JP6550752B2 - Rigid composite laminate, method of manufacturing the same, laminate, and method of manufacturing device using the laminate - Google Patents

Description

The first invention of the present application relates to a method for producing a rigid composite laminate composed of a polyimide layer and two inorganic substrates. Specifically, in the present invention, a laminated plate temporarily or semi-permanently bonded to another inorganic substrate serving as a support plate on the reverse side of the polyimide layer of a flexible laminate formed by bonding a polyimide layer and an inorganic substrate. With respect to the manufacturing method, such a laminate is useful when a device made of a thin film and requiring fine processing, such as a semiconductor element, a MEMS element, and a display element, is formed on the surface of an inorganic substrate of a flexible laminate. More specifically, the rigid composite laminate according to the present invention includes a thin polyimide layer excellent in heat resistance and insulation, and an inorganic substance (for example, a glass plate, a ceramic plate, a silicon wafer, A rigid composite laminate with a support made of one type selected from metal plates, which can mount a precise circuit and is excellent in dimensional stability, heat resistance and insulation. Therefore, the first invention of the present application relates to such a laminate and a method of manufacturing the same.
The second invention of the present application relates to an FPD (flat panel display) typified by a liquid crystal display or a glass used as a substrate of a thin film solar cell, or an inorganic substrate such as a wafer of crystalline silicon or a compound semiconductor used for manufacturing semiconductor devices. It relates to handling technology. More particularly, the present invention relates to a handling technique that is useful when handling extremely thin inorganic substrates.

In recent years, with the aim of reducing the weight and reducing the size and thickness of functional elements such as semiconductor elements, MEMS elements, and display elements, technological development has been actively conducted to form these elements on a polymer film. For example, materials of base materials of electronic parts such as information communication devices (broadcast devices, mobile radios, mobile communication devices, etc.), radars, high-speed information processing devices, etc. conventionally have heat resistance and are signals of information communication devices Ceramics that can cope with high frequency band (reaching to the GHz band) have been used, but since ceramic is not flexible and it is difficult to thin, there has been a drawback that the applicable field is limited.

In forming functional devices such as semiconductor devices, MEMS devices, and display devices on the surface of a polymer film, it is ideal to process by the so-called roll to roll process using the flexibility that is the characteristic of the polymer layer. ing. In order to correspond to the process technology for rigid flat substrates built in the semiconductor industry, MEMS industry and display industry, as a realistic choice, the polymer layer is made of, for example, glass plate, ceramic plate, silicon wafer It has been considered to bond to a rigid inorganic substrate made of an inorganic material such as a metal plate and form a desired element, and then peel from the inorganic substrate.

As a polymer layer to be bonded to an inorganic substrate, a polymer layer having a low melting point is not suitable from the viewpoint of heat resistance. Epoxy or the like is used. In particular, a polymer layer made of polyimide is excellent in heat resistance and tough, and thus has an advantage of being able to be thinned.

Conventionally, bonding of a polymer layer to an inorganic substrate has been widely performed using a pressure-sensitive adhesive or an adhesive. However, when a desired functional element is formed on a laminate obtained by bonding a polymer layer and an inorganic substrate, the surface smoothness, dimensional stability, cleanness, and process temperature at a level that does not hinder formation of the functional element. The laminate is required to have a resistance to a liquid, a resistance to a chemical solution used for fine processing, and the like. In particular, in formation of functional elements such as polysilicon and oxide semiconductor, a process in a temperature range of about 200 to 500 ° C. is required. For example, in the fabrication of low-temperature polysilicon thin film transistors, heat treatment at about 450 ° C. for about 2 hours may be necessary for dehydrogenation. In the fabrication of hydrogenated amorphous silicon thin films, temperatures of about 200 ° C. to 300 ° C. May join the film. As described above, when the temperature at which the functional element is formed is high, the polymer layer needs to have heat resistance as well as the bonding surface of the polymer layer and the inorganic substrate (that is, the bonding adhesive or pressure-sensitive adhesive). Must withstand the processing temperature. However, since conventional adhesives and adhesives for bonding do not have sufficient heat resistance, at present, they can not be applied when the temperature at which the functional element is formed is high.

In addition, when forming a thin film of Si having a very small linear expansion coefficient of about 3 ppm / ° C. among the semiconductor thin films on the polymer layer, the difference between the linear expansion coefficient between the polymer layer and the thin film is large. Also, there is a problem that stress accumulates in the thin film, causing deterioration of performance, warping or peeling. In particular, when a high temperature is applied during the thin film formation process, stress due to a difference in linear expansion coefficient between the polymer layer and the thin film increases during the temperature change.

In addition, attempts have been made to provide an adhesive layer such as a thermoplastic resin on these polyimide films and to provide other structural reinforcements. However, even though it is satisfactory in terms of rigidity improvement according to this, the low heat resistance of the thermoplastic resin or the like as the adhesive layer tends to ruin the heat resistance of the polyimide film of the angle. It was. In addition, thermoplastic resins generally have a large linear expansion coefficient, and there is a limit to making this layer thin, so that they tend to adversely affect the dimensional stability when heated.

In order to solve the heat resistance as a laminate, a technique for bonding a polyimide layer and an inorganic substrate without providing an adhesive layer has also been developed (Patent Document 1). This technology is to bond a polyimide layer and an inorganic substrate by surface treatment, and has very high heat resistance. In this method, functional elements are processed on the surface of the polymer layer, but the surface of the polymer layer is lower in surface smoothness than inorganic substrates such as glass plates, ceramic plates, silicon wafers, and metal plates. Such a problem is attached. In order to solve this surface smoothness problem, development of a thin glass having flexibility capable of a roll to roll process is also in progress. The problem with this thin glass is that it is very low in strength and fragile. In view of this, a method has been proposed in which a film is bonded to the surface opposite to the functional element processed surface of thin glass to compensate for the problem of low strength and ease of cracking (Patent Document 2). However, in this technique, since an adhesive is used for joining the laminated body in which the thin glass and the film are bonded to the support substrate, the heat resistance against the process temperature has been a problem for the above reason.

In addition, flat panel displays (FPDs) and thin film solar cells represented by liquid crystal displays are generally manufactured using a glass plate as a substrate material. Further, many semiconductor devices can be obtained by processing a wafer such as crystalline silicon or a compound semiconductor. Inorganic substrates such as glass plates and silicon wafers exemplified here are hard and rigid, and a processing apparatus that handles them is also designed on the assumption that such inorganic substrates are rigid.

In recent years, attempts have been made to impart flexibility to inorganic substrates by thinning these inorganic substrates. Such an attempt aims to reduce the thickness, weight and flexibility of FPDs, solar cells, or various semiconductor devices. For example, it is known that a glass plate thinned to about several tens of μm can be bent to a curvature radius of about several cm.
Such a thinned inorganic substrate is fragile as compared with a general polymer film, and breaks when the curvature limit is exceeded. This point is a large difference from a polymer film which is not broken even when it is bent until it is creased, and which is not easily broken even if it is deformed due to a slight external force during conveyance. In addition, it is difficult to cut a thin inorganic substrate with a knife such as scissors, and if it is forcibly cut, there is a possibility that debris may be scattered as in the case of cracking. One solution to such problems is to handle other flexible materials, such as polymer films, in a state of being bonded to an inorganic substrate.

By attaching a polymer film to a thin inorganic substrate, handling is improved, and the probability of breakage during transportation is reduced. Even if the inorganic substrate breaks, the scattering of fragments to the surroundings is minimized. be able to.
However, in general, when FPDs, solar cells, and various semiconductor devices are manufactured using an inorganic substrate, they are often exposed to a high temperature of about several hundred degrees Celsius. Of course, even in a state where the polymer film is bonded, it is required to withstand the same high temperature environment. Therefore, it is not possible to use a polymer film generally sold under the names of a protective film, a scattering prevention film, and the like. Most of the polymer film materials used for these are thermoplastic and can not withstand a temperature environment of about 200 ° C. or higher.

  Polyimide films are known as materials having the highest heat resistance among polymer films. Among polyimide films, there is a film that can withstand a temperature environment of 300 ° C. or higher and 400 ° C. or higher for a short time. Therefore, if handling can be performed in a state in which a polyimide film is attached to an inorganic substrate, it can be expected that fabrication of devices can be performed using considerably high temperature conditions. However, in reality, since the heat resistance of the adhesive for bonding the inorganic substrate and the polyimide film is low, the expected practicality is not obtained.

In order to solve such a situation, the present inventors advanced research and development of technology of bonding a polyimide film and an inorganic substrate without using an adhesive, and reached the inventions shown in Patent Documents 3 to 7.
If this invention is used, it will become possible to use for the processing process including high temperature exposure of 400 degreeC or more with the state which joined inorganic substrates, such as glass, and a polyimide film. If the inorganic substrate is extremely thin and flexible, the inorganic substrate can be handled as if it had been bonded with a heat-resistant anti-scattering film. Realization of inorganic substrate processing by

  However, as described above, most of manufacturing apparatuses such as FPDs, solar cells, and semiconductor devices are designed on the premise of using a rigid substrate. Therefore, even if the extremely thin and flexible inorganic substrate as described above is improved in the handling property in a flexible state by bonding it to a polymer film, it will be in some form in the case of actually processing a device etc. It is required that it can be handled in the same manner as an apparently rigid substrate.

International Publication WO2011 / 071145 International Publication WO2011 / 030716 JP 2010-283262 A JP 2011-11455 A JP2011-245684A JP 2011-245675 A JP 2012-232594 A

The first invention of the present application was made paying attention to the above-mentioned circumstances, and the purpose thereof was to laminate a first inorganic substrate for laminating various devices and a polyimide layer for reinforcing it. A rigid composite laminate in which a second inorganic substrate is laminated on the opposite side of the polyimide layer on the flexible laminate, and the device is not peeled off even in a high-temperature process during device fabrication, and on the first inorganic substrate. It is to provide a rigid composite laminate that can easily peel the flexible laminate from the second inorganic substrate after the fabrication.
In this situation, the second invention of the present application is a process that can be applied to an extremely thin and flexible inorganic substrate that can be handled safely, and a processing apparatus and processing process for an existing rigid substrate. It is an object of the present invention to provide a laminated body having both compatibility and a method for manufacturing a device using the laminated body.

As a result of intensive studies to solve the above problems, the present inventors have determined that at least one of the surfaces of the first inorganic substrate and the polyimide layer facing each other, and at least the surface of the second inorganic substrate and the polyimide layer facing each other. By applying a surface treatment to one side, it is possible to bond each surface, and then inactivate a part of the surface treatment applied to at least one of the surfaces where the second inorganic substrate and the polyimide layer face each other to obtain a predetermined If a good adhesion part and an easy peel part with different peel strengths are made to exist by forming a pattern, sufficient peel strength that does not peel even in a high temperature process at the time of device fabrication is exhibited at the good adhesion part. The device-provided flexible laminate can be easily peeled off from the second inorganic substrate by cutting the easily peelable portion after device fabrication. Headlines, and completed the present first invention.

Furthermore, as a result of intensive studies conducted by the present inventors, it is possible to safely handle an inorganic substrate having extremely thin and flexible properties by using the following laminates, and for existing rigid substrates The inventors have found that the processing apparatus of the present invention and the process compatibility to which the processing process can be applied are compatible, and the second invention of the present application has been reached.

That is, the present invention has the following configuration.
(1) A surface opposite to the bonding surface (first bonding surface) of the polyimide layer of a flexible laminate having a total thickness of 300 μm or less consisting of a polyimide layer directly bonded to the first inorganic substrate A rigid composite laminate obtained by directly bonding a second inorganic substrate having a thickness of 300 μm or more to the bonding surface of 2).
(2) The rigid composite laminate according to (1), wherein the absolute value of the difference between the linear expansion coefficient (CTE) of the polyimide layer and the CTE of the first inorganic substrate is 30 ppm / ° C. or less.
(3) The bonding of the first inorganic substrate and the polyimide layer on the first bonding surface is performed after surface treatment is performed on at least one of the first inorganic substrate surface and the polyimide layer surface. The rigid composite laminate according to any one of (1) to (2).
(4) The bonding of the second inorganic substrate and the polyimide layer on the second bonding surface is performed after performing surface treatment on at least one of the second inorganic substrate surface and the polyimide layer surface. The rigid composite laminate according to any one of (1) to (3).
(5) The bonding between the second inorganic substrate and the polyimide layer on the second bonding surface is performed after the surface treatment by further subjecting a part of the surface treatment surface to an inactivation treatment, and a good adhesion portion and an easily peelable portion. A rigid composite laminate according to (4), characterized in that a predetermined pattern is formed.
(6) The surface treatment performed at the time of joining the first inorganic substrate and the polyimide layer on the first joining surface is selected from plasma treatment, corona treatment, active energy ray irradiation treatment, flame treatment, and coupling agent treatment. The rigid composite laminate according to any one of (1) to (5), wherein the rigid composite laminate is at least one selected from the group consisting of:
(7) The surface treatment performed at the time of joining the second inorganic substrate and the polyimide layer on the second joining surface is selected from plasma treatment, corona treatment, active energy ray irradiation treatment, flame treatment, and coupling agent treatment. The rigid composite laminate according to any one of (1) to (6), wherein the rigid composite laminate is at least one selected from the group consisting of:
(8) As the inactivation treatment, at least one kind of inactivation selected from the group consisting of blast treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, corona treatment, actinic radiation irradiation treatment, active gas treatment and chemical treatment. The rigid composite laminate according to (5), wherein the treatment is performed.
(9) The rigid composite as described in any one of (5) and (8) above, wherein the difference in adhesive strength between the good adhesion portion and the easily peelable portion in the second joining surface is 0.1 N / cm or more Laminated board.
(10) The rigid composite laminate according to any one of (1) to (9), wherein the maximum peeling force in the first bonding surface is 0.1 N / cm or more.
(11) A first laminating step of laminating a first inorganic substrate on one side of the polyimide layer by applying pressure and heating, and heating and pressurizing a second inorganic substrate on the opposite side of the polyimide layer. A method of producing a rigid composite laminate including a second laminating step of laminating by a step of adjusting the moisture content of the polyimide layer within a range of 0.1 to 1.7% before the second laminating step The manufacturing method of the rigid composite laminated sheet in any one of 1)-(10).
(12) A method for producing a structure in which a device is formed on the surface of a first inorganic substrate in a flexible laminate using the rigid composite laminate according to any one of (5) to (9). After forming a device on the first inorganic substrate in the flexible laminate, the flexible laminate is peeled off from the second inorganic substrate by making a cut in the polyimide layer of the easily peelable portion of the rigid composite laminate. A method for manufacturing a device structure.

(13) In a laminate in which a polyimide film and an inorganic substrate are directly bonded, the first inorganic substrate is directly bonded to one surface of the polyimide film, and the second inorganic substrate is directly bonded to the opposite surface of the polyimide film. The adhesion between the first inorganic substrate and the polyimide film and the adhesion between the second inorganic substrate and the polyimide film are measured, respectively, and the larger of the two adhesion values measured is F1. When the small value is F2,
F1 / F2 ≧ 1.5
A laminate characterized by satisfying the relational expression:
(14) The laminate according to (13), wherein at least one of the first inorganic substrate and the second inorganic substrate is an inorganic substrate having a thickness of 3 to 1500 μm.
(15) The direct bonding of the polyimide film and the first inorganic substrate and the polyimide film and the second inorganic substrate is to bond the surface-treated polyimide film surface and the surface-treated inorganic substrate surface. The laminate according to any one of (13) and (14), wherein
(16) The laminate according to (15), wherein the surface treatment of the inorganic substrate is a coupling agent treatment.
(17) The laminate according to any one of (15) or (16), wherein the surface treatment of the polyimide film is plasma treatment.
(18) Using the laminate according to any one of the above (13) to (17), device processing is performed on the first inorganic substrate or the second inorganic substrate, and then the adhesion between the polyimide film and the inorganic substrate A method of manufacturing a device, comprising the step of peeling the polyimide film and the inorganic substrate at a bonding surface where the bonding strength is weak (a bonding surface where the adhesive strength is F2).

The rigid composite laminate obtained by the production method of the first invention of the present application includes a first inorganic substrate (glass plate, ceramic plate, silicon wafer, metal, etc.), a polyimide layer, and a second inorganic substrate (glass plate, ceramic). Plate, silicon wafer, metal, etc.) and polyimide layer bonded together without an adhesive layer, and the adhesive peel strength between the flexible laminate and the second inorganic substrate according to a predetermined pattern Since it is divided into a good adhesion part and an easily peelable part that are different from each other, after making a device on the first inorganic substrate of the flexible laminate, it is easy to cut and peel off the polyimide layer of the easily peelable part. Can obtain a flexible laminate with a device.

According to the first invention of the present application, a circuit or the like can be formed on a thin flexible laminate having insulating properties, flexibility, and heat resistance. Furthermore, when an electronic component is mounted and an electronic device is manufactured, even if it is a thin flexible laminate, precise positioning can be performed by being laminated and fixed to the second inorganic substrate excellent in dimensional stability, and multilayer Thin film formation, circuit formation, and the like. Moreover, the laminate of the present invention does not peel off even if heat is applied during the process, and it is possible to combine the flexible laminate and the second inorganic substrate when peeling off from the second inorganic substrate as required after device fabrication. Peeling can be carried out smoothly. Furthermore, since the rigid composite laminate of the present invention is a rigid composite laminate having a peel strength that does not peel off in the process passing process, it is possible to use a conventional electronic device manufacturing process as it is. In particular, when producing a device on a flexible laminate, the surface properties of the first inorganic substrate are excellent in adhesion and smoothness, so that device fabrication can be carried out stably and accurately. As described above, the rigid composite laminate of the present invention is extremely significant for the production of an electronic device in which a circuit or the like is formed on a thin flexible laminate which is both insulating, flexible, and heat resistant.

According to the first invention of this application, by using a polyimide film as the polyimide layer, the surface treatment process can be performed by roll to roll, and the treatment can be performed efficiently. In particular, if a polyimide film roll that has been subjected to plasma treatment contains a lubricant, the handling property as a roll is equivalent to that before the plasma treatment. A protective film may be attached in order to prevent damage during the process. However, since the protective film has a lubricant, roll conveyance can be performed without any problem. It is significant in implementation that the process is excellent in productivity.

Since the rigid composite laminate according to the first invention of the present application is supported by the second inorganic substrate made of heat-resistant inorganic material, precise positioning is carried out at the time of circuit wiring production and semiconductor formation, thereby producing thin films in multiple layers. Circuit formation and the like can be performed, and thin film deposition and the like can be performed without peeling even in a high temperature process at the time of semiconductor fabrication. Further, this laminated body can be easily peeled off when only the easily peelable portion of the pattern is peeled off after the addition of the semiconductor, so that the manufactured semiconductor is not broken. Then, by peeling off the flexible laminated body used for the semiconductor added laminated body in which the circuit added laminated body and the semiconductor element are formed, the device added flexible laminated body with the circuit added and the semiconductor added device in which the semiconductor element is formed A flexible laminate can be provided.

Positioning for device fabrication is difficult if a flexible laminate with poor dimensional stability and large shape change is used as the substrate when precise positioning is performed during circuit wiring fabrication and thin film fabrication and circuit formation are performed in multiple layers. become. On the other hand, in the method of the first invention of the present application in which the flexible laminate is fixed to a hard support excellent in dimensional stability, and the flexible laminate is peeled off from the hard support after device fabrication, positioning for device fabrication is easy. A conventional electronic device manufacturing process can be used as it is, and device manufacturing on the flexible laminate can be carried out stably and accurately. In particular, the rigid composite laminate of the present invention is a rigid composite laminate which is significant for circuit formation and the like at high temperatures and for fine circuit formation.

In addition, while solar cells made of single crystal and polycrystalline Si etc. are becoming thinner, they are easily broken and there is a problem with handling during the process and durability after completion, but a flexible laminate to be used as a substrate These problems can be solved by forming a laminate with the second inorganic substrate as in the first invention of the present application. In addition, since there is a portion that can be easily peeled off at this time, a reinforcing substrate capable of drawing out an electrode can be manufactured.

The second invention of the present application improves the handleability of a brittle and fragile inorganic substrate by directly bonding a heat-resistant polymer film to an inorganic substrate having flexibility, and is similar to a conventional inorganic substrate. In particular, the present invention relates to a reinforced laminate that realizes process compatibility including exposure to a high temperature environment and a device manufacturing method using the laminate.
Also in such a reinforced inorganic substrate (laminate), since flexibility is maintained, it is difficult to use for the processing process designed and manufactured on the premise of the existing rigid inorganic substrate as described above. However, as shown in the present invention, if the reinforced inorganic substrate is temporarily bonded and supported by the second inorganic substrate, it can be handled in the same manner as a conventional rigid inorganic substrate. The present invention also has process suitability including exposure to a high temperature environment and the like in order to use the direct bonding method as this temporary bonding method.
Since the purpose of producing a device or the like using the composite plate of such a form is to obtain a flexible device, it is necessary to finally peel off from the support substrate. Further, the final peeled layer structure is either in the form of an inorganic substrate reinforced with a polymer film or in an inorganic substrate state without reinforcement. However, when the both surfaces of the polymer film and the inorganic substrate have the same adhesive strength, it is difficult to peel off at any arbitrary adhesive surface.
In the second invention of the present application, a difference is provided in the adhesive strength between the two adhesive surfaces, and the ratio between them is 1.5 times or more, so that the desired adhesive surface can be peeled off.

FIG. 1 is a schematic view showing a pattern example of the first invention of the present application. FIG. 2: is a schematic diagram which shows one embodiment of the manufacturing method of the rigid composite laminated board of 1st invention of this application. FIG. 3 is a schematic view showing an embodiment of a method for producing a device structure using the rigid composite laminate of the first invention of the present application. It is the schematic process figure which illustrated the process of laminating | stacking simultaneously the 1st inorganic substrate, polyimide film, and 2nd inorganic substrate in this-application 2nd invention. The setting of the difference in adhesion indicates that there may be cases where only the inorganic substrate on the side provided with the device is peeled off and cases where the polyimide film is adhered like a reinforcing film to the device side and peeled off This is a process example in which the first inorganic substrate and the polyimide film in the second invention of the present application are laminated and then laminated on the second inorganic substrate. It is an example of a process of laminating the polyimide film and the second inorganic substrate in the second invention of the present application and then laminating the first inorganic substrate. It is the schematic which illustrated the magnitude relationship of the polyimide film and inorganic substrate in 2nd invention of this application. The magnitude relationship is appropriately selected depending on whether the device manufacturing process, the peeling process, the peeling surface is used, or the like. It is a figure which shows the measuring method of the adhesive force of 2nd invention of this application.

Hereinafter, the present invention will be described in detail. 1st invention of this application is the opposite side of the said bonding surface (1st bonding surface) of a polyimide layer of the flexible laminated body which consists of a polyimide layer directly bonded to the 1st inorganic substrate and whose total thickness is 300 micrometers or less The second embodiment is a rigid composite laminate in which a second inorganic substrate having a thickness of 300 μm or more is directly bonded to the second surface (second bonding surface).
In the second invention of the present application, in the laminate formed by directly bonding the polyimide film and the inorganic substrate, the first inorganic substrate is directly bonded to one surface of the polyimide film, and the second surface is opposite to the polyimide film. The inorganic substrate is directly bonded, and the adhesion between the first inorganic substrate and the polyimide film and the adhesion between the second inorganic substrate and the polyimide film are respectively measured, and among the two adhesion values measured. When a large value is F1 and a small value is F2,
F1 / F2 ≧ 1.5
It is a laminated body characterized by satisfying the following relational expression.
Hereinafter, items common to the first invention and the second invention will be shown unless otherwise specified.

<Method for producing rigid composite laminate>
The method for producing a rigid composite laminate of the first invention of the present application is a method for producing a rigid composite laminate comprising at least a first inorganic substrate, a polyimide layer, and a second inorganic substrate. In addition, based on evaluation of a present Example, when a composite laminated board 370 mm in width and 470 mm in length is arrange | positioned on flat surfaces, such as a desk, and rigid end is arrange | positioned so that tip 100mm may be extended from a plane, it is based on dead weight. The case where the deflection is less than 3 mm is sufficient, and flexible means that the laminate having a width of 350 mm and a length of 450 mm is bent to a radius of curvature of less than 20 mm without causing problems such as cracking and cracking. Say.

<Inorganic substrate>
The first inorganic substrate and the second inorganic substrate in the present invention may be plate-like ones made of an inorganic substance and usable as a substrate. For example, a glass plate, a ceramic plate, a silicon wafer, a metal or the like is mainly used And glass plates, ceramic plates, silicon wafers, composites of metals, those obtained by laminating them, those in which they are dispersed, and those in which these fibers are contained. The same kind of substrate may be used as the first inorganic substrate and the second inorganic substrate, or different substrates may be used.

Examples of the glass plate used as the first inorganic substrate and / or the second inorganic substrate include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass ( Pyrex (registered trademark), borosilicate glass (alkali-free), borosilicate glass (microsheet), aluminosilicate glass and the like are included. Among these, those having a linear expansion coefficient of 5 ppm / ° C. or less are desirable.
The first inorganic substrate in the present invention is preferably 280 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less, and preferably 30 μm or more. If it is 280 μm or more, sufficient flexibility can not be obtained, and if it is 30 μm or less, the rigidity is too much and handling becomes very difficult. For example, it is desirable to use “OA10-G” manufactured by Nippon Electric Glass Co., Ltd. having a thickness of 50 μm to 100 μm, “Spool” manufactured by Asahi Glass Co., “Willow glass” manufactured by Corning. Moreover, as a 2nd inorganic substrate, 300 micrometers or more and 2000 micrometers (2 mm) or less are preferable, and 500 micrometers or more and 1200 micrometers (1.2 mm) or less are more preferable. As commercial products, "Corning 7059" or "Corning 1737" or "EAGLE" manufactured by Corning, which is a glass for liquid crystal, "AN 100" manufactured by Asahi Glass, "OA 10" manufactured by Nippon Electric Glass, manufactured by SCHOTT "AF32" is desirable.

As the ceramic plate used as the first inorganic substrate and / or the second inorganic substrate, Al ₂ O ₃ , Mullite, AlN, SiC, Si ₃ N ₄ , BN, crystallized glass, Cordierite, Spodumene, PB-BSG Substrates such as + CaZrO ₃ + Al ₂ O ₃ , Crystallized glass + Al ₂ O ₃ , Crystallized CA-BSG, BSG + Quartz, BSG + Al ₂ O ₃ , PB + BSG + Al ₂ O ₃ , Glass-Ceramic, Zerodur use ceramic, TiO _2, strontium titanate, calcium titanate, magnesium titanate, alumina, MgO, _{steatite, BaTi 4 O 9, BaTiO 3} , BaTi 4 + CaZrO 3, BaSrCaZrTiO 3, Ba (TiZr) O 3, PMN -Capacitor materials such as PT and PFN-PFW, PbNb ₂ O ₆ , Pb _0.5 Be _0.5 Nb ₂ O ₆ , PbTiO ₃ , BaTiO ₃ , PZT, 0.855PZT-95PT-0.5BT, 0.873PZT-0.97PT-0.3BT, Piezoelectric materials such as PLZT are included. Regarding the thickness when used for the first inorganic substrate and the second inorganic substrate, the same thickness as that of the glass plate is preferable.

  The silicon wafer used as the first inorganic substrate and / or the second inorganic substrate includes all n-type or p-type doped silicon wafers, intrinsic silicon wafers and the like, and the surface of the silicon wafer In addition to silicon wafers, germanium, silicon-germanium, gallium-arsenic, aluminum-gallium-indium, nitrogen-phosphorus-arsenic-antimony are often used in addition to silicon wafers. There is. Further, general-purpose semiconductor wafers such as InP, InGaAs, GaInNAs, LT, LN, ZnO, CdTe, and ZnSe are also included. Regarding the thickness when used for the first inorganic substrate and the second inorganic substrate, the same thickness as that of the glass plate is preferable.

  Examples of the metal used as the first inorganic substrate and / or the second inorganic substrate include single element metals such as W, Mo, Pt, Fe, Ni, and Au, Inconel, Monel, Nimonic, carbon copper, and Fe-Ni series. Alloys such as Invar alloy and Super Invar alloy are included. In addition, multi-layer metal plates formed by adding other metal layers and ceramic layers to these metals are 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 properties such as adhesion to the polyimide layer, no diffusion, and good chemical resistance and heat resistance. Although not preferred, chromium, nickel, TiN and Mo-containing Cu are mentioned as preferred examples. Regarding the thickness when used for the first inorganic substrate and the second inorganic substrate, the same thickness as that of the glass plate is preferable.

   It is desirable that the surface of the first inorganic substrate and the second inorganic substrate to be bonded to the polyimide layer be sufficiently flat. Specifically, the P-V value of the surface roughness is 50 nm or less, more preferably 20 nm, still more preferably 5 nm or less. If it is rougher than this, the adhesion between the first inorganic substrate and the polyimide layer, and the polyimide layer and the second inorganic substrate may be insufficient.

It is desirable that the surface (device fabrication surface) opposite to the surface to be bonded to the polyimide layer of the first inorganic substrate be sufficiently flat and smooth. Specifically, the P-V value of the surface roughness is 20 nm or less, more preferably 10 nm, more preferably 3 nm or less, and the _Ra value is 1 nm or less, more preferably 0.6 nm or less, more preferably 0.4 nm or less Is particularly preferable for producing a fine electric circuit or a semiconductor device. If R _a is large, it may not have the required degree of smoothness, and the metal thin film formed thereon may be adversely affected in terms of adhesion, smoothness and the like.

In the present invention, as the first inorganic substrate and the second inorganic substrate, an inorganic substrate having a defect density of not less than 100 μm / 100 cm ² at a height of 1 μm or more in the surface to be bonded to the polyimide layer is used. preferable. The defect existing density is more preferably 40 pieces / 100 cm ² or less, further preferably 15 pieces / 100 cm ² or less, and still more preferably 5 pieces / 100 cm ² or less. If the defect density exceeds this range, the practical contact area between the polyimide layer and the inorganic substrate may be reduced, and the necessary adhesive strength may not be obtained in a good bonding area, and conversely, due to the anchor effect. Adhesiveness of easily peelable parts becomes strong, which may cause troubles at the time of peeling. When the defect density exceeds this range, the degree of light scattering on the surface of the inorganic substrate increases, and the boundary between a good adhesion part and an easy peeling part formed by patterning becomes unclear, and peeling occurs. There may be inconveniences such as making it difficult to cut properly. If the defect density exceeds this range and the temperature of the rigid laminate is heated to 175 ° C. or more during device processing, the defect part becomes a nucleus and partial peeling such as blistering or floating occurs. May occur. Furthermore, if the defect density exceeds this range, defects with a high height will increase, and as a result, asperities of the device formation surface of the flexible laminate become large, and combined with the above-mentioned swelling and floating, the device When forming the device, it may cause blurring of the image in the exposure process for forming the device fine pattern, thereby obstructing device formation.

The surface of the first inorganic substrate opposite to the surface to be bonded to the polyimide layer (device manufacturing surface) is preferably an inorganic substrate having a defect existence density of 1 μm or more and 100 defects / 100 cm ² or less. The defect density is more preferably 40 pieces / 100 cm ² or less, further preferably 15 pieces / 100 cm ² or less, and still more preferably 5 pieces / 100 cm ² or less. If the defect density exceeds this range, it will not have the necessary smoothness during device fabrication, and may adversely affect the metal thin film formed on it in terms of adhesion and smoothness. .

   The defect of the inorganic substrate in the present invention is the irregularities formed by foreign matters such as scratches, dents, protrusions, etc., the shape singularity of the surface of the inorganic substrate which should be originally flat, and dust adhering to the surface of the inorganic substrate. Say. The height of the defect means the vertical length from the surface of the inorganic substrate to the top or bottom of the irregularities. The defect density in the present invention is measured by the method described in the examples. The defect density of the inorganic substrate defined in the present invention refers to the state immediately before bonding, that is, the state after surface treatment when surface treatment is performed before bonding, and the state without surface treatment when surface treatment is not performed. Refers to the defect density in

In order to keep the defect density of the surface of the inorganic substrate within a predetermined range, it is desirable to use a substrate with a low density of defects originally and to handle in a clean environment, specifically, the density of the original defects is Using a substrate of 100 pcs / 100 cm ² or less, preferably 20 pcs / 100 cm ² or less, according to United States Federal Standard (Federal Standard 209D (1988)), class 1000 or less, preferably class 100 or less, more preferably class 10 or less It is desirable to handle in a controlled clean environment. In addition, it is desirable to clean the substrate so that the original density of defects is 100/100 cm ² or less, preferably 20/100 cm ² or less. For cleaning the substrate, there are a method using dry cleaning such as a UV / O ₃ cleaning device or plasma treatment, and a method using wet cleaning using a surfactant, ultrapure water or the like. Any method can be used for dry cleaning as long as it removes other organic substances such as corona treatment. In addition, wet cleaning is effective only by immersing it in a solution, but a method such as ultrasonic cleaning that can increase the cleaning effect without directly contacting the surface is desirable. As the cleaning liquid, an acid solution or an alkaline solution that does not corrode the inorganic substrate can be used in place of the surfactant or ultrapure water.

<Polyimide layer, polyimide film>
The polyimide layer in the first invention of the present application is a polyimide film solution (also referred to as “polyimide precursor solution”) obtained by reacting at least a diamine and a tetracarboxylic acid in a solvent. It is coated and dried to form a green film (also referred to as “precursor film” or “polyamic acid film”), and then the green film is subjected to high-temperature heat treatment on the polyimide film support or in a state peeled from the support. A polyimide layer obtained by performing a dehydration ring-closing reaction, a polyimide layer obtained from a polyimide film, a polyimide obtained by applying a polyamic acid solution as a polyimide precursor on a substrate and then chemically reacting by heating to imidize Layer, a solution of polyimide dissolved in a solvent is applied to the substrate and then dried Polyimide layer obtained by points to either. From the viewpoint of handleability and productivity, it is more preferable to use a polyimide film as the polyimide layer. In the second invention of the present application, the above-mentioned polyimide film is used.

  There is no restriction | limiting in particular as diamine which comprises a polyamic acid, The aromatic diamines normally used for polyimide synthesis | combination, aliphatic diamines, alicyclic diamines etc. can be used. From the viewpoint of heat resistance, aromatic diamines are preferable, and further, aromatic diamine having a benzoxazole structure is more preferable. When an aromatic diamine having a benzoxazole structure is used, it is possible to exhibit high heat resistance, high elastic modulus, low heat shrinkage, and low linear expansion coefficient. Moreover, when light transmittance is required, what substituted the hydrogen of the hydrocarbon group of alicyclic diamines and diamines with the fluorine is preferable. The use of alicyclic diamines and diamines having a structure in which hydrogen of the hydrocarbon group of the diamines is substituted with fluorine makes it possible to express high transparency, low yellow index, and low haze. Diamines may be used alone or in combination of two or more.

  The aromatic diamine having a benzoxazole structure is not particularly limited, and examples thereof include 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'-diaminodipheny) ) 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 ′] bisoxazole, 2,6- (3,3′-diaminodiphenyl) benzo [1,2- d: 4, 5-d '] bis oxazole etc. are mentioned. Among these, each isomer of amino (aminophenyl) benzoxazole is preferable, and 5-amino-2- (p-aminophenyl) benzoxazole is more preferable. Here, "each isomer" means that the bonding position of two amino groups possessed by amino (aminophenyl) benzoxazole is different. 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 corresponds to the isomer.

  The alicyclic diamine is not particularly limited, and 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,1-bis (4-aminophenyl) Cyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-methylenebis (2-methylcyclohexylamine), 4,4′-methylenebis (2,6-dimethylcyclohexylamine), 4,4′-diaminodicyclohexylpropane, Bicyclo [2.2.1] heptane-2,3-diamine, bicyclo [2.2.1] heptane-2,5-diamine, bicyclo [2.2.1] heptane-2,6-diamine, bicyclo [2.2.1] heptane 2,7-diamine, 2,3-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) ) -Bicyclo [2.2.1] heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 (2,6)] deca And hydrogen in these hydrocarbons substituted with fluorine.

  As the diamine, other diamines exemplified below can be used in addition to the diamine having the benzoxazole structure and the alicyclic diamine described above. Other diamines include, for example, 2,2′-dimethyl-4,4′-diaminobiphenyl, bisaniline, 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 2,2′-ditrithio Fluoromethyl-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) phenyl] propane, 2 , 2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 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 '-Diaminobenzophenone, 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-a Minophenoxy) 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 Enyl] 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] sulfo Sid, 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-aminophenoxy) 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 4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzene) phenoxy] diphenyl sulfone, 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) pheno Cis-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-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-phenoxybenzofe 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-biphenoxy Benzophenone, 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-biphenoxybe) Zoyl) 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 part or all of hydrogen atoms on the aromatic ring of the above aromatic diamine Is a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group, a cyano group, or an alkyl group or an alkoxyl group. And aromatic diamines substituted with a group or alkoxyl group.

  Furthermore, the following aliphatic diamines can also be used. Examples of aliphatic diamines include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane and 1,8-diaminooctane. Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 4,4'-methylenebis (2,6-dimethylcyclohexylamine), diaminodicyclohexylmethane and the like. 20 mass% or less of all diamines is preferable, and, as for the total amount of diamine (aliphatic diamines and alicyclic diamines) other than aromatic diamines, more preferably 10 mass% or less, still more preferably 5 mass% or less It is.

The tetracarboxylic acids constituting the polyamic acid are not particularly limited, and aromatic tetracarboxylic acids, aliphatic tetracarboxylic acids, alicyclic tetracarboxylic acids, or acid anhydrides thereof or the like which are usually used for polyimide synthesis are used. be able to. Among them, aromatic tetracarboxylic acids and alicyclic tetracarboxylic acids are preferable. In particular, when heat resistance is required, aromatic tetracarboxylic acids are more preferable, and when light transmittance is required, alicyclic tetracarboxylic acids are more preferable. When these are acid anhydrides, the number of anhydride structures in the molecule may be one or two, but preferably those having two anhydride structures (dianhydrides) Good. Tetracarboxylic acids may be used alone or in combination of two or more. As alicyclic tetracarboxylic acids, for example, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid , bicyclo [2, 2, 1] heptane -2 3, 5, 6-tetracarboxylic acid, Tetorashikurodo [6, 2, 1, 1, 0 ^{2, 7]} dec -4, 5, 9, 10-tetracarboxylic Acids, and their acid anhydrides.

Aromatic tetracarboxylic acid anhydrides are not particularly limited, but are preferably those having a pyromellitic acid residue, that is, a structure derived from pyromellitic acid. Examples of such aromatic tetracarboxylic acids include pyromellitic dianhydride, 3, 3 ′, 4, 4′-biphenyltetracarboxylic dianhydride, 4, 4′-oxydiphthalic dianhydride, 3 , 3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2-bis [4- (3,4-di) Carboxyphenoxy) phenyl] propanoic dianhydride 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 polyamide acid is preferably composed of diamines and tetracarboxylic acids in the following combination, particularly when heat resistance is required.
A. Combination of an aromatic tetracarboxylic acid having a pyromellitic acid residue and an aromatic diamine having a benzoxazole structure.
B. A combination of an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton and an aromatic diamine having a phenylenediamine skeleton.
C. Combination of an aromatic tetracarboxylic acid having pyromellitic acid and an aromatic diamine having a diaminodiphenyl ether skeleton.
In particular, C is preferably mixed with a silica-based compound from the viewpoint of improving physical properties. In addition to the above-mentioned diamines and tetracarboxylic acids, the polyamic acid may contain, for example, tricarboxylic acids such as cyclohexane-1, 2, 4-tricarboxylic acid anhydride.

The polyamic acid is preferably composed of diamines and tetracarboxylic acids in the following combinations, particularly when light transmittance is required.
D. A combination of an alicyclic tetracarboxylic acid having a cyclobutane skeleton and a mixture of a diamine having a benzidine skeleton in which a hydrocarbon group is fluorinated and a diamine having a phenyl ether skeleton in which a hydrocarbon group is fluorinated.
The blending ratio of the diamine having a benzidine skeleton and the diamine having a phenyl ether skeleton may be any of 0: 100 to 100: 0 by weight.

  The ratio of diamines to tetracarboxylic acids is preferably 0.9 to 1.1 mol, more preferably 0.95 to 1.05 mol, still more preferably 0.98 to 1.02 mol of tetracarboxylic acids per 1 mol of diamines.

   The solvent used for reacting (polymerizing) the diamines and the tetracarboxylic acids to obtain the polyamic acid is not particularly limited as long as it can dissolve both of the monomer serving as the raw material and the polyamic acid to be produced. Solvents are preferred, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric Amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, halogenated phenols and the like can be mentioned. These solvents may be used alone or in combination of two or more. The amount of the solvent used may be an amount sufficient to dissolve the monomer as the raw material, and as the specific amount used, the amount of all monomers in the reaction solution (solution in which the monomer is dissolved) is usually The amount may be 5 to 40% by mass, preferably 10 to 30% by mass.

   The conditions for the polymerization reaction for obtaining the polyamic acid (hereinafter, also simply referred to as “polymerization reaction”) may be a conventionally known condition, for example, in an organic solvent at a temperature range of 0 to 80 ° C. for 10 minutes. Stirring and / or mixing continuously for 30 hours may be mentioned. If necessary, the polymerization reaction may be divided, or the reaction temperature may be increased or decreased. Although there is no restriction | limiting in particular in the addition order of a monomer, It is preferable to add tetracarboxylic acids in the solution of diamines.

  Further, vacuum degassing during the polymerization reaction is also effective for producing a good quality polyamic acid solution. Further, the polymerization may be controlled by adding a small amount of a terminal blocking agent to the diamine before the polymerization reaction. Examples of the terminal blocking agent include dicarboxylic acid anhydrides, tricarboxylic acid anhydrides, and aniline derivatives. Among these, specifically, phthalic anhydride, maleic anhydride, 4-ethynyl phthalic acid, 4-phenylethynyl phthalic acid and ethynyl aniline are preferable, and in particular, maleic anhydride is preferable. The amount of the end-capping agent used is preferably 0.001 to 1.0 mol with respect to 1 mol of the diamine.

   The reduced viscosity of the polyamic acid solution obtained by the polymerization reaction is preferably in the range of 1.6 to 7.0 dl / g, more preferably in the range of 1.8 to 5.8 dl / g, and still more preferably in the range of 2.1 to 5.3 dl / g. The mass of the polyamic acid in the polyamic acid solution obtained by the polymerization reaction is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. The viscosity of the polyamic acid solution is preferably 10 to 2000 Pa · s, more preferably 100 to 1000 Pa · s, as measured by a Brookfield viscometer (25 ° C.), from the viewpoint of stability of liquid transfer. is there.

  Various additives such as an antifoaming agent, a leveling agent, and a flame retardant may be added to the polyamic acid solution obtained by the polymerization reaction for the purpose of further improving the performance of the polyimide film. These addition methods and addition times are not particularly limited.

  In the present invention, a filler may be added to the polyamic acid solution for the purpose of improving the performance of the polyimide layer. The filler in the present invention is a fine particle made of an inorganic substance having a deposition average particle size of 0.001 to 10 μm, and is a metal, metal oxide, metal nitride, metal carbonate, metal salt, phosphate, carbonate, talc, Particles made of mica, clay, other clay minerals 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, etc. , Phosphates and carbonates can be used.

  In order to form a polyimide film from a polyamic acid solution obtained by a polymerization reaction, a green film (a self-supporting precursor film) is obtained by applying the polyamic acid solution on a support for producing a polyimide film and drying it. Next, a method of imidizing the green film by subjecting it to a heat treatment can be employed. The application of the polyamic acid solution to the support includes, for example, spin coating, doctor blade, applicator, comma coater, screen printing method, slit coating, reverse coating, dip coating, etc., casting from a slit nozzle, extruder However, the present invention is not limited thereto, and conventionally known solution coating means can be appropriately used. What is necessary is just to set the application quantity of a polyamic-acid solution suitably according to the film thickness of the desired polyimide film. 50 degreeC-120 degreeC are preferable, and, as for the heating temperature at the time of drying the apply | coated polyamic acid solution, 80 degreeC-100 degreeC is more preferable. The drying time is preferably 5 minutes to 3 hours, more preferably 15 minutes to 2 hours. The residual solvent amount in the green film after drying is preferably 25 to 50% by mass, and more preferably 35 to 45% by mass. The temperature at which the green film is heat-treated is preferably, for example, 150 to 550 ° C, more preferably 280 to 520 ° C. The heat treatment time is preferably 0.05 to 10 hours.

   From the viewpoint of heat resistance, the polyimide layer and the polyimide film have a glass transition temperature of 250 ° C. or more, preferably 300 ° C. or more, more preferably 350 ° C. or more, or no glass transition point is observed in the region of 500 ° C. or less Is most preferred. From the viewpoint of transparency, the average light transmittance at 380 nm to 700 nm (hereinafter simply referred to as “average light transmittance”) is preferably 85% or more, more preferably 87% or more, and still more preferably 89% or more. The haze value (HAZE) is preferably 1.0% or less, more preferably 0.8% or less, still more preferably 0.6% or less, and further, the YI value (yellow index) is preferably 20 or less, more preferably 10 or less, more preferably Is 5 or less, still more preferably 3 or less. The glass transition temperature in the present invention is determined by differential thermal analysis (DSC), and the average light transmittance, the haze value, and the YI value can be measured, for example, by the method described later in the Examples.

  In the present invention, the tensile modulus of the polyimide layer and the polyimide film is preferably 0.3 to 12.0 GPa, more preferably 0.6 to 11.2 GPa, and still more preferably 1.2 to 10.0 GPa. If the tensile elastic modulus of the film is lower than the above range, deformation due to the tension applied by the conveying device or the like may increase, and there is a risk of trouble during handling and device formation. On the other hand, if it is higher than the above range, the rigidity of the film is strong. In addition, there is a risk that tear strength and flexibility may be reduced. In addition, the tensile elasticity modulus of a film can be measured by the method mentioned later by an Example, for example.

  The average linear expansion coefficient (CTE) between 30 ° C. and 300 ° C. of the polyimide layer and the polyimide film is preferably −10 ppm / ° C. to +50 ppm / ° C., more preferably −5 ppm / ° C. to +20 ppm / ° C. ° C, more preferably -5 ppm / ° C to +15 ppm / ° C, and particularly preferably -3 ppm / ° C to +10 ppm / ° C. If the temperature is out of this range, the difference in linear expansion coefficient with the inorganic substrate becomes large, and thus the polyimide layer and the inorganic substrate may be easily peeled off during the process of applying heat. Although CTE often does not change in the temperature range with an inorganic substrate such as metal or ceramic, CTE may change in the temperature range with a polyimide layer. Therefore, the measurement lower limit may be replaced with 0 ° C., 30 ° C., 50 ° C., or the measurement upper limit may be replaced with 200 ° C., 300 ° C., 400 ° C. For example, in the present invention, although the linear expansion coefficient of the polyimide layer uses an average value of 30 ° C. to 300 ° C. or an average value of 30 ° C. to 210 ° C., the temperature range of interest changes depending on the application and the process at high temperature Considering the range of 30 ° C to 400 ° C, it may be in the range of 100 ° C to 400 ° C. When examining the range of -50 ° C to 280 ° C with the reflow process in mind, 0 as the operating temperature range In some cases, the range of ° C to 280 ° C may be emphasized.

  The breaking strength of the polyimide 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 polyimide film means an average value in the vertical direction and the horizontal direction of the polyimide film.

  The thermal shrinkage rate of the polyimide film of the present invention is preferably 0.5% or less when heated at 400 ° C. for 1 hour. Such a characteristic is that among the raw materials for the polyimide film, pyromellitic acid is used as a tetracarboxylic dianhydride in an amount of 50 mol% or more and at the same time a paraphenylene diamine or a diamine having a benzoxazole structure is used in an amount of 50 mol% or more, or an aromatic ring is used. It can be obtained by using 1 or 2 tetracarboxylic anhydride and 85 mol% or more of paraphenylenediamine as a diamine component.

The thickness unevenness of the polyimide 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%, application to narrow portions tends to be difficult. 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 x (maximum film thickness-minimum film thickness) / average film thickness

  The thickness of the polyimide layer in the present invention is not particularly limited, but is preferably 1 μm to 200 μm, and more preferably 3 μm to 60 μm. The thickness unevenness of these polyimide layers is also preferably 20% or less, and more preferably 10% or less. If the thickness of the polyimide layer is less than 1 μm, it is difficult to control the thickness and there is a possibility that it will be difficult to peel off from the support. Or the flexibility of the flexible laminate may be lost. Use of a polyimide layer having a thickness in the above-described range can greatly contribute to the enhancement of performance of elements such as sensors and the reduction in size and thickness of electronic components.

  When a polyimide film is used as the polyimide layer, a film obtained in the form of being wound up 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 its production is preferred. More preferred are those in the form of a polyimide film.

  When a polyimide film is used as the polyimide layer, a sliding material (particle) is added to and contained in the polyimide constituting the film in order to ensure handling and productivity, and the polyimide film surface is provided with fine irregularities and slips. It is preferable to ensure the property. The lubricant (particle) is a fine particle made of an inorganic substance, and includes metal, metal oxide, metal nitride, metal carbonized product, metal acid salt, phosphate, carbonate, talc, mica, clay, and other clay minerals. , Etc. 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, and 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 polyimide film becomes difficult, and if the upper limit is exceeded, the surface unevenness becomes too large and the bonding strength becomes weak, and the number of air bubbles during bonding increases, etc. There is a risk of practical problems.

   The addition amount of the lubricant is 0.02 to 50% by mass as the addition amount with respect to the polymer solid content in the polyamic acid solution, and the upper limit of the addition amount is preferably 5% by mass, more preferably 3% by mass, and still more preferably. 1.0 mass%, particularly preferably 0.4 mass%, and the lower limit of the amount added is preferably 0.04 mass%, more preferably 0.08 mass%, still more preferably 0.20 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 there is not enough slipperiness to cause trouble when winding the polyimide film roll. Therefore, even if the slipperiness is ensured, the smoothness may be lowered, the breaking strength or breaking elongation of the polyimide film may be lowered, or the CTE may be raised.

  When a lubricant (particle) is added to and contained in a polyimide film, it may be a single-layer polyimide film in which the lubricant is uniformly dispersed. For example, one surface is composed of a polyimide film containing a lubricant, The other side may be a multilayer polyimide film composed of a polyimide film containing no lubricant or containing a small amount of lubricant even if contained. In such a multilayer polyimide film, fine irregularities are imparted to the surface of one layer (film), and slipperiness can be secured with the layer (film), and good handling properties and productivity can be secured. . Hereinafter, the production of such a multilayer polyimide film will be described.

  For example, as a polyamic acid solution (precursor solution of a polyimide), a multilayer polyimide film has a lubricant (preferably having an average particle diameter of about 0.05 to 2.5 μm) in an amount of 0.05% by mass to polymer solid content in the polyamic acid solution Those containing 50% by mass (preferably 0.1 to 3% by mass, more preferably 0.20 to 1.0% by mass) and those containing no lubricant or having a small content (preferably polymer solid content in a polyamic acid solution) Preferably, it is produced using two polyamic acid solutions which are 0.3% by mass or less, more preferably 0.01% by mass or less). The multilayering (lamination) method of the multilayer polyimide film is not particularly limited as long as no problem arises in the adhesion between the two layers, as long as the adhesion can be achieved without the use of an adhesive layer or the like. For example, i) a method in which one polyimide film is prepared and then the other polyamide acid solution is continuously applied on the polyimide film for imidization, ii) one polyamide acid solution is cast to prepare a polyamide acid film After that, the other polyamic acid solution is continuously coated on the polyamic acid film and subsequently imidized, iii) co-extrusion method, iv) polyamic acid containing no lubricant or having a small content thereof On the film formed with a solution, the method of apply | coating and imidating the polyamic-acid solution which contains many lubricating materials by spray coating, T-die coating etc. is mentioned. The methods i) and ii) are preferable.

  The ratio of the thickness of each layer in the multilayer polyimide film is not particularly limited, but the film (layer) formed of a polyamic acid solution containing a large amount of lubricant (a) layer, does not contain lubricant or contains it When a film (layer) formed of a polyamic acid solution having a small amount is referred to as (b) layer, (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, while if it is less than 0.05, the improvement effect of the surface properties may be insufficient and the slipperiness may be lost .

  As a polyimide layer, a polyamic acid solution is coated on an inorganic substrate, dried and then imidized by heating or chemical treatment to form a polyimide layer, or a solvent-soluble polyimide resin is coated and dried to form a polyimide layer, Further, when a polyimide layer is formed by proceeding with drying and partial imidization from a mixed state of a polyamic acid solution and a solvent-soluble polyimide resin that have not been partially imidized, a polyamic acid solution and / or a polyimide resin solution For example, spin coating, doctor blade, applicator, comma coating, screen printing method, fluency from a nozzle with a slit, extrusion with an extruder, slit coating, reverse coating, dip coating, etc. Without using any known solution coating method. Can. Hereinafter, when a polyamic acid solution is applied onto this inorganic substrate and dried and then imidized by heating or chemical treatment to form a polyimide layer, or when a solvent-soluble polyimide resin is applied and dried to form a polyimide layer, Summarizes the case where a polyimide layer is formed by proceeding with drying and partial imidization from a mixed state of a polyamic acid solution and a solvent-soluble polyimide resin that have not been partially imidized. In the case of forming a polyimide layer, it is referred to as ".

  When using the polyimide layer which made the solution the polyimide layer on the inorganic board | substrate as a polyimide layer, 50-120 degreeC is preferable and the heating temperature at the time of drying a polyamic-acid solution has more preferable 80 to 100 degreeC. The treatment time is preferably 5 minutes to 3 hours, and more preferably 15 minutes to 2 hours. The residual solvent amount after drying is preferably 25% to 50%, more preferably 35 to 45%.

   150-500 degreeC is preferable and, as for the heating temperature at the time of producing the polyimide layer by heating the polyamic acid after drying, 300-450 degreeC is more preferable. The heating time is preferably 3 minutes to 10 hours. The heat treatment is usually performed while stepwise or continuously raising the temperature. The temperature rising rate is preferably 0.2 to 20 ° C./min, more preferably 0.3 to 10 ° C./min or less, and particularly preferably 0.5 to 5 ° C./min or less.

   When performing imidization by heating while continuously increasing the temperature, the temperature is continuously increased from 100 ° C. to a maximum temperature of 150 ° C. to 500 ° C. at a temperature increase rate of 0.5 to 20 ° C./min. The conditions for holding for 120 minutes are preferable. More preferably, the temperature rising rate is 1 to 10 ° C./min, the highest reaching temperature is 300 to 480 ° C., the holding time at the highest reaching temperature is 1 to 60 minutes, and most preferably the temperature rising rate is 2 to 5 ° C. / Min, maximum reaching temperature is 400 to 450 ° C., and holding time at the maximum reaching temperature is 5 to 30 minutes. Although the drying step and the imidization step are described separately for convenience, the drying and the imidization actually proceed in parallel. In the relatively low temperature drying process, drying is dominant, and in the relatively high temperature imidization process, the imidization reaction is dominant. It is a preferred embodiment for industrial production that the drying step and the imidization step are not performed separately and are performed continuously as a heat treatment.

  Regarding drying by heating and temperature rising conditions in imidization, after drying for 30 minutes at 80 ° C., then 90 minutes at 100 ° C., raising the temperature to 400 ° C. at a temperature rising rate of 5 ° C./min, 5 minutes at 400 ° C. It is particularly preferable to hold.

  In the present invention, as a polyimide layer, a solution-soluble polyimide resin or the like is used, and when a polyimide layer formed into a polyimide layer on an inorganic substrate is used, the drying temperature after applying the resin solution is 150 to 380 ° C. Preferably, it is 185-330 degreeC. The heating time is preferably 3 minutes to 10 hours. The heat treatment is usually performed while stepwise or continuously raising the temperature. The temperature rising rate is preferably 0.2 to 20 ° C./min, more preferably 0.3 to 10 ° C./min or less, and particularly preferably 0.5 to 5 ° C./min or less.

   In the present invention, when a thermoplastic polyimide resin or the like is used as the polyimide layer and cured on an inorganic substrate, the resin material is melted at a temperature higher by 35 ° C. or more than the melting point or softening temperature It is preferable to cool to room temperature at a rate slower than 20 ° C./min. If the melting temperature does not fall within this range, uneven coating tends to occur. There is no particular upper limit for the melting temperature, but it is preferable not to exceed 300 ° C. or lower, or 200 ° C. higher than the melting point or softening temperature. When this temperature is exceeded, deterioration of the resin material becomes remarkable, and the mechanical strength of the finished product may be insufficient.

<Surface treatment>
It is important to surface-treat the said polyimide layer, a polyimide film, and / or an inorganic substrate. By applying the surface treatment, the surface of the polyimide layer, the polyimide film and / or the inorganic substrate is modified to a state in which a functional group is present (a so-called activated state), and adhesion between the polyimide layer and the inorganic substrate is improved.

  The surface treatment is a dry or wet surface treatment, and is not particularly limited. However, as the dry treatment, plasma treatment, corona treatment, active energy ray irradiation treatment such as ultraviolet light, electron beam, X-ray, frame treatment As a wet treatment, a coupling agent treatment and a treatment of bringing the film surface into contact with an acid or alkaline solution are preferable. Among these, plasma treatment and coupling agent treatment are particularly preferable. Plasma processing includes RF plasma processing in vacuum, microwave plasma processing, microwave ECR plasma processing, atmospheric pressure plasma processing, corona processing, etc., gas processing containing fluorine, ion implantation using an ion source, PBII Also includes legal processing, frame processing and nitro processing. Among these, RF plasma treatment in vacuum, milo wave plasma treatment and atmospheric pressure plasma treatment are particularly preferable. The coupling agent treatment includes silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents and the like. Among these, silane coupling agents are particularly preferable, and among them, silane coupling agents having an amine group or an epoxy group are most preferable.

<Plasma treatment>
Appropriate conditions for the plasma treatment include oxygen plasma, plasma containing fluorine such as CF ₄ and C ₂ F _6, plasma known to have a high etching effect, or physical energy such as AR plasma with polyimide. A treatment with a plasma having a high effect of applying to the layer surface and physically etching is desirable. Further, it is also preferable to add plasma such as CO ₂ , H ₂ , N _2, etc., and a mixed gas of these, and further, steam. 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 processing, microwave ECR plasma processing, plasma irradiation by an ion source that can easily implant ions of high energy, PBII method, etc. are also desirable.

  The effects of plasma treatment include the addition of the above-described surface functional group, the change in contact angle, the improvement in adhesion, the removal of surface contamination, etc., as well as the irregular shaped object during processing called desmear. There is a surface etching effect such as removal. In particular, since polymer and ceramic are completely different in etching ease, only a polymer having a lower binding energy than ceramic is selectively etched. For this reason, under the gas species and the discharge conditions having the etching action, only the polymer is selectively etched to expose the lubricant (also referred to as particles or a filler).

  In addition to the plasma treatment, as a means for obtaining the etching action on the surface of the polyimide layer, polishing with a pad including the case where a chemical solution is used together, brush polishing, polishing with a sponge soaked with a chemical solution, polishing particles in the polishing pad Examples thereof include polishing by sanding, sand blasting, wet blasting, etc., and these means may be employed together with plasma treatment.

  The plasma treatment may be performed only on one side of the polyimide layer or the polyimide film, or may be performed on both sides. When performing plasma treatment on one side, by placing the polyimide layer or polyimide film in contact with the electrode on one side in the plasma treatment with parallel plate electrodes, only on the side that is not in contact with the electrode of the polyimide layer or polyimide film Plasma treatment can be performed. If a polyimide layer or a polyimide 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 is attained by performing plasma processing in the state which stuck the protective film on the single side | surface of the polyimide layer or the polyimide film. As the protective film, not only a PET film or an olefin film with a pressure-sensitive adhesive but also a highly heat-resistant PI substrate or a PEN substrate coated with a pressure-sensitive adhesive can be used.

  The step of applying the plasma treatment to the polyimide layer or the polyimide film (raw material) is preferably performed by a roll to roll process from the viewpoint of processing efficiency. When a polyimide film is used as the polyimide layer, since the lubricant is also present on the plasma-treated polyimide film roll, the handling property of the roll is equivalent to that before the plasma treatment.

The surface morphology of the polyimide layer or a polyimide film subjected to plasma treatment as described above, when observed with an AFM method described later one surface thereof, it is preferable that both surfaces of R _a is 0.1Nm～0.95Nm, 0.25 nm More preferably, it is -0.7 nm. As a result, the adhesiveness is improved, and a surface having a degree of smoothness more suitable for bonding / lamination without an adhesive to the inorganic substrate is provided. When _Ra is 0.1 nm or less, when producing a roll for handling a polyimide layer or a polyimide film in a roll to roll process, defects such as wrinkles and blocking are not likely to occur during roll winding. On the other hand, when _Ra is 0.95 nm or more, the bonding strength with the inorganic substrate may be insufficient, and bubbles are likely to be generated at the polyimide layer or polyimide film-inorganic substrate interface on the bonding surface.

It is also possible to inorganic substrate subjected to plasma treatment, R _a inorganic substrate-side surface of the flexible laminate after the plasma treatment (the opposite side of the junction surface of the polyimide layer or polyimide film) 0.05nm~0.7nm Preferably, the thickness is 0.05 nm to 0.5 nm, and more preferably 0.05 nm to 0.3 nm. It is particularly preferred in order to produce a precise electrical circuits and semiconductor devices R _a inorganic substrate-side surface of the flexible laminate is 0.05Nm～0.7Nm, for example, when R _a is more than 0.7nm is It will not have the necessary smoothness, and may adversely affect the metal foil film or device formed thereon in terms of adhesion and smoothness.

<Coupling agent treatment>
The coupling agent used for the coupling agent treatment is used as a compound which physically or chemically intervenes between the inorganic substrate and the polyimide layer and has an action of enhancing the adhesion between the two. The coupling agent is not particularly limited, but in particular, coupling agents having an amino group or an epoxy group are preferable. Preferred specific examples of the coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilanevinyltrichlorosilane, vinyl Trimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ether Titrilymethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxymethane Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane 3-Mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, tris- (3-trimethoxysilylpropyl) isocyanurate, chloromethylphenethyl trimethoxysilane, chloromethyltrimethoxysilane Examples thereof include silane, tris- (3-trimethoxysilylpropyl) isocyanurate, and oligomers thereof, and mixtures of oligomers and monomers.

  As the coupling agent used in the present invention, in addition to the above, for example, 1-mercapto-2-propanol, methyl 3-mercaptopropionate, 3-mercapto-2-butanol, butyl 3-mercaptopropionate, 3 -(Dimethoxymethylsilyl) -1-propanethiol, 4- (6-mercaptohexaroyl) benzyl alcohol, 11-amino-1-undecenthiol, 11-mercaptoundecylphosphonic acid, 11-mercaptoundecyltrifluoroacetic acid 2,2 '-(Ethylenedioxy) diethanethiol, 11-mercaptoundecyltri (ethylene glycol), (1-Mercaptoundec-11-yl) tetra (ethylene glycol), 1- (methylcarboxy) undec -11-yl) hexa (ethylene glycol), hydroxyundecyldi , Carboxyundecyl disulfide, hydroxyhexadodecyl disulfide, carboxyhexadecyl disulfide, tetrakis (2-ethylhexyloxy) titanium, titanium dioctyloxybis (octylene glycolate), zirconium tributoxy monoacetylacetonate, zirconium monobutoxy acetyl Acetonate bis (ethylacetoacetate), zirconium tributoxy monostearate, acetoalkoxyaluminum diisopropylate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate , Titanium ethyl acetoacetate, Titanium octylene glycolate Titanium lactate, titanium lactate ammonium salt, titanium triethanolaminate, tertiary amyl titanate, tetra-tert-butyl titanate, tetrastearyl titanate, titanium-1, 3-propanedioxybis (ethylacetoacetate), titanium isostearate, Titanium diethanol aminate, titanium aminoethyl aminoethanolate, normal propyl zirconate, normal butyl zirconate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium stearate, zirconium lactate ammonium salt, and their oligomers, and oligomers It is also possible to use a mixture of oligomer and monomer.

  Particularly preferred coupling agents 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, aminophenyltrimethoxysilane, Aminophenethyl trimethoxysilane, aminophenylaminomethylphenethyl trime Examples thereof include toxisilane, tris- (3-trimethoxysilylpropyl) isocyanurate, and oligomers thereof, and further, mixtures of oligomers and monomers. When the process requires particularly high heat resistance, it is desirable to connect an aromatic group between Si and an amino group.

  As a method of forming a coupling treatment layer by applying a coupling agent treatment, a method of directly or directly diluting the coupling agent with a solvent, applying and drying the inorganic substrate and / or polyimide layer, and heat treatment, the coupling agent itself Alternatively, a method of immersing the inorganic substrate and / or the polyimide layer in a solution diluted with a solvent or the like, followed by drying and heat treatment, a method of adding it at the time of forming the polyimide layer and treating the coupling agent simultaneously with the preparation of the polyimide layer, etc. it can. What is necessary is just to set suitably the application quantity (adhesion amount or content) of a coupling agent so that the film thickness of the coupling process layer formed may become the thickness mentioned later. The conditions for the heat treatment are preferably 50 to 250 ° C., more preferably 75 to 165 ° C., still more preferably 95 to 155 ° C., preferably 10 seconds to 5 hours, more preferably 30 seconds to 2 It may be heated for a while. If the heating temperature is too high or the time is too long, the coupling agent may be decomposed or inactivated. If the heating temperature is too low or the time is too short, the fixing may be insufficient. As the coating method in the liquid phase, spin coating method, curtain coating method, dip coating method, slit die coating method, gravure coating method, bar coating method using a solution obtained by diluting a silane coupling agent with a solvent such as alcohol. Common liquid application methods such as a comma coating method, an applicator method, a screen printing method, and a spray coating method can be exemplified. When the coating method in the liquid phase is used, it is preferable to quickly dry after coating and to perform heat treatment under the above heat treatment conditions. By the heat treatment, the coupling agent and the surface of the surface to be coated are bonded by a chemical reaction. In addition, when performing a coupling agent treatment, it is known that the pH during treatment greatly affects performance, and aggregation occurs depending on the pH, so adjust the pH appropriately to reduce aggregation as much as possible. Is desirable.

As a coating method of the silane coupling agent in the present invention, a coating method in a gas phase can be used in addition to the coating method in the liquid phase described above.
Application by the vapor phase method is by exposing the substrate to the vapor of the silane coupling agent, ie, the silane coupling agent in a substantially gaseous state. The vapor of the silane coupling agent can be obtained by heating the liquid state silane coupling agent to a temperature of 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 under which the silane coupling agent is heated may be under pressure, under normal pressure or under reduced pressure, but when promoting vaporization of the silane coupling agent, it is preferably under normal pressure or under reduced pressure. Since many silane coupling agents are flammable liquids, it is preferable to carry out the vaporization operation in an enclosed container, preferably after replacing the container with an inert gas.
The time for which the inorganic substrate is exposed 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 the exposure of the inorganic substrate to the silane coupling agent is controlled to an appropriate temperature between -50.degree. C. and 200.degree. C. depending on the type of silane coupling agent and the thickness of the silane coupling agent layer required. 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 this heating, hydroxyl groups on the surface of the inorganic substrate react 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 10 seconds or more and about 10 minutes or less. If the temperature is too high or the time is too long, deterioration of the coupling agent may occur. 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 hold the surface of the inorganic substrate coated with the silane coupling agent downward and expose it to the silane coupling agent vapor. In the liquid phase coating method, since the coated surface of the inorganic substrate necessarily faces upward during and before coating, the possibility that floating foreign matter and the like in the working environment may be deposited on the surface of the inorganic substrate can not be denied. However, in the vapor phase coating method, the inorganic substrate can be held downward. It is possible to significantly reduce the adhesion of foreign matter in the environment.
Note that cleaning the surface of the inorganic substrate prior to the silane coupling agent treatment with means such as short wavelength UV / ozone irradiation or cleaning with a liquid detergent is a meaningful and preferable operation.

<Pattern formation>
In the method for manufacturing a rigid composite laminate according to the first invention of the present application, after the surface treatment of the second joint surface, a part of the surface treatment layer of the second joint surface is inactivated and subjected to a predetermined pattern. Form Thereby, the part with strong peeling strength between a 2nd inorganic substrate and a flexible laminated body (2nd junction surface) and a weak part can be created intentionally. In addition, the surface treatment layer is inactivated by physically removing the surface treatment layer partially (so-called etching), physically masking the surface treatment layer microscopically, And chemically modifying.
As a means for selectively inactivating a part of the surface treatment layer to form a predetermined pattern, a portion corresponding to the predetermined pattern is temporarily covered or shielded with a mask, and then the entire surface is etched. Then, the mask may be removed, or if possible, etching or the like may be performed according to a predetermined pattern by a direct drawing method. As a mask, a material generally used as a resist, a photomask, a metal mask or the like may be appropriately selected and used according to an etching method.

  The pattern shape may be appropriately set according to the type of device to be stacked, and is not particularly limited. For example, as shown in FIG. 1, as shown in (1) of FIG. 1, the good adhesion portion 11 is arranged only on the outer peripheral portion of the rigid composite laminate, and the easily peelable portion is inside the rigid composite laminate. As shown in FIGS. 1 (2) and (3), there are a pattern in which the good adhesion portion 1 is linearly arranged inside as well as the outer peripheral portion of the laminate.

  As the inactivation treatment, it is preferable to perform at least one selected from the group consisting of blast treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, corona treatment, actinic radiation irradiation treatment, active gas treatment, and chemical treatment.

The blast treatment refers to a treatment in which particles having an average particle diameter of 0.1 to 1000 μm are sprayed on an object together with gas or liquid. In the present invention, it is preferable to use blasting using particles having a small average particle size within the possible range.
The vacuum plasma treatment refers to a process in which an object is exposed to plasma generated by a discharge in a decompressed gas, or a process in which ions generated by the discharge collide with the object. As the gas, neon, argon, nitrogen, oxygen, carbon fluoride, carbon dioxide, hydrogen or the like alone or a mixed gas can be used.
In the atmospheric pressure plasma treatment, an object is exposed in a plasma generated by a discharge generated in a gas generally placed under an atmospheric pressure, or a treatment in which ions generated by the discharge are made to collide with the object say. As the gas, a single or mixed gas of neon, argon, nitrogen, oxygen, carbon dioxide, hydrogen and the like can be used.

The corona treatment refers to a treatment in which an object is exposed to a corona discharge atmosphere generated in a gas that is generally in an atmospheric pressure atmosphere, or ions generated by the discharge collide with the object.
The actinic radiation irradiation treatment refers to treatment of irradiating radiation such as electron beam, alpha ray, X ray, beta ray, infrared ray, visible light, ultraviolet ray, laser light irradiation treatment and the like. In addition, when performing a laser beam irradiation process, it becomes easy to process especially by a direct drawing system. In this case, even a visible light laser has much higher energy than general visible light, so it can be treated as a kind of actinic radiation in the present invention.
The active gas treatment is a gas having an activity to cause chemical or physical change in the surface treatment layer, such as halogen gas, hydrogen halide gas, ozone, high concentration oxygen gas, ammonia, organic alkali, organic acid This refers to a process of exposing an object to a gas.
The chemical solution treatment is a liquid having an activity to cause chemical or physical change in the surface treatment layer, for example, a liquid such as an alkaline solution, an acid solution, a reducing agent solution, an oxidizing agent solution or a solution to a solution. The treatment to be exposed.

  In particular, from the viewpoint of productivity, a method combining actinic radiation and a mask, or a method combining atmospheric pressure plasma processing and a mask is preferably used as the inactivation processing. The actinic radiation treatment is preferably an ultraviolet irradiation treatment, that is, a UV irradiation treatment, from the viewpoints of economy and safety. In the case of UV irradiation treatment, the second inorganic substrate is surface-treated by selecting the second inorganic substrate having UV transparency, and then the surface opposite to the surface on which the treatment is performed. Therefore, UV irradiation can also be performed through direct drawing or a mask. From the above, in the present invention, it is preferable to perform inactivation treatment by UV irradiation, which will be described in detail below.

  The UV irradiation treatment in the present invention is a treatment in which the surface-treated polyimide layer and / or the second inorganic substrate are placed in a device that generates ultraviolet light (UV light) having a wavelength of 400 nm or less, and the UV irradiation is performed. The UV light wavelength is preferably 260 nm or less, more preferably 200 nm or less. When UV light of such a short wavelength is irradiated in the presence of oxygen, the energy of the UV light is added to the sample (surface treatment layer), and active oxygen and ozone in an excited state are generated in the vicinity of the sample. The inactivation treatment of the present invention can be performed more effectively. However, at a wavelength of 170 nm or less, since the absorption of UV light by oxygen is significant, it is necessary to consider that the UV light can reach the surface treatment layer. In irradiation under a perfect oxygen-free atmosphere, the effect of surface modification (inactivation) by active oxygen and ozone does not appear, so it is necessary to devise that UV light passes while active oxygen and ozone also reach . For example, by placing a UV light source in a nitrogen atmosphere and transmitting quartz glass and applying UV light, the distance from the quartz glass to the surface treatment layer is shortened to suppress absorption of UV light. In addition, the method of controlling the oxygen absorption of UV light by controlling the amount of oxygen instead of the normal atmosphere, UV light source, controlling the flow of gas between coupling treatment layers, etc. This is an effective method for controlling the amount of ozone generated.

The irradiation intensity of UV light is preferably 5 mW / cm ² or more when measured using an ultraviolet actinometer having a sensitivity peak in at least a wavelength range of 150 nm to 400 nm, and 200 mW / cm ² or less is used to prevent deterioration of the inorganic substrate. This is desirable. The irradiation time of the UV light is preferably 5 seconds to 30 minutes, more preferably 10 seconds to 20 minutes, and still more preferably 15 seconds to 15 minutes. In terms of integrated light quantity is preferably ^{25mJ / cm 2 ~360000mJ / cm 2} , more preferably ^{50mJ / cm 2 ~240000mJ / cm 2} , more preferably from ^{75mJ / cm 2 ~120000mJ / cm 2} .

  Pattern formation at the time of UV irradiation treatment is performed by intentionally forming a portion to be irradiated with light and a portion not to be irradiated. As a method of forming a pattern, a method of forming a part shielding and not shielding UV light or a method of scanning UV light may be mentioned. In order to clarify the end of the pattern, it is effective to block the UV light and cover the second inorganic substrate with a mask. It is also effective to scan by parallel rays of UV laser.

   There are no particular restrictions on the light source that can be used for UV irradiation treatment. , Ar laser, D2 lamp, etc. Among them, excimer lamps, low pressure mercury lamps, Xe excimer lasers, ArF excimer lasers, KrF excimer lasers and the like are preferable.

  The surface treatment layer that has been subjected to the inactivation treatment as described above has a good adhesion portion that has a strong peel strength between the second inorganic substrate and the flexible laminate depending on whether or not the surface treatment layer has been inactivated (etched). And the pattern which consists of an easily peelable part which is a part with weak peel strength of a 2nd inorganic substrate and a flexible laminated body is formed. For example, as illustrated in Examples 1 to 27 described later, when 3-aminopropyltrimethoxysilane is applied to glass or when UV irradiation is performed on a polyimide layer that has been subjected to plasma treatment, It becomes a well-bonded part with strong peel strength, and breaks the functional group such as amino group by UV irradiation, so that the peel strength is weakened and the UV-irradiated part becomes an easily peelable part. Especially in the case of 3-aminopropyltrimethoxysilane, as shown in measurement examples 1 to 6 described later, the atomic percent of nitrogen (N) element is lowered by UV irradiation, and subsequently carbon (C) is also reduced. It can be inferred from the fact that the amino group and propyl group are broken. On the other hand, when the surface treatment layer is formed on the second inorganic substrate with a coupling agent having no functional group such as N-propyltrimethoxysilane, on the other hand, the part that is not irradiated with UV becomes an easily peelable part. A good adhesion portion is formed by irradiating UV light and breaking the propyl group portion. As the second inorganic substrate, it is industrially advantageous to use glass as the substrate. In this case, it is more practical to lower the peel strength by UV irradiation. Depending on the strength, it may be considered to make the UV light irradiated part a good adhesive part.

<Pressurization and heat treatment>
In the manufacturing method of the rigid composite laminate of the first invention of the present application and the manufacturing method of the laminate of the second invention of the present application, after the surface treatment of the inorganic substrate and / or the polyimide layer and the polyimide film, the inorganic substrate and the polyimide The layer or the polyimide film is superposed and subjected to pressure and heat treatment. Thereby, an inorganic substrate and a polyimide layer or a polyimide film can be adhere | attached. In general, as a method of obtaining a laminate of an inorganic substrate and a polyimide layer or a polyimide film, a method in which a polyimide varnish (polyamic acid solution described above) is directly applied on an inorganic substrate and imidized to form a film, and a polyimide film A method of laminating on an inorganic substrate after the formation is possible.

  When pressurized and heated, the moisture content in the polyimide layer or in the polyimide film is preferably 0.1 to 1.7 wt%, more preferably 0.3 to 1.5 wt%, and still more preferably 0.7 wt% to 1.3 wt%. When the moisture content in the polyimide layer is less than 0.1 wt%, the adhesive force between the polyimide layer or polyimide film and the inorganic substrate is not sufficiently exhibited, and the function as a laminate is not achieved. If the moisture content in the polyimide layer is more than 1.7 wt%, the amount of volatilized water from the polyimide layer or the polyimide film increases during heating, so many bubbles are generated at the polyimide layer or the polyimide film-inorganic substrate interface. , Surface smoothness and flatness are lost. Since the smoothness and flatness greatly affect the quality during device fabrication, it is important to control the moisture content of the polyimide layer or polyimide film within the moisture content. For example, a polyimide layer comprising a combination of an aromatic tetracarboxylic acid having a pyromellitic acid residue and an aromatic diamine having a benzoxazole structure is stored for at most 6 hours in a general clean room environment (50% RH at 23 ° C.). Thus, it is possible to control the moisture content within the range. Not requiring treatment for special moisture content control before pressurization and heating is a great production advantage.

As a method of pressurization and heat treatment, for example, pressurization by pressing, laminating, roll laminating or the like is performed while applying temperature, or a method of applying temperature after pressurizing and pressing is considered. A method of applying pressure and heating in a flexible bag can also be applied. In view of productivity, a method using rolls (roll lamination or the like) is particularly preferable. The pressure during the pressurization and heat treatment is preferably 0.05 MPa to 5 MPa when performed using a roll, more preferably 0.1 MPa to 3 MPa, and preferably 0.5 MPa when performed using a press. MPa to 50 MPa, more preferably 1 MPa to 20 MPa. If the pressure is too high, the inorganic substrate may be damaged. If the pressure is too low, a non-adhering part may be produced, and adhesion may be insufficient. The temperature during the pressurization and heat treatment is 50 ° C to 400 ° C, more preferably 80 ° C to 300 ° C. If the temperature is too high, the polyimide layer may be damaged or the adhesive force may be weakened. If the temperature is too low, the adhesive force tends to be weakened.
The pressurization and heat treatment can be performed in the air, but it is preferably performed under vacuum in order to obtain a stable peel strength on the entire surface. At this time, the degree of vacuum by a normal oil rotary pump is sufficient, and about 10 Torr is sufficient. Further, in order to prevent foreign matter from entering the joint surface, it is preferable to perform the cleaning in a clean environment of US standard 1000 (Federal Standard 209D (1988)), preferably class 1000, more preferably class 100, and even more preferably class 10.
As an apparatus that can be used for pressurization and heat treatment, for example, “11FD” manufactured by Imoto Seisakusho can be used to perform pressing in a vacuum, and a roll-type film laminator or a vacuum in vacuum can be used. For example, “MVLP” manufactured by Meiki Seisakusho Co., Ltd. can be used for vacuum lamination such as a film laminator that applies pressure to the entire glass surface at once with a thin rubber film.

  The pressurization and heat treatment can be performed separately in the pressurization process and the heating process. In this case, first, the polyimide layer and the inorganic substrate are pressurized at a relatively low temperature (for example, a temperature of less than 150 ° C., more preferably 90 ° C. or less). 0.5 to 50 MPa to secure close contact between the two, and then high pressure (eg, 50 ° C. or more, preferably 60 to 250 ° C.) at low pressure (preferably 0.2 MPa or less, more preferably 0.1 MPa or less) or normal pressure More preferably, the chemical reaction at the adhesion interface is promoted by heating at 80 to 200 ° C., and the polyimide layer and the inorganic substrate can be bonded.

  The order of forming the bonding of the first inorganic substrate and the polyimide layer (bonding of the first bonding surface) and the bonding of the second inorganic substrate and the polyimide layer (bonding of the second bonding surface) is the first There is no problem even if the bonding surfaces are bonded first or the second bonding surface is bonded first, and it is also possible to simultaneously bond the first bonding surface and the second bonding surface. However, assuming that the flexible laminate is separated by cutting the easily peelable part of the second inorganic substrate and the polyimide layer, the area of the first bonding surface in the flexible laminate is larger than that of the second bonding surface. It is preferable that the size is smaller than the easily peelable portion, and therefore, it is better to apply the second bonding surface first and then apply the entire surface uniform pressure when bonding each bonding surface. This is more preferable because it becomes easier.

<Application>
In the manufacturing method of the rigid composite laminate of the first invention of the present application, as an application example, if necessary, a hole portion penetrating in the film thickness direction of the flexible laminate or the entire rigid composite laminate in the rigid composite laminate is provided. By providing, you may provide a non-polyimide layer part. The part is not particularly limited, but is preferably filled with a metal whose main component is Cu, Al, Ag, Au, or the like, or formed by a mechanical drill or laser drilling. What has a metal film formed by sputtering, electroless-plating seed layer formation, etc. is mentioned to the wall surface of the void | hole and the void | hole of these.

<Rigid composite laminates>
In the rigid composite laminate of the present invention, a flexible laminate comprising a first inorganic substrate and a polyimide layer bonded via a surface treatment layer is further bonded via a second inorganic substrate and a surface treatment layer. Composite laminate. The second inorganic substrate and the flexible laminate have a good adhesion portion and an easy peel portion having different peel strengths, and the good adhesion portion and the easy peel portion form a predetermined pattern. Is preferred. As a result, it becomes a rigid composite laminate that can be easily peeled off from the second inorganic substrate after the device is produced on the flexible laminate without peeling off even in a high-temperature process during device production. . Moreover, it is also one of the preferable methods to produce the rigid composite laminated board whose whole surface is a favorable adhesion part and to make whole surface easy-to-peel and peel in post-treatment. This method can also be used as a rigid composite laminate in which the second inorganic substrate flexible laminate is easily peeled off after the device is fabricated on the flexible laminate as described above. The rigid composite laminate of the present invention can be obtained by the production method of the rigid composite laminate of the present invention, and details of the inorganic substrate, polyimide layer, surface treatment, etc. are as described above.

In the rigid composite laminate of the first invention of the present application, when bubbles or foreign matters enter the joint surface and the smoothness and flatness are lost, the device fabrication surface (polyimide of the first inorganic substrate in the flexible laminate) The smoothness and flatness of the surface opposite to the surface facing the layer are lost. Therefore, the number of bubbles bonding surface is preferably 30 or / 100 cm ² or less, more preferably 15/100 cm ² or less, more preferably 5 or / 100 cm ² or less, 0/100 cm Most preferably, it is ² . In order to prevent air bubbles and foreign matters from entering the bonding surface, as described above, the moisture content of the film should be controlled before the pressurizing / heating treatment, the film production and packaging, and the inorganic substrate and polyimide layer should be It is preferable to perform the work at the time of joining in a clean environment. Preferable conditions for the moisture content of the film before pressurization and heat treatment are as described above. In addition, the environment for film production, packaging, and bonding is preferably a clean environment managed to class 1000 or less in accordance with the Federal Standard 209D (1988), and a clean environment managed to class 100 or less. The environment is more preferable, and a clean environment managed to be class 10 or lower is further preferable.

  The good adhesion portion in the present invention refers to a portion where the peel strength of the second inorganic substrate and the flexible laminate is strong by changing the surface property depending on the presence or absence of UV light irradiation. The easily peelable portion in the present invention refers to a portion where the peel strength of the second inorganic substrate and the flexible laminate is weak by changing the surface property depending on the presence or absence of UV light irradiation.

  In the present invention, the 180 ° peel strength between the second inorganic substrate and the flexible laminate may be appropriately set according to the type and process of the device laminated thereon, and is not particularly limited. The difference between the 180 ° peel strength of the easily peeled portion and the 180 ° peel strength of the well-bonded portion is preferably 0.1 N / cm or more, and more preferably 0.2 N / cm or more. In general terms, the 180 ° peel strength of the well-bonded portion is preferably 0.1 N / cm or more and 20 N / cm or less, more preferably 0.5 N / cm or more and 10 N / cm or less. The 180 ° peel strength of the easy peel portion is preferably 0.01 N / cm or more and less than 0.5 N / cm, more preferably 0.01 N / cm or more and 0.2 N / cm or less. Here, the lower limit of the 180 ° peel strength of the easily peelable portion is a value that takes into account the bending energy of the flexible laminate. The 180 ° peel strength in the present invention can be measured by the method described later in Examples. In addition, the heat-resistant peel strength, the acid-resistant peel strength, and the alkali-resistant peel strength described later in the examples are preferably 0.1 N / cm or more and 20 N / cm or less, respectively, but the figure of this requirement may change depending on the process. It can be. In particular, after producing a rigid composite laminate, an easily peelable part is formed entirely or partially by post-treatment, and peeling is performed, or when the flexible laminate is used without peeling from the second inorganic substrate. It is desirable that the entire surface is well bonded, and the 180 ° peel strength in that case is preferably 0.1 N / cm or more and 20 N / cm or less, and is 0.3 N / cm or more and 10 N / cm or less Is more preferable. In particular, when the adhesive force of the second bonding surface is reduced by laser treatment or the like, it is preferable to use a rigid composite laminate having the entire surface bonded well.

  In the present invention, the 180 ° peel strength between the first inorganic substrate and the polyimide layer may be appropriately set according to the type and process of the device stacked thereon, and is not particularly limited, but the entire surface is favorably It is preferable to adhere. In general, the 180 ° peel strength of a good adhesion portion is preferably 0.1 N / cm or more and 20 N / cm or less, more preferably 0.5 N / cm or more and 10 N / cm or less. Here, the lower limit of the 180 ° peel strength of the easily peelable portion is a value that takes into account the bending energy of the flexible laminate. The 180 ° peel strength in the present invention can be measured by the method described later in Examples. In addition, the heat-resistant peel strength, the acid-resistant peel strength, and the alkali-resistant peel strength described later in the examples are preferably 0.1 N / cm or more and 20 N / cm or less, respectively, but the figure of this requirement may change depending on the process. It can be. In particular, if it is considered that peeling is performed between the first inorganic substrate and the polyimide layer, a pattern is formed of a good adhesion portion and an easily peeling portion as in the second inorganic substrate-flexible laminate. It is desirable that the peel strength thereof is 180 N peel strength of 0.1 N / cm or more and 20 N / cm or less like the 180 ° peel between the second inorganic substrate-flexible laminate. Is preferably 0.5 N / cm or more and 10 N / cm or less, and the 180 ° peel strength of the easily peelable portion is preferably 0.01 N / cm or more and less than 0.5 N / cm, and more preferably 0.01 N / cm or more And 0.2 N / cm or less is more preferable.

  In the rigid composite laminate of the present invention, there is no adhesive layer or pressure-sensitive adhesive layer between the first inorganic substrate and the polyimide layer and between the second inorganic substrate and the flexible laminate. For example, in the case of the coupling agent treatment which is an example of the surface treatment, only a material containing 10 mass% or more of Si derived from the coupling agent treatment is contained. The surface treatment layer that is the intermediate layer between the first inorganic substrate and the polyimide layer, and the second inorganic substrate and the flexible laminate can be easily made into a very thin layer of 10 nm or less. Therefore, it is difficult to elute even in the wet process, and even if the elution occurs, the effect of staying in a very small amount can be obtained. For example, when the process includes a step of cleaning the composite laminate using an acid solution or an alkali solution before device fabrication, it is desirable that the peel strength does not change due to the treatment with acid or alkali. In particular, in the treatment with a coupling agent, there are usually many silicon oxide components, and not only heat resistance at about 500 ° C. for 4 hours, but also acid resistance and alkali resistance can be obtained. The plasma treatment is the same and does not dramatically deteriorate the heat resistance of the polyimide layer. For example, it can be obtained by combining an aromatic tetracarboxylic acid having a pyromellitic acid residue and an aromatic diamine having a benzoxazole structure. The resulting polyimide layer has a heat resistance of about 470 ° C. for 3 hours.

  When coupling agent treatment is used for surface treatment in the rigid composite laminate of the present invention, the thickness of the coupling agent treated layer is smaller than that of the inorganic substrate, polyimide layer or general adhesive or pressure-sensitive adhesive in the present invention. It is also extremely thin, a thickness that is negligible from the viewpoint of mechanical design, and in principle, a thickness of the order of a monolayer is sufficient as a minimum. In general, it is less than 400 nm (less than 0.4 μm), preferably 200 nm (0.2 μm or less), more preferably 100 nm or less (0.1 μm or less) for practical use, more preferably 50 nm or less, still more preferably 10 nm or less. However, if the thickness is less than 1 nm, the peel strength may be reduced, or a part not partially attached may be generated, so 1 nm or more is preferable. In addition, as an example of the measurement of the film thickness of a surface treatment layer, the film thickness of a coupling agent treatment layer can be calculated and calculated from the concentration of the coupling agent solution at the time of application, and the application amount.

(Device structure manufacturing method)
The manufacturing method of the device structure of the first invention of the present application uses the rigid composite laminate of the present invention having the flexible laminate and the second inorganic substrate, and the first inorganic in the flexible laminate as a base material. This is a method of manufacturing a structure in which a device is formed on a substrate surface. In the method for producing a device structure of the present invention, after forming a device on the first inorganic substrate in the flexible laminate of the present invention, a slit is made in the polyimide layer of the easily peelable portion of the rigid composite laminate. The flexible laminate is peeled from the second inorganic substrate.

  As a method of making a cut in the polyimide layer of the easy-to-peel portion of the above-mentioned rigid composite laminate, a method of cutting the polyimide layer with a blade, or a relative scanning of the laser and the rigid composite laminate is performed. There are a method of cutting, a method of cutting the polyimide layer by relatively scanning the waiter jet and the rigid composite laminate, and a method of cutting the polyimide layer while slightly cutting the inorganic substrate layer with a dicing apparatus for semiconductor chips. The method is not particularly limited.

  When making a cut in the polyimide layer of the easily peelable portion of the rigid composite laminate, it is sufficient that the position where the cut is made includes at least a part of the easily peelable portion, and basically it is cut according to the pattern. is there. However, if you try to cut at the boundary between the good adhesion part and the easy peeling part exactly according to the pattern, there is a possibility that only the good adhesion part may be cut due to an error. It is preferable at the point which raises property. In addition, in order to prevent unintentional peeling, there may be a production method of cutting into a slightly better bonding portion than the pattern. Furthermore, if the width of the good adhesion portion is set narrow, the polyimide layer remaining in the good adhesion portion at the time of peeling can be reduced, the use efficiency of the polyimide layer is improved, and the device area relative to the rigid composite laminate is improved. Increases productivity. Furthermore, an easy peeling portion is provided in a part of the outer peripheral portion of the flexible laminate, and the method of peeling off the outer peripheral portion without actually making a cut is also an extreme form of the present invention. It can be.

  The method of peeling the flexible laminate from the support is not particularly limited, but a method of twisting from the end with tweezers, an adhesive tape is attached to one side of the cut portion of the polyimide layer in the flexible laminate with the device. It is possible to employ a method in which the tape portion is later rolled up, a method in which one side of the cut portion of the polyimide layer in the flexible laminate with device is vacuum-sucked and then rolled out from that portion. In addition, if bending with small curvature occurs in the cut portion of the polyimide layer in the flexible laminate with device during peeling, stress may be applied to the device in that portion, which may destroy the device. It is desirable to peel off in a state of large curvature. 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.

  The device structure (flexible laminate with a device) of the first invention of the present application can have a reinforcing member fixed before the final product. In this case, the reinforcing member may be fixed after peeling from the second inorganic substrate, but after the reinforcing member is fixed, the flexible laminate is cut and peeled from the support, or the flexible laminate is cut. It is preferable to fix the reinforcing member to the cut portion after putting in and then peel off. In the case where the reinforcing member is fixed before peeling, by taking into consideration the elastic modulus and the film thickness of the flexible laminate and the reinforcing member, it is possible to make the device portion as unlikely to be stressed as possible.

  When the reinforcing member is fixed before peeling, a polymer film, ultrathin glass, SUS, or the like is preferably used as the reinforcing member. The polymer film has an advantage that the lightness of the device is maintained, and further includes transparency, various workability, and difficulty in cracking. Ultra-thin glass has the advantage that gas barrier properties, chemical stability and transparency can be obtained. SUS has the advantages of being able to shield electrically and being hard to break. In addition, since it is after passing through the process which already requires high temperature as a polymer film, there are few restrictions of heat resistance, and various polymer films can be selected. Fixation of these reinforcing members can be easily performed by adhesion or adhesion.

  As a method for obtaining a laminate having a difference in adhesive strength between F1 and F2 in the second invention of the present application, a method using a polyimide film having different surface irregularities on both sides can be exemplified. In general, a polyimide film is blended with an inorganic filler called a lubricant, which forms fine projections on the film surface and causes friction between the two by bringing a thin air layer between other objects in close proximity. While having the effect of reducing the coefficient, the adhesive force is also reduced. The adhesive force ratio in the present invention can be realized by providing a difference of 1.8 times or more, preferably 4 times or more, in the lubricant compounding ratio in the vicinity of the first surface and the second surface.

  As a method of obtaining a laminate having a difference in adhesive strength between F1 and F2 in the second invention of the present application, a method of giving a difference in the strength of the surface treatment on both sides of the polyimide film (represented for convenience) . For example, in plasma processing, a method of changing the input power during the front and back processing, a method of changing the processing time, a method of changing the distance from the plasma to the processing surface, a method of introducing different gases, and a different plasma processing are performed. A method etc. can be illustrated.

  As a method of obtaining a laminate having an adhesive force difference between F1 and F2 in the second invention of the present application, for example, another surface treatment, for example, ultraviolet irradiation of short wavelength is applied to any surface of the film surface treated on both surfaces by plasma treatment. By doing this, it is possible to give a difference in adhesion by making the surface treatment effect different. In the present invention, an ultraviolet lamp having a wavelength of 250 nm is used, and an ultraviolet irradiation treatment (UV ozone treatment) that can be used in combination with the effect of ozone exposure generated during irradiation can be preferably used. The amount of irradiation necessary to develop the difference in adhesive strength necessary in the present invention is 20 mW / cm 2 or more, preferably 50 mw / cm 2, more preferably 250 mW / cm 2 or more. Such second-stage surface treatment may be performed on only one side of the film, or the second-stage surface treatment having different strengths may be performed on both sides of the film.

As a method of obtaining a laminate having a difference in adhesive strength in the second invention of the present application, a method of changing the thickness or the amount of application of the coupling agent applied to both the first inorganic substrate and the second inorganic substrate can be exemplified. .

  In a second invention of the present application, as a method of obtaining a laminate having a difference in adhesive strength, either the first inorganic substrate after surface treatment with a coupling agent or the second inorganic substrate after surface treatment with a coupling agent Examples of methods for differentiating the surface treatment activity by performing other surface treatments, for example, ultraviolet irradiation treatment. As an effective example, the activity of the coupling agent can be changed by subjecting the treated surface of the inorganic substrate treated with the coupling agent to ultraviolet light treatment of short wavelength. The second stage surface treatment may be performed on only one side of the inorganic substrate, or both substrates may be subjected to the second stage surface treatment having different strengths.

  As a method of obtaining a laminate having a difference in adhesive force in the second invention of the present application, without simultaneously bonding the polyimide film, the first inorganic substrate, and the second inorganic substrate, sequentially under different methods and different conditions It is also possible to provide an adhesive force difference by performing a bonding process. As an application of such a method, for example, a method of laminating a first inorganic substrate and a polyimide film by pressing and then laminating with a second inorganic substrate and a roll laminator or vice versa is exemplified. Can do.

Device processing is performed on the first inorganic substrate or the second inorganic substrate using the laminate according to the second invention of the present application, and then the adhesion surface of the polyimide film and the inorganic substrate is weak (the adhesion is F2) The device can be manufactured by peeling the polyimide film and the inorganic substrate at the bonding surface).

   In the present invention, a method for forming a device on the surface of the first inorganic substrate in the flexible laminate as a substrate may be appropriately performed according to a conventionally known method. The device in the present invention is not particularly limited, and examples thereof include only electronic circuit wiring, electrical resistance, passive devices such as coils and capacitors, active devices including semiconductor elements, and electronic circuit systems combining them. is there. As a semiconductor element, a solar cell, a thin film transistor, a MEMS element, a sensor, a logic circuit, etc. are mentioned.

  For example, a film-like solar cell using the flexible laminate of the present invention has a laminate X including a photoelectric conversion layer made of a semiconductor formed on the substrate using the flexible laminate of the present invention as a substrate. This laminate X has a photoelectric conversion layer that converts sunlight energy into electrical energy as an essential component, and usually further includes an electrode layer for taking out the obtained electrical energy. Hereinafter, as a typical example of the laminate X formed to constitute a film-like solar cell, a laminate structure in which a photoelectric conversion layer is sandwiched between a pair of electrode layers will be described. However, a structure in which several photoelectric conversion layers are stacked can be said to be a solar cell of the present invention if it is fabricated by PVD (physical vapor deposition) or CVD (scientific vapor deposition). Of course, the laminated structure of the laminated body X is not limited to the embodiment described below, and the structure of the laminated body included in the solar cell of the prior art may be referred to as appropriate, and a protective layer and known auxiliary means may be added. It ’s good.

One electrode layer (hereinafter also referred to as a back electrode layer) of the pair of electrode layers is preferably formed on the surface of the first inorganic substrate in the flexible laminate of the base material. The back electrode layer is obtained by laminating a conductive inorganic material by a conventionally known method such as a CVD method or a sputtering method. As the conductive inorganic material, metal thin films such as Al, Au, Ag, Cu, Ni, stainless steel, etc., In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (In ₂ O ₃ with Sn added Conductive materials such as oxide semiconductors). Preferably, the back electrode layer is a metal thin film. The thickness of the back electrode layer is not particularly limited, and usually about 30 to 1000 nm. In addition, a film forming method such as Ag paste which does not use a vacuum may be adopted in part of electrode extraction.

A photoelectric conversion layer for converting sunlight energy into electric energy is a layer made of a semiconductor, and is a compound semiconductor thin film (a chalcopyrite structure semiconductor thin film) composed of a group I element, a group III element and a group VI element CuInSe ₂ (CIS) film, or a Cu (In, Ga) Se ₂ (CIGS) film (hereinafter both are collectively referred to as a CIS film) in which Ga is solid-solved therein, and a layer made of a silicon-based semiconductor. Examples of the silicon-based semiconductor include a thin film silicon layer, an amorphous silicon layer, and a polycrystalline silicon layer. The photoelectric conversion layer may be a laminate having a plurality of layers made of different semiconductors. Moreover, the photoelectric converting layer using a pigment | dye may be sufficient. Further, an organic thin film semiconductor made of an organic compound such as a conductive polymer or fullerene may be used.

  The thin film silicon layer is a silicon layer obtained by a plasma CVD method, a thermal CVD method, a sputtering method, a cluster ion beam method, an evaporation method or the like. The amorphous silicon layer is a layer consisting of silicon which is substantially non-crystalline. Substantially no crystallinity can be confirmed by irradiating X with no diffraction peak. Means for obtaining an amorphous silicon layer are known, and such means include, for example, plasma CVD method, thermal CVD method and the like. The polycrystalline silicon layer is a layer made of an aggregate of microcrystals made of silicon. It is distinguished from the above-mentioned amorphous silicon layer by giving a diffraction peak by X-ray irradiation. Means for obtaining a polycrystalline silicon layer are known, and such means include means for heat treating amorphous silicon. The photoelectric conversion layer is not limited to the silicon-based semiconductor layer, and may be, for example, a thick film semiconductor layer. The thick film semiconductor layer is a semiconductor layer formed of a paste of titanium oxide, zinc oxide, copper iodide or the like.

As a means for constituting the semiconductor material as the photoelectric conversion layer, a known method may be adopted as appropriate. For example, about 20 nm of a-Si (n layer) is formed by performing high frequency plasma discharge in a gas in which PH ₃ is added to SiH ₄ at a temperature of 200 to 500 ° C., followed by only SiH ₄ gas A 500 nm a-Si (i-layer) can be formed, followed by the addition of diborane (B ₂ H ₆ ) to SiH ₄ to form an approximately 10 nm p-Si (p-layer).

Among the pair of electrode layers sandwiching the photoelectric conversion layer, the electrode layer provided on the side opposite to the flexible laminate base (hereinafter also referred to as a current collection electrode layer) is formed of a conductive paste containing a conductive filler and a binder resin. An electrode layer may be used, or a transparent electrode layer may be used. As the transparent electrode layer, an oxide semiconductor material such as In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (in which Sn is added to In ₂ O ₃ ) can be preferably used. Thus, the preferred embodiments of the present invention are laminated in the order of transparent electrode / p-type a-Si / i-type a-Si / n-type a-Si / metal electrode / polyimide layer / first inorganic substrate Filmy solar cells are obtained. Alternatively, the p layer may be a-Si, and the n layer may be polycrystalline silicon, and a thin undoped a-Si layer may be inserted between the two. In particular, when the a-Si / polycrystalline silicon hybrid type is used, the sensitivity to the sunlight spectrum is improved. In manufacturing a solar cell, an antireflection layer, a surface protective layer, or the like may be added in addition to the above structure.

   The thin film transistor (TFT) refers to a semiconductor layer that constitutes a transistor, an insulating film that constitutes an element, an electrode, a protective insulating film, and the like, which are manufactured by depositing a thin film. It is usually distinguished from the use of silicon in silicon wafers as semiconductor layers. Usually, a thin film is produced by a method using a vacuum such as PVD such as vacuum evaporation, or CVD such as plasma CVD. For this reason, the thing which is not a single crystal like a silicon wafer is included. Even if SI is used, microcrystalline silicon TFT, high temperature polysilicon TFT, low temperature polysilicon TFT, and oxide semiconductor TFT, organic semiconductor TFT, etc. are included.

  The MEMS element means an element manufactured using MEMS technology, and includes an inkjet printer head, a probe for a scanning probe microscope, a contactor for an LSI prober, an optical spatial modulator for maskless exposure, an optical integrated element, an infrared ray Includes sensors, flow sensors, acceleration sensors, MEMS gyro sensors, RF MEMS switches, internal and external blood pressure sensors, and video projectors using grating light valves, digital micro mirror devices, etc.

  The sensors include strain gauges, load cells, semiconductor pressure sensors, optical sensors, photoelectric elements, photodiodes, magnetic sensors, contact temperature sensors, thermistor temperature sensors, resistance thermometer temperature sensors, thermocouple temperature sensors. Non-contact temperature sensor, radiation thermometer, microphone, ion concentration sensor, gas concentration sensor, displacement sensor, potentiometer, differential transformer displacement sensor, rotation angle sensor, linear encoder, tachometer generator, rotary encoder, optical position sensor (PSD Ultrasonic distance meter, capacitance displacement meter, laser doppler vibrometer, laser doppler flow meter, gyro sensor, acceleration sensor, seismic sensor, one-dimensional image / linear image sensor, two-dimensional image / CCD image sensor , CMOS image sensor, liquid / leakage sensor (leakage sensor), liquid detection sensor (level sensor), hardness sensor, electric field sensor, current sensor, voltage sensor, power sensor, infrared sensor, radiation sensor, humidity sensor, odor sensor, Includes a flow rate sensor, an inclination sensor, a vibration sensor, a time sensor, a compound sensor that combines these sensors, and a sensor that outputs another physical quantity or sensitivity value based on some calculation formula from the values detected by these sensors .

  The logic circuit includes logic circuits based on NAND, OR, and those synchronized by a clock.

Each embodiment of the manufacturing method of the rigid composite laminate of the first invention of the present application and the manufacturing method of the device structure of the present invention described in detail above will be described with reference to the drawings. It is street.
FIG. 2 is a schematic view showing an embodiment of a method for producing a rigid composite laminate according to the first invention of the present application, wherein (1) shows a second inorganic substrate 21 and (2) shows a second inorganic substrate. (3) shows the stage where UV light was irradiated after the UV light blocking mask 23 was installed, (4) shows the stage where the coupling agent 22 was applied and dried on 21. It shows a stage in which the UV light blocking mask 23 is removed after the light irradiation. Here, in the coupling process layer 2, the UV exposure part becomes the UV irradiation part 24, and the remaining part remains the coupling process layer 22. (5) shows a stage where the polyimide film 25 is attached. (6) shows the first inorganic substrate 26, and (7) shows the stage where the coupling treatment layer 27 is formed by applying and drying a coupling agent on the first inorganic substrate 26. (8) shows the stage where the coupling agent treatment layer 27 formed on the first inorganic substrate 26 is pasted on the opposite side of the second inorganic substrate side of the polyimide film 25, and (9) is on the UV irradiation unit 24 A stage in which the polyimide film 28 is cut and the flexible laminate 210 is peeled off from the glass substrate 21 is shown.

FIG. 3 is a schematic view showing an embodiment of a method for producing a device having a flexible laminate as a substrate using the rigid composite laminate of the first invention of the present application, and (1) is a second inorganic substrate 31 (2) shows the step of coating and drying the coupling agent on the second inorganic substrate 31 to form the coupling treated layer 32, and (3) shows the UV light after the UV light blocking mask 33 is installed. The irradiation stage is shown, and (4) shows the stage where the UV light blocking mask 33 is removed after the UV light irradiation. Here, in the coupling process layer 32, the UV exposure part becomes the UV irradiation part 34, and the remaining part remains the coupling process layer 32. (5) shows the stage where the polyimide film 35 is pasted. (6) shows the first inorganic substrate 36, and (7) shows the stage in which the coupling treatment layer 37 is formed by applying and drying the coupling agent on the first inorganic substrate 36. (8) The coupling agent treated layer of the first inorganic substrate is formed after the coupling agent treated layer 37 formed on the first inorganic substrate 36 is attached to the opposite side of the polyimide film 35 on the second inorganic substrate side. And (9) show a stage in which the polyimide film 38 on the UV irradiation section 34 is cut and the flexible laminate 311 with device is peeled off from the glass substrate 31.

  EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited by the following examples. 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-methyl-2-pyrrolidone or N, N-dimethylacetamide so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. using an Ubbelohde type viscosity tube. At this time, when the solvent used for preparing the polyamic acid solution is N, N-dimethylacetamide, the polymer is dissolved using N, N-dimethylacetamide; otherwise, N-methyl-2- The polymer was dissolved and measured using pyrrolidone.

<Thickness of polyimide layer>
The thickness of each of the polyimide layer and the polyimide film, and the layers (a layer and b layer) constituting the same was measured using a micrometer ("Miritron 1245D" manufactured by FINE LUG, Inc.).

<Thickness unevenness of polyimide layer>
The thickness unevenness of the polyimide layer and the polyimide film was obtained by randomly extracting 10 points from the film to be measured using a micrometer ("Miritron 1245D" manufactured by FINE LUG, Inc.) and measuring the film thickness. The maximum value of 10 values was set as “maximum film thickness”, the minimum value was set as “minimum film thickness”, and the average value was set as “average film thickness”.
Film thickness unevenness (%) = 100 × (maximum film thickness−minimum film thickness) / average film thickness

<Tensile modulus, tensile strength and tensile elongation at break of polyimide layer>
From the polyimide layer to be measured, strip test pieces each having a flow direction (MD direction) and a width direction (TD direction) of 100 mm × 10 mm are cut out, and a tensile tester ("Autograph (R)" manufactured by Shimadzu Corporation) The tensile elastic modulus, the tensile strength and the tensile elongation at break were measured in 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 using model name AG-5000A ′ ′).

<Average light transmittance of polyimide layer>
The light transmittance in a wavelength region of 380 nm to 700 nm is measured at a scanning speed of 100 nm / min using a spectrophotometer (“U-2001” manufactured by Hitachi, Ltd.), and the transmittance values every 10 nm are arithmetically averaged to obtain the average The value was converted to a thickness of 20 μm according to the Lambert-Beer law, and the obtained value was taken as the average light transmittance of the polyimide layer.

<Haze value of polyimide layer (HAZE)>
According to JIS K 7105 "Optical property test method of plastic" haze (cloudiness value), it measured using a haze meter ("NDH-300A type turbidity meter" by Nippon Denshoku Industries Co., Ltd. make).

<YI value of polyimide layer (yellowness index, yellow index)>
The tristimulus value XYZ value of the polyimide layer is measured according to ASTM D1925 using a color difference meter (“TC1500MC-88 type” manufactured by Tokyo Denshoku Kogyo Co., Ltd.) and a C light source, and the yellowness index (YI) Was calculated.
YI = 100 × (1.28X−1.06Z) ÷ Y

<Linear expansion coefficient (CTE) of polyimide layer>
For the flow direction (MD direction) and width direction (TD direction) of the polyimide layer to be measured, the expansion / contraction rate is measured under the following conditions, and the intervals of 15 ° C (30 ° C to 45 ° C, 45 ° C to 60 ° C, ... ), And the measurement was performed up to 210 ° C and the average value of all measurements was CTE _210. The measurement was performed up to 300 ° C and the average of all measurements was CTE _300. Calculated.
Device name: “TMA4000S” manufactured by MAC Science
Sample length: 20 mm
Sample width: 2 mm
Temperature rise start temperature; 25 ° C
Heating end temperature; 400 ° C
Heating rate: 5 ° C / min
Atmosphere; Argon initial load; 34.5g / mm ²

<Evaluation of polyimide film: slipperiness>
Two polyimide films are stacked on different surfaces (that is, the wound outer surface and the wound inner surface are not stacked on the same surface but in the case of being wound as a film roll), and the stacked polyimide films are sandwiched between the thumb and forefinger, When lightly rubbed, the case where the polyimide film and the polyimide film slip was evaluated as “◯”, and the case where it did not slip was evaluated as “x”. In addition, although it may not slip | slide by winding outer surfaces or winding inner surfaces, this is not considered as an evaluation item. Also, when evaluating the slipperiness, the protective film on one side of the polyimide film was removed.

<Evaluation of polyimide film: roll winding property>
When winding a long polyimide film on a roll (outer diameter of the mandrel: 15 cm) at a speed of 2 m / min, when 皺 can be taken up smoothly without wrinkles, "○", The case where wrinkles were partially generated was evaluated as "」 ", and the case where wrinkles were not generated or wound smoothly on rolls was evaluated as" × ".

<Evaluation of polyimide film: Degree of warpage>
&shy; A square of 100 mm × 100 mm was cut out from the obtained polyimide film and used as a film test piece. When cutting out a film test piece, each side of the square is aligned with the longitudinal direction and width direction of the film, and the center of the square is (a) center in the film width direction, and (b) 1 from the left end to the entire width. It cut out from three places so that it might be located in the point which corresponds to / 3, and the point which corresponds to 1/3 of the full width length from the right end (c). The above film test pieces (a) to (c) are each placed on a plane so as to be concave, and the distances from the plane of the four corners (h ₁ , h ₂ , h ₃ , h ₄ : unit mm) are measured. The average value was taken as the amount of warpage (mm). The amount of warpage is divided by the distance (70.71 mm) from each vertex of the test piece to the center and expressed in percentage (%) (100 × (warpage amount (mm)) / 70.71) as the degree of warpage (%) The curvature of the film test pieces (a) to (c) was averaged.

<Evaluation of polyimide film: degree of curl>
The film test pieces (a) to (c) similar to those used for the measurement of the degree of warpage of the polyimide film are subjected to a heat treatment for 30 minutes in a dry oven at 250 ° C. The curling degree (%) of the film after heat treatment was taken as the curling degree.

< _Ra value of polyimide film surface>
The measurement of the _Ra value (surface morphology) of the polyimide film surface was carried out using a scanning probe microscope with surface physical properties evaluation function ("SPA 300 / nanonavi" manufactured by SII Nano Technology Co., Ltd.). The measurement is performed in the DFM mode, the cantilever uses the "DF3" or "DF20" made by SII Nano Technology Co., Ltd., the scanner uses the "FS-20A" made by SII Nano Technology Co., Ltd., and the scanning range is The measuring resolution was 512 × 512 pixels. After performing secondary inclination correction with the software attached to the device for the measurement image, if noise associated with the measurement is included, use other flattening processing (for example, flat processing) as appropriate, and use the software attached to the device to set the _Ra value Was calculated. Measurement was performed on three arbitrary places to obtain an _Ra value, and the average value thereof was adopted.

<Thickness of coupling layer>
The thickness (nm) of the coupling treated layer (SC layer) is a spectral ellipsometer ("PH-5000 manufactured by Photal") by ellipsometry for the thickness of the coupling treated layer formed on the cleaned Si wafer. ) Using the following conditions. In addition, when glass was used as a support body, the sample obtained by coating-drying a coupling agent by the method similar to each Example and a comparative example on separately wash | cleaned Si wafer was used.
Reflection angle range; 45 ° to 80 °
Wavelength range; 250nm to 800nm
Wavelength resolution: 1.25nm
Spot diameter: 1mm
tanΨ; Measurement accuracy ± 0.01
cosΔ; Measurement accuracy ± 0.01
Measurement; Method Rotating Analyzer Method Deflector Angle; 45 °
Incident angle; 70 ° fixed analyzer; 0 to 360 ° in 11.25 ° steps
Wavelength: 250nm to 800nm
The film thickness was calculated by non-linear least squares fitting. At this time, the model is Air / thin film / Si model,
n = C ₃ / λ ₄ + C ₂ / λ ₂ + C ₁
k = C ₆ / λ ₄ + C ₅ / λ ₂ + C ₄
The wavelength dependence C _{1 to} C ₆ was determined by the following formula.

<Defect existence density of inorganic substrate>
First, an inspection area having a side of 5 cm was arbitrarily extracted from the surface of the inorganic substrate facing the polyimide layer, and a reference point from which coordinates were derived was marked. Next, using a differential interference microscope having an XY stage capable of observing the entire inspection area, the inspection area was observed at 200 times, the defect position was detected visually, and the position coordinates were recorded. When the number of defects visually recognized at this time exceeds 500, the inorganic substrate was determined to have a defect existing density of 1 μm or more and a height of 100 μm / 100 cm ² or more. For the inorganic substrate whose number of defects is 500 or less, the vicinity of the defect position coordinates recorded in the inspection area is observed again with a laser microscope ("VK-9700" manufactured by Keyence Corporation), and the plane direction of each defect The number of defects having a height of 1 μm or more was counted, and the number of defects obtained was multiplied by 4 to obtain the number of defects per 100 cm ² .

<Peeling strength>
Peeling strength (180 degree peeling strength) was measured under the following conditions according to the 180 degree peeling method described in JIS C6471. In the sample to be subjected to this measurement, the unadhered portion of the polyimide film is provided on one side by designing the size of the polyimide film to 110 mm × 2000 mm with respect to the support (glass) of 100 mm × 1000 mm. It is said to hold.
Device name: “Autograph AG-IS” manufactured by Shimadzu Corporation
Measurement temperature; Room temperature peeling speed: 50 mm / min
Atmosphere; Atmospheric measurement sample width; 10 mm

(1) Peel strength of UV unirradiated parts
For the measurement of the peel strength of the UV non-irradiated part, the part not subjected to UV irradiation was used, and the measurement was performed in each of the first inorganic substrate-polyimide layer and the second inorganic substrate-polyimide layer. The peel strength between the first inorganic substrate and the polyimide layer was almost the same as the peel strength between the second inorganic substrate and the polyimide layer where UV irradiation was not performed. .
(2) Peel strength of UV irradiated area
The peel strength of the UV irradiated part was measured on the second inorganic substrate and the polyimide layer in the UV irradiated part.
(3) Weak heat-resistant peel strength of UV unirradiated parts
Measurement of weak heat-resistant peel strength of UV unirradiated part was done by placing the laminate in a muffle furnace with a nitrogen atmosphere, heating it to 300 ° C at a heating rate of 10 ° C / min, and holding it at 300 ° C for 2 hours. Using a sample obtained by opening the door of the muffle furnace and leaving it to cool in the atmosphere, in each of the first inorganic substrate-polyimide layer and the second inorganic substrate-polyimide layer in a portion not subjected to UV irradiation went.
(4) Weak heat-resistant peel strength of UV irradiated area
The measurement of the weak heat-resistant peel strength of the UV-irradiated part was placed in a muffle furnace where the laminate was placed in a nitrogen atmosphere, heated to 300 ° C at a heating rate of 10 ° C / min, and held at 300 ° C for 2 hours. The sample obtained by opening the door of the muffle furnace and allowing it to cool in the atmosphere was used between the second inorganic substrate and the polyimide layer in the UV irradiated portion.
(5) Strong heat-resistant peel strength of UV unirradiated parts
To measure the heat-resistant peel strength of the UV unirradiated part, put the laminate in a muffle furnace with a nitrogen atmosphere, heat it to 450 ° C at a heating rate of 10 ° C / min, and hold it at 450 ° C for 2 hours. Using a sample obtained by opening the door of the muffle furnace and leaving it to cool in the atmosphere, in each of the first inorganic substrate-polyimide layer and the second inorganic substrate-polyimide layer in a portion not subjected to UV irradiation went.

(6) Strong heat-resistant peeling strength of UV irradiated part
The measurement of the strong heat-resistant peeling strength of the UV irradiation part puts the laminate in a muffle furnace with nitrogen atmosphere, heats this to 450 ° C at a heating rate of 10 ° C / min, and holds it at 450 ° C for 2 hours as it is Using the sample obtained by opening the door of the muffle furnace and allowing it to cool in the air, it was carried out between the second inorganic substrate-polyimide layer in the portion irradiated with UV.
(7) Acid resistant peel strength Measurement of acid resistant peel strength was carried out by immersing the laminate in an 18% by mass hydrochloric acid solution at room temperature (23 ° C.) for 30 minutes, washing three times with water and then air-drying the sample It was carried out only in the first inorganic substrate-polyimide layer and the second inorganic substrate-polyimide layer in the portions not used for UV irradiation.
(8) Alkali resistance peel strength The alkali resistance peel strength is measured by immersing the laminate in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) (room temperature (23 ° C.) for 30 minutes and then washing it three times with air. The sample obtained by performing the above-described procedure was used only in the first inorganic substrate-polyimide layer and the second inorganic substrate-polyimide layer in the portion not subjected to UV irradiation.
In any of the measurements, when peeling the flexible laminate from the rigid composite laminate, that is, when peeling at the second bonding surface, the first bonding surface did not peel.
(9) Film moisture content (mass method)
Each film is cut into squares about 150 mm on a side, left in a predetermined temperature and humidity environment for 24 hours, and then the film mass Mw is measured, and then dried by heating in a dry nitrogen substituted inert oven at 150 ° C. for 1 hour. After cooling to near room temperature, the film mass Md was measured within 3 minutes after being taken out from the oven, and the film moisture content was determined by the following formula.
Film moisture content [%] = 100 × (Mw−Md) / Md
The moisture content at 18 ° C. and 38% RH as the predetermined temperature and humidity is moisture content A, the moisture content B at 25 ° C. 50% RH is moisture content B, and the moisture content C at 28 ° C. 65% RH.
(10) Film moisture content (TGA method)
In particular, when the moisture content of the film was high or low, the moisture content of the film was determined by a method using TGA. This will be described in individual examples and comparative examples including a method for adjusting the moisture content.

<Degree of warpage of flexible laminate>
The rigid composite laminate was heated at 300 ° C. for 1 hour, and then cut along the periphery of the first inorganic substrate to peel the flexible laminate from the second inorganic substrate to obtain a test piece of 350 mm × 450 mm. The test pieces were each placed on a plane so as to be concave, and the distances from the plane of the four corners (h ₁ , h ₂ , h ₃ , h ₄ : unit mm) were measured, and the average value was used as the amount of warpage. (Mm). The amount of warping divided by the distance (285.0 mm) from each vertex of the test piece to the center and expressed as a percentage (%) (100 × (amount of warping (mm)) / 285.0) after peeling is a flexible laminate The degree of warpage (%) was used.

<Lubricant particle size>
The particle size of the lubricant (silica) used in each production example is in the form of a dispersion dispersed in a solvent (dimethylacetamide) using a laser scattering particle size distribution system “LB-500” manufactured by HORIBA, Ltd. The distribution was determined, and the calculated volume average particle size was taken as the particle size.

<Number of bubbles in rigid composite laminate>
After heating the rigid composite laminate at 300 ° C. for 1 hour, the polyimide layer-inorganic substrate interface of the rigid composite laminate was measured using Digital Microscope VHX-2000 manufactured by Keyence Corporation. In the measurement, when measuring the interface between the first inorganic substrate and the polyimide layer, the incident light is measured from the first inorganic substrate side, and when the interface between the second inorganic substrate and the polyimide layer is measured, the incident light is measured from the second inorganic substrate The incident was carried out from the inorganic substrate side. All measurements were performed at a magnification of 1000, and the error for each measurer was eliminated by using 1-click automatic measurement. The measurement uses an image connection function, and a range of 100 mm × 100 mm including the top of the second inorganic substrate in the 370 mm × 470 mm range where the polyimide layer exists on the opposite side from the second inorganic substrate side is From the inorganic substrate side, measure the range of 100 mm × 100 mm including the top of the first inorganic substrate, analyze the obtained image using attached software, and use automatic area measurement to measure the inorganic substrate and polyimide layer The total number of bubbles having a major axis of 0.5 mm or more existing at the interface was measured for each interface.

<Rigidity of Composite Laminates>
When the composite laminate of 370 mm in width and 470 mm in length is placed on a flat surface such as a desk and the tip 100 mm is placed out of the plane, the case where the deflection by its own weight is less than 3 mm is “○”. The case where the rigidity was 3 mm or more and less than 10 mm was evaluated as “△”, and the case where the rigidity was 10 mm or more was evaluated as “X”. Those having an evaluation of “◯” were judged to be composite laminates having rigid properties.

<Flexibility of Laminate>
Bending a composite laminate with a width of 350 mm and a length of 450 mm and bending it to a radius of curvature of less than 20 mm without causing cracks or cracks The case where it became 50 mm or more was evaluated as "x". What was evaluated as ○ was determined to be a composite laminate having flexibility.

<Surface composition ratio>
The surface composition ratio was measured by X-ray photoelectron spectroscopy (ESCA). The measurement was performed under the following conditions using ULVAC-PHI "ESCA 5801 MC". At the time of measurement, first, a total element scan was performed to confirm the presence or absence of other elements, and then a narrow scan of existing elements was performed to measure the abundance ratio. The sample to be subjected to the measurement is put into the measuring chamber after the preliminary evacuation is sufficiently performed, and the operation of scraping off the surface of the sample before the measurement by the ion irradiation or the like is not performed.
Excitation X-ray: Mg, K _α- ray photoelectron escape angle: 45 °
Analysis diameter: φ800μm
Pass energy: 29.35 eV (narrow scan), 187.75 eV (all element scan)
Steps: 0.125 eV (narrow scan), 1.6 eV (all element scan)
Analytical element: C, O, N, Si, Total element vacuum degree: 1 × 10 ^-8 Torr or less

<Adhesive force>
The adhesive strength (90-degree peel strength) between the film and glass was measured according to the 90-degree peel method described in JIS C6471 under the following apparatus and conditions.
Device name: “Autograph AG-IS” manufactured by Shimadzu Corporation
Measurement temperature; Room temperature peeling speed: 50 mm / min
Atmosphere; Atmospheric measurement sample width; 10 mm
The test piece is shown in FIG. It was produced by the structure and method shown in FIG.
First, as shown in FIG. 5 (A), 7 on a support plate, 1 first inorganic substrate, 2 polyimide film, 3 second inorganic substrate, 5 first dummy inorganic substrate, 6 second dummy inorganic substrate Arrange the substrates as shown in the figure,
Next, as shown in FIG. 5 (B), bonding is performed by a roll laminator,
Next, as shown in FIG. 5C, the dummy substrate is removed, and heat treatment is performed as needed.
Next, as shown in FIG. 5D, the polyimide film and the first inorganic substrate are peeled by 90 degrees, and the adhesive strength is measured.
Next, as shown in FIG. 5E, the polyimide film and the second inorganic substrate are peeled by 90 degrees to give adhesive strength.
In this example, the first inorganic substrate, the polyimide film, and the second inorganic substrate are simultaneously laminated by roll lamination, but the same film and glass are sequentially laminated in two steps with the arrangement of the films, Simultaneous or sequential lamination using a press, or roll laminator, press, or other lamination means can also be combined sequentially. The test piece was produced by the bonding method described in each Example and comparative example.

[Production Examples 1-2]
(Preparation of Polyamic Acid Solutions A1 and A2)
After nitrogen-substituting the inside of a reaction vessel equipped with a nitrogen introducing tube, a thermometer, and a stirring rod, 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole and 4416 parts by mass of N, N-dimethylacetamide Next, a dispersion formed by dispersing colloidal silica in dimethylacetamide as a lubricant together with 217 parts by mass of pyromellitic dianhydride (Snowtex (registered trademark) DMAC- manufactured by Nissan Chemical Industries, Ltd.) ST30 ") is added so that the amount of silica (lubricant) is as shown in Table 1 (mass% based on the total amount of polymer solids in the polyamic acid solution), and stirred for 24 hours at a reaction temperature of 25 ° C. Thus, viscous polyamic acid solutions A1 and A2 were obtained.

Production Examples 3 and 4
(Preparation of Polyamic Acid Solutions B1 to B2)
After displacing the inside of a reaction vessel equipped with a nitrogen introducing pipe, a thermometer and a stirring rod with nitrogen, 8000 parts by mass of N, 8000 parts by mass of 545 parts by mass of pyromellitic anhydride and 500 parts by mass of 4,4'-diaminodiphenyl ether Silica (sliding material) is a dispersion ("Snowtex® DMAC-ST30" manufactured by Nissan Chemical Industries, Ltd.) made by dissolving colloidal silica in dimethylacetamide as a lubricant by dissolving in N-dimethylacetamide and adding it. It added so that it might become the addition amount (mass% with respect to the polymer solid content total amount in a polyamic-acid solution) of 1, and stirred for 24 hours, keeping temperature at 20 degrees C or less, and polyamic-acid solutions B1-B2 were obtained.

(Production Examples 5-6)
(Preparation of polyamic acid solutions C1 to C2)
After nitrogen-substituting the inside of a reaction vessel equipped with a nitrogen introducing pipe, thermometer, and a stirring rod, 398 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride and 147 parts by mass of paraphenylene diamine Is dissolved in 4600 parts by mass of N, N-dimethylacetamide, and a dispersion obtained by dispersing colloidal silica as a lubricant in dimethylacetamide (Nissan Chemical Industry Co., Ltd. “Snowtex® DMAC-ST30”) Is added so that the silica is added in the amount described in Table 1 (% by mass relative to the total amount of polymer solids in the polyamic acid solution), and stirred for 24 hours at a reaction temperature of 25.degree. C. to obtain a brownish viscous polyamic acid solution C1. ~ C2 was obtained.

Production Example 7
(Preparation of Polyamic Acid Solution D1)
After nitrogen-substituting the inside of a reaction vessel equipped with a nitrogen introducing tube, thermometer, and a stirring rod, 176.5 parts by mass of 2,2'-bis (trifluoromethyl) benzidine (TFMB) as a diamine component and N, N-dimethylacetamide 1200 After charging and dissolving parts by weight and cooling the reaction vessel, 122.9 parts by mass of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (PMDA-H) as a tetracarboxylic acid component (diamine component 1 (Corresponding to 0.995 mol relative to mol) was added in portions as solids and stirred at room temperature for 18 hours. Next, a dispersion ("Snowtex® DMAC-ST30" manufactured by Nissan Chemical Industries, Ltd.) made by dispersing colloidal silica having a volume average particle diameter of 80 nm in N, N-dimethylacetamide as a lubricant is added as shown in Table 1 It added so that it might become (mass% with respect to the polymer solid total amount in a polyamic-acid solution), and it diluted with 500 mass parts of N, N- dimethylacetamide after that, and obtained polyamic-acid solution D1.

Production Example 8
(Preparation of Polyamic Acid Solution E1)
After nitrogen substitution in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, 143.1 parts by mass of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 1,4-bis (4) are used as diamine components. After charging and dissolving 47.8 parts by mass of -amino-2-trifluoromethylphenoxy) benzene (p-6FAPB) and 1200 parts by mass of N, N-dimethylacetamide, the reaction container is cooled to obtain a tetracarboxylic acid component 109.1 parts by mass of cyclobutanetetracarboxylic acid dianhydride (CBDA) (corresponding to 0.995 mol with respect to 1 mol of the diamine component) was added in solid while being divided and stirred at room temperature for 12 hours. Next, a dispersion ("Snowtex® DMAC-ST30" manufactured by Nissan Chemical Industries, Ltd.) made by dispersing colloidal silica having a volume average particle diameter of 80 nm in N, N-dimethylacetamide as a lubricant is added as shown in Table 1 The reaction solution was added so as to be (% by mass relative to the total amount of polymer solids in the polyamic acid solution), and the resulting reaction solution was diluted with 1000 parts by mass of N, N-dimethylacetamide to obtain a polyamic acid solution E1.

(Production Example 9)
(Preparation of polyamic acid solution E2)
After replacing the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, 2,2′-bis (trifluoromethyl) benzidine (TFMB) 122.7 parts by mass and 1,4-bis (4 -Amino-2-trifluoromethylphenoxy) benzene (p-6FAPB) 70.3 parts by mass and N, N-dimethylacetamide 1200 parts by weight were charged and dissolved, and then the reaction vessel was cooled while the tetracarboxylic acid component was used. 107.0 parts by mass of cyclobutanetetracarboxylic acid dianhydride (CBDA) (corresponding to 0.995 mol with respect to 1 mol of the diamine component) was added in solid while being divided and stirred at room temperature for 12 hours. Next, a dispersion (“Snowtex (registered trademark) DMAC-ST30” manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica having a volume average particle diameter of 80 nm is dispersed in N, N-dimethylacetamide as a lubricant is shown in Table 1. The resulting reaction solution was diluted with 1000 parts by mass of N, N-dimethylacetamide to obtain a polyamic acid solution E2.

<Film production example 1>
On the non-slip surface of a 1500 mm wide polyethylene terephthalate (PET) film (“A-4100” manufactured by Toyobo Co., Ltd.) as a film-forming support, the polyamide acid solution A1 shown in Table 2 ) Coat with a comma coater to a dry film thickness indicated as “thickness”, then use a die coater to coat the polyamic acid solution A2 with the dry film thickness indicated as “(a layer) thickness” in Table 2. In such a manner, the coating was applied over the polyamic acid solution A1 and dried at 110 ° C. for 20 minutes to obtain a multilayer polyamic acid film having a two-layer structure on the PET film of the film forming support.

Next, the obtained multilayer polyamide acid film having a two-layer structure was peeled from the PET film of the film-forming support to obtain a self-supporting polyamide acid film having a width of 1380 mm. This self-supporting polyamic acid film is passed through a pin tenter having three heat treatment zones, and heat treatment is performed at the first stage 150 ° C. × 4 min, the second stage 220 ° C. × 4 min, the third stage 475 ° C. × 8 min, and a slit of 1300 mm width As a result, a polyimide film 1 having a multilayer structure was obtained. After heat treatment, as a peelable non-polyimide protective film, a PET film (protective film A) provided with a slight adhesion layer on one side is laminated on the a layer side (polyamide acid solution A2 side in this example) and then wound. I took it. Table 2 shows the properties of the obtained polyimide film. The protective film A is attached for the purpose of preventing adhesion of foreign matter to the film surface, damage and the like, and when carrying by roll to roll at a relatively low temperature, or by hand when handling it. When performing, operation was performed in the state where protective film A was stuck. However, for example, when pressing or laminating under conditions exceeding 130 ° C., or when performing each treatment on the surface to which the protective film A is attached, each operation was performed after the protective film A was peeled off. .

<Film Preparation Example 2>
A polyimide film 2 was obtained in the same manner as in Film Preparation Example 1 except that the coating amounts of the polyamic acid solutions A1 and A2 were changed so as to obtain the dry film thickness shown in Table 2, respectively. The properties of the obtained polyimide film are shown in Table 2.

<Film Preparation Example 3>
The order of application of the polyamic acid solutions A1 and A2 is changed (that is, the b layer is formed with the polyamic acid solution A2 and the a layer is formed with the polyamic acid solution A1), and the application amounts of the polyamic acid solutions A1 and A2 are respectively A polyimide film 3 was obtained in the same manner as in Film Production Example 1 except that the film thickness was changed to the dry film thickness shown in Table 2. The properties of the obtained polyimide film are shown in Table 2.

<Film Preparation Example 4>
A polyimide film 4 was obtained in the same manner as in the film production example 1 except that the coating amounts of the polyamic acid solutions A1 and A2 were changed to the dry film thicknesses shown in Table 2, respectively. The properties of the obtained polyimide film are shown in Table 2.

<Film production example 5>
Film Preparation Example 1 and Example 2 except that the polyamic acid solution A2 was not applied (that is, no a layer was formed), and the application amount of the polyamic acid solution A1 was changed to the dry film thickness shown in Table 2. Similarly, a polyimide film 5 was obtained. The properties of the obtained polyimide film are shown in Table 2.

<Film Production Example 6>
Except that the polyamic acid solution A1 was changed to B1 and the polyamic acid solution A2 was changed to B2, and the application amounts of the polyamic acid solutions B1 and B2 were changed to the dry film thickness shown in Table 2 respectively In the same manner as in Film Production Example 1, a polyimide film 6 was obtained. The properties of the obtained polyimide film are shown in Table 2.

<Film Production Example 7>
The polyamic acid solution A1 was changed to C1, the polyamic acid solution A2 was changed to C2, and the coating amounts of the polyamic acid solutions C1 and C2 were changed to the dry film thicknesses shown in Table 2, respectively. In the same manner as in Film Production Example 1, a polyimide film 7 was obtained. The properties of the obtained polyimide film are shown in Table 2.

<Film Preparation Example 8>
The polyamic acid solution A1 is changed to C1, and the polyamic acid solution A2 is not applied (that is, the a layer is not formed), and the applied amount of the polyamic acid solution C1 is changed to the dry film thickness shown in Table 2. Except for the above, a polyimide film 8 was obtained in the same manner as in Film Production Example 1. The properties of the obtained polyimide film are shown in Table 2.

<Film Preparation Example 9>
Using the polyamic acid solution D1, polyimide films 9 to 11 were produced according to the following procedure. Table 2 shows the film thickness after imidization of each polyamic acid solution on the smooth surface (non-lubricant surface) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) having a width of 1050 mm using a slit die. The composition was coated to a thickness as shown and dried at 80 ° C. for 8 minutes, and then peeled off from the PET film of the film-forming support to obtain a self-supporting polyamic acid film having a width of 920 mm. The self-supporting polyamic acid film thus obtained was passed through a pin tenter having three heat treatment zones, and in an inert oven under an N2 gas atmosphere, the first stage 150 ° C. × 2 min, the second stage 220 ° C. × 2 min, the third stage 475 A heat treatment at 4 ° C. for 4 minutes was imidized to obtain a long polyimide film (1000 m roll) having a width of 840 mm.
After heat treatment, as a non-polyimide protective film that can be peeled off, a PET film (protective film A) provided with a slightly adhesive layer on one side is laminated on the a layer side (polyamic acid solution D side or E1, E2 in this example). Then I took it up. The properties of the obtained polyimide film are shown in Table 2. The protective film A is attached for the purpose of preventing adhesion of foreign matter to the film surface, damage and the like, and when carrying by roll to roll at a relatively low temperature, or by hand when handling it. When performing, operation was performed in the state which the protective film A stuck. However, for example, when pressing or laminating under conditions exceeding 130 ° C., or when performing each treatment on the surface to which the protective film A is adhered, each operation was performed after the protective film A was peeled off. .

<Film Preparation Examples 10 to 12>
A film was prepared in the same manner as in Film Preparation Example 9 except that the polyamic acid solution D was changed to E1 and E2 and the coating amounts of the polyamic acid solutions E1 and E2 were changed to the dry film thickness shown in Table 2 respectively. , And polyimide films 10 to 12 were obtained. The properties of the obtained polyimide film are shown in Table 2.

<Film Preparation Examples 13 to 15>
A commercially available Toray DuPont "Kapton (registered trademark) 100H" is a film 13, a commercially available Ube Industries "UPILEX (registered trademark) 25S" is a film 14, and a commercially available Arakawa Chemical Industries "Pomilan T25" is a film 15. .

<Film processing example 1>
With respect to the films 1 to 15, both surfaces of each polyimide film were subjected to vacuum plasma treatment. As the vacuum plasma process, an RIE mode using parallel plate type electrodes and a process by RF plasma are adopted, N ₂ gas and O ₂ gas are introduced into the vacuum chamber at a flow ratio of 5: 95, 13.56 MHz The high frequency power was introduced, and the processing time was 3 min. Although the characteristic of each obtained polyimide film after the process was evaluated, there was no item which changed greatly with any film before processing.

<Film processing example 2>
Film 1 was subjected to atmospheric pressure plasma treatment on both sides of the polyimide film. Atmospheric pressure plasma processing is performed using an atmospheric pressure plasma processing apparatus having a direct type, a slit-like, and a long type head moving automatically on the workpiece, and a flow ratio of nitrogen / oxygen = 95/5 (usually (Pressure-volume ratio) gas mixture was used as the processing gas, and the discharge output was 2 kW. The time during which the glass plate was exposed to the plasma was approximately 60 seconds. Although the characteristic of each obtained polyimide film after the process was evaluated, there was no item which changed greatly with any film before processing.

<Film processing example 3>
The film 1 was subjected to vacuum plasma treatment on both sides of each polyimide film. As the vacuum plasma treatment, RIE mode using parallel plate type electrodes and RF plasma treatment are adopted, N ₂ gas and O ₂ gas are introduced into the vacuum chamber at a flow ratio of 5:95, and 13.56 MHz The high frequency power was introduced, and the processing time was 15 seconds. Although the characteristic of each obtained polyimide film after the process was evaluated, there was no item which changed greatly with any film before processing.

<Examples 1 to 16>
The silane coupling agent 3-aminopropyltrimethoxysilane is diluted to 0.5% by mass with isopropyl alcohol while flowing N ₂ gas in a nitrogen-substituted glove box, and then separately washed and dried as a first inorganic substrate. Place the glass ("Spool" manufactured by Asahi Glass Co., Ltd .; 350mm x 450mm x 0.1mm thick) on the spin coater, drop the silane coupling agent on the center of rotation and rotate at 500rpm, then at 1500rpm Then, the entire surface of the inorganic substrate was applied by being rotated to be wet, and then dried. This was heated for 1 minute on a hot plate heated to 110 ° C. placed in a clean bench, and the first inorganic substrate treated with the coupling agent was provided with a coupling treated layer having a thickness shown in Table 3 Obtained.

  Next, a glass (Corning's “Corning EAGLE XG”; 370 mm × 470 mm × 0.7 mm thickness) which has been separately washed and dried as a second inorganic substrate is placed in a spin coater, and the first inorganic substrate is obtained. By applying a coupling agent in the same procedure as in the case, a coupling agent-treated second inorganic substrate having a coupling agent-treated layer having a thickness shown in Table 3 was obtained.

Next, the polyimide film cut out to 360 mm × 460 mm was placed as a mask on the coupling treatment layer surface of the first inorganic substrate and the second inorganic substrate provided with the coupling agent treatment layer obtained above, and the first The UV irradiation treatment was performed within the range of 360 mm × 460 mm, leaving 5 mm around each of the inorganic substrate and the second inorganic substrate. For UV irradiation, a UV / O ₃ cleaning and reforming device (“SKT2005Y-02”) and a UV lamp (“SE-2003W03”) manufactured by Run Technical Service Co., Ltd. were used, and about 1 cm away from the UV lamp. 2 min from the distance. At the time of irradiation, no special gas was put in the UV / O ₃ cleaning and reforming apparatus, and UV irradiation was performed in an air atmosphere and at room temperature. The UV lamp emits an emission line with a wavelength of 185 nm (short wavelength that can generate O ₃ that promotes deactivation) and a wavelength of 254 nm. At this time, the illuminance is about 46 mW / cm ² (illuminance meter (“SEC SM Measured at a wavelength of 254 nm).

Next, the treated polyimide films obtained in Film Processing Examples 1 to 16 were cut into a width of 370 mm and a length of 470 mm, and separately washed and dried. The coupling agent-treated / UV-irradiated surface of the first inorganic substrate after UV irradiation treatment faces the surface-treated surface of the polyimide film, and each side of the glass is 10 mm inside from each side of the film After pressure is applied by roll lamination with a roll pressure (linear pressure) of 20 N / cm (for a pressure effective width of 5 mm, an estimated effective pressure of about 0.4 MPa) at room temperature, normal pressure in a dry oven at 100 ° C. The flexible laminate was obtained by heating at 30 min.
Film No. 1.2.3.4.6.7. Produced using different polyamic acid solutions on the front and back. In the case of using, the a layer side in the film preparation example was combined so as to be the first inorganic substrate side.
Moreover, the polyimide film after film processing is stored at least at room temperature in the range of 18 ° C. to 27 ° C. and humidity in the range of 38 to 72% for 24 hours or more, and the moisture content at that time is 0.45% to 1.48. %.

  Next, the coupling agent treatment / UV irradiation treatment surface of the second inorganic substrate and the polyimide film surface of the flexible laminate are opposed to each other so that the polyimide film and the second inorganic substrate are not displaced, After pressurizing with roll lamination at a roll pressure (linear pressure) of 20 N / cm at room temperature (effective effective pressure of 5 mm and an estimated effective pressure of about 0.4 MPa), heat at 100 ° C in a dry oven for 30 min at normal pressure. As a result, a rigid composite laminate was obtained. Table 3 shows the evaluation results of the obtained rigid composite laminate.

Example 17
When laminating the second inorganic substrate and the polyimide layer, instead of using a polyimide film with vacuum plasma treatment on both sides, a coating film layer of the polyamic acid solution A2 is formed on the second inorganic substrate under the following conditions The rigid composite laminate of the present invention is obtained in the same manner as in Example 1 except that the polyimide layer is heated and cured, and the polyimide layer is further subjected to vacuum plasma treatment and then laminated with the first inorganic substrate. The When laminating the polyimide layer, the polyamic acid solution A2 was coated with a bar coater to a final film thickness of 4 μm, then dried at 220 ° C. for 10 min using an explosion-proof dryer, and then a muffle with nitrogen substitution Heat treatment was performed at 450 ° C. for 10 minutes in a furnace to form a polyimide layer on the second inorganic substrate. Table 3 shows the evaluation results of the obtained rigid composite laminate.

Example 18
A rigid composite laminate of the present invention was obtained in the same manner as in Example 10, except that the polyimide film 10 of the film treatment example 10 was replaced with the polyimide film 10 that was not subjected to the surface treatment. Table 3 shows the evaluation results of the obtained rigid composite laminate.

<Example 19>
A rigid composite according to the present invention is prepared in the same manner as in Example 1, except that the moisture content of the polyimide layer in the flexible laminate is adjusted to 1.53% and then the flexible laminate and the second inorganic substrate are joined. A laminate was obtained. Table 3 shows the evaluation results of the obtained rigid composite laminate. The moisture content was adjusted by leaving it to stand for 12 hours in water and then heating and drying in air at 150 ° C. for 1.5 minutes. The moisture content of the polyimide layer was measured by TGA measurement and calculated based on the weight loss at 150 ° C. for 10 minutes. It was separately confirmed by GC-MS analysis that the contribution other than moisture in the calculated weight loss was 1% or less.

<Example 20>
A rigid composite according to the present invention is prepared in the same manner as in Example 1, except that the moisture content of the polyimide layer in the flexible laminate is adjusted to 0.15% and then the flexible laminate and the second inorganic substrate are joined. A laminate was obtained. Table 3 shows the evaluation results of the obtained rigid composite laminate. Preparation of the moisture content was achieved by leaving in an atmosphere of 25 ° C. and 50% RH for 2 days and then drying by heating in an atmosphere of 150 ° C. for 4 minutes. The moisture content of the polyimide layer was confirmed in the same manner as in Example 20.

Example 21
A rigid composite laminate of the present invention was obtained in the same manner as in Example 1 except that a silicon wafer (Si wafer) having a thickness of 0.725 μm was used as the first inorganic substrate. Table 3 shows the evaluation results of the obtained rigid composite laminate. The same procedure as in Example 23 was repeated except that a Si wafer was used instead of glass as the first inorganic substrate, but a rigid composite laminate was obtained. The evaluation results of the plates were almost the same as when the glass was the first inorganic substrate.

<Example 22>
Instead of UV irradiation treatment to the second inorganic substrate, a polyimide film cut out to 360 mm × 460 mm is placed as a mask, leaving 5 mm each around the surface of the polyimide film facing the second inorganic substrate. A rigid composite laminate of the present invention was obtained in the same manner as in Example 1 except that the UV irradiation treatment was carried out within the range of 360 mm × 460 mm. Table 3 shows the evaluation results of the obtained rigid composite laminate. The UV irradiation treatment was performed under exactly the same conditions as the irradiation treatment for the second inorganic substrate except that the irradiation time was 4 min.
A rigid composite laminate was obtained in the same manner as in Example 22 except that the UV irradiation treatment to the polyimide layer was used instead of the UV irradiation treatment to the second inorganic substrate. However, the evaluation results of the obtained rigid composite laminate were all substantially the same as when the UV irradiation treatment was performed on the second inorganic substrate.

<Example 23>
In addition to UV irradiation treatment to the second inorganic substrate, a polyimide film cut out to 360 mm x 460 mm is placed as a mask, leaving 5 mm each around the surface of the polyimide film facing the second inorganic substrate. A rigid composite laminate of the present invention was obtained in the same manner as in Example 1 except that the UV irradiation treatment was performed within the range of 360 mm × 460 mm. Table 3 shows the evaluation results of the obtained rigid composite laminate. The UV irradiation treatment was performed under exactly the same conditions as the irradiation treatment for the second inorganic substrate except that the irradiation time was 4 min.
For each of the examples other than Example 23, a rigid composite laminate was obtained in the same manner except that the UV irradiation treatment was performed on the polyimide layer in addition to the UV irradiation treatment on the second inorganic substrate. The evaluation results of the obtained rigid composite laminate were almost the same as when the UV irradiation treatment was performed only on the second inorganic substrate, respectively, except that the peel strength of the UV irradiation portion was further weakened. It was.

<Example 24>
Instead of joining the first inorganic substrate and the polyimide layer by pressing and heating and then joining the second inorganic substrate and the polyimide layer by pressing and heating, the second inorganic substrate and the polyimide layer are joined by pressing and heating. A rigid composite laminate of the present invention was obtained in the same manner as in Example 1 except that the first inorganic substrate and the polyimide layer were bonded by pressing and heating after bonding. Table 3 shows the evaluation results of the obtained rigid composite laminate. For each of the examples other than Example 26, a rigid composite laminate was obtained by bonding the first inorganic substrate and the polyimide layer after bonding the second inorganic substrate and the polyimide layer. The evaluation results of the composite laminate were almost the same as those obtained when the second inorganic substrate and the polyimide layer were bonded after the first inorganic substrate and the polyimide layer were bonded.

<Example 25>
Instead of joining the first inorganic substrate and the polyimide layer by pressure and heating and then joining the second inorganic substrate and the polyimide layer by pressure and heating, the first inorganic substrate, the polyimide layer, the polyimide layer, and the second A rigid composite laminate of the present invention was obtained in the same manner as in Example 1 except that bonding of the inorganic substrate by pressing and heating was simultaneously performed. Table 3 shows the evaluation results of the obtained rigid composite laminate. For each of the examples other than Example 25, the first inorganic substrate and the polyimide layer and the polyimide layer and the second inorganic substrate were simultaneously bonded to obtain a rigid composite laminate, but the obtained rigid composite laminate was obtained. The evaluation results of the plates were almost the same as when the first inorganic substrate and the polyimide layer were joined and then the second inorganic substrate and the polyimide layer were joined.

Example 26
Pressurization and heat treatment when laminating the first inorganic substrate and the second inorganic substrate-polyimide film laminate to form a rigid laminate, reduced pressure of about 10 ⁴ Pa at 300 ° C and 8 MPa pressure A rigid composite laminate of the present invention was obtained in the same manner as in Example 1 except that the pressing was performed for 20 minutes below. Table 3 shows the evaluation results of the obtained rigid composite laminate. In each of the examples other than this Example 26, a rigid composite laminate was obtained using a press instead of a roll laminate, but the evaluation results of the obtained rigid composite laminate were all using a roll laminate. It was almost the same as when the polyimide layer was bonded.

<Example 27>
The procedure of Example 1 is repeated except that the polyimide film 1 of the film processing example 3 is used instead of the polyimide film of the film processing example 1 and that the second inorganic substrate is not subjected to the UV treatment. The inventive rigid composite laminate was obtained. Table 3 shows the evaluation results of the obtained rigid composite laminate.

Example 28
Using the rigid composite laminate obtained in Example 1, a thin film transistor array fabrication using low temperature polysilicon on the first inorganic substrate of the laminate was simulated. Using a predetermined test pattern, a silicon oxide layer formed by a reactive sputtering method as a planarizing and gas barrier layer, a tantalum layer formed by a sputtering method as a source and drain electrode layer, a barrier metal layer, and a CVD as a semiconductor layer Amorphous silicon layers formed by the above method were stacked. Next, the silicon layer was micropolycrystallized by annealing at 400 ° C. for 75 minutes, and then an SiN layer as a gate insulating layer and aluminum as a gate electrode layer were stacked. Each layer was patterned by masking or photolithography according to a predetermined test pattern to form a simulated device: a thin film transistor array. The device part was formed in the UV irradiation part (opening part of the mask) at the time of inactivation processing. During the above process, the laminate was exposed to a resist solution, a developing solution, an etching solution, and a stripping solution used in a photolithographic method under a vacuum atmosphere and at a high temperature, but peeling or the like did not occur between the layers of the rigid composite laminate. , Process suitability was good.

Comparative Example 1
A comparative composite laminate was obtained in the same manner as in Example 1 except that neither the vacuum plasma treatment on the polyimide layer nor the coupling agent treatment on the second inorganic substrate was performed. Table 4 shows the evaluation results of the obtained composite laminate. Further, the adhesive force between the polyimide layer and the second inorganic substrate was weak, and even if a slight force was applied between the layers, it was easily peeled off.

Comparative Example 2
A composite laminate for comparison was obtained in the same manner as in Example 1, except that thick glass ("Corning EAGLE XG" manufactured by Corning; 350 mm x 450 mm x 0.7 mm thickness) was used as the first inorganic substrate. Table 4 shows the evaluation results of the obtained composite laminate. The flexible laminate portion was peeled off from the obtained composite laminate, and a force was applied to bend the obtained flexible laminate to a curvature radius of 50 mm. As a result, the first inorganic substrate was cracked at a curvature radius of 12 mm. Therefore, it was found that the laminate was not flexible.

<Comparative Example 3>
A comparative composite laminate was obtained in the same manner as in Example 1 except that “Spool” (370 mm × 470 mm × 0.1 mm thickness) manufactured by Asahi Glass Co., Ltd. was used as the second inorganic substrate. Table 4 shows the evaluation results of the obtained composite laminate. The obtained laminated board had very low rigidity, and when the both ends of the 50 mm portion from the apex in the long side direction were supported with both hands, the first inorganic substrate was cracked by its own weight.

Comparative Example 4
A composite laminate plate for comparison in the same manner as in Example 1 except that the flexible laminate and the second inorganic substrate were joined after adjusting the moisture content of the polyimide layer in the flexible laminate to 0.04%. I got Table 4 shows the evaluation results of the obtained composite laminate. Preparation of the moisture content was achieved by leaving in an atmosphere of 25 ° C. RH 50% for 2 days and then drying by heating for 5 minutes in the atmosphere at 150 ° C. The moisture content of the polyimide layer was confirmed in the same manner as in Example 20. The composite laminate of this comparative example had weak adhesion between the polyimide layer and the second inorganic substrate, and was easily peeled off even if a slight force was applied between the layers.

<Comparative Example 5>
Except that the moisture content of the polyimide layer in the flexible laminate was adjusted to 2.12% and then the flexible laminate and the second inorganic substrate were joined, in the same manner as in Example 1, the composite laminate of the present invention I got a plate. Table 4 shows the evaluation results of the obtained composite laminate. The moisture content was adjusted by leaving it in water for 12 hours. The moisture content of the polyimide layer was confirmed in the same manner as in Example 20. In the composite laminate of this comparative example, a large number of bubbles are observed at the first inorganic substrate-polyimide layer interface and the second inorganic substrate-polyimide layer interface, and it cannot be said that the entire surface is adhered. It was.

<Comparative Example 6>
When bonding between the second inorganic substrate and the flexible laminate, instead of performing surface treatment on glass and surface treatment on the polyimide layer, Nitto Denko's heat-resistant double-sided adhesion between the second inorganic substrate and flexible laminate A composite laminate for comparison was obtained in the same manner as in Example 1 except that the tape "No. 5919ML" was used for bonding. Table 4 shows the evaluation results of the obtained composite laminate. What is described as “cut” in the peel strength results in the table refers to a phenomenon in which the adhesive force between the inorganic substrate and the polyimide layer is too strong and the film is cut during measurement. With respect to this laminate, although a cut was made in a polyimide film and it was tried to peel the film from the support, it could not be peeled well, and if it was tried to force it off, the film was torn. In addition, many bubbles were generated at the interface of the second inorganic substrate-polyimide layer, and it was not possible to say that the entire surface was adhered.

Comparative Example 7
When bonding between the second inorganic substrate and the flexible laminate, instead of performing surface treatment on glass and surface treatment on the polyimide layer, a thermoplastic polyimide film is used as an adhesive between the second inorganic substrate and the flexible laminate. A composite laminate for comparison was obtained in the same manner as in Example 1 except that bonding was performed as The preparation of the thermoplastic polyimide film was performed according to the following procedure. First, the inside of a reaction vessel equipped with a nitrogen introduction tube, thermometer, and a stirring rod is purged with nitrogen, and then 368.4 parts by mass of 4,4'-bis (3-aminophenoxy) biphenyl, 59.24 parts by mass of phthalic anhydride, 174.5 parts A portion of pyromellitic anhydride and 172 parts by mass of m-cresol were added and stirred at 200 ° C. for 6 hours. After adding toluene to this stirred solution, the precipitate was filtered off, further washed with toluene three times, and then dried at 250 ° C. for 6 hours under a nitrogen atmosphere to give 512 parts by mass (yield 90.5%) The polyimide powder of The polyimide powder is kneaded, melted and extruded at 380 to 410 ° C. using a twin-screw extruder to form pellets. The obtained pellet is supplied to a 50 mm diameter single screw extruder (forming temperature 420 ° C.), passed through a 10 μm leaf disc type filter attached to the front of a T die, extruded from a 1100 mm wide T die, and 25 μm thick The thermoplastic polyimide film of The thermoplastic polyimide film is allowed to stand for 24 hours in a clean room at 23 ° C. and 50% RH to make the water content 0.78%, and then set between the second inorganic substrate and the polyimide layer and heated at 300 ° C. by a heating press. A composite laminate was obtained by applying pressure for 5 minutes at 1 MPa. Table 4 shows the evaluation results of the obtained composite laminate. With respect to this laminate, although a cut was made in a polyimide film and it was tried to peel the film from the support, it could not be peeled well, and if it was tried to force it off, the film was torn. In addition, many bubbles were generated at the interface of the second inorganic substrate-polyimide layer, and it was not possible to say that the entire surface was adhered. The 5% heating weight reduction temperature (heating rate: 10 ° C./min) of the thermoplastic polyimide film was 580 ° C., and the glass transition point Tg was 270 ° C.

<Measurement examples 1 to 6>
Six Si wafers 50 mm × 50 mm (□ 50 mm) were prepared as a support (substrate), sufficiently cleaned, and then coated with a silane coupling agent in the same manner as in Example 1. Heating was carried out with a 110 ° C. hot plate to form a 23 nm thick coupling treatment layer. Subsequently, UV irradiation was performed on the surface of this coupling treatment layer under the same conditions as in Example 1 except that the UV irradiation time was changed, and the surface composition ratio of each sample obtained was measured. The results are shown in Table 5. Note that the nitrogen surface composition ratio is the value of the atomic percent (%) of nitrogen after UV irradiation, assuming that the nitrogen atomic percent before UV irradiation (Measurement Example 1) is 100%.

<Example of application>
Each rigid composite laminate obtained in Examples 1 to 27 and Comparative Examples 1 to 7 was fixed to a substrate holder in a sputtering apparatus by covering a stainless steel frame having an opening. The temperature of the first inorganic substrate in the rigid composite laminate can be set by fixing the substrate holder and the second inorganic substrate in the rigid composite laminate in close contact and flowing the refrigerant into the substrate holder. Thus, the temperature of the first inorganic substrate was set to 2 ° C. First, plasma treatment was performed on the surface of the first inorganic substrate. The plasma processing conditions were a frequency of 13.56 MHz, an output of 200 W, and a gas pressure of 1 × 10 ⁻³ Torr in argon gas, the temperature at the time of processing was 2 ° C., and the processing time was 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, using a nickel-chromium (chromium 10 mass%) alloy target by a DC magnetron sputtering method in an argon atmosphere, 1 nm / A nickel-chromium alloy film (underlayer) having a thickness of 11 nm was formed at a rate of sec. Next, the temperature of the first inorganic substrate is set to 2 ° C. by bringing the back surface of the sputtered surface of the substrate into contact with the SUS plate of the substrate holder in which the refrigerant whose temperature is controlled to 3 ° C. flowed. Did. Then, copper was deposited at a rate of 10 nm / sec to form a copper thin film having a thickness of 0.22 μm. Thus, the rigid composite laminated board with a base metal thin film formation film was obtained from each film. The thicknesses of the copper and NiCr layers were confirmed by the fluorescent X-ray method.

Next, a rigid composite laminate with a base metal thin film forming film is fixed to a Cu frame, and a copper sulfate plating bath is used. immersed in), by an electrical flow 1.5Adm ^2, it was formed thickly copper plating layer having a thickness of 4μm (the thickening layer). Subsequently, it was dried by heat treatment at 120 ° C. for 10 minutes to obtain a rigid composite laminate having a metallized surface of the first inorganic substrate.

After applying and drying a photoresist (“FR-200” manufactured by Shipley Co., Ltd.) on each of the obtained metalized rigid composite laminates, they were closely exposed with a glass photomask and further developed with a 1.2 mass% KOH aqueous 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 row of lines / spaces = 20 μm / 20 μm as a test pattern. Next, electroless tin plating was performed to a thickness of 0.5 μm, and annealing treatment was performed at 125 ° C. for 1 hour. Then, the formed pattern was observed with an optical microscope to evaluate the presence or absence of sag, pattern remaining, pattern peeling and the like.

  When the rigid composite laminates of Examples 1 to 27 were used, good patterns with no sagging, pattern residue, or pattern peeling were obtained. Further, after this, the temperature is raised to 400 ° C. at a temperature rising rate of 10 ° C./min in a muffle furnace purged with nitrogen, and then held for 1 hour at 400 ° C. There was no. Moreover, when peeling a flexible laminated body after a process, it was possible to peel easily, without generating a crack, a crack, etc. in a metallized surface layer. On the other hand, when the rigid composite laminate of each comparative example is used, the film peeling, the waviness of the metal layer, the crack of the metal layer at the time of the flexible laminate peeling, etc. are generated, and a good pattern is obtained. The formed flexible laminate could not be obtained.

  From the results of the above application examples, the laminate in which the peeling strength between the support and the polyimide film is appropriately adjusted by the production method of the present invention can withstand each process such as metallization, and the subsequent pattern It has been confirmed that a good pattern can be formed also in production.

<Production Example of Polyamic Acid Solution)>
After nitrogen-substituting the inside of a reaction vessel equipped with a nitrogen introducing tube, a thermometer, and a stirring rod, 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole and 4416 parts by mass of N, N-dimethylacetamide Dispersion made by adding colloidal silica as a lubricant in dimethylacetamide together with 217 parts by mass of pyromellitic dianhydride (Snowtex® DMAC-, manufactured by Nissan Chemical Industries, Ltd.) ) And add silica (sliding material) to the addition amount shown in Table 1 (% by mass relative to the total amount of polymer solids in the polyamic acid solution) and stir at a reaction temperature of 25 ° C for 24 hours to obtain brown Thus, viscous polyamic acid solutions a1 to a3 were obtained.
After displacing the inside of a reaction vessel equipped with a nitrogen introducing pipe, a thermometer and a stirring rod with nitrogen, 8000 parts by mass of N, 8000 parts by mass of 545 parts by mass of pyromellitic anhydride and 500 parts by mass of 4,4'-diaminodiphenyl ether Silica (sliding material) is a dispersion ("Snowtex® DMAC-ST30" manufactured by Nissan Chemical Industries, Ltd.) made by dissolving colloidal silica in dimethylacetamide as a lubricant by dissolving it in N-dimethylacetamide and adding it. The addition amount was as described in 1 (% by mass relative to the total amount of polymer solids in the polyamic acid solution), and stirring was performed for 24 hours while maintaining the temperature at 20 ° C. or less to obtain a polyamic acid solution a4.

In the table,
PMDA :: Pyromellitic dianhydride
DAMBO: 5-amino-2- (p-aminophenyl) benzoxazole
ODA: 4,4′-diaminodiphenyl ether.

<Example of film production>
The polyamic acid solution a3 was added to the non-slippery surface of a 1500 mm long polyethylene terephthalate (PET) film ("A-4100" manufactured by Toyobo Co., Ltd.) as a film-forming support in Table 2 (layer B). Apply a comma coater so as to obtain a dry film thickness as shown, and then use a die coater to obtain a dry film thickness as shown in Table 7 (A layer) in Table 7. Apply a layer on top of a1, Table 7 The polyamic acid film was obtained on the PET film of the film-forming support.

Next, the obtained polyamic acid film was peeled from the PET film of the film-forming support to obtain a self-supporting polyamic acid film having a width of 1380 mm. This self-supporting polyamic acid film is passed through a pin tenter having three heat treatment zones, and the first stage 150 ° C. × 6 min, the second stage 220 ° C. × 6 min, and the third stage 480 ° C. × 12 min (maximum heat treatment temperature 480 ° C., A total heat treatment time of 24 minutes was carried out and slit to a width of 1300 mm to obtain a polyimide film F1. Table 7 shows the properties of the obtained polyimide film.
Subsequently, the polyamide acid film was heat-treated under the conditions shown in Table 7 to obtain polyimide films shown in Table 7.
Hereafter, the B layer side of the film is the B surface, the A layer side of the film is the A surface, and when the polyimide film layer is a single layer, the side that was in contact with the film-forming support at the time of application is the B surface, The opposite side is referred to as the A side.

(Example 29)
<Plasma treatment of polyimide film VP1 treatment>
The polyimide film F1 was subjected to vacuum plasma treatment on both sides. As the vacuum plasma process, an RIE mode using parallel plate type electrodes and a process by RF plasma are adopted, N 2 gas and O 2 gas are introduced into the vacuum chamber at a flow ratio of 5: 95, 13.56 MHz high frequency power The processing time was 3 min. Hereinafter, this processing is referred to as VP1 processing.
The polyimide film after the plasma treatment was cut to a necessary size, and then kept in an air-conditioned room, so that the film moisture percentage was maintained at 0.3% by mass to 0.8% by mass.
<First inorganic substrate SC1 treatment>
The silane coupling agent 3-aminopropyltrimethoxysilane is diluted to 0.5% by mass with isopropyl alcohol while flowing N 2 gas in a nitrogen-substituted glove box, and then separately washed and dried as a first inorganic substrate. Place a tempered glass ("Spool" manufactured by Asahi Glass Co., Ltd .; 350 mm x 450 mm x 0.1 mm thickness) in a spin coater, drop the silane coupling agent onto the central portion of rotation, rotate at 500 rpm, and then 1500 rpm. After the entire surface of the inorganic substrate was applied in a wet state by rotating it, it was dried. This was heated for 1 minute on a hot plate heated to 110 ° C. placed in a clean bench to obtain a first inorganic substrate that had been treated with a coupling agent. The thickness of the coupling agent layer was in the range of 35 nm ± 12 nm. This process is SC1 process.

<Second inorganic substrate>
A glass (Corning “Corning EAGLE XG”; 370 mm × 470 mm × 0.7 mm thick) which has been separately washed and dried in advance is placed in a spin coater, and the coupling agent is processed in the same manner as in the case of the first inorganic substrate. The SC1 treatment was performed by applying a coating to obtain a second inorganic substrate that had been treated with a coupling agent.

<Dummy board>
Asahi Glass Co., Ltd. glass "Spool" used as the first inorganic substrate; 370 mm x 470 mm x 0.1 mm thick; Corning Co. glass used as the second inorganic substrate "Corning EAGLE XG"; 370 mm x 470 mm x 0.7 mm thick) Each was cut into a required size, and further, a release treatment was performed on the surface by forming a fluorine-based vacuum thin film, which was used as a dummy substrate.
<Lamination>
Using a stainless steel plate having a thickness of 1 mm as a supporting substrate, FIG. As shown in FIG. 1, on the supporting substrate, first, the second inorganic substrate and the second dummy substrate are disposed so that the respective processing surfaces are on top, and then the A surface of the surface-treated polyimide film is the second inorganic substrate. The substrate and the second dummy substrate are arranged to be in contact with each other, and then the first inorganic substrate and the first dummy substrate are arranged such that the treated surface sides thereof are in contact with the B surface of the polyimide film. ) To (C), followed by roll lamination, followed by heat treatment in an oven at 150 ° C. for 30 minutes to obtain a laminate.
<Evaluation>
Of the obtained laminate,
Adhesive force 1: Adhesive force between first inorganic substrate and polyimide film Adhesive force 2: Adhesive force between second inorganic substrate and polyimide film is measured, Adhesive force ratio: Ratio of adhesive force 1 and adhesive force 2 Calculated. In calculating the adhesive force ratio, the larger side of adhesive force 1 or adhesive force 2 is F1, and the smaller side is F2.
The adhesion ratio was calculated as F1 / F2. The results are shown in Table 8.

(Examples 30 to 31, Comparative examples 8 to 11)
Thereafter, the polyimide film was changed, and the same procedure as in Example 29 was performed under the conditions shown in Table 8 to obtain a laminate. The evaluation results are shown in Table 8. In the following Examples, Examples 36 to 38 are replaced with Reference Examples 36 to 38, Examples 43 to 47 are replaced with Reference Examples 43 to 47, and Example 59 is replaced with Reference Example 59.

(Examples 32-35)
<Polyimide film surface treatment VP1 + UV1 treatment>
The VP1 treatment was applied to both surfaces of the polyimide film F2 in the same manner as in Example 1. Next, use UV / O3 cleaning and reforming device ("SKT2005Y-02") and UV lamp ("SE-2003W03") manufactured by Run Technical Service Co., Ltd. on the B side, from a distance of about 1 cm from the UV lamp. UV irradiation was performed for 3 minutes. At the time of irradiation, no special gas was introduced into the UV / O3 cleaning and reforming apparatus, and the UV irradiation was performed in the air at room temperature. The UV lamp emits an emission line with a wavelength of 185 nm (short wavelength that can generate O3 that promotes deactivation) and a wavelength of 254 nm. At this time, the illuminance is about 45 mW / cm2 (illuminance meter (“SEC SM-254 )) At a wavelength of 254 nm. Hereinafter, this process is referred to as UV1 process.
Thereafter, the laminate was obtained by laminating with the inorganic substrate under the conditions shown in Table 9 in the same manner as in Example 29. The results are shown in Table 9.
Furthermore, the polyimide film was replaced and the laminated body was obtained on the conditions shown in Table 9. The results are shown in Table 9.

(Examples 36 to 38)
<Surface treatment of polyimide film VP1 + UV1 treatment>
The VP1 treatment was applied to both surfaces of the polyimide film F2 in the same manner as in Example 1. Next, use a UV / O3 cleaning and reforming device ("SKT2005Y-02") and a UV lamp ("SE-2003W03") manufactured by Run Technical Service Co., Ltd. on the A side, from a distance of about 1 cm from the UV lamp. UV irradiation was performed for 3 minutes. At the time of irradiation, no special gas was introduced into the UV / O3 cleaning and reforming apparatus, and the UV irradiation was performed in the air at room temperature. The UV lamp emits an emission line with a wavelength of 185 nm (short wavelength that can generate O3 that promotes deactivation) and a wavelength of 254 nm. At this time, the illuminance is about 45 mW / cm2 (illuminance meter (“SEC SM-254 And measured at a wavelength of 254 nm). Hereinafter, this process is referred to as UV1 process.
Thereafter, the laminate was obtained by laminating with the inorganic substrate under the conditions shown in Table 9 in the same manner as in Example 29. The results are shown in Table 9.
Furthermore, the polyimide film was replaced and the laminated body was obtained on the conditions shown in Table 9. The results are shown in Table 9.

(Examples 39 to 42)
The polyimide film F2 was subjected to VP1 treatment on both sides in the same manner as in Example 29.
<Surface treatment of second inorganic substrate SC1 + UV1 treatment>
The second inorganic substrate used in Example 29 was similarly subjected to SC1 treatment, and the UV / O3 cleaning / reforming apparatus ("SKT2005Y-02") and UV lamp manufactured by Run Technical Service Co., Ltd. were further treated on the treated surface. ("SE-2003W03") and UV1 treatment was performed.
Thereafter, the laminate was laminated with the inorganic substrate under the conditions shown in Table 10 in the same manner as in Example 29 to obtain a laminate. The results are shown in Table 5.
Furthermore, the polyimide film was replaced and the laminated body was obtained on the conditions shown in Table 10. The results are shown in Table 10.

(Examples 43 to 45)
The polyimide film F2 was subjected to VP1 treatment on both sides in the same manner as in Example 29.
<Surface treatment of first inorganic substrate SC1 + UV1 treatment>
The first inorganic substrate used in Example 29 was similarly subjected to SC1 treatment, and the UV / O3 cleaning / reforming apparatus ("SKT2005Y-02") and UV lamp manufactured by Run Technical Service Co., Ltd. were further applied to the treated surface. ("SE-2003W03") and UV1 treatment was performed.
Thereafter, the laminate was laminated with the inorganic substrate under the conditions shown in Table 10 in the same manner as in Example 29 to obtain a laminate. The results are shown in Table 10.
Furthermore, the polyimide film was replaced and the laminated body was obtained on the conditions shown in Table 10. The results are shown in Table 10.

(Examples 46 to 47)
The polyimide film F3 was subjected to VP1 treatment on both sides in the same manner as in Example 29.
<Surface treatment of first inorganic substrate SC2 treatment>
The silane coupling agent 3-aminopropyltriethoxysilane is diluted to 0.1% by mass with isopropyl alcohol while flowing N 2 gas in a nitrogen-substituted glove box, and then separately washed and dried as a first inorganic substrate. Installed glass ("Spool" manufactured by Asahi Glass Co., Ltd .; 350mm x 450mm x 0.1mm thickness) on the spin coater, dripping the silane coupling agent on the center of rotation and rotating at 500rpm, then at 1500rpm It was made into the dry state, after apply | coating as the state which wetted the whole inorganic substrate by rotating. This was heated for 1 minute on a hot plate heated to 110 ° C. placed in a clean bench to obtain a first inorganic substrate that had been treated with a coupling agent. The thickness of the coupling agent layer was in the range of 11 nm ± 3 nm. This process is SC2 process.
Thereafter, the laminate was obtained by laminating with the inorganic substrate under the conditions shown in Table 11 as in Example 29. The results are shown in Table 11.
Furthermore, the polyimide film was replaced and the laminated body was obtained on the conditions shown in Table 11. The results are shown in Table 11.

(Examples 48 to 49)
The polyimide film F3 was subjected to VP1 treatment on both sides in the same manner as in Example 29. Hereinafter, the surface treatment of the first inorganic substrate was treated as SC1 treatment, and the surface treatment of the second inorganic substrate as SC2 treatment, and similarly, the laminate was laminated with the inorganic substrate under the conditions shown in Table 11 to obtain a laminate. The results are shown in Table 11.
Furthermore, the polyimide film was replaced and the laminated body was obtained on the conditions shown in Table 11. The results are shown in Table 11.

(Comparative Examples 12-13)
The surface treatment of the inorganic substrate was performed in the same manner as in the first and second embodiments except that the SC2 treatment was performed, and a laminate shown in Table 11 was obtained. The results are shown in Table 11.

(Examples 50 to 59, Comparative Examples 14 to 17)
<Plasma treatment of polyimide film VP2 treatment>
The polyimide film F1 was subjected to vacuum plasma treatment on both sides. As the vacuum plasma process, an RIE mode using parallel plate type electrodes and a process by RF plasma are adopted, N 2 gas and O 2 gas are introduced into the vacuum chamber at a flow ratio of 5: 95, 13.56 MHz high frequency power The processing time was 45 seconds. Hereinafter, this process is referred to as a VP2 process.
The polyimide film after the plasma treatment was cut to a necessary size, and then kept in an air-conditioned room, so that the film moisture percentage was maintained at 0.3% by mass to 0.8% by mass.
Thereafter, the laminate was obtained by laminating with the inorganic substrate under the conditions shown in Table 12 in the same manner as in Example 29. The results are shown in Table 12.
Furthermore, the polyimide film was replaced and the laminated body was obtained on the conditions shown in Table 12 and Table 13. The results are shown in Tables 12 and 13.

As described above, in the laminate in which the first inorganic substrate and the second inorganic substrate are directly bonded to both surfaces of the polyimide film according to the embodiment, the adhesion between the first inorganic substrate and the polyimide film, and the second When the adhesion between the inorganic substrate and the polyimide film is measured, and the larger of the two adhesion values measured is F1 and the smaller is F2,
F1 / F2 ≧ 1.5
The laminated body satisfying the above relational expression, the conditions for realizing it, and the like are illustrated. In this embodiment, although an example is shown in which the individual effects of the realization means are confirmed, it is within the scope of the present invention to provide such an adhesive force difference by combining a plurality of means, including the example shown here. .
In addition, as described above, the first or second order indicating the front and back of the inorganic substrate and the polyimide film in the present invention is a matter of convenience, and the present invention is established even when the two are interchanged. There is no particular limitation on which side to use in terms of application.

The rigid laminate obtained by the manufacturing method of the first invention of the present application can be easily peeled off from the second inorganic substrate by cutting out the flexible laminate of the easily peelable part when laminating the devices. In addition, these rigid laminates can withstand steps such as metallization, and good patterns can be obtained also in the subsequent pattern preparation. Therefore, the rigid laminate of the present invention can be effectively used in the production process of a device structure on a very thin flexible laminate, etc., and on a glass and a film excellent in extremely thin insulation, heat resistance and dimensional stability. The circuit and device can be formed with high accuracy. Therefore, sensors, display devices, probes, integrated circuits, and composite devices thereof, amorphous Si thin film solar cells, Se and CIGS compound semiconductor thin film solar cell substrates, and device structures such as solar cells and flexible displays using these It is useful for manufacturing and has a great contribution to the industry.

[Figure 1]
11 Good adhesion area
12 Easy peeling part
[Figure 2]
21 Second inorganic substrate
22 Coupling agent treatment layer applied to the second inorganic substrate
23 Mask
24 Coupling agent treated layer after UV irradiation
25 Polyimide layer
26 First inorganic substrate
27 Coupling agent treatment layer applied to the first inorganic substrate
28 Polyimide layer
29 Polyimide layer
210 Flexible laminate
[Figure 3]
31 Second inorganic substrate
32 Coupling agent treatment layer applied to the second inorganic substrate
33 Mask
34 Coupling agent treated layer after UV irradiation
35 Polyimide layer
36 First inorganic substrate
37 Coupling agent treatment layer applied to the first inorganic substrate
38 devices
39 Polyimide layer
310 Polyimide layer
311 Flexible Laminates with Devices [Figures 4-8]
1: first inorganic substrate 2: polyimide film 3: second inorganic substrate 4: device 5: first dummy substrate 6: second dummy substrate 7: support plate 8: cushion film 9: laminate roll

Claims (12)

A flexible laminate having a total thickness of 300 μm or less, which is a polyimide layer directly bonded to a first inorganic substrate which is a glass plate having a thickness of 280 μm or less or a silicon wafer having a thickness of 280 μm or less A rigid composite laminate in which a second inorganic substrate having a thickness of 300 μm or more is directly bonded to the surface ( second bonding surface) opposite to the bonding surface (first bonding surface) of the polyimide layer ,
When the adhesion between the first inorganic substrate and the polyimide layer is F1, and the adhesion between the second inorganic substrate and the polyimide layer is F2,
F1 / F2 ≧ 1.5
A laminate characterized by satisfying the following equation .   The rigid composite laminate according to claim 1, wherein the absolute value of the difference between the linear expansion coefficient (CTE) of the polyimide layer and the CTE of the first inorganic substrate is 30 ppm / ° C or less.   The bonding of the first inorganic substrate and the polyimide layer on the first bonding surface is performed after performing surface treatment on at least one of the first inorganic substrate surface and the polyimide layer surface. The rigid composite laminated board in any one of 1-2.   Bonding of the second inorganic substrate and the polyimide layer in the second bonding surface is performed after surface treatment is performed on at least one of the second inorganic substrate surface and the polyimide layer surface. The rigid composite laminate according to any one of Items 1 to 3.   Bonding of the second inorganic substrate and the polyimide layer in the second bonding surface has a good adhesion portion and an easily peelable portion by further inactivating treatment on a part of the surface treated surface after the surface treatment The rigid composite laminate according to claim 4, wherein a predetermined pattern is formed.   A group selected from the group consisting of a plasma treatment, a corona treatment, an active energy ray irradiation treatment, a flame treatment, and a coupling agent treatment as a surface treatment performed when joining the first inorganic substrate and the polyimide layer on the first joining surface. The rigid composite laminate according to any one of claims 1 to 5, which is at least one selected from the group consisting of   The surface treatment to be carried out at the time of bonding of the second inorganic substrate and the polyimide layer in the second bonding surface is a group selected from plasma treatment, corona treatment, active energy ray irradiation treatment, flame treatment, and coupling agent treatment The rigid composite laminate according to any one of claims 1 to 6, wherein the rigid composite laminate is at least one or more selected.   As the inactivation treatment, at least one inactivation treatment selected from the group consisting of blast treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, corona treatment, active radiation irradiation treatment, active gas treatment and chemical treatment is performed. The rigid composite laminate according to claim 5.   The rigid composite laminate according to any one of claims 5 and 8, wherein an adhesive force difference between a good adhesion portion and a peelable portion in the second bonding surface is 0.1 N / cm or more.   The rigid composite laminate according to any one of claims 1 to 9, wherein the maximum peeling force in the first bonding surface is 0.1 N / cm or more.   The first inorganic substrate is laminated by pressing and heating the first inorganic substrate on one side of the polyimide layer, and the second inorganic substrate is laminated on the opposite surface of the polyimide layer by heating and pressing. A method for producing a rigid composite laminate including a second lamination step, comprising the step of adjusting the moisture content of the polyimide layer within a range of 0.1 to 1.7% before the second lamination step. The manufacturing method of the rigid composite laminated board in any one of Claims 1-10.   A method for producing a structure in which a device is formed on the surface of a first inorganic substrate in a flexible laminate using the rigid composite laminate according to claim 5, wherein the flexible laminate is a flexible laminate A device structure by forming a device on the first inorganic substrate and then cutting the polyimide layer at the easily peelable portion of the rigid composite laminate to peel the flexible laminate from the second inorganic substrate. Manufacturing method.