JPWO2014119648A1 - LAMINATE, METHOD FOR PRODUCING LAMINATE, AND METHOD FOR PRODUCING FLEXIBLE ELECTRONIC DEVICE - Google Patents

Abstract

Provided are a high-quality laminate for forming a flexible electronic device by laminating a polymer film such as a polyimide film or a polyester film on an inorganic substrate and peeling it after forming the device, and a method for producing the same. SOLUTION: A silane coupling agent layer is formed on an inorganic substrate such as a glass plate via a gas phase, and then superimposed on a polymer film subjected to an activation treatment, and heated under pressure, thereby polymer film / inorganic. A laminated body with few foreign substances between the substrates is obtained. An electronic device can be formed with high yield in the obtained laminate, and a flexible electronic device can be efficiently manufactured by peeling from the inorganic substrate. [Selection figure] None

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 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 the production of 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.

  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 laminate in which a polymer film and an inorganic substrate are bonded via a silane coupling agent layer, and the number of foreign matters having a major axis of 10 μm or more existing between the polymer film and the inorganic substrate is 3 / cm. ² or less, and the adhesive strength between the polymer film and the inorganic substrate is ½ or less of the breaking strength of the polymer film.
2. The foreign matter is a foreign matter containing a silicon atom. The laminated body as described in.
3. The polymer film is a polyimide film having a thickness of 3 μm or more. Or 2. The laminated body as described in.
4). 1. The inorganic substrate is a glass plate having an area of 1000 cm ² or more. ~ 3. The laminated body in any one of.
5. The silane coupling agent has a chemical structure having one silicon atom per molecule. ~ 4. The laminated body in any one of.
6). A laminate in which a polymer film and an inorganic substrate are bonded via a silane coupling agent layer, and a good adhesion portion and an easily peelable portion having different adhesion strengths between the polymer film and the inorganic substrate The good adhesion portion and the easily peelable portion form a predetermined pattern. ~ 5. The laminated body in any one of.

7). 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 the inorganic substrate by exposing the inorganic substrate to the gasified silane coupling agent;
(2) A step of superposing a polymer film subjected to surface activation treatment on the silane coupling agent layer
(3) Step of bonding the two by heating and pressing 8. 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 gasified silane coupling agent
(2) A step of applying a polymer solution or polymer precursor solution onto the silane coupling agent layer
(3) Step of drying and heating the polymer solution or the polymer precursor solution to obtain a laminate as a polymer film 9. 6. The step (1) is performed under substantially atmospheric pressure. Or 8. The manufacturing method of the laminated body in any one of.
10. 6. The step (1) is performed under reduced pressure. Or 8. The manufacturing method of the laminated body in any one of.
11. The laminate has a good adhesion part and an easy peeling part with different adhesive strengths between the polymer film and the inorganic substrate, and the good adhesion part and the easy peeling part have a predetermined pattern. 6. It is formed, -10. The manufacturing method of the laminated body in any one of.
12 10. When forming the silane coupling agent layer, by masking a part of the inorganic substrate, the good adhesion part and the easy peeling part form a predetermined pattern. The manufacturing method of the laminated body.
13. After the formation of the silane coupling agent layer, by irradiating a part of the silane coupling agent layer with active energy rays, the good adhesion portion and the easily peelable portion form a predetermined pattern. 11. The manufacturing method of the laminated body.

14.7. -10. Using the laminate obtained by any one of the manufacturing methods, an electronic device is formed on the polymer film of the laminate, and then the polymer film is peeled from the inorganic substrate together with the electronic device. A method for manufacturing a flexible electronic device.
15.11. -13. Using the laminate obtained by any of the production methods of
Forming an electronic device on a portion corresponding to the easily peelable portion of the polymer film of the laminate,
Next, a method for producing a flexible electronic device is characterized in that the polymer film is cut along the outer periphery of the easily peelable portion of the laminate, and the polymer film is peeled off 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 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 intentionally obtaining the presence / absence or strength / weakness of the adhesive force by irradiating a part of the coupling agent layer along a predetermined pattern with active energy rays, a device formation process Sometimes it is possible to create a desired pattern of a good adhesion part having sufficient adhesive strength that does not cause peeling of the polymer film 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 part and peel off the functional element part 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.

(Laminated body and manufacturing method)
The laminate of the present invention is a laminate comprising at least an inorganic substrate, a silane coupling agent, and a polymer film.

<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.

As the ceramic plate, Al2O3, Mullite, AlN, SiC, Si3N4, BN, crystallized glass, Cordierite, Spodumene, Pb-BSG +
CaZrO3 + Al2O3, Crystallized glass + Al2O3, Cr
Ystallized Ca-BSG, BSG + Quartz, BSG + Quartz, BSG + Al2O3, Pb + BSG + Al2O3, Glass-ceramic, Zero-durer ceramics for substrates, TiO2, Strontium titanate, Calcium titanate, Magnesium titanate, Alumina, MgO, Ti4B BaTi4 + CaZrO3, BaSrCaZrTiO3, Ba (TiZr) O3, capacitor materials such as PMN-PT and PFN-PFW, PbNb2O6, Pb0.5Be0.5Nb2O6, PbTiO3, BaTiO3, PZT, 0.855PZT-95PT-B Piezoelectric materials such as 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 even more 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 thickness is not particularly limited, but 0.07 mm or more, preferably 0.15 mm or more, and 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, 150
It is more preferably 0 cm ² and 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 via 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. The vapor | steam of a silane coupling agent can be obtained by heating a silane coupling agent in a liquid state to a temperature from 40 ° C. to the boiling point of the silane coupling agent. Although the boiling point of a silane coupling agent changes with chemical structures, it is the range of about 100-250 degreeC in general. However, heating at 200 ° C. or higher is not preferable because the organic group of the silane coupling agent may cause a side reaction.
The environment for heating the silane coupling agent may be under pressure, at about normal pressure, or under reduced pressure, but is preferably at about normal pressure or under reduced pressure in order to promote vaporization of the silane coupling agent. Since many silane coupling agents are flammable liquids, it is preferable to perform the vaporizing operation in an airtight container, preferably after replacing the inside of the container with an inert gas.
The time for exposing the inorganic substrate to the silane coupling agent is not particularly limited, but is within 20 hours, preferably within 60 minutes, more preferably within 15 minutes, and even more preferably within 1 minute.
The inorganic substrate temperature during exposure of the inorganic substrate to the silane coupling agent is controlled 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.
The inorganic substrate exposed to the silane coupling agent is preferably heated to 70 ° C. to 200 ° C., more preferably 75 ° C. to 150 ° C. after the exposure. By such heating, the hydroxyl group on the surface of the 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.

As for the coating amount and thickness of the coupling agent, a single molecular layer is theoretically sufficient, and a thickness that can be ignored in terms of mechanical design is sufficient. Generally, it is less than 400 nm (less than 0.4 μm), preferably 200 nm or less (0.2 μm or less), more practically 100 nm or less (0.1 μm or less), more preferably 50 nm or less, still more preferably 10 nm or less. However, when the calculation is in the region of 5 nm or less, it is assumed that the coupling agent is present not in the form of a uniform coating but in a cluster shape, which is not preferable.
The film thickness of the coupling agent layer can be determined by ellipsometry or calculation from the concentration of the coupling agent solution at the time of coating and the coating amount.

<Patterning treatment on the inorganic substrate>
In the present invention, patterning treatment can be performed on the inorganic substrate side. Here, patterning refers to creating a region where the coating amount or activity of the 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 polyimide film support and drying it to obtain a green film (“precursor film”). Or a “polyamic acid film”), and further, a green film is subjected to a high temperature heat treatment on a support for forming a polyimide film or in a state of being peeled 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 1,4-diaminocyclohexane, 4,4′-methylenebis (2,6-dimethylcyclohexylamine), 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 alicyclic tetracarboxylic acids such as cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 3,3 ′, 4,4′-bicyclohexyltetracarboxylic acid. Carboxylic acids and their acid anhydrides are mentioned. Among these, dianhydrides having two anhydride structures (for example, cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4 '-Bicyclohexyltetracarboxylic dianhydride and the like) are preferred. In addition, alicyclic tetracarboxylic acids may be used independently and may use 2 or more types together.
In the case where importance is attached to transparency, the alicyclic tetracarboxylic acids are, for example, preferably 80% by mass or more of all tetracarboxylic acids, more preferably 90% by mass or more, and further 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 adhesive strength between the polymer film and the inorganic substrate needs to be ½ or less of the breaking strength of the polymer film.
Suppose that in the laminate of the present invention using a film having a thickness of 10 μm, the adhesive strength of the film was 0.5 N / cm.
The breaking force applied to the film having a width of 10 mm is 0.5 N / (10 μm × 10 mm) = 0.5 N / 0.1 square mm = 5 MPa. In such a case, if the film has a breaking strength of about 10 times, that is, 50 MPa or more, the peeling operation can be performed without any trouble when the film is peeled off.
The adhesive strength is preferably 1/3 or less, more preferably 1/4 or less of the breaking strength 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%) based on 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. 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 plasma treatment, which is a combination of plasma treatment and 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 surface of the polymer film 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 a polymer film is bonded, a laminated body is obtained by overlaying the activated surface of the polymer film on a temporary supporting inorganic substrate on which a silane coupling agent layer is formed, and heating and pressing.
The pressurizing / heating treatment may be performed while heating a press, a laminate, a roll laminate, or the like, for example, in an atmospheric atmosphere or in a vacuum. A method of heating under 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 heat 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 heat treatment is within a range not exceeding the heat resistance temperature of the polymer film to be used. In the case of a non-thermoplastic polyimide film, treatment at 150 ° C. to 400 ° C., more preferably 250 ° C. to 350 ° C. is preferable.
The pressure heat treatment can be performed in an atmospheric pressure atmosphere as described above, but is preferably performed under vacuum in order to obtain a stable adhesive strength on the entire surface. At this time, the degree of vacuum by a normal oil rotary pump is sufficient, and about 10 Torr or less is sufficient.
As an apparatus that can be used for pressure heat treatment, for example, “11FD” manufactured by Imoto Seisakusho can be used to perform pressing in a vacuum, and a roll-type film laminator in vacuum or a vacuum is used. For example, “MVLP” manufactured by Meiki Seisakusho Co., Ltd. can be used to perform vacuum laminating such as a film laminator that applies pressure to the entire glass surface at once with a thin rubber film.

  The pressure heat treatment can be performed separately in a pressure process and a heating process. In this case, first, the polymer film and the inorganic substrate are pressed (preferably about 0.2 to 50 MPa) at a relatively low temperature (for example, a temperature of less than 120 ° C., more preferably 95 ° C. or less) to ensure adhesion between the two. Then, at a low pressure (preferably less than 0.2 MPa, more preferably 0.1 MPa or less) or at a normal pressure, a relatively high temperature (for example, 120 ° C. or more, more preferably 120 to 250 ° C., further preferably 150 to 230 ° C.). ), The chemical reaction at the adhesion interface is promoted, and the polymer film and the temporary supporting inorganic substrate can be laminated.

<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 resin, a polyamic acid solution obtained by polycondensation of a diamine and a tetracarboxylic acid or an acid anhydride thereof as a raw material for the polyimide resin in a solution is predetermined on the temporary support inorganic substrate of the present invention. The polyimide film is formed on an inorganic substrate for temporary support by applying the film so as to have a thickness of 5 mm and drying, heat treatment or chemical imidization treatment. In this case, a preferable film thickness is 7 to 100 μm, preferably 15 to 80 μm, and more preferably 23 to 45 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. In addition, a combination of these methods, a method of superimposing ultrasonic waves on a cutting tool, or adding a reciprocating operation or an up / down operation to improve cutting performance can be appropriately employed.

  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.

<Recycling of inorganic substrates>
In the present invention, the inorganic substrate can be reused by completely removing the remaining polymer film from the supporting substrate after peeling off the target electronic device and performing a simple cleaning treatment or the like. When a conventional silane coupling agent layer is formed by liquid coating, the polymer film is peeled off on the surface of the inorganic substrate due to the adhesion of silane coupling agent aggregates or other foreign substances, and irregularities or silane cups are formed. The thickness of the ring agent layer is present, and in order to reuse it, it is necessary to polish the surface layer of the inorganic substrate to ensure a flat surface. According to the coating method of the present invention, the quality of the inorganic substrate surface after peeling of the polymer film is good, and re-polishing is unnecessary.

  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).

<Thickness unevenness of polymer film>
Ten thicknesses of the polymer film were obtained by randomly extracting 10 points from the film to be measured using a micrometer ("Millitron 1245D" manufactured by Finelfu) and measuring the film thickness. From the maximum value (maximum film thickness), the minimum value (minimum film thickness), and the average value (average film thickness), the following values were calculated.
Film thickness variation (%) = 100 × (maximum film thickness−minimum film thickness) ÷ average film thickness

<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

<Glass transition temperature>
Using a DSC differential thermal analyzer, the glass transition temperature of the polymer film was determined from the presence or absence of heat absorption / dissipation due to the structural change in the range from room temperature to 500 ° C.

<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.

<Thickness of coupling agent layer>
The thickness (nm) of the coupling agent layer (SC layer) is separately prepared on a cleaned Si wafer by preparing a sample obtained by applying and drying the coupling agent in the same manner as in each example and comparative example, The film thickness of the coupling agent layer formed on this Si wafer was measured by the ellipsometry method using a spectroscopic ellipsometer (“FE-5000” manufactured by Photo) under the following conditions.
Reflection angle range: 45 ° to 80 °
Wavelength range: 250 nm to 800 nm
Wavelength resolution: 1.25 nm
Spot diameter: 1mm
tan Ψ; Measurement accuracy ± 0.01
cosΔ; Measurement accuracy ± 0.01
Measurement: Method Rotating analyzer method Deflector angle: 45 °
Incident angle: 70 ° fixed Analyzer: 0-360 ° in 11.25 ° increments
Wavelength: 250 nm to 800 nm
The film thickness was calculated by fitting by a non-linear least square method. At this time, the model is Air / thin film / Si,
n = C3 / λ4 + C2 / λ2 + C1
k = C6 / λ4 + C5 / λ2 + C4
The wavelength dependence C1 to C6 was determined by the following formula.

<Adhesive strength>
A silane coupling agent is applied to the temporary support inorganic substrate by a predetermined method, and then a polymer film is laminated through a predetermined process. The adhesive strength between the temporary support inorganic plate and the polymer film is defined in JIS C6471. According to the described 180 degree peeling method, it measured on condition of the following. In addition, the sample used for this measurement masks a half of 60 mm × 120 mm with respect to a square substrate of 120 mm × 120 mm, performs thin film processing on the remaining half of the region, and provides a temporary supporting inorganic substrate for evaluation. did. In addition, when laminating a polymer film, the size of the film is 110 mm × 200 mm, an unadhered portion of the polyimide film is provided on one side, this portion is used for “grabbing”, and the film portion of the measurement sample is cut with a knife, The width was measured to be 10 mm.

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.
<Dust density>
Sampling a 30mm x 30mm area, observing the sampling area with a microscope with a length measurement function of 100x magnification, and measuring the major axis length of foreign matter confirmed by 100x magnification with a magnification of 400x Then, the number of those having a size of 10 μm or more was factored and divided by the observation area to obtain the foreign substance density.

<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)
(Instead of the polyamic acid solution V1, the polyamic acid solution V2 obtained above is used, and by a pin tenter, the first stage 150 ° C. × 5 minutes, the second stage 220 ° C. × 5 minutes, the third stage 485 ° C. × 10 minutes) It heat-processed and imidized, the pin holding part of both ends was dropped with the slit, and the long polyimide film F2 (1000 m winding) of width 850mm was obtained. 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 and subjected to imidization by performing heat treatment at the first stage 180 ° C. × 5 minutes, the second stage 220 ° C. × 5 minutes, the third stage 495 ° C. × 10 minutes, The pin grip portions at both ends were 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.

<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.
Instead of the polyimide film F1, a 100 μm thick polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) was used to obtain a plasma-treated film P4.
Similarly, instead of the polyimide film F1, a 100 μm thick polyethylene naphthalate film “Teonex” (manufactured by Teijin Limited) was used to obtain a plasma-treated film P5.
A predetermined mask made of a stainless steel plate having a thickness of 1 mm is overlaid on the plasma-treated polyimide film P2 obtained by using the polyimide film F2, and UV / ozone for 120 seconds using a UV / ozone irradiation apparatus manufactured by LAN Technical Service. Irradiation was performed to obtain a patterned plasma treated film PP2.
Table 2 shows the characteristics of the obtained plasma treated film and the patterned plasma treated film.

<Coupling agent layer formation on inorganic substrate>
<Application example 1>
Using a vacuum chamber having a hot plate, a silane coupling agent was applied to the inorganic substrate under the following conditions.
100 parts by mass of a silane coupling agent (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) was filled in a petri dish and allowed to stand on a hot plate. At this time, the hot plate temperature is 25 ° C. Next, a 300 mm × 350 mm × 0.7 mmt Pyrex glass plate is held horizontally at a location 300 mm away from the liquid surface of the silane coupling agent, the vacuum chamber is closed, and the oxygen concentration is 0.1 at atmospheric pressure. Nitrogen gas was introduced until it became less than%, then nitrogen gas was stopped, the inside of the chamber was depressurized to 3 × 10 −4 Pa, the hot plate temperature was raised to 120 ° C. and held for 10 minutes, and the silane coupling agent vapor was maintained. After that, the hot plate temperature is lowered, and at the same time, clean nitrogen gas is gently introduced into the vacuum chamber to return to atmospheric pressure, the glass plate is taken out, and the hot plate is heated to 100 ° C. in a clean environment. The inorganic substrate S1 on which the silane coupling agent application surface is placed and heat-treated for about 3 minutes to form a silane coupling agent layer It was.
<Application example 2>
The silane coupling agent was applied to the inorganic substrate under the following conditions. On a hot plate installed in a ventilation experiment table with 100 parts by mass of a silane coupling agent (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) filled in a petri dish and covered. The hot plate was heated to 160 ° C. Next, a 100 mm × 100 mm × 1.0 mmt soda-lime glass plate is horizontally held at a location 100 mm away from the liquid surface of the silane coupling agent, and the petri dish lid is opened and held for 15 minutes for silane coupling. Inorganic substrate S2 on which a glass plate is placed on a hot plate at 100 ° C. with the silane coupling agent application surface facing upward and heat-treated for about 3 minutes to form a silane coupling agent layer. Got.
<Application example 3>
Silane coupling agent (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) 0.5 parts by mass and 99.5 parts by mass of isopropyl alcohol were stirred and mixed in a clean glass container. A coupling agent solution was obtained. On the other hand, a Pyrex glass plate of 300 mm × 350 mm × 0.7 mmt was set on a spin coater manufactured by Japan Create Co., Ltd. First, 50 ml of isopropyl alcohol was dropped onto the center of the glass and washed by shaking off at 500 rpm, and then prepared in advance. About 30 ml of the silane coupling agent solution was dropped on the center of the glass plate, and the solution was shaken off by shaking the silane coupling agent solution at 500 ml for 10 seconds and then rotating the rotation speed to 1500 rpm for 20 seconds. Next, the glass plate is taken out from the stopped spin coater, placed on a hot plate at 100 ° C. in a clean environment with the silane coupling agent applied surface facing up, and heat-treated for about 3 minutes to form a silane coupling agent layer. The obtained inorganic substrate S3 was obtained.
<Application example 4>
In the same manner as in Application Example 3, a silane coupling agent layer was formed on a 100 mm × 100 mm × 1.0 mmt soda-lime glass plate by a spin coater to obtain an inorganic plate S4.
<Application Example 5> Patterning A predetermined mask made of a stainless steel plate having a thickness of 1 mm is overlaid on the inorganic substrate S1 obtained in Application Example 1, and 120 seconds using a UV / ozone irradiation device manufactured by LAN Technical Service. UV / ozone irradiation was performed to obtain a patterned inorganic substrate SP1.
The obtained inorganic plate is shown in Table 3.

<Example 1>
The plasma processing surface of the plasma processing film P1 trimmed into a 280 mm × 330 mm rectangle is superimposed on the silane coupling agent layer side of the obtained inorganic substrate S1 so that the inorganic substrate surface is exposed 10 mm, and a laminator manufactured by Climb Products Co., Ltd. Was used for temporary lamination at an inorganic substrate side temperature of 100 ° C., a roll pressure during lamination of 5 kg / cm 2, and a roll speed of 5 mm / second. The polymer film after temporary lamination did not peel off due to its own weight, but had such adhesiveness that it was easily peeled off when the film edge was scratched. Thereafter, the obtained temporary laminate 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 of the present invention. Table 4 shows the properties of the obtained laminate.
<Examples 2 to 5>
Hereinafter, a laminate was produced using the inorganic substrate S1 and the plasma treatment film shown in the table. In the case of the plasma-treated film P4, the heating temperature in the clean oven was 140 ° C., and in the case of the plasma-treated film P5, it was 175 ° C. Table 4 shows the properties of the obtained laminate.
<Example 6>
Using the obtained inorganic substrate S1 and the patterned plasma treatment film PP2, the same operation was performed to obtain a laminate L6. For the laminate L6, the part of the patterned plasma-treated film that was not irradiated with UV / ozone was evaluated as a normal part, and the irradiated part was evaluated as an easily peelable part.
(Comparative Example 1)
The plasma treatment surface of the plasma treatment film P1 trimmed into a 280 mm × 330 mm rectangle is overlapped on the silane coupling agent layer of the obtained inorganic substrate S1C so that the inorganic substrate surface is exposed 10 mm, and a laminator manufactured by Climb Products Co. is applied. The laminate was temporarily laminated at an inorganic substrate temperature of 100 ° C., a roll pressure of 5 kg / cm 2 during lamination, and a roll speed of 5 mm / second. The polymer film after temporary lamination did not peel off due to its own weight, but had such adhesiveness that it was easily peeled off when the film edge was scratched. Thereafter, the obtained temporary laminate 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 C1 of the present invention. Table 4 shows the properties of the obtained laminate.

<Examples 7 to 11>
The plasma processing surface of the plasma processing film P1 trimmed into a 90 mm × 90 mm rectangle is stacked on the side of the silane coupling agent layer of the inorganic substrate S2 so that the edge of the inorganic substrate surface is exposed by 5 mm, and the vacuum pressing machine manufactured by Imoto Seisakusho is used. The laminate was sandwiched between upper and lower cushioning materials, pressed at a hot plate temperature of 300 ° C. for 20 minutes under vacuum, and cooled to room temperature to obtain a laminate L7. Similarly, laminates were similarly obtained using the plasma-treated films P2 to P5. In the case of the plasma-treated film P4, the vacuum press temperature was 140 ° C., and in the case of the plasma-treated film P5, it was 175 ° C. Table 4 shows the properties of the obtained laminate.
<Comparative example 2>
A laminate C2 was obtained in the same manner as in Example 7 except that the inorganic substrate S4 was used. Table 4 shows the properties of the obtained laminate.
<Example 12>
Using the patterned inorganic substrate SP1 and the plasma-treated film P2, the same procedure as in Example 1 was followed to obtain a laminate L12. For the laminate L6, the portion of the patterned inorganic plate that was not irradiated with UV / ozone was evaluated as a normal portion, and the irradiated portion was evaluated as an easily peelable portion.
<Example 13>
Using the patterned inorganic substrate SP1 and the patterned plasma-treated film PP2, the same procedure as in Example 1 was followed to obtain a laminate L13. The shape of the mask used for the patterning process on the inorganic plate side and the shape of the mask used for the patterning process on the plasma processing film side are the same, and both the processed parts are arranged so as to overlap each other. . As for the layered product L13, the part where UV / ozone irradiation was not performed was evaluated as a normal part, and the irradiated part was evaluated as an easily peelable part. The results are shown in Table 4.
<Example 14>
The polyamic acid solution obtained in Production Example 2 was applied to the patterned inorganic substrate SP1 with a die coater so that the final film thickness was 25 μm, placed in an explosion-proof oven and dried at 80 ° C. for 100 minutes, and then 200 The temperature was raised to 5 ° C./minute up to 5 ° C., held at 200 ° C. for 60 minutes, then heated up to 480 ° C. at 10 ° C./minute, held at 480 ° C. for 5 minutes, and then 30 ° C./minute at 100 ° C. The laminate L14 was obtained by opening the oven door and cooling to near room temperature to form a polymer film layer directly on the inorganic substrate surface. The results are shown in Table 4.

(Application 1)
Using the laminates obtained in Examples 1 to 6, Example 12, Example 13, Example 14, and Comparative Example 1, 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 the laminate C1 as a comparative example, the display of 12 lines in the vertical direction and 5 lines in the horizontal direction was defective.
In each of the pixels that were defective in the comparative example C1, 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 L6, L12, L13, and L14 subjected to patterning, after overlapping the front plane, the polymer film part is burned out with a UV-YAG laser along the outer periphery of the patterning processing part, and thin from the edge of the cut When peeling was performed using a blade on a razor to scoop up, both 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 has practically sufficient flexibility without deterioration in display performance even when it is wound around a cylinder having a diameter of 3 mm, except for the one obtained from L14. For the flexible electrophoretic display device obtained from L14, there was no problem with winding around a cylinder with a diameter of 5 mm, but when wound around a cylinder with a diameter of 3 mm, the end of the polymer film was torn. This is because the polymer film itself is slightly brittle.

<Application example 2>
In the laminate L1 obtained in Example 1, after peeling the flexible electrophoretic display device in Application Example 1, the Pyrex glass plate that was the original substrate was placed in a 10% aqueous sodium hydroxide 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 could be fully recycled.
<Comparative application>
In the laminate C1 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. It increased to 46 pieces / cm < ² >, and it was confirmed that the quality reduction is remarkable.
(Application 3)
The laminates obtained in Examples 7 to 11 and Comparative Example 2 were covered with a stainless steel frame having an opening and fixed to the 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 7 to 11 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 2, 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 laminate in which a polymer film and an inorganic substrate are bonded via a silane coupling agent layer, and the number of foreign matters having a major axis of 10 μm or more existing between the polymer film and the inorganic substrate is 3 / cm. ² or less, and the adhesive strength between the polymer film and the inorganic substrate is ½ or less of the breaking strength of the polymer film.   The laminate according to claim 1, wherein the foreign matter is a foreign matter containing silicon atoms.   The laminate according to claim 1, wherein the polymer film is a polyimide film having a thickness of 3 μm or more. The inorganic substrate is a glass plate having an area of 1000 cm ² or more.
4. The laminate according to any one of 3 above.   The laminate according to any one of claims 1 to 4, wherein the silane coupling agent has a chemical structure having one silicon atom per molecule.   A laminate in which a polymer film and an inorganic substrate are bonded via a silane coupling agent layer, and a good adhesion portion and an easily peelable portion having different adhesion strengths between the polymer film and the inorganic substrate The laminate according to any one of claims 1 to 5, wherein the good adhesion portion and the easily peelable portion form a predetermined pattern. 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 gasified 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 heating and pressing 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 gasified silane coupling agent
(2) A step of applying a polymer solution or polymer precursor solution onto the silane coupling agent layer
(3) A step of drying and heating the polymer solution or the polymer precursor solution to obtain a laminate as a polymer film   The method for producing a laminate according to claim 7, wherein the step (1) is performed under substantially atmospheric pressure.   The method for producing a laminate according to claim 7, wherein the step (1) is performed under reduced pressure.   The laminate has a good adhesion part and an easy peeling part with different adhesive strengths between the polymer film and the inorganic substrate, and the good adhesion part and the easy peeling part have a predetermined pattern. It forms, The manufacturing method of the laminated body in any one of Claims 7-10 characterized by the above-mentioned.   The said good adhesion part and the said easily peelable part form a predetermined pattern by masking a part of said inorganic substrate when forming the said silane coupling agent layer. A manufacturing method of a layered product.   After the formation of the silane coupling agent layer, by irradiating a part of the silane coupling agent layer with active energy rays, the good adhesion portion and the easily peelable portion form a predetermined pattern. The manufacturing method of the laminated body of Claim 11. Using the laminate obtained by the production method according to claim 7,
Forming an electronic device on the polymer film of the laminate,
Next, the method for producing a flexible electronic device, wherein the polymer film is peeled off from the inorganic substrate together with the electronic device. Using the laminate obtained by the production method according to claim 11,
Forming an electronic device on a portion corresponding to the easily peelable portion of the polymer film of the laminate,
Then, along the outer periphery of the easily peelable portion of the laminate, cut into the polymer film,
A method for producing a flexible electronic device, comprising peeling the polymer film together with the electronic device from an inorganic substrate.