a drawback of a type in which a gap is formed 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.

<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. ..
As a base material, a rectangular polyimide film having an effective size of 360 mm × 460 mm, in which the periphery was fixed with a stainless steel frame, was used.
First, as the first step, a dip coater was used, and the base material was immersed in the treatment liquid whose temperature was adjusted to 25 ° C. for 60 seconds. The treatment of contacting with the washing solvent in the second step was omitted, and the film was dried as it was at 120 ° C. for 15 minutes to obtain a silane coupling agent-treated film. The water content of the obtained silane coupling agent-treated film was measured, and the results are shown in Table 1.

The obtained silane coupling agent-treated film was cut out from the frame, placed on a UV ozone-treated glass substrate (370 mm × 470 mm) at a distance of 5 mm from the surroundings, and temporarily used with a laminator (SE650nH manufactured by Climb Products Co., Ltd.). Lamination was performed 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 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 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. When the blister density corresponds to 500 pieces / square meter or more, the counting is stopped there and indicated as "> 500".

Below, Table 1. Experiments were carried out in sequence according to the base material, processing device and conditions shown in Table 2, and the characteristics of the obtained base material were evaluated. The results are shown in Tables 1 and 2.
The meanings of the abbreviations in Tables 1 and 2 are as follows.
Polyimide film: XENOMAX-F38LR manufactured by Toyobo Co., Ltd.
Dip coater: Immersion coater with 2 tanks of 120 liter capacity dipping layer + water washing tank Spin coater: Spin coater manufactured by Japan Create Co., Ltd. Shower coater: Continuous type of 1m in the first process and 2m in the second process 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

<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.
The 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 array. Obtained. 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 3 mmφ round bar, and maintained good ON / OFF characteristics.

The silane coupling agent treatment method of the present invention, the method for producing a silane coupling agent-treated base material using the same, and the laminate using the treated base material are of high quality with few foreign substances, especially in the silane coupling agent treatment. It is possible to form a treated film of. 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.
Further, in the present invention, a long polymer film can be used as a base material. 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 the base material, 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. Can be done.
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.

Claims (5)

The substrate is brought into contact with a silane coupling agent treatment solution at -18 ° C. or higher and 40 ° C. or lower for 1 second or longer and 10 minutes or shorter, and then in a cleaning solvent containing substantially no silane coupling agent for 3 seconds. above, it is contacted more than 10 minutes,
Wherein the substrate, the thickness of 1μm or more, a silane coupling agent treatment method, characterized in that Ru following polymeric film Der 500 [mu] m. The silane coupling agent treatment method according to claim 1, wherein the silane coupling agent treatment liquid is a liquid silane coupling agent or a solution containing at least 0.1% or more of the silane coupling agent. 1 or claim, wherein the cleaning solvent is 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. 2. The method for treating a silane coupling agent according to 2. A method for producing a silane coupling agent-treated base material, which comprises a step of drying the base material after performing the silane coupling agent treatment according to any one of claims 1 to 3 on the base material. .. A method for producing a laminate by laminating a silane coupling agent-treated substrate obtained by the production method according to claim 4 and another substrate.