JP2015178237A - Laminated inorganic substrate, laminate, method of producing laminate and method of producing flexible electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic substrate and a laminate good in quality and their production methods which enable efficient manufacture of a flexible electronic devices by forming a device on a polymer film, e.g. a polyimide film laminated on an inorganic substrate through a silane coupling agent layer and peeling.SOLUTION: A laminate reduced in foreign matter between a polymer film and an inorganic substrate is obtained by forming a silane coupling agent layer on an inorganic substrate, e.g. glass, through a gas phase, superimposing a polymer film subjected to an activation treatment on the silane coupling layer and pressing. Electron devices can be formed efficiently on the laminate obtained, and a flexible electronic device can be manufactured by peeling from the inorganic substrate.

Description

  In the present invention, a flexible polymer film is temporarily fixed on a rigid temporary supporting inorganic substrate to form a laminate, and then various electronic devices are formed on the polymer film, and then the polymer film is peeled off together with the electronic device portion. The present invention relates to a manufacturing technique for obtaining a flexible electronic device, and the inorganic substrate and the laminate.

  Functional elements (devices) such as semiconductor elements, MEMS elements, and display elements are used as electronic components in information communication equipment (broadcast equipment, mobile radio, portable communication equipment, etc.), radar, high-speed information processing devices, etc. Conventionally, it is generally formed or mounted on an inorganic substrate such as glass, a silicon wafer, or a ceramic substrate. However, in recent years, attempts have been made to form various functional elements on a polymer film, as electronic components are required to be lighter, smaller, thinner, and flexible.

  In forming various functional elements on the surface of the polymer film, it is ideal to process by a so-called roll-to-roll process using the flexibility that is a characteristic of the polymer film. However, in the industries such as the semiconductor industry, the MEMS industry, and the display industry, a process technology for a rigid flat substrate such as a wafer base or a glass substrate base has been mainstream. Therefore, in order to form various functional elements on the surface of the polymer film using the existing infrastructure, the polymer film is bonded to a rigid support made of an inorganic material (glass plate, ceramic plate, silicon wafer, metal plate, etc.). A process has been devised in which a desired element is formed and then peeled off from the support.

  In general, a relatively high temperature is often used in the step of forming a functional element. For example, a temperature range of about 200 to 500 ° C. is used in forming a functional element such as polysilicon or an oxide semiconductor. In manufacturing a low-temperature polysilicon thin film transistor, heating at about 450 ° C. may be required for dehydrogenation. Also in the production of a hydrogenated amorphous silicon thin film, a temperature range of about 200 to 300 ° C. is required. The temperature range exemplified here is not so high for inorganic materials, but it can be said that it is considerably high for polymer films and adhesives generally used for laminating polymer films. I don't get it. Adhering the above-mentioned polymer film to an inorganic substrate and peeling off after forming the functional element, the polymer film used, the adhesive used for bonding, and the adhesive also require sufficient heat resistance. However, as a practical matter, there are limited polymer films that can be practically used in such a high temperature range, and conventional adhesives and adhesives have sufficient heat resistance. There was no current situation.

Since there is no heat-resistant adhesive means for temporarily attaching the polymer film to the inorganic substrate, in such applications, the polymer film solution or precursor solution is applied onto the inorganic substrate and then dried and cured on the inorganic substrate. A technique for forming a film and using it for the application is known. However, since the polymer film obtained by such means is brittle and easily torn, the functional element is often destroyed when it is peeled from the inorganic substrate. In particular, it is extremely difficult to peel off a device having a large area, and it is not possible to obtain a yield that can be industrially established.
In view of such circumstances, the present inventors, as a laminate of a polymer film and a support for forming a functional element, use a polyimide film that has excellent heat resistance and is strong and can be made into a thin film as a coupling agent. The laminated body formed by bonding to the support body (inorganic layer) which consists of an inorganic substance through this was proposed (patent documents 1-3).

JP 2010-283262 A JP 2011-11455 A JP 2011-245675 A

  According to the laminate described in Patent Documents 1 to 3 described above, it is possible to bond the polymer film and the inorganic substrate without using a so-called adhesive or adhesive element, and the laminate is a thin film. Exfoliation of the polymer film does not occur even when exposed to the high temperatures required to fabricate the device. Therefore, it is possible to produce an electronic device on a polymer film by subjecting the laminate to a process for forming an electronic device directly on an inorganic substrate such as a conventional glass plate or silicon wafer. A flexible electronic device can be realized by peeling the molecular film from the inorganic substrate.

However, this technique still has the following problems in industrial production. In particular, when manufacturing a high-definition electronic device, yield is an issue. When foreign matter is mixed between the polymer film and the inorganic substrate, a tent-like structure in which the foreign matter is regarded as a support is formed on and around the foreign matter. This creates voids between the polymer film and the inorganic substrate, resulting in locations that are not partially bonded. Since the gas confined in the gap tends to swell in a heating environment or a reduced pressure environment, it causes a swell defect (also called blistering). Further, since the void portion is not bonded, when the bonding strength is macroscopically grasped, the variation in the bonding strength becomes large. In the vicinity where foreign matter exists, the polymer film itself is in a raised state, which becomes an obstructive factor in pattern formation using photolithographs and high-definition patterns such as microcontact printing, and good electronic device formation There is a case that cannot be performed.

Such foreign matter can be reduced by cleaning the surface of the inorganic substrate and the surface of the polymer film and cleaning the work environment. However, an essential problem of this technique is the generation of foreign matters due to the silane coupling agent itself. In the illustrated prior art, an example in which a solvent solution of a silane coupling agent is directly applied in liquid form to an inorganic substrate is described. Silane coupling agents are easily affected by moisture and other factors present in the handling environment, and aggregates can easily be formed. In the illustrated direct coating method, aggregates of silane coupling agents that are generated unintentionally in solution or the like are also present. As a result, the inventors of the present application have found that the aggregate is dispersed as a foreign substance together with the silane coupling agent on the inorganic substrate. The adverse effects of such foreign substances are as described above.

  The present invention has been made paying attention to the above-mentioned circumstances, and by fundamentally changing the coating method of the silane coupling agent, the aggregate of the silane coupling agent is prevented from adhering to the inorganic substrate. In addition, the present invention provides a laminate with excellent quality and a uniform adhesive force between the polymer film / inorganic substrate and solves the problems in industrial production.

  Furthermore, according to the present invention, the roughness of the surface of the inorganic substrate after peeling the polymer film is small, and it becomes possible to re-apply the silane coupling agent after a simple cleaning operation and use it as a substrate. Sexually improves.

  In addition, according to the present invention, it is possible to cope with the increase in area which is a problem in industrial production while maintaining the uniformity of the adhesive force between the polymer film and the inorganic substrate, which contributes to the improvement of productivity. it can.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have successfully applied a silane coupling agent to an inorganic substrate in a gas phase so that no foreign matter is present between the polymer film and the inorganic substrate. As a result, it has been found that high-definition flexible electronic devices can be manufactured with high yield and the recyclability of the inorganic substrate is improved, and the present invention has been completed.

That is, the present invention has the following configuration.
1. A silane coupling agent layer laminated inorganic substrate having a silane coupling agent layer formed on at least one surface, the silane coupling agent layer having a thickness of 5 nm or more and 50 nm or less, and a three-dimensional surface roughness (Sa) A silane coupling agent layer laminated inorganic substrate characterized by having a thickness of 2 nm or less.
2. 1. The silane coupling agent layer forms a predetermined pattern. A silane coupling agent layer laminated inorganic substrate as described in 1.
3. 1. The number of foreign matters containing silicon having a major axis of 10 μm or more is 2000 pieces / m ² or less. Or 2. A silane coupling agent layer laminated inorganic substrate as described in 1.
4). The inorganic substrate is glass having an area of 1000 cm ² or more. ~ 3. The silane coupling agent layer laminated inorganic substrate according to any one of the above.
5. 1. A silane coupling agent layer is formed by exposing an inorganic substrate to a vaporized silane coupling agent. ~ 4. 5. Manufacturing method of silane coupling agent layer laminated inorganic substrate in any one of 6. 4. A silane coupling agent vaporized by a bubbling method is used. The manufacturing method of the silane coupling agent layer lamination | stacking inorganic board | substrate of description.
7). 5. When vaporizing the silane coupling agent by the bubbling method, a dry gas having a dew point of 0 ° C. or lower is used as a carrier gas. The manufacturing method of the silane coupling agent layer lamination | stacking inorganic board | substrate of description.
8). 4. When the inorganic substrate is exposed to the vaporized silane coupling agent, a gas having a dew point of 5 ° C. or higher is allowed to coexist. ~ 7. The manufacturing method of the silane coupling agent layer lamination | stacking inorganic substrate in any one of.
9. 1. A pattern is formed by masking a part of an inorganic substrate when forming a silane coupling agent layer. ~ 4. The manufacturing method of the silane coupling agent layer lamination | stacking inorganic substrate in any one of.
10. 1. A predetermined pattern is formed by irradiating a part of the silane coupling agent layer with active energy rays after the formation of the silane coupling agent layer. ~ 4. The manufacturing method of the silane coupling agent layer lamination | stacking inorganic substrate in any one of.
11. 1. With polymer film ~ 4. A laminate obtained by bonding the silane coupling agent layer laminated inorganic substrate according to any one of the above, wherein the adhesive strength between the polymer film and the inorganic substrate is 0.2 N / cm or more and 15 N / cm or less. A laminate characterized by things.
12 1. With polymer film ~ 4. A laminated body obtained by bonding the silane coupling agent layer laminated inorganic substrate according to any one of the above, wherein a good adhesion portion and an easily peelable portion having different adhesion strengths between the polymer film and the inorganic substrate are provided. And a laminate having a peel strength of 0.2 N / cm or more and 15 N / cm or less, and a peel strength of an easily peelable portion of less than 0.2 N / cm.
13. It has the process of following (1)-(3), The manufacturing method of a laminated body characterized by the above-mentioned.
(1) Forming a silane coupling agent layer on an inorganic substrate by exposing the inorganic substrate to a vaporized silane coupling agent
(2) A step of superposing a polymer film subjected to surface activation treatment on the silane coupling agent layer
(3) Adhering both by pressurization and heating 14.11. A method for producing a flexible electronic device, comprising: forming an electronic device on a polymer film of the laminate, and then peeling the polymer film together with the electronic device from an inorganic substrate. .
14.12. An electronic device is formed on a portion corresponding to the easily peelable portion of the polymer film of the laminate, and then along the outer periphery of the easily peelable portion of the laminate, A method of manufacturing a flexible electronic device, comprising cutting the polymer film and peeling the polymer film from the inorganic substrate together with the electronic device.

According to the present invention, it is possible to obtain a good laminate with no foreign matter between the polymer film and the inorganic substrate, and as a result, the adhesive strength between the polymer film and the inorganic substrate is homogenized.
Further, according to the present invention, the silane coupling agent layer is masked on a part of the laminated inorganic substrate in a predetermined pattern when the silane coupling agent is formed, or after the silane coupling agent layer is formed, When forming an electronic device by irradiating active energy rays to a part of the silane coupling agent layer along a predetermined pattern and intentionally obtaining the presence / absence or strength / weakness of the adhesive force to form an electronic device It is possible to create a desired pattern with a good adhesion part having sufficient adhesive force that does not cause peeling of the polymer film during the process and an easy peeling part that can peel the polymer film relatively easily. It is possible to make a cut along the periphery of the easily peelable portion and peel off the functional element portion formed in the area.
Still further, the surface of the inorganic substrate after peeling of the polymer film in the present invention has high smoothness, and a silane coupling layer is formed again by a relatively simple cleaning operation to be used as a material for the laminate. It also has the effect of being able to.
More preferably, in the present invention, if a polymer film having high heat resistance is used, bonding can be performed without using an adhesive or pressure-sensitive adhesive that is inferior in heat resistance. The element can be formed using a high temperature of preferably 230 ° C. or higher, more preferably 260 ° C. or higher. In general, semiconductors, dielectrics, and the like can be formed at a high temperature to obtain a thin film with better film quality, so that higher performance functional elements can be expected. According to the present invention, for manufacturing a flexible electronic device in which devices 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 are formed on a film substrate. Useful.

<Inorganic substrate>
In the present invention, an inorganic substrate is used as a support for the polymer film. The inorganic substrate may be any plate-like material that can be used as a substrate made of an inorganic material, for example, a glass plate, a ceramic plate, a semiconductor wafer, a material mainly made of metal, etc., and these glass plates, ceramic plates, Examples of silicon wafers and metal composites include those obtained by laminating them, those in which they are dispersed, and those containing these fibers.

  Examples of the glass plate include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (non-alkali), Borosilicate glass (microsheet), aluminosilicate glass and the like are included. Among these, those having a linear expansion coefficient of 5 ppm / K or less are desirable, and if it is a commercial product, “Corning (registered trademark) 7059” or “Corning (registered trademark) 1737” manufactured by Corning, which is a glass for liquid crystal, “EAGLE”, “AN100” manufactured by Asahi Glass, “OA10” manufactured by Nippon Electric Glass, “AF32” manufactured by SCHOTT, etc. are desirable.

  Examples of the ceramic plate include Al2O3, Mullite, AlN, SiC, Si3N4, BN, crystallized glass, Cordierite, Spodumene, Pb-BSG + CaZrO3 + Al2O3, Crystallized glass + Al2OQ, SG3B, SG3, SG3, SG3 Glass-ceramics, ceramics for substrates such as zero-dur materials, TiO2, strontium titanate, calcium titanate, magnesium titanate, alumina, MgO, steatite, BaTi4O9, BaTiO3, BaTi4 + CaZrO3, BaSrCaZrTiO3, Ba (TiZr) O3, PMN-PT And PFN-PFW Capacitor materials such as PbNb2O6, Pb0.5Be0.5Nb2O6, PbTiO3, BaTiO3, PZT, 0.855PZT-95PT-0.5BT, 0.873PZT-0.97PT-0.3BT, and PLZT are included.

  As the semiconductor wafer, a silicon wafer, a semiconductor wafer, a compound semiconductor wafer, or the like can be used. The silicon wafer is obtained by processing single crystal or polycrystalline silicon on a thin plate, and is n-type or p-type. This includes all doped silicon wafers, intrinsic silicon wafers, etc., and also includes silicon wafers with silicon oxide layers and various thin films deposited on the surface of silicon wafers. Besides silicon wafers, germanium, silicon- Germanium, gallium-arsenic, aluminum-gallium-indium, nitrogen-phosphorus-arsenic-antimony, SiC, InP (indium phosphorus), InGaAs, GaInNAs, LT, LN, ZnO (zinc oxide), CdTe (cadmium tellurium), ZnSe ( Semiconductor wafers and compounds such as zinc selenide) A semiconductor wafer or the like can be used.

  Examples of the metal include single element metals such as W, Mo, Pt, Fe, Ni, and Au, alloys such as inconel, monel, mnemonic, carbon copper, Fe-Ni invar alloy, and super invar alloy. In addition, a multilayer metal plate formed by adding other metal layers and ceramic layers to these metals is also included. In this case, if the total CTE with the additional layer is low, Cu, Al or the like is also used for the main metal layer. The metal used as the additional metal layer is limited as long as it has strong adhesion to the polyimide film, no diffusion, and good chemical resistance and heat resistance. Although it is not, chromium, nickel, TiN, and Mo containing Cu are mentioned as a suitable example.

The planar portion of the inorganic substrate is desirably sufficiently flat. Specifically, the PV value of the surface roughness is 50 nm or less, more preferably 20 nm or less, and further preferably 5 nm or less. If it is rougher than this, the adhesive strength between the polymer film and the inorganic substrate may be insufficient.
The thickness of the inorganic substrate is not particularly limited, but is preferably 10 mm or less, more preferably 3 mm or less, and still more preferably 1.3 mm or less from the viewpoint of handleability. The lower limit of the thickness is not particularly limited, but 0.07 mm or more, preferably 0.15 mm or more, more preferably 0.3 mm or more is preferably used.

The area of the inorganic substrate is preferably a large area from the viewpoint of production efficiency and cost of the laminate and the flexible electronic device. It is preferably 1000 cm ² or more, more preferably 1500 cm ^2, further preferably 2000 cm ^2.

<Silane coupling agent>
The silane coupling agent in the present invention refers to a compound having a function of physically or chemically interposing between the temporary support and the polymer film and enhancing the adhesive force between the two.
Preferable specific examples of the silane coupling agent 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, vinyltrichlorosilane, Vinyltrimethoxysilane, vinyltriethoxysila 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryl Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyl Limethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, tris- (3-trimethoxysilylpropyl) isocyanurate Chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, aminophenyltrimethoxysilane, aminophenethyltrimethoxysilane, aminophenylaminomethylphenethyltrimethoxysilane, hexamethyldisilazane and the like.

  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.

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.

<Application method of silane coupling agent>
In the conventional technique, the silane coupling agent is applied in a solution state in which the silane coupling agent is diluted with a solvent such as alcohol. However, the present invention is characterized in that this silane coupling agent coating step is performed in a gas phase. That is, in the present invention, the coating is performed by exposing the inorganic substrate to the vapor of the silane coupling agent, that is, the substantially gaseous silane coupling agent. In the present invention, by applying the silane coupling agent to the inorganic substrate in a gas state, the number of foreign substances containing silicon derived from the silane coupling agent can be greatly reduced as compared with the case of applying in a solution state. The vapor of the silane coupling agent can be obtained by a bubbling method, a baking method, or the like, but when accompanied by heating at 200 ° C. or higher, it may cause a side reaction of the silane coupling agent. Is preferred. More preferably, the silane coupling agent vapor is obtained by a bubbling method at 100 ° C. or lower, more preferably 40 ° C. or lower.

Further, it is preferable to use a dry gas having a dew point of 0 ° C. or lower as the carrier gas used for obtaining the silane coupling agent vapor by the bubbling method. It is more preferable to use a dry gas having a dew point of −30 ° C. or lower, and more preferably a dew point of −50 ° C. or lower. Moisture mixing into the carrier gas causes a side reaction of the silane coupling agent, hinders the stable supply of the silane coupling agent vapor, and also causes generation of foreign substances derived from the silane coupling agent into the apparatus.

Further, since many silane coupling agents are flammable liquids, it is preferable to use an inert gas as a carrier gas, particularly when a heat source is used.

When the silane coupling agent layer is formed on the inorganic substrate by introducing the silane coupling agent vapor obtained by the bubbling method into the device where the inorganic substrate is installed, the exposure time is not particularly limited, but within 1 hour , Preferably within 20 minutes, more preferably within 5 minutes, even more preferably within 1 minute.

Further, when the silane coupling agent layer is formed on the inorganic substrate, it is preferable that a gas containing moisture coexists because the processing time is shortened. The gas containing moisture is preferably introduced by a different route from the silane coupling agent vapor, and the introduction order is not particularly limited, but is preferably introduced at the same time or after the silane coupling agent vapor. The dew point of the gas containing water is preferably 5 ° C. or higher, more preferably 8 ° C. or higher, and still more preferably 12 ° C. or higher.

The inorganic substrate temperature during the formation of the silane coupling agent layer on the inorganic substrate is set to an appropriate temperature between −50 ° C. and 200 ° C. depending on the type of silane coupling agent and the desired thickness of the silane coupling agent layer. It is preferable to control. However, from the viewpoint of work efficiency, it is preferable to set the temperature lower than the temperature at which the silane coupling agent vapor is generated. The temperature is preferably set to 5 ° C. or higher, more preferably 10 ° C. or lower.

The silane coupling agent layer inorganic substrate on which the silane coupling agent layer is formed is preferably heated to 70 ° C. to 200 ° C., more preferably 75 ° C. to 150 ° C. after exposure. By such heating, the hydroxyl group on the surface of the silane coupling agent layer inorganic substrate reacts with the alkoxy group or silazane group of the silane coupling agent, and the silane coupling agent treatment is completed. The time required for heating is about 10 seconds to 10 minutes. If the temperature is too high or the time is too long, the coupling agent may be deteriorated. If it is too short, the treatment effect cannot be obtained. If the substrate temperature being exposed to the silane coupling agent is already 80 ° C. or higher, the subsequent heating can be omitted.

In the present invention, it is preferable to expose the inorganic substrate to the silane coupling agent vapor while holding the silane coupling agent application surface of the inorganic substrate downward. In the conventional method of applying a solution of a silane coupling agent, the coated surface of the inorganic substrate inevitably faces up before and after coating, so there is a possibility that floating foreign substances and the like in the working environment are deposited on the surface of the inorganic substrate. I can't deny it. However, in the present invention, the inorganic substrate can be held downward. It is possible to greatly reduce the adhesion of foreign substances in the environment.
It is preferable to clean the surface of the inorganic substrate before the silane coupling agent treatment by means such as short wavelength UV / ozone irradiation, or cleaning with a liquid cleaning agent.

The number of silicon-containing foreign matters having a major axis of 10 μm or more present on the surface of the silane coupling agent layer laminated inorganic substrate is 2000 pieces / m ² or less, preferably 1000 pieces / m ² or less, and more preferably 500 pieces / m ² or less. This is a preferred form for producing an electronic device or the like using the laminate of the present invention. In addition, the number of foreign substances containing silicon can be achieved by combining the above operations.

As for the coating amount and thickness of the silane coupling agent, a single molecular layer is theoretically sufficient, and a thickness that can be ignored in terms of mechanical design is sufficient. However, when the region is less than 5 nm, the silane coupling agent may exist in a cluster form rather than as a uniform coating film, and in consideration of stable production, the thickness is preferably 5 nm or more. In consideration of work efficiency, recyclability of the inorganic substrate, and patterning described later, it is important that the silane coupling agent layer is not too thick, and is preferably set to 50 nm or less. Furthermore, it is more preferable to set it as 30 nm or less.

The film thickness of the silane coupling agent layer can be determined by the X-ray reflectivity method or the like.

  Furthermore, if the surface of the silane coupling agent layer is not smooth, sufficient adhesion to bonding may not be achieved, so the amount of silane coupling agent during deposition, processing time, and substrate temperature are controlled. By doing so, it is preferable that the three-dimensional surface roughness is 2 nm or less, preferably 1 nm or less.

<Patterning treatment on the inorganic substrate>
In the present invention, patterning treatment can be performed on the inorganic substrate side. Here, patterning means creating a region where the application amount or activity of the silane coupling agent is intentionally manipulated. Thereby, the laminate has a good adhesion part and an easy peeling part with different adhesive strengths between the inorganic substrate and the polymer film, and the good adhesion part and the easy peeling part form a predetermined pattern. it can. An example of the patterning treatment is a method of manipulating the coating amount of the silane coupling agent using a mask prepared in advance with a predetermined pattern when applying the silane coupling agent. It is also possible to perform patterning by irradiating the surface to which the silane coupling agent is applied with active energy rays and using a technique such as masking or scanning operation at the same time. Here, the active energy ray irradiation means the operation of irradiating energy rays such as ultraviolet rays, electron rays, X-rays, etc., and ozone gas generated near the irradiated surface simultaneously with the ultraviolet ray irradiation light effect as in the ultraviolet ray irradiation treatment of an extremely short wavelength. Include gas exposure effects. In addition to these, patterning can be performed by corona treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, sandblasting and treatment, or the like.

<Polymer film>
As the polymer film in the present invention, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, wholly aromatic polyester, other copolymerized polyester, polymethyl methacrylate, other copolymerized acrylate, polycarbonate, polyamide, poly Sulfone, polyether sulfone, polyether ketone, polyamideimide, polyetherimide, aromatic polyimide, alicyclic polyimide, fluorinated polyimide, cellulose acetate, cellulose nitrate, aromatic polyamide, polyvinyl chloride, polyphenol, polyarylate, polyphenylene A film made of sulfide, polyphenylene oxide, polystyrene or the like can be used. In the present invention, what is particularly remarkable and useful is a polymer having a heat resistance of 100 ° C. or higher, that is, a so-called engineering plastic film. Here, the heat resistance refers to a glass transition temperature or a heat distortion temperature.

  Regarding the polymer film of the present invention, a thermoplastic polymer material among the polymer materials can be obtained by a melt stretching method. For non-thermoplastic polymers, a solution casting method is mainly used. As a special example of the present invention, a technique of applying a polymer material itself or a precursor solution onto an inorganic substrate and drying it to form a film can be used.

  The thickness of the polymer film of the present invention is preferably 3 μm or more, more preferably 11 μm or more, further preferably 24 μm or more, and still more preferably 45 μm or more. The upper limit of the thickness of the polymer film is not particularly limited, but is preferably 250 μm or less, more preferably 150 μm or less, and even more preferably 90 μm or less, as required for a flexible electronic device.

  The polymer film particularly preferably used in the present invention is a polyimide film, and aromatic polyimide, alicyclic polyimide, polyamideimide, polyetherimide, and the like can be used. When the present invention is used particularly for the production of flexible display elements, it is preferable to use a polyimide-based resin film having colorless transparency, but particularly when forming a back element of a reflective or self-luminous display. This is not the case.

  In general, a polyimide film is obtained by applying a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent to a support and drying it to obtain a green film (“precursor film” or “polyamide”). It is also referred to as an “acid film”), and is further obtained by subjecting the green film to high-temperature heat treatment on the support or in a state of peeling off from the support to cause a dehydration ring-closing reaction.

  There is no restriction | limiting in particular as diamine which comprises a polyamic acid, The aromatic diamine, aliphatic diamine, alicyclic diamine etc. which are normally used for a polyimide synthesis | combination can be used. From the viewpoint of heat resistance, aromatic diamines are preferable, and among aromatic diamines, aromatic diamines having a benzoxazole structure are more preferable. When aromatic diamines having a benzoxazole structure are used, it is possible to develop a high elastic modulus, a low heat shrinkage, and a low linear expansion coefficient as well as a high heat resistance. Diamines may be used alone or in combination of two or more.

  The aromatic diamine having a benzoxazole structure is not particularly limited. For example, 5-amino-2- (p-aminophenyl) benzoxazole, 6-amino-2- (p-aminophenyl) benzoxazole, 5 -Amino-2- (m-aminophenyl) benzoxazole, 6-amino-2- (m-aminophenyl) benzoxazole, 2,2'-p-phenylenebis (5-aminobenzoxazole), 2,2 ' -P-phenylenebis (6-aminobenzoxazole), 1- (5-aminobenzoxazolo) -4- (6-aminobenzoxazolo) benzene, 2,6- (4,4'-diaminodiphenyl) benzo [1,2-d: 5,4-d ′] bisoxazole, 2,6- (4,4′-diaminodiphenyl) benzo [1,2-d 4,5-d '] bisoxazole, 2,6- (3,4'-diaminodiphenyl) benzo [1,2-d: 5,4-d'] bisoxazole, 2,6- (3,4 ' -Diaminodiphenyl) benzo [1,2-d: 4,5-d '] bisoxazole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2-d: 5,4-d'] Examples thereof include bisoxazole and 2,6- (3,3′-diaminodiphenyl) benzo [1,2-d: 4,5-d ′] bisoxazole.

  Examples of the aromatic diamine other than the aromatic diamine having the benzoxazole structure described above include 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,4-bis [2- (4-aminophenyl). ) -2-propyl] benzene (bisaniline), 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 4,4 '-Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl ] Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phene Ru] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylene Diamine, m-aminobenzylamine, p-aminobenzylamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,3 '-Diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone 3,3′-Diaminobenzopheno 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy ) Phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- ( 4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3- Bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3 , 5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl -1,1,1,3,3,3-hexafluoropropane, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4 -Aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [ 4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) Phenyl] ether, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophene) Xyl) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [(3-aminophenoxy) benzoyl] benzene, 1,1-bis [4- ( 3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis [3- (3-aminophenoxy) Phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4′-bis [ 3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethyl) Benzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, , 3-bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α- Dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4 , 4′-diamino-5,5′-diphenoxybenzophenone, 3,4′-diamino-4,5′-diphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 4,4′-diamino- 5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino -4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4 -Biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4- Bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxyben) Yl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-) 5-biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile, and some or all of the hydrogen atoms on the aromatic ring of the aromatic diamine Is a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxyl group, a cyano group, or an alkyl group or alkoxyl group in which some or all of the hydrogen atoms are substituted with halogen atoms. An aromatic diamine substituted with a group or an alkoxyl group.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, and the like.
Examples of the alicyclic diamines include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,1-bis (4-aminophenyl) cyclohexane, 4 , 4′-diaminodicyclohexylmethane, 4,4′-methylenebis (2-methylcyclohexylamine), 4,4′-methylenebis (2,6-dimethylcyclohexylamine), 4,4′-diaminodicyclohexylpropane, bicyclo [2 2.1] heptane-2,3-diamine, bicyclo [2.2.1] heptane-2,5-diamine, bicyclo [2.2.1] heptane-2,6-diamine, bicyclo [2.2 .1] Heptane-2,7-diamine, 2,3-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) -bi Cyclo [2.2.1] heptane, 2,6-bis (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2 1.0 (2,6)] decane and the like.

  The total amount of diamines other than aromatic diamines (aliphatic diamines and alicyclic diamines) is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less of the total diamines. It is. In other words, the aromatic diamine is preferably 80% by mass or more of the total diamines, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

  The tetracarboxylic acids constituting the polyamic acid include aromatic tetracarboxylic acids (including acid anhydrides), aliphatic tetracarboxylic acids (including acid anhydrides), and alicyclic tetracarboxylic acids that are commonly used for polyimide synthesis. Acids (including acid anhydrides thereof) can be used. Among them, aromatic tetracarboxylic acid anhydrides and alicyclic tetracarboxylic acid anhydrides are preferable, aromatic tetracarboxylic acid anhydrides are more preferable from the viewpoint of heat resistance, and alicyclic from the viewpoint of light transmission. Group tetracarboxylic acids are more preferred. In the case where these are acid anhydrides, the number of anhydride structures in the molecule may be one or two, but those having two anhydride structures (dianhydrides) are preferred. Good. Tetracarboxylic acids may be used alone or in combination of two or more.

  Examples of the alicyclic tetracarboxylic acids include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,1] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2,2,2] octane-2,3,5, Examples include 6-tetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, 1,2,4-cyclohexanetricarboxylic anhydride, and the like. 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-bicyclohexyltetracarboxylic dianhydride It is. Alicyclic tetracarboxylic acids may be used alone or in combination of two or more. On the other hand, those containing unsaturated bonds such as bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride are colored during heat treatment, and the optical properties of the film are improved. It is not preferable because it tends to decrease. In addition, when importance is attached to the alicyclic tetracarboxylic acids, for example, 80% by mass or more of all tetracarboxylic acids are preferable, more preferably 90% by mass or more, and still more preferably 95% by mass or more. .

The aromatic tetracarboxylic acids are not particularly limited, but are preferably pyromellitic acid residues (that is, those having a structure derived from pyromellitic acid), and more preferably acid anhydrides thereof. Examples of such aromatic tetracarboxylic acids include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3 , 3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis [4- (3,4-di Carboxyphenoxy) phenyl] propanoic anhydride and the like.
In the case of placing importance on heat resistance, the aromatic tetracarboxylic acids are, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more of all tetracarboxylic acids.

  The polyimide film of the present invention preferably has a glass transition temperature of 250 ° C. or higher, preferably 300 ° C. or higher, more preferably 350 ° C. or higher, or no glass transition point is observed in the region of 500 ° C. or lower. The glass transition temperature in the present invention is determined by differential thermal analysis (DSC).

  The linear expansion coefficient (CTE) of the polymer film of the present invention is preferably −5 ppm / K to +20 ppm / K, more preferably −5 ppm / K to +15 ppm / K, and further preferably 1 ppm / K to +10 ppm / K. When the CTE is in the above range, the difference in coefficient of linear expansion from a general support can be kept small, and the polyimide film and the support made of an inorganic material can be prevented from being peeled even when subjected to a process of applying heat. .

  The breaking strength of the polymer film in the present invention is 60 MPa or more, preferably 120 MP or more, more preferably 240 MPa or more. The upper limit of the breaking strength is not limited, but is practically less than about 1000 MPa. Here, the breaking strength of the polymer film refers to an average value in the vertical direction and the horizontal direction of the polymer film.

  In the present invention, the good adhesion portion refers to a portion where the adhesive strength between the inorganic substrate and the polyimide film is strong, and the easy peelable portion refers to a portion where the adhesion strength between the inorganic substrate and the polyimide film is weak. The adhesive strength of the easily peelable portion is preferably 1/2 or less, more preferably 1/3 or less, and further preferably 1/4 or less of the adhesive strength of the good adhesive portion. Although the lower limit value of the adhesive strength is not particularly limited, it is preferably 0.5 N / cm or more at the good adhesion portion and 0.01 N / cm or more at the easy peel portion.

The thickness unevenness of the polymer film in the present invention is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. When the thickness unevenness exceeds 20%, it tends to be difficult to apply to narrow portions. In addition, the thickness unevenness of a film can be calculated | required based on the following formula, for example, extracting about 10 points | pieces positions from a film to be measured at random with a contact-type film thickness meter, measuring film thickness.
Film thickness spots (%)
= 100 × (maximum film thickness−minimum film thickness) ÷ average film thickness

  The polymer film in the present invention is preferably obtained in the form of being wound as a long polyimide film having a width of 300 mm or more and a length of 10 m or more at the time of production, and is a roll wound around a winding core. The thing of the form of a polyimide film is more preferable.

  In polymer films, in order to ensure handling and productivity, lubricants (particles) are added to and contained in the film to provide fine irregularities on the polymer film surface to ensure slipperiness. Is preferred. The lubricant (particles) are preferably fine particles made of an inorganic substance, such as metals, metal oxides, metal nitrides, metal carbonides, metal acid salts, phosphates, carbonates, talc, mica, clay, and others. Particles made of clay minerals and the like can be used. Preferably, metal oxides such as silicon oxide, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, calcium carbonate, glass filler, phosphates, and carbonates can be used. Only one type of lubricant may be used, or two or more types may be used.

  The volume average particle diameter of the lubricant (particles) is usually 0.001 to 10 μm, preferably 0.03 to 2.5 μm, more preferably 0.05 to 0.7 μm, still more preferably 0.05 to 0.3 μm. The volume average particle diameter is based on a measurement value obtained by a light scattering method. If the particle diameter is smaller than the lower limit, industrial production of the polymer film becomes difficult, and if the particle diameter exceeds the upper limit, the surface irregularities become too large and the sticking strength becomes weak, which may cause practical problems.

  The addition amount of the lubricant is 0.02 to 50% by mass, preferably 0.04 to 3% by mass, more preferably 0.08 to 1% as the addition amount with respect to the polymer component in the polymer film. 2% by mass. If the amount of lubricant added is too small, it is difficult to expect the effect of lubricant addition, and there is a case where the slipperiness is not sufficiently secured, which may hinder the production of polymer film. Even if the slipperiness is ensured, the smoothness may be lowered, the breaking strength or breaking elongation of the polymer film may be lowered, or the CTE may be raised.

  When a lubricant (particles) is added to and contained in a polymer film, a single-layer polymer film in which the lubricant is uniformly dispersed may be used. For example, one surface may be a polymer film containing a lubricant. It is good also as a multilayer polymer film comprised by the polymer film which is comprised and the other surface does not contain a lubricant, or contains the lubricant, even if it contains a lubricant. In such a multilayer polymer film, fine unevenness is given to the surface of one layer (film), so that the slipperiness can be secured by the layer (film), and good handling properties and productivity are secured. it can.

  In the case of a film produced by a melt-stretching film-forming method, for example, a multilayer polymer film is first formed into a film using a raw material for a polymer film that does not contain a lubricant, and is placed on the film at least on one side of the process. It can obtain by apply | coating the resin layer containing this. Of course, conversely, film formation is performed using a polymer film material containing a lubricant, and a film is obtained by applying a polymer film material not containing a lubricant during the process or after film formation is completed. You can also

  The same applies to a polymer film obtained by using a solution casting method such as a polyimide film. For example, as a polyamic acid solution (polyimide precursor solution), a lubricant (preferably an average particle size of 0.05 to About 2.5 μm) to 0.02 mass% to 50 mass% (preferably 0.04 to 3 mass%, more preferably 0.08 to 1.2 mass%) with respect to the polymer solid content in the polyamic acid solution. Containing polyamic acid solution and no lubricant or a small amount thereof (preferably less than 0.02% by mass, more preferably less than 0.01% by mass with respect to polymer solids in the polyamic acid solution) Can be produced using two types of polyamic acid solutions.

The method of multilayering (lamination) of the multilayer polymer film is not particularly limited as long as no problem occurs in the adhesion between both layers, and any method may be used as long as the adhesion is achieved without using an adhesive layer or the like.
In the case of a polyimide film, for example, i) a method in which one polyimide film is produced and then the other polyamic acid solution is continuously applied onto the polyimide film to imidize, and ii) one polyamic acid solution is cast. After producing the polyamic acid film, the other polyamic acid solution is continuously applied onto the polyamic acid film and then imidized, iii) a method by co-extrusion, iv) a lubricant is not contained or the content thereof is An example is a method of imidizing a polyamic acid solution containing a large amount of a lubricant on a film formed with a small amount of a polyamic acid solution by spray coating, T-die coating, or the like. In the present invention, it is preferable to use the methods i) to ii).

  The ratio of the thickness of each layer in the multi-layer polymer film is not particularly limited, but the polymer layer containing a large amount of the lubricant (a) is a layer, the polymer does not contain the lubricant or the content thereof is small. When the layer is the (b) layer, the (a) layer / (b) layer is preferably 0.05 to 0.95. If the (a) layer / (b) layer exceeds 0.95, the smoothness of the (b) layer tends to be lost. On the other hand, if it is less than 0.05, the effect of improving the surface properties is insufficient and the slipperiness is lost. May be.

<Surface activation treatment of polymer film>
The polymer film used in the present invention is preferably subjected to a surface activation treatment. By the surface activation treatment, the surface of the polymer film is modified to a state in which a functional group is present (so-called activated state), and adhesion to the inorganic substrate is improved.

  The surface activation treatment in the present invention is a dry or wet surface treatment. As the dry treatment of the present invention, treatment of irradiating active energy rays such as ultraviolet rays, electron beams, and X-rays on the surface, corona treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, flame treatment, and intro treatment can be used. . Examples of the wet treatment include a treatment in which the film surface is brought into contact with an acid or alkali solution. The surface activation treatment preferably used in the present invention is a plasma treatment, which is a combination of a plasma treatment and a wet acid treatment.

  The plasma treatment is not particularly limited, but includes RF plasma treatment in vacuum, microwave plasma treatment, microwave ECR plasma treatment, atmospheric pressure plasma treatment, corona treatment, etc., gas treatment containing fluorine, ion Includes ion implantation using a source, treatment using PBII, flame treatment exposed to thermal plasma, and intro treatment. Among these, RF plasma treatment, microwave plasma treatment, and atmospheric pressure plasma treatment in vacuum are preferable.

  Appropriate conditions for the plasma treatment include oxygen plasma, plasma containing fluorine such as CF4 and C2F6, plasma known to have a high etching effect, or physical energy such as Ar plasma on the polymer surface. It is desirable to use plasma with a high effect of applying and physically etching. Further, it is also preferable to add plasma such as CO2, H2, and N2, a mixed gas thereof, and further water vapor. When aiming at processing in a short time, a plasma having a high plasma energy density, a high kinetic energy of ions in the plasma, and a high number density of active species are desirable. From this point of view, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation with an ion source that easily implants high-energy ions, PBII method, and the like are also desirable.

Such surface activation treatment cleans the polymer surface and produces more active functional groups. The generated functional group is bonded to the coupling agent layer by hydrogen bonding or chemical reaction, and the polymer film layer and the coupling agent layer can be firmly bonded.
In the plasma treatment, the effect of etching the surface of the polymer film can also be obtained. In particular, in a polymer film containing a relatively large amount of lubricant particles, protrusions due to the lubricant may inhibit the adhesion between the film and the inorganic substrate. In this case, it is possible to remove the lubricant particles in the vicinity of the film surface by thinly etching the polymer film surface by plasma treatment to expose a part of the lubricant particles and then treating with hydrofluoric acid. .

  The surface activation treatment may be performed only on one side of the polymer film or on both sides. When plasma treatment is performed on one side, the polymer film is placed in contact with the electrode on one side in the plasma treatment with parallel plate electrodes, so that only the side of the polymer film not in contact with the electrode is subjected to plasma treatment. be able to. If a polymer film is placed in a state where it is electrically floated in the space between the two electrodes, plasma treatment can be performed on both sides. Moreover, single-sided processing becomes possible by performing plasma processing in the state which stuck the protective film on the single side | surface of the polymer film. In addition, as a protective film, a PET film with an adhesive or an olefin film can be used.

<Pattern processing on the film side>
In the present invention, the patterning treatment can be performed on the polymer film side. Here, patterning refers to creating a region where the activity of the surface activation treatment is intentionally manipulated. Thereby, the laminate has a good adhesion part and an easy peeling part with different adhesive strengths between the inorganic substrate and the polymer film, and the good adhesion part and the easy peeling part form a predetermined pattern. it can. An example of the patterning process is a method of manipulating the surface activation process amount using a mask prepared in a predetermined pattern in advance when the surface activation process is performed. Further, when performing the surface activation treatment, it is possible to form a pattern by using a technique such as masking or scanning operation together. The surface of the polymer film after the surface activation can be further subjected to another active energy ray treatment in combination with masking or scanning to realize the intensity of activity. Here, the active energy ray irradiation means the operation of irradiating energy rays such as ultraviolet rays, electron rays, X-rays, etc., and ozone gas generated near the irradiated surface simultaneously with the ultraviolet ray irradiation light effect as in the ultraviolet ray irradiation treatment of an extremely short wavelength. Include gas exposure effects. In addition to these, patterning can be performed by corona treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, sandblasting and treatment, or the like.

<Film laminating method>
In the present invention, an inorganic substrate on which a silane coupling agent layer thin film is formed in a predetermined pattern is used as a temporary support, and a polymer film is bonded through the silane coupling agent layer, or dry film formation is performed. Thus, a laminate is obtained. When the polymer film is bonded, the activated surface of the polymer film is overlapped on the temporary supporting inorganic substrate on which the silane coupling agent layer is formed, and pressed to obtain a laminate.
The pressure treatment may be performed, for example, by pressing, laminating, roll laminating, etc. in an atmospheric pressure atmosphere or in a vacuum. A method of applying pressure in a flexible bag can also be applied. From the viewpoint of improving productivity and reducing the processing cost brought about by high productivity, press or roll lamination in an air atmosphere is preferable, and a method using rolls (roll lamination or the like) is particularly preferable.

  The pressure during the pressure treatment is preferably 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa. If the pressure is too high, the support may be damaged. If the pressure is too low, a non-adhering part may be produced, resulting in insufficient adhesion.

  The temperature during the pressure treatment can be arbitrarily set within the range not exceeding the heat resistance temperature of the polymer film to be used, but from the viewpoint of improving productivity and reducing processing costs brought about by high productivity. Is preferably treated at room temperature.

<Polymer film layer formation by solution application and drying>
As a method for producing the laminate of the present invention, a polymer film layer is formed by applying a polymer solution or a polymer precursor solution onto an inorganic substrate on which a silane coupling agent layer is formed, and drying and forming a film. Is possible. As a method for applying the solution, known methods such as dip coating, spin coating, curtain coating, and slit die coating can be used.
In the polyimide-based resin, the polyamic acid solution obtained by polycondensation of diamines and tetracarboxylic acid or acid anhydrides as raw materials for the polyimide resin in the solution is used as the temporary support silane coupling agent of the present invention. It is applied to the layer-laminated inorganic substrate so as to have a predetermined thickness, and dried, heat-treated or chemically imidized to form a polyimide film on the temporary supporting silane coupling agent layer-laminated inorganic substrate. In this case, a preferable film thickness is 3 to 100 μm, preferably 5 to 50 μm, more preferably 5 to 20 μm.
Usually, the polyimide resin layer obtained by such a method is relatively brittle, often tearing during the peeling, and often difficult to peel off from the inorganic substrate. In the present invention, the silane coupling agent Since there are few foreign substances and aggregates present in the layer, the film based on such defects is hardly torn, and as a result, the yield at the time of peeling is greatly improved.

<Method for manufacturing flexible electronic device>
When the laminate of the present invention is used, an electronic device is formed on the polymer film of the laminate using existing equipment and processes for manufacturing electronic devices, and the polymer film is peeled off from the laminate, so that the flexible film is flexible. An electronic device can be fabricated.
The electronic device in the present invention refers to an electronic circuit including an active element such as a wiring board, a transistor, and a diode that carries electric wiring, and a passive device such as a resistor, a capacitor, and an inductor, and others such as pressure, temperature, light, and humidity. An image display element such as a sensor element, a light emitting element, a liquid crystal display, an electrophoretic display, and a self-luminous display, a wireless, wired communication element, an arithmetic element, a memory element, a MEMS element, a solar cell, a thin film transistor, and the like.
As a method of peeling a polymer film from a laminate, a method in which strong light is radiated from the inorganic substrate side and the adhesive part between the inorganic substrate and the polymer film is thermally decomposed or photodecomposed and peeled off is used. Weaker, peel off the polymer film with a force less than the elastic strength limit value of the polymer film, expose to heated water, heated steam, etc., weaken the bond strength between the inorganic substrate and the polymer film interface, etc. Can be illustrated.

  In the present invention, when the patterning process is performed on the inorganic substrate side or the polymer film side, or both, the region where the adhesive force between the polymer film and the inorganic substrate is reduced by the patterning process (easy peeling part) The flexible electronic device can be obtained by forming an electronic device on the outer peripheral portion of the region and then cutting off the area where the electronic device of the polymer film is formed from the inorganic substrate. By this method, peeling of the polymer film and the inorganic substrate becomes easier.

  As a method of cutting the polymer film along the outer periphery of the easily peelable portion of the laminate, a method of cutting the polymer film with a cutting tool such as a blade or a method of relatively scanning the laser and the laminate can be used. A method of cutting a molecular film, a method of cutting a polymer film by relatively scanning a water jet and a laminate, a method of cutting a polymer film while cutting a glass layer slightly with a semiconductor chip dicing device, etc. are used. be able to.

  When cutting into the polymer film on the outer periphery of the easily peelable portion of the laminate, the position where the cut is made only needs to include at least part of the easily peelable portion, and basically may be cut according to a predetermined pattern. From the viewpoint of error absorption, productivity, etc., it may be determined as appropriate.

The method of peeling the polymer film from the support is not particularly limited, but is a method of rolling from the end with tweezers, etc., and sticking the adhesive tape to one side of the cut portion of the polymer film with the device, and then the tape part For example, a method of winding from a part of a polymer film with a device after vacuum suction of one side of the cut part can be employed. In addition, when the bend with a small curvature occurs in the cut portion of the polymer film with the device at the time of peeling, stress may be applied to the device at that portion and the device may be destroyed. It is desirable to peel off with. For example, it is desirable to roll while winding on a roll having a large curvature, or to roll using a machine having a configuration in which the roll having a large curvature is located at the peeling portion.
In addition, a method in which another reinforcing base material is attached in advance to the part to be peeled and the whole reinforcing base material is peeled off is also useful. When the flexible electronic device to be peeled off is the backplane of the display device, it is also possible to obtain a flexible display device by pasting the front plane of the display device in advance and integrating them on the inorganic substrate before peeling them off at the same time. is there.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by a following example. In addition, the evaluation method of the physical property in the following examples is as follows.

<Reduced viscosity of polyamic acid solution>
A solution dissolved in N, N-dimethylacetamide so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. using an Ubbelohde type viscosity tube.

<Thickness of polymer film>
The thickness of the polymer film was measured using a micrometer ("Millitron 1245D" manufactured by FineLuf).

<Tensile modulus, tensile strength and tensile elongation at break of polymer film>
A strip-shaped test piece having a flow direction (MD direction) and a width direction (TD direction) each of 100 mm × 10 mm was cut out from a polymer film to be measured, and a tensile tester (manufactured by Shimadzu Corporation “Autograph (registered) (Trademark); model name AG-5000A "), and the tensile modulus, tensile strength, and tensile elongation at break were measured in each of the MD direction and the TD direction under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 40 mm.

<Linear expansion coefficient (CTE) of polymer film>
About the flow direction (MD direction) and the width direction (TD direction) of the polymer film to be measured, the stretch rate is measured under the following conditions, and the intervals of 15 ° C. (30 ° C. to 45 ° C., 45 ° C. to 60 ° C., ...) was measured, and this measurement was performed up to 300 ° C., and an average value of all measured values measured in the MD direction and the TD direction was calculated as a linear expansion coefficient (CTE).
Device name: “TMA4000S” manufactured by MAC Science
Sample length; 20mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rising end temperature: 400 ° C
Temperature increase rate: 5 ° C./min Atmosphere: Argon initial load: 34.5 g / mm 2

<Evaluation of polymer film: slipperiness>
Two polymer films are stacked on different surfaces (that is, not on the same surface but on the wound outer surface and the wound inner surface when wound as a film roll), and the polyimide film is sandwiched between the thumb and index finger When lightly rubbed, the case where the polymer film and the polymer film slip were evaluated as “◯” or “good”, and the case where the polymer film did not slip was evaluated as “x” or “bad”. In addition, although it may not slip on winding outer surfaces or between winding inner surfaces, this is not made into an evaluation item.

<PV value measurement>
The surface morphology was measured using a scanning probe microscope with a surface property evaluation function (SPA300 / SPI3800N manufactured by SII Nanotechnology). The measurement was performed in the DFM mode, the scanner using DF3 or DF20 manufactured by SII Nanotechnology Co., Ltd. was FS-20A, the scanning range was 2 μm square, and the measurement resolution was 512 × 512 pixels. For the measurement image, the secondary inclination correction was performed, and then the PV value was calculated with the software attached to the apparatus.

<Thickness of coupling agent layer>
The thickness (nm) of the coupling agent layer (SC layer) was determined by preparing a sample obtained by applying and drying a coupling agent on the washed inorganic substrate in the same manner as in each example and comparative example. The X-ray reflectance measurement of the SC agent layer formed on the substrate was performed under the following conditions, and was determined from the observed fringe spacing. The film thickness was analyzed using the Rigaku Co., Ltd. GlobalFit thin film comprehensive analysis software, GlobalFit, and a model with a single film on the glass substrate was used.
Device name: Rigaku X-ray diffraction device SmartLab
Target: Cu
Voltage, current value: 40kV, 30mA
Slit: Before sample Sollar / PSC 5.0deg, IS 0.1mm, IS length, 10mm
After sample RS1 0.2mm, PSA Open, Sollar 5.0deg, RS2 0.4mm
Photodetector: Scintillation counter scan axis: 2θ / ω
Scanning speed: 2 / 3deg / min

<Three-dimensional arithmetic average roughness (S _a ) of the coupling agent layer>
The three-dimensional arithmetic average roughness (S _a ) of the SC layer was determined using a non-contact surface / layer cross-sectional shape measurement system (“VertScan ^(R) 2.0” manufactured by Ryoka Systems Inc.). The measurement was performed under the following conditions.
Measurement mode: Phase mode Field size: 640 × 480
Use filter: 520nm filter Objective lens magnification: × 5
Zoom lens magnification: x1
Measurement range for each measurement: 1.4mm x 1.8mm
Number of integrations: 1 time The raw data obtained under the above conditions was subjected to only quaternary surface correction without interpolation and used as measurement data. It calculated and calculated | required based on the following formula | equation from this measurement data.

(l _x and l _y are the ranges in the x and y directions, respectively, and Z (x, y) is the height from the mean plane)

<Dust density>
Sampling the area of 100mm x 100mm, observing the sampling area with a microscope with a length measurement function of 100 times magnification, and measuring the major axis length of the foreign matter confirmed by the 100 times observation with a magnification of 400 times Then, the number of particles having a size of 10 μm or more was counted and divided by the observation area to obtain the foreign substance density.

<Adhesive strength>
A silane coupling agent is applied to an inorganic substrate for temporary support by a predetermined method, and then a laminated body obtained through a predetermined process such as lamination of a polymer film and heat treatment of the obtained temporary laminate substrate is temporarily bonded. The adhesive strength between the supporting inorganic substrate and the polymer film was measured under the following conditions in accordance with the 90-degree peeling method described in JIS K6854-1.
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

<Appearance>
About quality, it is the result in the visual inspection of the whole laminated body. The case where there was peeling or floating with a major axis of 2 mm or more between the inorganic substrate and the polymer film was evaluated as “×” or “defective”, and the case where there was no “good” or “good”.

<Manufacture of polyimide film>
[Production Example 1]
(Preparation of polyamic acid solution)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 398 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and paraphenylenediamine ( (PDA) 147 parts by mass is dissolved in 4600 parts by mass of N, N-dimethylacetamide, and a dispersion obtained by dispersing colloidal silica as a lubricant in dimethylacetamide (“Snowtex (registered trademark)” manufactured by Nissan Chemical Industries, Ltd. ) DMAC-ST30 ”) was added so that the silica (lubricant) was 0.15% by mass with respect to the total amount of polymer solids in the polyamic acid solution, and the mixture was stirred at a reaction temperature of 25 ° C. for 24 hours. A brown and viscous polyamic acid solution V1 having a reduced viscosity as shown in FIG.

(Preparation of polyimide film)
The final thickness of the polyamic acid solution V1 obtained above is applied on the smooth surface (non-sliding material surface) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) having a width of 1050 mm using a slit die. The film was applied so that (film thickness after imidization) was 25 μm, dried at 105 ° C. for 20 minutes, and then peeled from the polyester film to obtain a self-supporting polyamic acid film having a width of 920 mm.
Next, the obtained self-supporting polyamic acid film was heated stepwise by a pin tenter in a temperature range of 150 ° C. to 420 ° C. (first stage 180 ° C. × 5 minutes, second stage 270 ° C. × 10 minutes, (Third stage 420 ° C. × 5 minutes) Heat treatment was performed to imidize, and pin grip portions at both ends were dropped with a slit to obtain a long polyimide film F1 (1000 m roll) having a width of 850 mm. Table 1 shows the characteristics of the obtained film F1.

[Production Example 2]
(Preparation of polyamic acid solution)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO), N, N-dimethylacetamide 4416 Next, a dispersion formed by dispersing colloidal silica in dimethylacetamide as a lubricant together with 217 parts by mass of pyromellitic dianhydride (PMDA) (“Snowtex” manufactured by Nissan Chemical Industries, Ltd.) (Registered trademark) DMAC-ST30 ") so that silica (lubricant) is 0.12% by mass in the total amount of polymer solids in the polyamic acid solution, and stirred for 24 hours at a reaction temperature of 25 ° C. Thus, a brown and viscous polyamic acid solution V2 having a reduced viscosity shown in Table 1 was obtained.

(Preparation of polyimide film)
After obtaining the polyamic acid film using the polyamic acid solution V2 obtained above instead of the polyamic acid solution V1, the first stage 150 ° C. × 5 minutes, the second stage 220 ° C. × 5 minutes, 3 A stage 485 ° C. × 10 minutes was subjected to heat treatment for imidization, and pin grip portions at both ends were dropped with a slit to obtain a long polyimide film F2 (1000 m roll) having a width of 850 mm. Table 1 shows the characteristics of the obtained film F2.

[Production Example 3]
(Preparation of polyamic acid solution)
The same procedure as in Production Example 2 was carried out except that a dispersion obtained by dispersing colloidal silica in dimethylacetamide (“Snowtex (registered trademark) DMAC-ST30” manufactured by Nissan Chemical Industries, Ltd.) was added, and the polyamic acid solution V3 Got.

(Preparation of polyimide film)
Using the comma coater, the polyamic acid solution V3 obtained as described above is formed on the smooth surface (non-sliding material surface) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) having a width of 1050 mm. (Film thickness after imidization) is applied so that it corresponds to 5 μm, and then the polyamic acid solution V2 is applied using a slit die so that the final film thickness is 38 μm including V3, and dried at 105 ° C. for 25 minutes. Then, it was peeled from the polyester film to obtain a self-supporting polyamic acid film having a width of 920 mm.
Next, the obtained self-supporting polyamic acid film was subjected to heat treatment with a pin tenter for the first stage 180 ° C. × 5 minutes, the second stage 220 ° C. × 5 minutes, the third stage 495 ° C. × 10 minutes, and imidized. The pin grip portion was dropped with a slit to obtain a long polyimide film F3 (1000 m roll) having a width of 850 mm. The properties of the obtained film F3 are shown in Table 1.

[Production Example 4]
(Preparation of polyamic acid solution)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, 210 parts by mass of 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB-HG), N, N -Add 3645 parts by weight of dimethylacetamide and completely dissolve, then disperse colloidal silica in dimethylacetamide as a lubricant with 195 parts by weight of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) The dispersion (“Snowtex (registered trademark) DMAC-ST30” manufactured by Nissan Chemical Industries, Ltd.) and silica (lubricant) is 0.5% by mass in terms of the total amount of polymer solids in the polyamic acid solution. In addition, the mixture was stirred at a reaction temperature of 25 ° C. for 24 hours to obtain a brown and viscous polyamic acid solution V4 having a reduced viscosity shown in Table 1.

(Preparation of polyimide film)
After obtaining a polyamic acid film using the polyamic acid solution V4 obtained above instead of the polyamic acid solution V1, the first stage 150 ° C. × 5 minutes, the second stage 250 ° C. × 5 minutes, 3 The stage was heated at 400 ° C. for 10 minutes for imidization, and pin grip portions at both ends were dropped with slits to obtain a long polyimide film F2 (1000 m roll) having a width of 850 mm. Table 1 shows the properties of the obtained film F4.

<Manufacture of plasma-treated film>
One side of the polyimide film F1 obtained in Production Example 1 was subjected to vacuum plasma treatment to obtain a plasma-treated polyimide film P1. Table 2 shows the properties of the obtained film P1.
As the vacuum plasma processing, RIE mode using parallel plate type electrodes and RF plasma processing are adopted, nitrogen gas is introduced into the vacuum chamber, high frequency power of 13.54 MHz is introduced, and the processing time is 3 minutes.

  A plasma-treated polyimide film P2 was obtained in the same manner except that the polyimide film F2 obtained in Production Example 2 was used instead of the polyimide film F1. Furthermore, plasma treatment was similarly performed on one side of the film F3 on the layer side not containing the lubricant to obtain a film P3.

  A plasma-treated polyimide film P4 was obtained in the same manner except that the polyimide film F4 obtained in Production Example 4 was used instead of the polyimide film F1.

  Instead of the polyimide film F1, a 25 μm thick Kapton film 100H (manufactured by Toray DuPont Co., Ltd.) was used to obtain a plasma-treated film P5.

  Table 2 shows the characteristics of the obtained plasma-treated film.

<Coupling agent layer formation on inorganic substrate>
Before applying the silane coupling agent, the inorganic substrate was used after removing the surface contamination with a UV / ozone irradiation device (manufactured by LAN Technical Service). All work was performed in a clean environment.

<Example 1>
A silane coupling agent layer was formed on the inorganic substrate under the following conditions using a vacuum chamber having a temperature control plate for setting the inorganic substrate and an apparatus for generating silane coupling agent vapor. A non-alkali glass (OA-10G manufactured by Nippon Electric Glass) of 370 mm × 470 mm × 0.7 mmt was used for the inorganic substrate, and it was set horizontally on a plate adjusted to 20 ° C. The PV value of the alkali-free glass used was 1.7 nm. Thereafter, the vacuum chamber whose temperature was adjusted to 25 ° C. was closed, and the pressure in the chamber was reduced to −0.099 MPa. Next, a silane coupling agent (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) is placed in an apparatus that generates silane coupling agent vapor by bubbling a carrier gas through the silane coupling agent. Then, the temperature was adjusted to 20 ° C. and bubbled with nitrogen gas having a purity of 99.9% or more. The generated silane coupling agent vapor was introduced into the vacuum chamber through a pipe adjusted to 25 ° C. until the degree of vacuum became −0.009 MPa, and held for 20 minutes. Then, after introducing nitrogen gas into the vacuum chamber and returning to atmospheric pressure, the inorganic substrate is taken out from the vacuum chamber and subjected to heat treatment with a hot plate at 100 ° C. for about 3 minutes, whereby the silane coupling agent layer of the present invention is obtained. A laminated inorganic substrate S1 was obtained.
Further, the obtained S1 silane coupling agent layer side and the plasma-treated surface of the plasma-treated film P3 trimmed to a size of 350 mm × 450 mm were subjected to a roll pressure of 8 kgf using a precision single wafer laminating machine (SE650nH manufactured by Climb Products). A film was temporarily laminated from the outer periphery of the glass to the inner side of 10 mm at a roll speed of 5 mm / sec. Although the film after temporary lamination was not peeled off by its own weight, it was adhesive enough to be easily peeled off when the film edge was scratched. Thereafter, the obtained temporary laminate substrate 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 L1.

<Example 2>
The silane coupling agent layer is the same as in Example 1 except that the temperature control plate in the vacuum chamber is set at 15 ° C. and the holding time after introducing the silane coupling agent vapor into the vacuum chamber is 2 minutes. A laminated inorganic substrate S2 was obtained. Moreover, the laminated body L2 was obtained by the same operation | work as Example 1 except using S2.

<Example 3>
The silane coupling agent vapor was introduced until the inside of the vacuum chamber depressurized to -0.099 MPa was -0.069 MPa, and then air having a dew point of 15 ° C was introduced until the degree of vacuum was -0.009 MPa. A silane coupling agent layer laminated inorganic substrate S3 was obtained in the same manner as in Example 1. Moreover, the laminated body L3 was obtained by the same operation | work as Example 1 except using S3.

<Example 4>
A mask made of a stainless steel plate having a thickness of 1 mm is overlaid on the silane coupling agent layer laminated inorganic substrate S2 obtained in Example 2, and a UV / ozone irradiation apparatus (manufactured by LAN Technical Service) is used for 120 seconds of UV. / Ozone irradiation was performed to obtain a silane coupling agent layer laminated inorganic substrate SP4 having a patterned silane coupling agent layer. A laminate L4 was obtained in the same manner as in Example 1 except that SP4 was used.
In addition, the adhesive strength of the laminated body was evaluated as a normal part where UV / ozone irradiation was not performed on the silane coupling agent layer, and an easily peelable part when irradiated.
<Examples 5-7>
A silane coupling agent layer laminated inorganic substrate S2 and laminated bodies L5 to L7 were obtained in the same manner as in Example 2 except that each of the plasma treated films shown in Table 3 was used.
<Example 8>
A silane coupling agent layer laminated inorganic substrate SP2 and a laminate L8 were obtained in the same manner as in Example 4 except that P4 was used for the plasma treated film.
<Comparative Example 1>
-Introduce silane coupling agent vapor until the inside of the vacuum chamber depressurized to -0.099 MPa returns to atmospheric pressure, and control it so that there is no air mixing or pressurization by liquid sealing, and further silane coupling agent vapor for 2 minutes. A silane coupling agent layer laminated inorganic substrate S4 was obtained in the same manner as in Example 1 except that the supply was continued. Moreover, the laminated body L9 was obtained by the same operation | work as Example 1 except using S4.
<Comparative Example 2>
A silane coupling agent layer laminated inorganic substrate S5 was obtained in the same manner as in Example 1 except that the temperature control plate in the vacuum chamber was set to 15 ° C. Moreover, the laminated body L10 was obtained by the same operation | work as Example 1 except using S5.
<Comparative Example 3>
The silane coupling agent vapor was introduced until the inside of the vacuum chamber depressurized to -0.099 MPa was -0.069 MPa, and then air having a dew point of 2 ° C was introduced until the degree of vacuum was -0.009 MPa. A silane coupling agent layer laminated inorganic substrate S6 was obtained in the same manner as in Example 1. Moreover, the laminated body L11 was obtained with the operation | work similar to Example 1 except using S6.
<Comparative Example 4>
Except for bubbling with air having a dew point of 10 ° C. in order to generate silane coupling agent vapor, the same operation as in Example 1 was performed, but the operation was stopped because white turbidity was confirmed in the silane coupling agent solution.
<Comparative Example 5>
Silane coupling agent (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) 1.0 part by mass and 99.0 parts by mass of isopropyl alcohol were stirred and mixed in a clean glass container. A coupling agent solution was obtained. First, 370 mm x 470 mm x 0.7 mmt non-alkali glass (OA-10G manufactured by Nippon Electric Glass) was set on a desktop spin coater (MSC-500S model manufactured by Japan Create), and 50 ml of isopropyl alcohol was dropped into the center of the glass at 500 rpm. Next, about 30 ml of the previously prepared silane coupling agent solution is dropped on the center of the glass plate, and is rotated at 500 rpm for 10 seconds, and then the rotation speed is increased to 1500 rpm for 20 seconds. The ring agent solution was shaken off. The PV value of the alkali-free glass used was 1.7 nm. Thereafter, the inorganic substrate was taken out from the stopped spin coater and subjected to heat treatment for about 3 minutes on a hot plate at 100 ° C. to obtain a silane coupling agent layer laminated inorganic substrate S7. Moreover, the laminated body L12 was obtained by the same operation | work as Example 1 except using S7.
<Comparative Example 6>
Silane coupling agent (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) 1.0 part by mass, isopropyl alcohol 89.0 parts by mass, propylene glycol monomethyl ether acetate 10.0 parts by mass The mixture was stirred and mixed in a clean glass container to obtain a silane coupling agent solution.
First, 370mm x 470mm x 0.7mmt non-alkali glass (OA-10G made by Nippon Electric Glass) was set on a spray coater, a 1mm thick stainless steel plate mask was layered, and a silane cup prepared using a low pressure atomizing nozzle The ring agent solution was coated at a discharge rate of 15 g / min. The PV value of the alkali-free glass used was 1.7 nm. Thereafter, the inorganic substrate was taken out and subjected to heat treatment with a hot plate at 100 ° C. for about 3 minutes to obtain a patterned silane coupling agent layer laminated inorganic substrate SP8. Moreover, the laminated body L12 was obtained by the same operation | work as Example 1 except using SP8.

Table 3 shows the properties of the obtained silane coupling agent layer-laminated inorganic substrate and laminate.

(Application 1)
Using the laminates obtained in Examples 1 to 8 and Comparative Examples 1 to 5, a bottom gate type thin film transistor array was prototyped by the following steps.
Formation of Gas Barrier Layer A 100 nm gas barrier film made of SiON was formed on the entire surface of the polymer film 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. Next, an epoxy resin-based gate insulating film (thickness 80 nm) was formed using a slit die coater. Further, a 5 nm chromium layer and a 40 nm gold layer were formed by sputtering, and a source electrode and a drain electrode were formed by photolithography. Next, using a slit die coater, an epoxy resin serving as an insulating layer and dam layer is applied, and a 250-nm thick dam layer for a semiconductor layer including a source electrode and a drain electrode is formed by ablation with a UV-YAG laser with a diameter of 100 μm. The via was also formed at the same time as a connection point with the upper electrode. Next, polythiophene, which is an organic semiconductor, was coated in the dam by ink jet printing, a silver paste was buried in the via portion, and an aluminum wiring was formed as an upper electrode to form a thin film transistor array having 640 × 480 pixels.

  The obtained thin film transistor array was used as a back plane, and an electrophoretic display medium was overlaid on the front plane to form a display element. The yield and display performance of the transistor were determined by ON / OFF of each pixel. As a result, the thin film transistor arrays obtained in the examples all had good display performance. On the other hand, in Comparative Examples C1 to C5, generation of voids and edge curling were confirmed between the inorganic substrate and the polymer film. In the laminate C4, the display of 10 lines in the vertical direction and 4 lines in the horizontal direction became defective.

  In each of the pixels having defects in Comparative Example 5, the gate wiring was disconnected or the upper electrode was disconnected. Foreign matter having a major axis of 10 μm or more was observed on the lower surface of the polymer film corresponding to the broken portion, that is, the adhesive surface with the glass plate, suggesting that the breakage hindered exposure in the photolithography process. As a result of the compositional analysis of the foreign matter that caused the disconnection, it was determined that the Si element accounted for 25% or more of the foreign matter and was an aggregate of the silane coupling agent.

  For L4 and L8 that have been patterned, after superimposing the front plane, the polymer film part is burned out with a UV-YAG laser along the outer periphery of the patterning part, and the blade on the thin razor is cut from the edge of the cut When the film was peeled so as to be scooped up, any of them could be easily peeled off, and a flexible electrophoretic display device could be obtained.

  For the remaining laminate that has not been patterned, irradiate the entire surface while scanning with a YAG laser from the glass substrate side, and use a thin blade in the same manner in a state where the adhesion between the polymer film and the glass plate is weakened. A peeling operation was performed so as to scoop up and a flexible electrophoretic display device was obtained in the same manner.

  It was confirmed that the obtained flexible electrophoretic display device did not deteriorate in display performance even when it was wound around a cylinder having a diameter of 3 mm, and had practically sufficient flexibility.

(Application example 2)
In the laminate L1 obtained in Example 1, after peeling the flexible electrophoretic display device in Application Example 1, the alkali-free glass that was the original substrate was placed in a 10% sodium hydroxide aqueous solution at room temperature. It was immersed for 20 hours, then washed with water, and then cleaned with a glass substrate glass cleaning device. Using the glass plate after washing, a silane coupling agent layer was formed on the same surface as that used in Example 1 again in the same manner as in Example 1, and the same procedure was followed to obtain a laminate. The quality of the obtained laminate was good, and the foreign matter density was 0.5 / cm ² , indicating that it can be fully recycled.
(Comparative application example)
In the laminate L12 obtained in the comparative example, the flexible electrophoretic display device was peeled off in the same manner as in the application example 2, and then the washing operation was performed in the same manner, and the laminate was formed again by the same operation. increased to 7200 / ^{m 2,} it was confirmed quality decreases significantly.
(Application 3)
The laminates obtained in Examples 1, 5, 6, 7 and Comparative Example 5 were covered with a stainless steel frame having an opening and fixed to a substrate holder in the sputtering apparatus. The substrate holder and the support of the laminate were fixed in close contact with each other, and a coolant was allowed to flow through the substrate holder so that the temperature of the laminate could be set. The temperature of the laminate was set to 2 ° C. First, plasma treatment was applied to the polymer film surface of the laminate. The plasma treatment conditions were as follows: argon gas, frequency 13.56 MHz, output 200 W, gas pressure 1 × 10 −3 Torr, treatment temperature 2 ° C., treatment time 2 minutes. Next, under the conditions of a frequency of 13.56 MHz, an output of 450 W, and a gas pressure of 3 × 10 −3 Torr, a nickel-chrome (chromium 10 mass%) alloy target is used to obtain a 1 nm / A nickel-chromium alloy coating (underlayer) having a thickness of 11 nm was formed at a rate of seconds. Subsequently, the temperature of the laminated body was set to 2 ° C., and sputtering was performed. Then, copper was vapor-deposited at a rate of 10 nm / second to form a copper thin film having a thickness of 0.22 μm. Thus, the laminated board with a base metal thin film formation film was obtained from each laminated body. The thicknesses of the copper and NiCr layers were confirmed by the fluorescent X-ray method.

  Next, a laminated board with a base metal thin film forming film from each film is fixed to a Cu frame, and an electroplating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, gloss, using a copper sulfate plating bath). A thick copper plating layer (thickening layer) having a thickness of 4 μm was formed by immersing in a small amount of the agent and flowing 1.5 A / dm 2 of electricity. Then, it heat-processed for 10 minutes at 120 degreeC, it dried, and the copper foil layer was formed in the polymer film surface of a laminated body.

After applying and drying a photoresist (“FR-200” manufactured by Shipley Co., Ltd.) on each metallized polyimide film / support laminate, the resulting metallized polyimide film / support laminate was subjected to off-contact exposure with a glass photomask, and further 1.2 mass%. Development was performed with an aqueous KOH solution. Next, etching was performed with a cupric chloride etching line containing HCl and hydrogen peroxide at 40 ° C. and a spray pressure of 2 kgf / cm 2 to form a line array of lines / spaces = 20 μm / 20 μm as a test pattern. Next, after electroless tin plating was performed to a thickness of 0.5 μm, annealing treatment was performed at 125 ° C. for 1 hour to obtain a wiring pattern.
The obtained wiring pattern was observed with an optical microscope, and the presence or absence of disconnection / short circuit was checked using the test pattern. As a result, the wiring patterns obtained from the laminates of Examples 1, 5, 6, and 7 had no disconnection or short circuit, and the pattern shape was good. On the other hand, in the wiring pattern obtained from the laminate of Comparative Example 5, disconnection was observed in part. It was concluded that the wiring shape of the disconnection part was such that the wiring was thin and faint, and that the exposure in the photoresist process was hindered. Further, it was found that the polymer film portion was in a convex state at the disconnection site, and foreign matter was present between the polymer film and the glass substrate. As a result of the compositional analysis, the foreign matter accounted for 25% or more of the Si element, and it was concluded that it was an aggregate of the silane coupling agent.
Subsequently, the polymer film was peeled from the glass plate by the same method as in Application Example 1 to obtain a flexible wiring board. The flexibility of the obtained flexible wiring board was good.
From the above results, it was shown that the laminate of the present invention is useful for the production of flexible electronic devices and is also excellent in substrate recyclability.

The laminate of the present invention is not only capable of easily peeling a polymer film with an electronic device from an inorganic substrate after the electronic device is prepared, but also an aggregate of silane coupling agents used for adhesion of the laminate. Is a layered product in which the adhesion between the polymer film and the inorganic substrate is homogenized, and the contribution to the industry is great. Furthermore, according to the present invention, the roughness of the inorganic substrate surface after peeling the polymer film is small, and it becomes possible to re-apply the silane coupling agent after a simple cleaning operation and use it as a substrate. Sexually improves.

Claims (15)

A silane coupling agent layer laminated inorganic substrate having a silane coupling agent layer formed on at least one surface, the silane coupling agent layer having a thickness of 5 nm or more and 50 nm or less, and a three-dimensional surface roughness (Sa) A silane coupling agent layer laminated inorganic substrate characterized by having a thickness of 2 nm or less. The silane coupling agent layer laminated inorganic substrate according to claim 1, wherein the silane coupling agent layer forms a predetermined pattern. ^3. The silane coupling agent layer laminated inorganic substrate according to claim 1, wherein the number of foreign matters containing silicon having a major axis of 10 μm or more is 2000 / m ² or less. The silane coupling agent layer laminated inorganic substrate according to claim 1, wherein the inorganic substrate is a glass having an area of 1000 cm ² or more. The silane coupling agent layer laminated inorganic substrate manufacturing method according to claim 1, wherein the silane coupling agent layer is formed by exposing the vaporized silane coupling agent to the inorganic substrate. 6. The method for producing a silane coupling agent layer laminated inorganic substrate according to claim 5, wherein a silane coupling agent vaporized by a bubbling method is used. The method for producing a silane coupling agent layer laminated inorganic substrate according to claim 6, wherein a dry gas having a dew point of 0 ° C or lower is used as a carrier gas when the silane coupling agent is vaporized by a bubbling method. The method for producing a laminated inorganic substrate having a silane coupling agent layer according to claim 5, wherein a gas having a dew point of 5 ° C. or higher is allowed to coexist when the inorganic substrate is exposed to the vaporized silane coupling agent. The method for producing a silane coupling agent layer laminated inorganic substrate according to claim 2, wherein a pattern is formed by masking a part of the inorganic substrate when forming the silane coupling agent layer. . 5. The silane coupling agent according to claim 2, wherein a predetermined pattern is formed by irradiating a part of the silane coupling agent layer with active energy rays after the formation of the silane coupling agent layer. A method for producing a layered inorganic substrate. A laminate in which the polymer film and the silane coupling agent layer laminated inorganic substrate according to claim 1 are joined, and the adhesive strength between the polymer film and the inorganic substrate is 0.2 N / cm or more, A laminate characterized by being 15 N / cm or less. A laminated body in which a polymer film and the silane coupling agent layer laminated inorganic substrate according to claim 1 are joined, wherein the adhesive strength between the polymer film and the inorganic substrate is different. And the peel strength of the good adhesion portion is 0.2 N / cm or more and 15 N / cm or less, and the peel strength of the easy peel portion is less than 0.2 N / cm. Laminated body. It has the process of following (1)-(3), The manufacturing method of a laminated body characterized by the above-mentioned.
(1) Forming a silane coupling agent layer on an inorganic substrate by exposing the inorganic substrate to a vaporized silane coupling agent
(2) A step of superposing a polymer film subjected to surface activation treatment on the silane coupling agent layer
(3) Adhesion process by applying pressure and heating   A flexible electronic device comprising the laminate according to claim 11, forming an electronic device on a polymer film of the laminate, and then peeling the polymer film together with the electronic device from an inorganic substrate. Manufacturing method.   An electronic device is formed on a portion corresponding to the easily peelable portion of the polymer film of the laminate using the laminate according to claim 12, and then on the outer periphery of the easily peelable portion of the laminate. A method for producing a flexible electronic device, comprising: cutting the polymer film along with the electronic device and peeling the polymer film from the inorganic substrate together with the electronic device.