JP2013010342A - Laminate, method of manufacturing the same, and method of manufacturing device structure using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate formed of a polyimide film and a support used as a base material for laminating various devices, configured to prevent the laminate from being separated even in a high temperature process in manufacturing the device and to allow easy separation of the polyimide film from the support after producing the device on the polyimide film.SOLUTION: A film, as a polyimide film 6, has a surface which is opposite at least the support 1 and plasma-treated. A patterning process of forming an easy-to-bond part and an easy-to-separate part which are different in adhesive/separation strength and almost the same in surface roughness is performed on at least one of facing surfaces of the support 1 and the polyimide film 6 using a coupling agent, and thereafter the support and the polyimide film are superimposed and pressed and heated. The polyimide film 6 is obtained by reaction between a diamine which mainly contains an aromatic diamine at least 70 mol% of which has a benzoxazole structure and a tetracarboxylic acid.

Description

  The present invention relates to a process for producing a laminate comprising a polyimide film and a support made of an inorganic material (hereinafter sometimes simply referred to as “support”). Specifically, the present invention relates to a method for producing a laminate in which a polyimide film is temporarily or semi-permanently bonded to an inorganic substrate serving as a support, and the laminate is a thin film such as a semiconductor element, a MEMS element, or a display element. This is useful when forming a device on the surface of the polyimide film, which requires fine processing. More specifically, the laminate according to the present invention includes a thin polyimide film excellent in heat resistance and insulation, and an inorganic substance having a linear expansion coefficient substantially equal to the thin polyimide film (for example, a glass plate, a ceramic plate, a silicon wafer, a metal plate). 1) selected from the above, and a laminated body excellent in dimensional stability, heat resistance and insulation, capable of mounting a precise circuit. Therefore, the present invention relates to such a laminate, a method for producing the same, and a method for producing a device structure using the laminate.

  In recent years, for the purpose of reducing the weight, size and thickness of functional elements such as semiconductor elements, MEMS elements, and display elements, and increasing flexibility, technological developments for forming these elements on polymer films have been actively conducted. For example, as a material for a base material of an electronic component such as an information communication device (broadcast device, mobile radio, portable communication device, etc.), a radar, a high-speed information processing device, etc. Ceramics that can cope with higher frequency bands (reaching the GHz band) have been used. However, ceramics are not flexible and are difficult to reduce in thickness, so that there is a drawback that applicable fields are limited.

  When functional elements such as semiconductor elements, MEMS elements, and display elements are formed on the surface of polymer films, it is ideal to process them using a so-called roll-to-roll process that uses the flexibility of polymer films. It is said that. However, in the semiconductor industry, the MEMS industry, and the display industry, a process technology for a rigid flat substrate such as a wafer base or a glass substrate base has been constructed so far. Therefore, as a practical choice, the polymer film is bonded to a rigid support made of an inorganic material such as a glass plate, a ceramic plate, a silicon wafer, or a metal plate, and after forming a desired element, the support film is used. It is conceivable to peel off, thereby making it possible to obtain a functional element formed on a polymer film using existing infrastructure.

  Conventionally, bonding of a polymer film to a support made of an inorganic material has been widely performed using a pressure-sensitive adhesive or an adhesive (Patent Document 1). However, when a desired functional element is formed on a laminate in which a polymer film and an inorganic support are bonded, surface smoothness, dimensional stability, and cleanliness that do not hinder the formation of the functional element. The laminate is required to have resistance to process temperature, resistance to chemicals used for fine processing, and the like. In particular, in the 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 production of a low-temperature polysilicon thin film transistor, heat treatment at 450 ° C. for about 2 hours may be required for dehydrogenation, and in the production of a hydrogenated amorphous silicon thin film, the temperature is from about 200 ° C. to about 300 ° C. Temperature can be applied to the film. Thus, when the formation temperature of the functional element is high, the polymer film needs to have heat resistance, as well as the joint surface between the polymer film and the support (that is, an adhesive or adhesive for bonding). Must withstand the processing temperature. However, since conventional adhesives and pressure-sensitive adhesives for bonding did not have sufficient heat resistance, they cannot be applied when the functional element is formed at a high temperature.

  Further, among the semiconductor thin films, when a Si thin film having a very small linear expansion coefficient of about 3 ppm / ° C. is formed on the polymer film, if the difference in the linear expansion coefficient between the film and the thin film is large, the thin film There is also a problem that stress accumulates in the interior, 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 film and the thin film increases during the temperature change.

  As a polymer film to be bonded to a support made of an inorganic material, a film having a low melting point is not suitable from the viewpoint of heat resistance. For example, a polymer film made of polyethylene naphthalate, polyethylene terephthalate, polyimide, polytetrafluoroethylene, or glass fiber. Reinforced epoxy or the like is used. In particular, a film made of polyimide has the advantage that it can be thinned because it has excellent heat resistance and is tough. However, a polyimide film generally has a large linear expansion coefficient and a significant dimensional change due to a temperature change, and thus has a problem that it is difficult to apply to the production of a circuit having fine wiring, and the fields that can be used are limited. Thus, a device using a polyimide film having sufficient physical properties for a substrate having heat resistance, high mechanical properties, and flexibility has not been obtained yet.

  As a polyimide film having a high tensile modulus, a polyimide benzoxazole film made of polyimide having a benzoxazole ring in the main chain has been proposed (Patent Document 2). In addition, printed wiring boards using this polyimide benzoxazole film as a dielectric layer have also been proposed (Patent Documents 3 and 4). However, the polyimide benzoxazole film made of polyimide having these benzoxazole rings in the main chain has improved tensile fracture strength and tensile elastic modulus and has a satisfactory range of linear expansion coefficient. In contrast to the mechanical properties, the thinner the film, the more difficult it is to handle, and the mechanical and mechanical properties are insufficient.

  Attempts have also been made to provide other structural reinforcements by providing an adhesive layer such as a thermoplastic resin on these polyimide films. However, according to this, even if satisfactory in terms of improving the rigidity, the low heat resistance of the thermoplastic resin used as the adhesive layer tends to ruin the heat resistance of the folded polyimide film. It was. In addition, the thermoplastic resin generally has a large linear expansion coefficient, and since there is a limit to making this layer thin, it has a tendency to adversely affect dimensional stability when heated.

On the other hand, as a flexible display device using a resin substrate, a step of forming a resin substrate on a fixed substrate through an amorphous silicon film serving as a peeling layer, and at least a TFT element is formed on the resin substrate And a step of detaching the resin substrate from the fixed substrate in the amorphous silicon film by irradiating the amorphous silicon film with laser light, and using the resin substrate for flexibility. It is disclosed that a display device having the same is manufactured (Patent Document 5). However, it is necessary to use laser irradiation or etching means for the adhesive layer at the time of peeling, which makes the process complicated and expensive.
It is known that polymer films are bonded to each other by UV irradiation, and it is disclosed that it is effective to use a coupling agent at this time (Patent Document 6). However, this technique is only related to the adhesion between polymer films, and does not control the adhesive peeling force of the coupling agent itself by UV light irradiation.

JP 2008-159935 A Japanese Patent Laid-Open No. 06-056792 Japanese National Patent Publication No. 11-504369 Japanese National Patent Publication No. 11-505184 JP 2009-260387 A JP 2008-19348 A

  The present invention has been made paying attention to the circumstances as described above, and the object thereof is a laminate of a polyimide film and a support for use as a base material for laminating various devices, An object of the present invention is to provide a laminate in which a polyimide film can be easily peeled off from a support without being peeled off even in a high temperature process at the time of production and after a device is produced on a polyimide film.

  As a result of intensive studies to solve the above problems, the present inventors have used a coupling agent on at least one of the surfaces of the support and the polyimide film facing each other, and have different adhesive peel strengths and substantially the same surface roughness. In the high temperature process at the time of device fabrication at the good adhesion part, if the patterning process to form the good adhesion part and the easy peeling part which is the It is possible to easily peel off the polyimide film with a device from the support by making a notch in the easily peelable part after the device is made to express sufficient adhesive peel strength that does not peel off, and also a polyimide film with a specific composition as a polyimide film To further improve the heat resistance and support the dimensional stability of the polyimide film. Since becomes closer to the body, it can be suppressed warpage or deformation of the laminate, find, and have completed the present invention.

That is, the present invention has the following configuration.
1) A method for producing a laminate comprising at least a support and a polyimide film, wherein a film having a plasma treatment applied to at least a surface facing the support is used as the polyimide film. At least one of the surfaces facing the polyimide film is subjected to a patterning treatment using a coupling agent to form a well-bonded portion and an easily-peelable portion having different adhesive peel strengths and substantially the same surface roughness. Then, the support and the polyimide film are overlapped and subjected to pressure heat treatment, and the polyimide film is composed mainly of diamines containing aromatic diamines and aromatic tetracarboxylic acids as main components. It is a film obtained by reaction with tetracarboxylic acids, and 70 mol of the aromatic diamines Or an aromatic diamine having a benzoxazole structure, method for producing a laminate, characterized in that.
2) The patterning treatment is performed by performing a coupling agent treatment to form a coupling treatment layer, and then performing a deactivation treatment on a part of the coupling treatment layer to form a predetermined pattern. The manufacturing method of the laminated body as described in).
3) As the deactivation treatment, 2) performing 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 manufacturing method of the laminated body as described in any one of.
4) The method for producing a laminate according to 3), wherein at least UV irradiation treatment is performed as the inactivation treatment.
5) The method for producing a laminate according to any one of 1) to 4), wherein the pressure heating treatment is performed in an atmospheric pressure atmosphere using a roll.
6) The pressure heat treatment is performed separately in a pressure process and a heating process, and after pressurizing at a temperature of less than 120 ° C., heating at a low pressure or normal pressure at a temperature of 120 ° C. or more is performed 1) to The manufacturing method of the laminated body in any one of 5).
7) The manufacturing method of the laminated body in any one of said 1) -6) using the film which gave the acid treatment after the said plasma treatment as said polyimide film.

8) A laminate in which a support and a polyimide film are laminated via a coupling treatment layer, and a good adhesion portion and an easily peelable portion having different peel strengths between the support and the polyimide film. A laminate having the good adhesion portion and the easy peeling portion forming a predetermined pattern.
9) The 180 degree peel strength between the support and the polyimide film in the easily peelable part is ½ or less of the 180 degree peel strength between the support and the polyimide film in the good adhesion part. The laminated body as described in.

  10) A method for producing a structure in which a device is formed on a polyimide film, wherein the laminate according to 8) or 9) having a support and a polyimide film is used. After forming a device on a polyimide film, the manufacturing method of the device structure characterized by cutting into the polyimide film of the easily peelable part of the said laminated body, and peeling this polyimide film from the said support body.

The laminate obtained by the production method of the present invention is a laminate in which one side of a support (glass plate, ceramic plate, silicon wafer, metal, etc.) and one side of a polyimide film are bonded without an adhesive layer interposed therebetween. Since the adhesive peel strength of the support and the polyimide film is different according to a predetermined pattern, it is divided into a good adhesion part and an easy peel part. Therefore, after making a device on the polyimide film, the polyimide of the easy peel part A polyimide film with a device can be easily obtained by cutting and peeling the film. In addition, since the polyimide film of the laminate according to the present invention is obtained by a reaction between a diamine having a specific composition and a tetracarboxylic acid, it exhibits higher heat resistance, and the dimensional stability of the polyimide film is a support. As a result, the effect of suppressing warpage and deformation of the laminate is also exhibited.
According to the present invention, a circuit or the like can be formed on a thin polyimide film having insulating properties, flexibility, and heat resistance. Furthermore, when manufacturing electronic devices by mounting electronic components, even thin polyimide films can be positioned accurately by being laminated and fixed on a support with excellent dimensional stability, and thin film production in multiple layers. Circuit formation can be performed. In addition, the laminate of the present invention does not peel off even when heat is applied during the process, and the polyimide film and the support can be smoothly peeled off even when peeled off from the support as necessary after device fabrication. Furthermore, since the laminate of the present invention is a laminate having a peel strength that does not peel in the process passing process, it is possible to use a conventional electronic device manufacturing process as it is. In particular, when a device is manufactured on a polyimide film, the device can be stably and accurately manufactured because the surface properties of the polyimide film are excellent in adhesion and smoothness. As described above, the laminate of the present invention is extremely useful for producing an electronic device in which a circuit or the like is formed on a thin polyimide film having insulating properties, flexibility, and heat resistance.

  According to the present invention, it is also possible to add plasma treatment and acid treatment to the polyimide film original. The process of this part can be made into a roll-to-roll process, and efficient processing is possible. In particular, since the polyimide film roll that has been subjected to the plasma treatment has a lubricant, the handling property as a roll is equivalent to that before the plasma treatment. Also about the roll conveyance after an acid treatment, roll conveyance becomes easy by attaching the protective film with an adhesive to the surface on the opposite side to the surface which performs an acid treatment. Since the surface opposite to the surface where acid treatment is performed is the surface where devices are manufactured, a protective film may be attached to prevent scratches, etc., so this will not increase the number of processes, and this protective film will be covered with a lubricant. The roll can be transported without any problems. Further, as another process configuration, since the plasma treatment can be performed with a roll and then the cut sheet can be used for the acid treatment, a simple implementation is possible. It is significant in implementation that the process is excellent in productivity.

  Since the laminate of the present invention is supported by a support made of a heat-resistant inorganic material, it can be precisely positioned at the time of circuit wiring production and semiconductor formation, and can be used for multi-layer thin film production, circuit formation, Thin film deposition and the like can be performed without peeling even in high-temperature processes during semiconductor fabrication. Moreover, since this laminated body can be easily peeled off when only the easy peeling portion of the pattern is peeled after the semiconductor is added, the produced semiconductor is not destroyed. Then, by removing the polyimide film laminate used for the circuit-added laminate and the semiconductor-added laminate in which the semiconductor element is formed, the device-added polyimide film having the circuit-added device and the semiconductor-added device-attached device having the semiconductor element are formed. A polyimide film can be provided.

  Precise positioning during circuit wiring fabrication, thin film fabrication in multiple layers, circuit formation, etc. If a polyimide film with poor dimensional stability and large shape change is used alone, positioning for device fabrication becomes difficult Become. On the other hand, in the method of the present invention in which the polyimide film is peeled off from the hard support after the device is manufactured and fixed to a hard support having excellent dimensional stability, positioning for device manufacture is easy, and the conventional electronic device Using the production process as it is, device production on a polyimide film can be carried out stably and accurately. In particular, the laminate of the present invention is a laminate that is significant for circuit formation or the like at high temperatures or for precise circuit formation.

  Also, solar cells made of single crystal and polycrystal Si are easy to break as the thickness is reduced, and there are problems in handling during the process and durability after completion. These problems can be solved by using a laminate with a support as in the invention. 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.

  In addition, for example, when a wafer is used as a support and a polyimide varnish is applied on the wafer and then removed to form a polyimide film, a concentric film thickness distribution can be formed on the wafer, and the front and back surfaces of the polyimide film Due to the difference in structure, it becomes a polyimide film that warps when peeled off, the adhesive strength between the polyimide film and the wafer is too strong, and the polyimide film is fragile, so peeling from the support itself is difficult There is a problem that the film is often damaged at the time of peeling. On the other hand, when a separately produced film is pasted as in the present invention, the film thickness in a narrow area is extremely high with respect to a support such as a wafer or glass, and the circuit was produced first. It is possible to apply the circuit later or to manufacture a circuit after the application, which is suitable for circuit manufacture.

FIG. 1 is a schematic view showing an embodiment of a method for producing a laminate according to the present invention. FIG. 2 is a schematic view showing one embodiment of the method for producing a device structure of the present invention. FIG. 3 is a schematic diagram showing a pattern example. FIG. 4 is an AFM image showing the crater portion. FIG. 5 is a cross-sectional AFM image of the straight portion of the crater portion shown in FIG. FIG. 6 is an AFM image (10 μm square) including a crater portion. FIG. 7 is an explanatory diagram for explaining a method of measuring the diameter of the crater portion. FIG. 8 is an explanatory diagram for explaining a method of measuring the number of craters. FIG. 9 is a cross-sectional view (a) and a top view (b) showing a display device (display panel) which is an example of a device structure. FIG. 10 is a cross-sectional view showing a display device (display panel) which is another example of the device structure.

(Laminate manufacturing method)
The manufacturing method of the laminated body of this invention is a method of manufacturing the laminated body comprised from these using a support body and a polyimide film at least.

<Support>
The support in the present invention may be a plate made of an inorganic material that can be used as a substrate, for example, a glass plate, a ceramic plate, a silicon wafer, a metal wafer or the like mainly, and these glass plates, Examples of the ceramic plate, silicon wafer, and metal composite include those obtained by laminating them, those in which they are dispersed, and those containing these fibers.

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

Examples of the ceramic plate include Al ₂ O ₃ , Mullite, AlN, SiC, Si ₃ N ₄ , BN, crystallized glass, Cordierite, Spodumene, Pb-BSG + CaZrO ₃ + Al ₂ O ₃ , Crystallized glass + Al ₂ O ₃ , Ceramics for substrates such as Crystallized Ca-BSG, BSG + Quartz, BSG + Quartz, BSG + Al ₂ O ₃ , Pb + BSG + Al ₂ O ₃ , Glass-ceramic, Zerodur material, TiO ₂ , Strontium titanate, Calcium titanate, Magnesium titanate, MgO, 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- Piezoelectric materials such as 0.3BT and PLZT are included.

  The silicon wafer includes all of n-type or p-type doped silicon wafers, intrinsic silicon wafers, etc., and silicon wafers in which a silicon oxide layer or various thin films are deposited on the surface of the silicon wafer. In addition to silicon wafers, germanium, silicon-germanium, gallium-arsenic, aluminum-gallium-indium, and nitrogen-phosphorus-arsenic-antimony are often used. Furthermore, general-purpose semiconductor wafers such as InP (indium phosphorus), InGaAs, GaInNAs, LT, LN, ZnO (zinc oxide), CdTe (cadmium tellurium), and ZnSe (zinc selenide) are also included.

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

  It is desirable that the planar portion of the support is sufficiently flat. Specifically, the PV value of the surface roughness is 50 nm or less, more preferably 20 nm or less, and further preferably 5 nm or less. If it is rougher than this, the peel strength between the polyimide film and the support may be insufficient.

<Polyimide film>
The polyimide film in the present invention is a film obtained by a reaction between a diamine having an aromatic diamine as a main component and a tetracarboxylic acid having an aromatic tetracarboxylic acid as a main component. Specifically, the polyimide film is a polyamic acid (polyimide precursor) solution obtained by reacting at least a diamine and a tetracarboxylic acid in a solvent. It is applied to the “support” described above as a component of the laminate of the present invention and dried to form a green film (also referred to as “precursor film” or “polyamic acid film”). The green film can be obtained by subjecting the green film to a high temperature heat treatment on the support or in a state of peeling off from the support to cause a dehydration ring-closing reaction.

  The diamines constituting the polyamic acid are mainly composed of aromatic diamines from the viewpoint of heat resistance. Specifically, the aromatic diamines are preferably 80% by mass or more of the total diamines, more preferably 90% by mass or more, still more preferably 95% by mass or more, and most preferably 100% by mass. In the present invention, it is important that 70 mol% or more of all aromatic diamines are aromatic diamines having a benzoxazole structure. By using a predetermined amount of diamine having a specific structure in this way, rigid molecules will be highly oriented, and a polyimide film having high heat resistance, high elastic modulus, low heat shrinkage, and low linear expansion coefficient. Can be obtained.

  The molecular structure of the aromatic diamine having a benzoxazole structure is not particularly limited, and specific examples include the following. The aromatic diamine having a benzoxazole structure may be used alone or in combination of two or more.

  Among these, from the viewpoint of easy synthesis, each isomer of amino (aminophenyl) benzoxazole is preferable, and 5-amino-2- (p-aminophenyl) benzoxazole is more preferable. Here, “each isomer” means one in which the bonding position (coordination position) of two amino groups of amino (aminophenyl) benzoxazole is different (for example, the 5-amino-2- (p -Aminophenyl) benzoxazole, 6-amino-2- (p-aminophenyl) benzoxazole, 5-amino-2- (m-aminophenyl) benzoxazole and 6-amino-2- (m-amino) Phenyl) benzoxazole corresponds to the isomer).

  The proportion of the aromatic diamine having a benzoxazole structure in the total aromatic diamines is 70 mol% or more as described above, preferably 75 mol% or more, more preferably 80 mol% or more, and still more preferably 85 mol%. More than mol%.

As the aromatic diamine, in addition to the aromatic diamine having the benzoxazole structure, other aromatic diamines as exemplified below may be used as long as they are in the range of 30 mol% or less of the total aromatic diamines. Can be used together. Other aromatic diamines may be used alone or in combination of two or more.
Examples of other aromatic diamines include 2,2′-dimethyl-4,4′-diaminobiphenyl, bisaniline, 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, and 2,2 ′. -Ditrifluoromethyl-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) ) Phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenyle Diamine, 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′-diaminodiphenylsulfone, 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-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl ] Ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4 -(4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3 -Methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4- Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide Bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4- Aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-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- ( -Amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4- Aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy- α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4- Amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethyl. Benzyl] benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4, 4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5 -Phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'- Diamino-5,5′-dibiphenoxybenzophenone, 3,4′-diamino-4,5′-dibiphenoxybenzophenone, 3,3′-diamino-4 Biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4′-diamino-4-biphenoxybenzophenone, 3,4′-diamino-5′-biphenoxybenzophenone, 1,3-bis ( 3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1, 3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybe) Zoyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile, and some or all of the hydrogen atoms on the aromatic ring of the aromatic diamine are halogen atoms An alkyl group having 1 to 3 carbon atoms or an alkoxyl group, a cyano group, an alkyl group or an alkoxyl group in which some or all of the hydrogen atoms are substituted with halogen atoms, or a halogenated alkyl group having 1 to 3 carbon atoms or an alkoxyl group And aromatic diamines substituted with

  As diamines constituting the polyamic acid, in addition to the aromatic diamines described above, for example, 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, Aliphatic diamines such as 1,8-diaminooctane, and alicyclic diamines such as 1,4-diaminocyclohexane and 4,4′-methylenebis (2,6-dimethylcyclohexylamine) may be used. However, in this case, the total amount of diamines other than aromatic diamines is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less of the total diamines.

  The tetracarboxylic acids constituting the polyamic acid include aromatic tetracarboxylic acids (including acid anhydrides), aliphatic tetracarboxylic acids (including acid anhydrides), and alicyclic tetracarboxylic acids that are commonly used for polyimide synthesis. Acids (including acid anhydrides thereof) can be used, but the aromatic tetracarboxylic acids are the main component from the viewpoint of heat resistance. Specifically, the aromatic tetracarboxylic acids are preferably 80% by mass or more of the total tetracarboxylic acids, more preferably 90% by mass or more, still more preferably 95% by mass or more, and most preferably 100% by mass. When the tetracarboxylic acid is an acid anhydride, the number of anhydride structures in the molecule may be one or two, but preferably one having two anhydride structures (dianhydride). Good). Tetracarboxylic acids may be used alone or in combination of two or more.

  The aromatic tetracarboxylic acids are not particularly limited, but are preferably pyromellitic acid residues (that is, those having a structure derived from pyromellitic acid), and more preferably acid anhydrides thereof. Specific examples include those exemplified below as preferred aromatic tetracarboxylic acids.

  Although it does not specifically limit as aliphatic tetracarboxylic acid or alicyclic tetracarboxylic acid, It is preferable that it is an acid anhydride. Specifically, for example, cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, etc. Is mentioned. The total amount of tetracarboxylic acids other than these aromatic tetracarboxylic acids (that is, aliphatic tetracarboxylic acids and alicyclic tetracarboxylic acids) is preferably 20% by mass or less, more preferably 10% by mass or less of all tetracarboxylic acids. More preferably, it is 5% by mass or less.

  In addition, although the polyimide film in this invention is a film obtained by reaction of diamines and tetracarboxylic acids as mentioned above, in the range which does not impair the effect of this invention, for example, cyclohexane-1,2,4- You may be comprised including tricarboxylic acids, such as a tricarboxylic acid anhydride. In this case, the content of tricarboxylic acids is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass or less with respect to 100 parts by mass of the total amount of tetracarboxylic acids and tricarboxylic acids.

  The solvent used in the reaction (polymerization) of diamines and tetracarboxylic acids to obtain a polyamic acid is not particularly limited as long as it dissolves both the raw material monomer and the produced polyamic acid. 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 Examples include amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols. These solvents may be used alone or in combination of two or more. The amount of these solvents used may be an amount sufficient to dissolve the raw material monomer. As a specific amount used, the amount of all monomers in the reaction solution (solution in which the monomer is dissolved) is usually The amount is 5 to 40% by mass, preferably 10 to 30% by mass.

  The conditions for the polymerization reaction (hereinafter also simply referred to as “polymerization reaction”) for obtaining the polyamic acid may be conventionally known conditions, 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. 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 anhydride, 4-phenylethynyl phthalic anhydride, and ethynylaniline are preferable, and maleic anhydride is particularly 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 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 liquid feeding stability. .

  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 order to form a polyimide film from the polyamic acid solution obtained by the polymerization reaction, a green film (self-supporting precursor film) is obtained by applying and drying the polyamic acid solution on a polyimide film production support, Next, a method of imidizing the green film by subjecting it to a heat treatment can be employed. Application of 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, casting from a nozzle with a slit, 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. The heating temperature for drying the applied polyamic acid solution is preferably 50 ° C to 120 ° C, more preferably 80 ° C to 100 ° C. 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 the time of heat-treating the green film is preferably, for example, 150 to 550 ° C, more preferably 280 to 520 ° C. The heat treatment time is desirably 0.05 to 10 hours.

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

  The average linear expansion coefficient between 30 ° C. and 300 ° C. of the polyimide film is preferably −5 ppm / ° C. to +20 ppm / ° C., more preferably −5 ppm / ° C. to +15 ppm / ° C., further preferably 1 ppm. / ° C. to +10 ppm / ° C. If it is out of this range, the difference in coefficient of linear expansion from the support becomes large, so that the support made of polyimide film and inorganic substance may be easily peeled off during the process of applying heat. In many cases, the linear expansion coefficient does not change in the temperature range for metals and ceramics, but the linear expansion coefficient (CTE) may change in the temperature range for polyimide films. Therefore, the measurement lower limit may be replaced with 0 ° C, 30 ° C, 50 ° C, and the measurement upper limit may be replaced with 200 ° C, 300 ° C, 400 ° C. For example, in the present invention, an average value between 30 ° C. and 300 ° C. is used as the linear expansion coefficient of the polyimide film, but the temperature range to be noticed varies depending on the application, and 30 ° C. in consideration of the process at high temperature. When examining the range from 100 to 400 ° C, the range may be from 100 ° C to 400 ° C. With the reflow process in mind, when examining the range from 50 ° C to 280 ° C, the operating temperature range is -50 ° C to 150 ° C. There may be cases where emphasis is placed on.

  The tensile elastic modulus of the polyimide film in the present invention is preferably 2 GPa or more in both the flow direction and the width direction of the film, more preferably 3 GPa or more, further preferably 6 GPa or more, and preferably 12 GPa or less, More preferably, it is 10 GPa or less, More preferably, it is 9 GPa or less. If the tensile elastic modulus is too low, it is not preferable because it is necessary to devise an idea that elongation occurs at the time of application, and it is practically difficult to produce a polyimide film having a tensile elastic modulus higher than the above range. In addition, the tensile elasticity modulus of a film can be measured by the method mentioned later in an Example, for example.

  Although the thickness of the polyimide film in this invention is not specifically limited, 1 micrometer-200 micrometers are preferable, More preferably, they are 3 micrometers-60 micrometers. The thickness unevenness of these polyimide films is also preferably 20% or less. If the thickness of the polyimide film is less than 1 μm, it may be difficult to control the thickness and may be difficult to peel from the support. If it exceeds 200 μm, the polyimide film may be bent when peeled from the support. There is a fear. By using a polyimide film having a thickness in the above-mentioned range, it can greatly contribute to the enhancement of the performance of elements such as sensors and the miniaturization of electronic parts.

  The polyimide film is preferably obtained in the form of being wound as a long polyimide film having a width of 300 mm or more and a length of 10 m or more at the time of production, and a form of a roll-shaped polyimide film wound on a winding core Are more preferred.

In the polyimide film, in order to ensure handling and productivity, a sliding material (particle) is added to and contained in the polyimide constituting the film, and the surface of the polyimide film is given fine irregularities to ensure slipperiness. It is preferable.
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, 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. If the particle diameter exceeds the upper limit, the unevenness of the surface becomes too large and the pasting strength becomes weak, which may cause practical problems.

  The addition amount of the lubricant is 0.05 to 50% by mass, preferably 0.1 to 3% by mass, and more preferably 0.20 to 1% as the addition amount with respect to the polymer solid content in the polyamic acid solution. 0% by mass. If the amount of the lubricant added is too small, it is difficult to expect the effect of the lubricant addition, and there is a case that the slipperiness is not secured so much that the polyimide film production may be hindered. Even if the slipperiness is ensured, there is a possibility that the smoothness is lowered, the breaking strength and breaking elongation of the polyimide film are lowered, and the CTE is 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, Even if the other surface does not contain or contains a lubricant, a multilayer polyimide film composed of a polyimide film having a small amount of lubricant may be used. 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.

The multilayer polyimide film is, for example, a polyamic acid solution (polyimide precursor solution) with a lubricant (preferably having an average particle size of about 0.05 to 2.5 μm) of 0 per polymer solids in the polyamic acid solution. 0.05% to 50% by mass (preferably 0.1 to 3% by mass, more preferably 0.20 to 1.0% by mass) and no lubricant or a small amount of the content ( It is preferable to produce using two polyamic acid solutions which are preferably 0.3% by mass or less, more preferably 0.01% by mass or less) based on the polymer solid content in the polyamic acid solution.
The method of multilayering (lamination) of the multilayer polyimide film is not particularly limited as long as no problem occurs in the adhesion between the two layers, and any method may be used as long as the adhesion is achieved without using an adhesive layer or the like. For example, i) a method in which one polyimide film is prepared and then the other polyamic acid solution is continuously applied onto the polyimide film to imidize; ii) one polyamic acid solution is cast to produce a polyamic acid film. After this, the other polyamic acid solution is continuously applied onto the polyamic acid film and then imidized, iii) a method by coextrusion, iv) a polyamic acid which does not contain a lubricant or has a small content Examples thereof include a method in which a polyamic acid solution containing a large amount of a lubricant is applied on a film formed by a solution by spray coating, T-die coating, or the like to imidize. 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 the polyamic acid solution containing a large amount of the lubricant (a) layer, does not contain the lubricant or contains it Assuming that the film (layer) formed of the polyamic acid solution in a small amount is the (b) layer, the (a) layer / (b) layer is preferably 0.05 to 0.95. If the (a) layer / (b) layer exceeds 0.95, the smoothness of the (b) layer tends to be lost. On the other hand, if it is less than 0.05, the effect of improving the surface properties is insufficient and the slipperiness is lost. May be.

  It is important that the polyimide film be subjected to plasma treatment on at least the surface facing the support. By applying the plasma treatment, the polyimide film surface is modified to a state in which a functional group exists (so-called activated state), and good adhesion to the support becomes possible.

  The plasma treatment is not particularly limited, but includes RF plasma treatment in vacuum, microwave plasma treatment, microwave ECR plasma treatment, atmospheric pressure plasma treatment, corona treatment, etc., gas treatment containing fluorine, ion Also includes ion implantation using a source, processing using a PBII method, frame processing, intro processing, and the like. Among these, RF plasma treatment, microwave plasma treatment, and atmospheric pressure plasma treatment in vacuum are preferable.

Appropriate conditions for the plasma treatment include oxygen plasma, plasma containing fluorine such as CF ₄ and C ₂ F _6, plasma known to have a high etching effect, or physical energy such as Ar plasma. It is desirable to use plasma with a high effect of applying to the polyimide surface and physically etching. Further, it is also preferable to add plasma such as CO ₂ , H ₂ , N ₂ , a mixed gas thereof, and further water vapor. When aiming at processing in a short time, a plasma having a high plasma energy density, a high kinetic energy of ions in the plasma, and a high number density of active species are desirable. From this point of view, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation with an ion source that easily implants high-energy ions, PBII method, and the like are also desirable.

  The effects of plasma treatment include the addition of the above-mentioned surface functional groups, the change in contact angle accompanying this, improvement in adhesion, removal of surface contamination, etc., as well as the removal of irregularly shaped objects associated with 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 discharge conditions that have an etching action, only the polymer is selectively etched to expose the lubricant (also referred to as particles or filler).

  In addition to the above plasma treatment, as a means of obtaining an etching effect on the film surface, polishing with a pad including the case where a chemical solution is used in combination, brush polishing, polishing with a sponge soaked with a chemical solution, and putting abrasive particles in the polishing pad Examples include polishing with sand, sand blasting, wet blasting, and the like, and these means may be employed together with plasma treatment.

  The plasma treatment may be performed only on one side of the polyimide film or on both sides. When performing plasma treatment on one side, it is possible to perform plasma treatment only on the side of the polyimide film that is not in contact with the electrode by placing the polyimide film in contact with the electrode on one side in the plasma treatment with parallel plate electrodes. it can. If 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 becomes possible by performing plasma processing in the state which stuck the protective film on the single side | surface of the polyimide film. In addition, as a protective film, a PET film with an adhesive or an olefin film can be used.

The polyimide film subjected to the plasma treatment is preferably subjected to an acid treatment after the plasma treatment. On the polyimide film surface containing the lubricant (particles), even if the lubricant has a convex shape near the surface, a very thin polyimide layer exists on the surface. Since polyimide has strong resistance to acid, even if it is a very thin layer, if polyimide is on the surface of the lubricant, the acid will not be in direct contact with the surface of the lubricant and will not be eroded by the acid treatment. After only the polymer (polyimide) is selectively etched due to the effect, the acid directly contacts the surface of the lubricant. Therefore, if an appropriate acid type is selected and acid treatment is performed, only the lubricant can be obtained in a very short time. Dissolution removal can be performed and a crater is formed.
This crater is considered to be the remaining part in which the lubricant exposed from the polyimide film surface by the plasma treatment is eluted by the acid, and is not a mere dent but a dent with its edge raised. As a reference, FIG. 4 shows an AFM image showing the crater part, FIG. 5 shows a cross-sectional image of the straight part of the crater part shown in FIG. 4, and FIG. 6 shows an AFM image (10 μm square) including the crater part. The edge portion of the crater is softer than the protrusion in which the lubricant particles are encapsulated, and is deformed with a relatively weak force when the polyimide film and the support are brought into pressure contact. The protrusion containing the lubricant is not easily deformed and inhibits the adhesion between the polyimide film and the support, but the adhesion between the polyimide film and the support is achieved by making the lubricant part into such a crater-like shape. And the peel strength between the polyimide film and the support can be further improved.

  The acid treatment can be performed by immersing the plasma-treated polyimide film in a chemical solution containing acid, or by applying or spraying the chemical solution on the plasma-treated polyimide film. You may use washing together. Moreover, the acid treatment of only one side becomes possible by performing an acid treatment in the state which stuck the protective film on the single side | surface of the polyimide film. As the protective film, a PET film with an adhesive or an olefin film can be used.

The acid used for the acid treatment is not particularly limited as long as it can etch only the lubricant. For example, HF, BHF and the like are preferably used, and these are usually used as an aqueous solution. This is because it is generally known that an aqueous HF solution or an aqueous BHF solution has an action of dissolving SiO ₂ or glass and is frequently used in the semiconductor industry. For example, SiO ₂ dissolution efficiency of HF has been well studied, 10% by weight of SiO ₂ etching rate of the aqueous HF solution is known to be about 12 Å / sec at room temperature, SiO ₂ lubricant of about 80nm is It can be sufficiently processed by contact with a chemical solution for about 1 minute. From such knowledge and results of use, when performing acid treatment with an HF aqueous solution or a BHF aqueous solution, it is preferable to use SiO ₂ as a lubricant, but of course, the type of the lubricant is not limited to SiO _2. .
As for the acid concentration in a chemical | medical solution, 20 mass% or less is preferable, More preferably, it is 3-10 mass%. If the acid concentration in the chemical solution is too thin, the etching time takes a long time, and the productivity is lowered.

  The step of applying plasma treatment and acid treatment to the polyimide film (raw fabric) is preferably performed by roll-to-roll from the viewpoint of increasing the efficiency of the treatment. Since the polyimide film roll subjected to the plasma treatment also has a lubricant, the handling property as a roll is equivalent to that before the plasma treatment. Moreover, after performing plasma treatment with a roll, it is also useful to perform acid treatment after making it into a cut sheet from the viewpoint that simple implementation is possible.

As described above, the surface morphology of the polyimide film subjected to the plasma treatment and the acid treatment has ² to 100 craters having a diameter of 10 to 500 nm per 100 μm ² when one surface thereof is observed by the AFM method described later. Preferably, Ra on the other surface is preferably 0.3 nm to 0.95 nm, which improves the adhesion and provides a smoothness suitable for bonding and lamination without an adhesive with the support. It has a given surface.

A polyimide film having ² to 100 craters having a diameter of 10 to 500 nm on one side per 100 μm ² has a more appropriate peel strength in bonding lamination without an adhesive with a support. Preferably, the number of craters is 5-30 per 100 μm ² and the crater diameter is 30-100 nm. If the diameter of the crater is less than 10 nm, the effect of improving the adhesiveness will be reduced. It becomes difficult. When the number of craters is less than 2, the effect of improving the adhesiveness is reduced, and when the number of craters exceeds 100, the polyimide film strength is adversely affected and the effect of improving the adhesiveness is hardly exhibited.

  It is particularly preferable that Ra on the other surface of the polyimide film is a smooth surface having a thickness of 0.3 nm to 0.95 nm in order to produce a precise electric circuit or semiconductor device. For example, when Ra exceeds 2.0 nm. In other words, it does not have the necessary degree of smoothness, and may adversely affect the metal foil film formed thereon in terms of adhesion and smoothness. Such a polyimide film having a smooth surface is produced by using a polyamide acid solution for forming a polyimide (polyimide precursor solution) with a combination of a lubricant and a non-added or a very small amount. In addition, roll roll-up property and proper slipping property at the time of polyimide film production are also given, and the polyimide film production becomes easy.

<Patterning process>
In the method for producing a laminate of the present invention, a good adhesion is obtained by using a coupling agent on at least one of the surfaces of the support and the polyimide film facing each other, having different adhesive peel strengths and substantially the same surface roughness. The patterning process which forms a part and an easy peeling part is performed. That is, the patterning process in the present invention is a very thin coupling process layer having a thickness of several nanometers to several tens of nanometers formed by the coupling agent treatment, and a good adhesion portion having a high adhesive peel strength and a low adhesive peel strength. It is to form two regions with an easily peelable portion in an intended pattern. And the surface roughness of this good adhesion part and an easy peeling part is substantially the same.
As a patterning treatment means, a coupling agent treatment is performed to form a coupling treatment layer, and then a part of the coupling treatment layer is subjected to an inactivation treatment to form a predetermined pattern. preferable. Thereby, the part with strong peeling strength (adhesion peeling strength) between a support body and a polyimide film can be produced intentionally. The deactivation treatment of the coupling treatment layer means physically removing the coupling treatment layer partially (so-called etching), physically masking the coupling treatment layer microscopically, It includes chemically modifying the coupling layer.

(Coupling agent treatment)
In the present invention, the coupling agent means a compound that is physically or chemically interposed between the support and the polyimide film and has an action of increasing the adhesive force between the two, and is generally a silane coupling. Compounds known as agents, phosphorus coupling agents, titanate coupling agents and the like.

  The coupling agent is not particularly limited, but a silane coupling agent having an amino group or an epoxy group is particularly preferable. Preferable specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrichlorosilane, Vinyltrimethoxysilane, vinyltriethoxysila 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryl Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyl Limethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, tris- (3-trimethoxysilylpropyl) isocyanurate Chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, aminophenyltrimethoxysilane, aminophenethyltrimethoxysilane, aminophenylaminomethylphenethyltrimethoxysilane, and the like.

  As the coupling agent that can be 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-mercaptohexaloyl) benzyl alcohol, 11-amino-1-undecenethiol, 11-mercaptoundecylphosphonic acid, 11-mercaptoundecyltrifluoro Acetic acid, 2,2 ′-(ethylenedioxy) diethanethiol, 11-mercaptoundecyltri (ethylene glycol), (1-mercaptoundec-11-yl) tetra (ethylene glycol), 1- (methylcarboxy) Undec-11-yl) hexa (d Lenglycol), hydroxyundecyl disulfide, carboxyundecyl disulfide, hydroxyhexadodecyl disulfide, carboxyhexadecyl disulfide, tetrakis (2-ethylhexyloxy) titanium, titanium dioctyloxybis (octylene glycolate), zirconium tributoxy monoacetyl Acetonate, zirconium monobutoxyacetylacetonate bis (ethyl acetoacetate), zirconium tributoxy monostearate, acetoalkoxyaluminum diisopropylate, n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltri Chlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, diethoxydimethyl Silane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltrichlorosilane, n -Octyltriethoxysilane, n-octyltrimethoxysilane, triethoxyethylsilane, triethoxymethylsilane, trimethoxymethylsilane, trimethoxyphenylsilane, pentyltriethoxysilane, pentyltrichlorosilane, triacetoxymethylsilane, trichlorohexylsilane , Trichloromethylsilane, trichlorooctadecylsilane, trichloropropylsilane, trichlorotetra Decylsilane, trimethoxypropylsilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, trichlorovinylsilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, trichloro-2- Cyanoethylsilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, 2,3-butanedithiol, 1-butanethiol, 2-butanethiol, cyclohexane Thiol, cyclopentanethiol, 1-decanethiol, 1-dodecanethiol, 3-mercaptopropionic acid-2-ethylhexyl , Ethyl 3-mercaptopropionate, 1-heptanethiol, 1-hexadecanethiol, hexyl mercaptan, isoamyl mercaptan, isobutyl mercaptan, 3-mercaptopropionic acid, 3-methoxybutyl 3-mercaptopropionic acid, 2-methyl-1 -Butanethiol, 1-octadecanethiol, 1-octanethiol, 1-pentadecanethiol, 1-pentanethiol, 1-propanethiol, 1-tetradecanethiol, 1-undecanethiol, 1- (12-mercaptododecyl) imidazole, 1 -(11-mercaptoundecyl) imidazole, 1- (10-mercaptodecyl) imidazole, 1- (16-mercaptohexadecyl) imidazole, 1- (17-mercaptoheptadecyl) imidazo It Le, 1- (15-mercapto) dodecanoic acid, 1- (11-mercapto) undecanoic acid, also be used such as 1- (10-mercapto) decanoic acid.

  Particularly preferred coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl). -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, aminophenyltrimethoxysilane, amino Phenethyltrimethoxysilane, aminopheny Such as aminomethyl phenethyltrimethoxysilane the like. In the case where particularly high heat resistance is required in the process, it is desirable to use an aromatic group between Si and an amino group.

As a method of forming a coupling treatment layer by performing a coupling agent treatment, a method in which the coupling agent is directly or diluted with a solvent or the like, applied to a support and / or a polyimide film, dried and heat-treated, or the coupling agent itself Alternatively, a method in which a support and / or a polyimide film is immersed in a solution diluted with a solvent, followed by drying and heat treatment, a method of adding at the time of polyimide film production, and a method of treating with a coupling agent at the same time as polyimide film production may be adopted. it can.
A conventionally known coating method may be employed as a coating method for the coupling agent or its diluted solution. Further, for example, a method of printing the entire surface of the coupling agent or a diluted solution thereof by inkjet, or a method using other existing printing methods may be employed. 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 during the heat treatment are preferably 50 to 250 ° C., more preferably 75 to 165 ° C., more preferably about 95 to 155 ° C., preferably 30 seconds or more, more preferably 2 minutes or more, still more preferably What is necessary is just to heat for 5 minutes or more. If the heating temperature is too high, decomposition or inactivation of the coupling agent may occur, and if it is too low, fixing will be insufficient. Moreover, even if the heating time is too long, the same problem may occur. The upper limit of the heating time is preferably 5 hours, more preferably about 2 hours. In addition, when performing a coupling agent process, since it is known that pH during process will influence a performance large, it is desirable to adjust pH suitably.

(Inactivation process)
As a means for selectively inactivating a part of the coupling treatment layer to form a predetermined pattern, the entire surface 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. An example is as shown in FIG. 3. As shown in FIG. 3 (1), the good adhesion portion 10 is arranged only on the outer peripheral portion of the laminate, and the easily peelable portion 20 is arranged inside the laminate. As shown in FIG. 3 (2), a pattern in which the good adhesion portion 10 is linearly arranged inside the outer peripheral portion of the laminated body can be given.

  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 diameter as much as possible.
The vacuum plasma treatment refers to a treatment in which an object is exposed to plasma generated by discharge in a decompressed gas, or 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.
The atmospheric pressure plasma treatment is a treatment in which an object is exposed to plasma generated by a discharge generated in a gas that is generally in an atmospheric pressure atmosphere, or ions generated by the discharge collide with the object. say. As the gas, neon, argon, nitrogen, oxygen, carbon dioxide, hydrogen or the like alone or a mixed gas 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 for irradiating radiation such as electron beam, alpha ray, X-ray, beta ray, infrared ray, visible ray, ultraviolet ray, laser beam 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 larger energy than general visible light, and therefore can be treated as a kind of actinic radiation in the present invention.
The active gas treatment is a gas having an activity that causes a chemical or physical change in the coupling 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 treatment refers to a liquid having an activity that causes a chemical or physical change in the coupling treatment layer, for example, a liquid such as an alkaline solution, an acid solution, a reducing agent solution, an oxidizing agent solution, or an object in the solution. The treatment to be exposed.

  In particular, from the viewpoint of productivity, as the inactivation treatment, a method combining actinic radiation and a mask, or a method combining an atmospheric pressure plasma treatment and a mask is preferably used. The actinic radiation treatment is preferably an ultraviolet irradiation treatment, that is, a UV irradiation treatment, from the viewpoints of economy and safety. Further, in the case of UV irradiation treatment, by selecting a support having UV transparency, the support is treated with a coupling agent, and then drawn directly from the surface opposite to the treated surface. Or UV irradiation can also be performed through 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 a polyimide film subjected to a coupling agent treatment and / or a support is placed in an apparatus that generates ultraviolet rays (UV light) having a wavelength of 400 nm or less, and UV irradiation is performed. The UV light wavelength is preferably 260 nm or less, and more preferably a short wavelength of 200 nm or less. Irradiation of such short-wavelength UV light in the presence of oxygen adds UV light energy to the sample (coupling layer) and generates active oxygen and ozone in an excited state near the sample. The inactivation treatment of the present invention can be performed more effectively. However, at a wavelength of 170 nm or less, the absorption of UV light by oxygen is significant, so that it is necessary to consider the UV light reaching the coupling layer. Irradiation in a completely oxygen-free atmosphere does not show the effect of surface modification (inactivation) with active oxygen or ozone, so it must be devised to allow active oxygen and ozone to reach while UV light passes. . For example, by placing a UV light source in a nitrogen atmosphere and transmitting UV light through quartz glass, the distance from the quartz glass to the coupling treatment layer is shortened to suppress UV light absorption. In addition to ingenuity, the method of controlling the absorption of UV light by controlling the amount of oxygen instead of the normal atmosphere, the control of the UV light source, the gas flow between the coupling layers, etc. It is effective as a 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 light meter having a sensitivity peak in a wavelength range of at least 150 nm to 400 nm, and 200 mW / cm ² or less is for preventing alteration of the support. This is desirable. The irradiation time of UV light is preferably 0.1 minutes or more and 30 minutes or less, more preferably 0.5 minutes or more, still more preferably 1 minute or more, particularly preferably 2 minutes or more, and more preferably 10 minutes or less. More preferably, it is 5 minutes or less, and particularly preferably 4 minutes or less. If the irradiation time of the UV light becomes long, the productivity may be reduced. If the irradiation time is too short, a higher-intensity light source is required, or accuracy is required for controlling the irradiation time. It is not preferable. In terms of integrated light quantity is preferably ^{30mJ / cm 2 ~360000mJ / cm 2} , more preferably ^{300mJ / cm 2 ~120000mJ / cm 2} , more preferably from ^{600mJ / cm 2 ~60000mJ / cm 2} .

  Pattern formation during the UV irradiation process is performed by intentionally creating a portion that irradiates light and a portion that does not irradiate light. As a method of forming a pattern, a method of making a portion that shields UV light and a portion that does not shield UV light, a method of scanning UV light, or the like can be given. In order to clarify the end of the pattern, it is effective to block the UV light and cover the support with a mask. It is also effective to scan with a parallel beam of a UV laser.

  The light source that can be used for the UV irradiation treatment is not particularly limited. , Ar laser, D2 lamp and the like. Among these, excimer lamps, low-pressure mercury lamps, Xe excimer lasers, ArF excimer lasers, KrF excimer lasers, and the like are preferable.

  As described above, the coupling treatment layer that has been subjected to the deactivation treatment has a good adhesion portion that is a portion where the peel strength between the support and the polyimide film is strong, depending on whether or not the deactivation (etching) is performed. A pattern composed of an easily peelable portion which is a portion where the peel strength between the body and the polyimide film is weak is formed. For example, as illustrated in Examples 1 to 4 and Examples 6 to 15 described later, when γ-aminopropyltrimethoxysilane is applied to glass, the UV non-irradiated part is a good adhesion part with strong peel strength, When the amino group is broken by UV irradiation, the peeling strength is weakened, and the UV irradiation part becomes an easy peeling part. This is because, as shown in measurement examples 1 to 5 described later, the atomic percentage of the nitrogen (N) element is lowered by UV irradiation, and subsequently carbon (C) is also reduced, so that the amino group and propyl may be broken. It can be inferred from the suggestion. On the other hand, when the coupling treatment layer is formed on the support with a coupling agent having no functional group such as n-propyltrimethoxysilane, on the other hand, the part not irradiated with UV becomes an easily peelable part, A good adhesion part is formed by irradiating light and breaking the propyl part. It is industrially advantageous to use glass as the substrate as the support. In this case, it is more practical to reduce the peel strength by UV irradiation, but depending on the application, the substrate used, and the required peel strength It is also conceivable that the UV light irradiated portion is a good adhesion portion.

<Pressurized heat treatment>
In the manufacturing method of the laminated body of this invention, after the said etching, the said support body and the said polyimide film are piled up, and it heat-processes by pressure. Thereby, a support body and a polyimide film can be adhere | attached.
In general, as a method for obtaining a laminate of a support and a polyimide film, a method in which a polyimide varnish (polyamic acid solution described above) is directly applied on a support and imidized to form a film is also considered. In the invention, the polyimide is formed into a film and then laminated on the support. For example, when a polyamic acid solution is imidized by heating on a support, for example, although it depends on the support, a concentric film thickness distribution can be easily formed, and the state of the front and back of the polyimide film (transfer of heat) This is because the film tends to be warped or lifted from the support due to the difference in the method, etc., whereas these problems can be avoided if the film is formed in advance. Furthermore, by superimposing the film on the support, it is possible to form a device (circuit or the like) on the film before superposition within a range where pressure heating treatment described later can be performed.

  The pressure heat treatment may be performed while heating a press, a laminate, a roll laminate, or the like, for example, in an atmospheric pressure atmosphere or in a vacuum. A method of heating under pressure in a flexible bag can also be applied. From the viewpoint of improving productivity and reducing the processing cost brought about by high productivity, press or roll lamination in an air atmosphere is preferable, and a method using rolls (roll lamination or the like) is particularly preferable.

The pressure during the pressure heat treatment is preferably 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa. If the pressure is too high, the support may be damaged. If the pressure is too low, a non-adhering portion may be produced, resulting in insufficient adhesion. The temperature during the pressure heat treatment is 150 ° C to 400 ° C, more preferably 250 ° C to 350 ° C. If the temperature is too high, the polyimide film may be damaged. If the temperature is too low, the adhesion tends to be weak.
The pressure heat treatment can be performed in an atmospheric pressure atmosphere as described above. However, in order to obtain a stable peel strength on the entire surface, it is preferably performed under vacuum. At this time, the degree of vacuum by a normal oil rotary pump is sufficient, and about 10 Torr or less is sufficient.
As an apparatus that can be used for pressure heat treatment, for example, “11FD” manufactured by Imoto Seisakusho can be used to perform pressing in a vacuum, and a roll-type film laminator in vacuum or a vacuum is used. For example, “MVLP” manufactured by Meiki Seisakusho Co., Ltd. can be used to perform vacuum laminating such as a film laminator that applies pressure to the entire glass surface at once with a thin rubber film.

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

<Application>
In the method for producing a laminate of the present invention, as an application example, a polyimide film in the laminate or a hole portion penetrating in the film thickness direction of the entire laminate is provided as necessary, thereby providing a non-polyimide portion. Also good. The part is not particularly limited, but is preferably filled with a metal whose main component is a metal such as Cu, Al, Ag, Au, or formed by a mechanical drill or laser drilling. And a hole in which a metal film is formed on the wall surface of the hole by sputtering, electroless plating seed layer formation, or the like.

(Laminate)
The laminate of the present invention is a laminate in which a support and a polyimide film are laminated via a coupling treatment layer, and a good adhesion portion having a different peel strength between the support and the polyimide film and an easy adhesion portion. The good adhesion part and the easy peeling part form a predetermined pattern. Thereby, after producing a device on a polyimide film without peeling even in a high temperature process at the time of device production, it becomes a laminated body which can peel a polyimide film from a support easily. The laminate of the present invention can be obtained by the method for producing a laminate of the present invention, and details of the support, the polyimide film, the coupling treatment layer and the like are as described above.

  The good adhesion portion in the present invention refers to a portion where the peel strength between the support and the polyimide film is strong by changing the surface properties 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 between the substrate made of an inorganic material and the polyimide film is weak by changing the surface properties depending on the presence or absence of UV light irradiation.

  In the present invention, the 180-degree peel strength between the support and the polyimide film may be appropriately set according to the type and process of the device laminated thereon, and is not particularly limited. The 180-degree peel strength is preferably 1/2 or less, more preferably 1/5 or less of the 180-degree peel strength of the good adhesion portion. As a general theory, the 180 degree peel strength of the good adhesion portion is preferably 0.5 N / cm or more and 5 N / cm or less, more preferably 0.8 N / cm or more and 2 N / cm or less. The 180 degree peel strength of the easily peelable part is preferably 0.01 N / cm or more and 0.40 N / cm or less, more preferably 0.01 N / cm or more and 0.2 N / cm or less. Here, the lower limit of the 180-degree peel strength of the easily peelable portion is a value that takes into account the bending energy of the polyimide film. 180 degree peel strength in this invention can be measured by the method mentioned later in an Example. In addition, the heat-resistant peel strength, acid peel strength, and alkali peel strength, which will be described later in the examples, are preferably 0.5 N / cm or more and 5 N / cm or less, respectively. There can be.

  In the laminate of the present invention, an adhesive layer or the like is not interposed between the support and the polyimide film as in the prior art, and the intervening is, for example, 10% by mass or more of Si derived from the coupling agent It contains only a lot. And since the coupling treatment layer, which is an intermediate layer between the support and the polyimide film, can be made very thin, there are few degassing components during heating, it is difficult to elute even in the wet process, and even if elution occurs, it will remain in a trace amount An effect is obtained. In addition, the coupling treatment layer usually has many heat-resistant silicon oxide components, and heat resistance at a temperature of about 400 ° C. can be obtained.

  The film thickness of the coupling treatment layer in the laminate of the present invention is extremely thin compared to the support, polyimide film or general adhesive or pressure-sensitive adhesive in the present invention, and is ignored from the viewpoint of mechanical design. In principle, a thickness of the order of a monomolecular layer is sufficient as a minimum. Generally, it is less than 400 nm (less than 0.4 μm), preferably 200 nm or less (0.2 μm or less), more practically 100 nm or less (0.1 μm or less), more preferably 50 nm or less, further preferably 10 nm or less. It is. For processes that desire as few coupling agents as possible, 5 nm or less is possible. However, if the thickness is less than 1 nm, the peel strength may be reduced, or a portion that is not partially attached may appear, and therefore, 1 nm or more is preferable. The film thickness of the coupling treatment layer can be determined by ellipsometry or calculation from the concentration of the coupling agent solution at the time of coating and the coating amount.

(Device structure manufacturing method)
The method for producing a device structure of the present invention is a method for producing a structure in which a device is formed on a polyimide film as a substrate, using the laminate of the present invention having a support and a polyimide film. .
In the method for producing a device structure of the present invention, after forming a device on the polyimide film of the laminate of the present invention, the polyimide film in the easily peelable portion of the laminate is cut and the polyimide film is used as the support. Peel from.

  As a method of cutting into the polyimide film of the easily peelable portion of the laminate, a method of cutting the polyimide film with a cutting tool such as a blade, or a method of cutting the polyimide film by relatively scanning the laser and the laminate There are a method of cutting the polyimide film by relatively scanning the water jet and the laminate, a method of cutting the polyimide film while cutting slightly to the glass layer with a semiconductor chip dicing device, etc., but the method is particularly limited. It is not a thing. For example, in adopting the above-described method, it is possible to appropriately employ a technique such as superimposing ultrasonic waves on the cutting tool or adding a reciprocating operation or an up-and-down operation to improve the cutting performance.

  When making a cut in the polyimide film of the easily peelable portion of the laminate, the position where the cut is made only needs to include at least a part of the easily peelable portion, and basically it is basically cut according to the pattern. However, if an attempt is made to accurately cut according to the pattern at the boundary between the good adhesion portion and the easily peelable portion, an error also occurs. Therefore, it is preferable to cut slightly to the easily peelable portion side from the pattern in terms of increasing productivity. Moreover, in order to prevent peeling without permission before peeling, there may be a production system that cuts into a bonded portion slightly better than the pattern. Furthermore, if the width of the good adhesion portion is set narrow, the polyimide film remaining on the good adhesion portion at the time of peeling can be reduced, the use efficiency of the film is improved, and the device area relative to the laminate area is large. Thus, productivity is improved. Furthermore, an easy peeling part is provided in a part of the outer peripheral part of the laminated body, and the method of peeling off the outer peripheral part as a cutting position without actually making a cut is also an extreme form of the present invention. Yeah.

  The method of peeling the polyimide film from the support is not particularly limited, but is a method of rolling from the end with tweezers, etc., and sticking an adhesive tape to one side of the cut portion of the polyimide film with a device, and then rolling from the tape portion. A method, a method in which one side of a cut portion of a polyimide film with a device is vacuum-adsorbed and then wound from that portion can be employed. In the case of peeling, if a bend with a small curvature occurs in the cut part of the polyimide film with the device, stress may be applied to the device in that part and the device may be destroyed. It is desirable to remove. For example, it is desirable to roll while winding on a roll having a large curvature, or to roll using a machine having a configuration in which the roll having a large curvature is located at the peeling portion.

  In addition, the reinforcing member can be fixed before the device structure (polyimide film with a device) of the present invention is a final product. In this case, the reinforcing member may be fixed after being peeled off from the support, but after fixing the reinforcing member, the polyimide film is cut off and peeled off from the support, or the polyimide film is cut into It is preferable that the reinforcing member is fixed to the cut portion and then peeled off. In the case where the reinforcing member is fixed before peeling, it is possible to make the device part less susceptible to stress by considering the elastic modulus and film thickness of the polyimide film and the reinforcing member. For example, a PET film with an adhesive is pasted as a reinforcing member only on the easily peelable portion of the laminate of the present invention, and the device with a device is cut into the easily peelable portion with the adhesive PET film attached. The polyimide film may be peeled off, or a PET film with an adhesive is attached as a reinforcing member to the entire laminate of the present invention, and an easy-peeled portion of the laminate is cut to provide an PET film with an adhesive. You may make it peel a polyimide film with a device in the stuck state.

  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 advantages of providing gas barrier properties, chemical stability, and transparency. SUS has the advantage that it can be shielded electrically and is difficult to break. In addition, since it is after passing 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. These reinforcing members can be fixed by adhesion or adhesion.

In the present invention, a method for forming a device on a polyimide film 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, electric resistance, passive devices such as coils and capacitors, active devices including semiconductor elements, and electronic circuit systems formed by combining them. is there. Examples of the semiconductor element include a solar cell, a thin film transistor, a MEMS element, a sensor, and a logic circuit.

For example, in a film-like solar cell using the laminate of the present invention, a laminate X including a photoelectric conversion layer made of a semiconductor is formed on the base material of the polyimide film of the laminate of the present invention. . This laminated body X has a photoelectric conversion layer that converts sunlight energy into electric energy as an essential component, and usually further includes an electrode layer for taking out the obtained electric energy.
Hereinafter, a laminated structure in which a photoelectric conversion layer is sandwiched between a pair of electrode layers will be described as a typical example of the laminate X formed to constitute a film-like solar cell. 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 produced by PVD or CVD. 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 of the solar cell of the prior art may be appropriately referred to, 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 one main surface of the polyimide film substrate. The back electrode layer is obtained by laminating a conductive inorganic material by a conventionally known method, for example, a CVD (chemical vapor deposition) method or a sputtering method. Examples of conductive inorganic materials include metal thin films such as Al, Au, Ag, Cu, Ni, and stainless steel, and In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (adding Sn to In ₂ O ₃ Oxide semiconductor-based conductive materials and the like. Preferably, the back electrode layer is a metal thin film. The thickness of the back electrode layer is not particularly limited, and is usually about 30 to 1000 nm. Alternatively, a film forming method that does not use a vacuum, such as Ag paste, may be employed for extracting some electrodes.

The photoelectric conversion layer for converting the energy of sunlight into electric energy is a layer made of a semiconductor, CuInSe ₂ which is a compound semiconductor thin film (chalcopyrite structure semiconductor thin film) made of a group I element, a group III element, and a group VI element. A (CIS) film, or a Cu (In, Ga) Se ₂ (CIGS) film (hereinafter, collectively referred to as a CIS film) in which Ga is dissolved, 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, a vapor deposition method, or the like.
The amorphous silicon layer is a layer made of silicon having substantially no crystallinity. The lack of crystallinity can be confirmed by not giving a diffraction peak even when irradiated with X-rays. Means for obtaining an amorphous silicon layer are known, and examples of such means include a plasma CVD method and a thermal CVD method.
The polycrystalline silicon layer is a layer made of an aggregate of microcrystals made of silicon. The above amorphous silicon layer is distinguished by giving a diffraction peak by irradiation with X-rays. 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 a silicon-based semiconductor layer, and may be, for example, a thick film semiconductor layer. The thick film semiconductor layer is a semiconductor layer formed from a paste such as titanium oxide, zinc oxide, or copper iodide.

As a means for configuring the semiconductor material as the photoelectric conversion layer, a known method may be adopted as appropriate. For example, an about 20 nm a-Si (n layer) is formed by performing high-frequency plasma discharge in a gas in which phosphine (PH ₃ ) is added to SiH ₄ at a temperature of 200 to 500 ° C., and subsequently SiH _4. An a-Si (i layer) of about 500 nm can be formed only with gas, and then diborane (B ₂ H ₆ ) can be added to SiH ₄ to form a p-Si (p layer) of about 10 nm.

Of the pair of electrode layers sandwiching the photoelectric conversion layer, an electrode layer (hereinafter also referred to as a current collecting electrode layer) provided on the side opposite to the polyimide film substrate is formed by consolidating a conductive paste containing a conductive filler and a binder resin. The electrode layer may be a transparent electrode layer. As the transparent electrode layer, an oxide semiconductor material such as In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (In ₂ O ₃ added with Sn) can be preferably used.
Thus, a film-like solar cell in which transparent electrode / p-type a-Si / i-type a-Si / n-type a-Si / metal electrode / polyimide film are laminated in this order, which is a preferred embodiment of the present invention. can get. Alternatively, the p layer may be a-Si, the n layer may be polycrystalline silicon, and a thin undoped a-Si layer may be inserted between the two. In particular, when an 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) is a semiconductor layer in which a transistor and an insulating film, an electrode, a protective insulating film, and the like constituting a transistor are formed by depositing a thin film. It is usually distinguished from silicon wafers that use silicon as the semiconductor layer. Usually, a thin film is produced by a technique using a vacuum such as PVD (physical vapor deposition) such as vacuum vapor deposition or CVD (chemical vapor deposition) such as plasma CVD. For this reason, what 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, oxide semiconductor TFT, organic semiconductor TFT, and the like 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 This 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 and digital micromirror devices.

  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 velocimeter, gyro sensor, acceleration sensor, earthquake sensor, one-dimensional image / linear image sensor, two-dimensional image / CCD image Sensor, CMOS image sensor, liquid / leak sensor (leak sensor), liquid sensor (level sensor), hardness sensor, electric field sensor, current sensor, voltage sensor, power sensor, infrared sensor, radiation sensor, humidity sensor, odor sensor , Flow sensor, tilt sensor, vibration sensor, time sensor, composite sensor that combines these sensors, sensors that output other physical quantities or sensitivity values based on some calculation formula from the values detected by these sensors, etc. Including.

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

Each embodiment of the method for producing a laminate of the present invention and the method for producing a device structure of the present invention described in detail above will be described with reference to the drawings as shown in FIGS.
FIG. 1 is a schematic view showing an embodiment of a method for producing a laminate according to the present invention, in which (1) shows a glass substrate 1 and (2) shows that a coupling agent is applied on the glass substrate 1 and dried. (3) shows the stage of irradiating the UV light after the UV light blocking mask 3 is installed, and (4) shows the stage of irradiating the UV light blocking mask 3 after irradiating the UV light. The removed stage is shown. Here, in the coupling processing layer 2, the UV exposure part is the UV irradiation part 5, and the remaining part is the UV non-irradiation part 4. (5) shows the stage where the polyimide film 6 is pasted, and (6) shows the stage where the polyimide film 7 on the UV irradiation part is cut and peeled from the glass substrate 1.
FIG. 2 is a schematic view showing an embodiment of the method for producing a device structure of the present invention, where (1) shows a glass substrate 1 and (2) shows a coating agent coated on the glass substrate 1 and dried. (3) shows a stage in which the UV light blocking mask 3 is installed and then irradiated with UV light, and (4) shows a stage in which the UV light blocking mask 3 is irradiated with UV light. The stage which removed is shown. Here, in the coupling processing layer 2, the UV exposure part is the UV irradiation part 5, and the remaining part is the UV non-irradiation part 4. (5) shows a stage where a polyimide film 6 is pasted and then a device 8 is formed on the surface of the polyimide film 7 on the UV irradiation part, and (6) shows a glass cut into the polyimide film 7 on the UV irradiation part. The stage which peeled from the board | substrate 1 is shown.

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

<Thickness of polyimide film>
The thicknesses of the polyimide film and each layer (a layer, b layer) constituting the polyimide film were measured using a micrometer (“Millitron 1245D” manufactured by Fine Reef).

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

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

<Evaluation of polyimide film: slipperiness>
Two polyimide films are overlapped on different surfaces (that is, not on the same surface but on the wound outer surface and the wound inner surface when wound as a film roll), and the overlapped polyimide film is 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 on winding outer surfaces or between winding inner surfaces, this is not made into an evaluation item. Further, when evaluating the slipperiness, the protective film on one side of the polyimide film was removed.

<Evaluation of polyimide film: roll winding property>
When a long polyimide film is wound on a winding roll (outer diameter of the mandrel: 15 cm) at a speed of 2 m / min, “皺” indicates that wrinkles do not occur and smooth winding is possible. A case where wrinkles occurred partially was evaluated as “Δ”, and a case where wrinkles were generated or wound around a roll and could not be smoothly wound was evaluated as “x”.

<Evaluation of polyimide film: degree of warpage>
From the obtained polyimide film, a 50 mm × 50 mm square was cut out to obtain a film test piece. When the film test piece is cut out, each side of the square coincides with the longitudinal direction and the width direction of the film, and the center of the square is (a) the center in the film width direction, and (b) 1 of the full width length from the left end. It was cut out from three places so as to be located at a point corresponding to / 3, and (c) a point corresponding to 1/3 of the full width from the right end.
The film test pieces (a) to (c) were left to be concave on the plane, and the distances from the four corner planes (h1, h2, h3, h4: unit mm) were measured, and the average The value was the amount of warpage (mm). The amount of warpage divided by the distance (35.36 mm) from each vertex to the center of the test piece and expressed as a percentage (%) (100 × (warp amount (mm)) / 35.36) is the degree of warpage ( %), And the degree of warpage of the film test pieces (a) to (c) was averaged.

<Evaluation of polyimide film: degree of curl>
The same film test pieces (a) to (c) used for the measurement of the degree of warpage of the polyimide film were subjected to heat treatment for 30 minutes in a 250 ° C. dry oven, and then the heat-treated film was warped in the same manner as described above. The degree of curling was defined as the degree of warpage (%) of the film after heat treatment.

<Number of craters and crater diameter on polyimide film surface>
Measurement was performed by the following AFM method. That is, the number of craters on the surface of the polyimide film was measured using a scanning probe microscope with a surface property evaluation function (“SPA300 / nonavivi” manufactured by SII Nanotechnology Inc.). The measurement is performed in DFM mode, the cantilever uses “DF3” or “DF20” manufactured by SII Nanotechnology, the scanner uses “FS-20A” manufactured by SII Nanotechnology, and the scanning range is The measurement resolution was 1024 × 512 pixels. After the quadratic tilt correction was performed on the measurement image using the software attached to the apparatus, the crater portion was observed. As shown in FIG. 7, the crater has a shape in which the center of the convex portion raised from the flat portion is depressed. Therefore, the diameter of the cross section (the distance between the maximum heights) at the position of the maximum height of the swell was defined as the diameter of the crater part ((1) in FIG. It is the figure (the position where white is high, the position where black is low), (2) is a cross-sectional display example of the unevenness | corrugation of the polyimide film of the white line part of (1), (3) shows the diameter of a crater part. ). And it measured about arbitrary three crater parts, the diameter of the crater part was calculated | required, and those average values were employ | adopted.

  The number of craters was measured by analyzing the obtained 10 μm square measurement image (AFM image) with image processing software “ImageJ”. “ImageJ” is an open source public domain image processing software developed by the National Institutes of Health (NIH). Specifically, first, a binarization operation is performed in which a certain threshold value is used to separate a higher portion and a lower portion (see (2) and (3) in FIG. 8). At this time, as a threshold value, a position that is 12% higher than the particle size of the lubricant used from the maximum point of the distribution with respect to the information in the height direction of the AFM image (a position that is 10 nm higher when the diameter of the lubricant is 80 nm). A threshold was used. By this binarization, an image of only black and white (see (3) in FIG. 8) was obtained, and the number of ring-shaped portions therein was obtained by image processing. That is, the recognition of the annular shape is performed by performing an operation of filling the enclosed circle, and reversing the image filled in the circle (see (4) of FIG. 8) and the image not filled ((( 5) and the image logical product (see (6) in FIG. 8) can be extracted, so that only the inside of the ring can be extracted ((1) in FIG. It is the figure (the position where white is high, the position where black is low) represented by shading, (2) is a cross-sectional display example (straight line is a threshold value) of the unevenness of the polyimide film of the white line part of (1), Is an example of binarization with a threshold value, (4) is an example in which the annular portion is filled, (5) is an example in which (3) is inverted, and (6) is (4) And (5)). The number of craters was calculated by counting craters with a diameter of 10 to 500 nm from the image logical product image obtained by this operation. And it measured about arbitrary three places, calculated | required the number of craters, and employ | adopted those average values.

<Ra value of polyimide film surface and surface roughness Ra of support surface>
The Ra value of the polyimide film surface and the surface roughness Ra (surface morphology) of the support surface (coupling treatment layer surface) were measured with a scanning probe microscope with a surface physical property evaluation function (SPA300 manufactured by SII Nanotechnology Inc.). / Nanonavi "). The measurement is performed in DFM mode, the cantilever uses “DF3” or “DF20” manufactured by SII Nanotechnology, the scanner uses “FS-20A” manufactured by SII Nanotechnology, and the scanning range is The measurement resolution was 512 × 512 pixels. After correcting the quadratic tilt with the software attached to the device for the measurement image, if noise accompanying the measurement is included, other flattening processing (for example, flat processing) is used as appropriate, and Ra with the software attached to the device is used. The value was calculated. Measurement was performed at arbitrary three locations to determine the Ra value, and an average value thereof was adopted.

<Glass transition temperature>
Using a DSC differential thermal analyzer, the glass transition temperature of the polyimide film was determined from the presence or absence of heat absorption / release due to structural changes in the range from room temperature to 500 ° C. No glass transition temperature was observed in any of the polyimide films.

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

<Peel strength>
The peel strength (180 degree peel strength) was measured under the following conditions according to the 180 degree peel method described in JIS C6471. In addition, the sample used for this measurement is provided with an unadhered portion of the polyimide film on one side by designing the size of the polyimide film to 110 mm × 2000 mm with respect to a 100 mm × 1000 mm support (glass). "Grasping."
Device name: “Autograph (registered trademark) AG-IS” manufactured by Shimadzu Corporation
Measurement temperature: Room temperature Peeling speed: 50 mm / min Atmosphere: Air Measurement sample width: 1 cm

(1) Peel strength of UV non-irradiated part For measuring the peel strength of the UV non-irradiated part, a laminate produced separately in the same manner as in each of the examples and comparative examples was used except that UV irradiation was not performed.
(2) Peeling strength of UV irradiated part The peeling strength of the UV irradiated part was measured on the UV irradiated part of the laminate subjected to UV irradiation.
(3) Heat-resistant peel strength The heat-resistant peel strength was measured by placing the laminate (laminated with UV irradiation) in a muffle furnace in a nitrogen atmosphere and heating it to 400 ° C at a temperature rising rate of 10 ° C / min. After holding at 400 ° C. for 1 hour, the sample obtained by opening the door of the muffle furnace and allowing to cool in the atmosphere was used.
(4) Acid peel strength The acid peel strength was measured by immersing the laminate (laminated with UV irradiation) in an 18% by mass hydrochloric acid solution at room temperature (23 ° C) for 30 minutes and washing with water three times. And then using a sample obtained by air drying.
(5) Alkali resistance peel strength The measurement of alkali resistance peel strength was performed by using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution (room temperature (23 ° C.)) for a laminate (a laminate subjected to UV irradiation). For 30 minutes, washed with water three times and then air-dried.

<Degree of film warpage after peeling>
Cut the UV irradiation part of the laminate to peel the polyimide film from the support, cut out a 50 mm x 50 mm square from the central part of the peeled polyimide film to make a film test piece, and the degree of warpage of the test piece (%) Was measured in the same manner as the degree of warpage of the polyimide film, and was taken as the degree of film warp after peeling.

<Lubricant particle size>
About the lubricant (inorganic particles) used in the production example, in the state of dispersion in a solvent (dimethylacetamide), the particle size distribution using a laser scattering particle size distribution analyzer “LB-500” manufactured by HORIBA, Ltd. The volume average particle size was calculated.

<Surface composition ratio>
The surface composition ratio was measured by X-ray photoelectron spectroscopy (ESCA). The measurement was performed under the following conditions using “ESCA5801MC” manufactured by ULVAC-PHI. In the measurement, first, all elements were scanned to confirm the presence or absence of other elements, and then the abundance ratio was measured by performing a narrow scan of the existing elements. Note that the sample to be used for measurement is put into the measurement chamber after sufficient preliminary evacuation, and the operation of scraping the sample surface before measurement by ion irradiation or the like is not performed.
Excitation X-ray: Mg, Kα-ray Photoelectron escape angle: 45 °
Analysis diameter: φ800μm
Pass energy: 29.35 eV (narrow scan), 187.75 eV (all element scan)
Step: 0.125 eV (narrow scan), 1.6 eV (all element scan)
Analytical elements: C, O, N, Si, all elements Vacuum degree: 1 × 10 ⁻⁸ Torr or less

[Production Examples 1 to 3]
(Preparation of polyamic acid solutions A1 to A3)
After purging the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole, 4416 parts by mass of N, N-dimethylacetamide, Next, a dispersion formed by dispersing colloidal silica as a lubricant in dimethylacetamide together with 217 parts by mass of pyromellitic dianhydride (“Snowtex (registered trademark) DMAC manufactured by Nissan Chemical Industries, Ltd.) -ST30 ") 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 at a reaction temperature of 25 ° C for 24 hours, Brown and viscous polyamic acid solutions A1 to A3 were obtained.

[Production Examples 4 to 5]
(Preparation of polyamic acid solutions B1 and B2)
After substituting the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer and a stirring rod with nitrogen, 398 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 147 parts by mass of paraphenylenediamine, Dispersed in 4600 parts by mass of N, N-dimethylacetamide and dispersed as colloidal silica in dimethylacetamide as a lubricant ("Snowtex (registered trademark) DMAC-ST30" manufactured by Nissan Chemical Industries) Is added so that the amount of silica is as shown in Table 2 (mass% with respect to the total amount of polymer solids in the polyamic acid solution) and stirred at a reaction temperature of 25 ° C. for 24 hours to give a brown and viscous polyamic acid solution B1. ~ B2 was obtained.

<< Film Production Example 1 >>
The polyamic acid solution A1 is formed on a non-slip material surface of a polyethylene terephthalate (PET) film (“A-4100” manufactured by Toyobo Co., Ltd.) as a film-forming support, and finally becomes a polyimide film. After coating with a comma coater so that the (film thickness at the time) becomes the “thickness of the (b layer)” shown in Table 3, and drying at 110 ° C. for 5 minutes, (with PET film) The single layer polyamic acid film was wound up (without peeling off from the film).
A single-layer polyamic acid film wound together with a PET film of the film-forming support is attached to the unwinding part of the film-forming machine, and the polyamic acid solution A3 is added to the final film thickness (the film when it finally becomes a polyimide film) The surface of the monolayer polyamic acid film is coated using a comma coater so that the thickness) becomes “thickness of (a layer)” shown in Table 3, and dried at 110 ° C. for 20 minutes to form a film-forming support. A multilayer polyamic acid film having a two-layer structure was obtained on the PET film.

Next, the obtained multilayer polyamic acid film having a two-layer structure is peeled off from the PET film as the film-forming support, passed through a pin tenter having three heat treatment zones, and the first stage 150 ° C. × 2 minutes, the second stage 220 ° C. Heat treatment was performed for 2 minutes and the third stage at 475 ° C. for 4 minutes, and slit to 500 mm width to obtain a polyimide film 1 having a multilayer structure. In addition, after heat-processing, after laminating | stacking on both surfaces of the obtained polyimide film as a non-polyimide protective film which can peel, the PET film (protective film A) provided with the slightly adhesion layer was wound up. Table 3 shows the properties of the obtained polyimide film.
In addition, the protective film A is attached for the purpose of preventing foreign matter adhesion or scratches on the film surface. When transported by roll-to-roll at a relatively low temperature, it is handled manually. When performing, the protective film A operated in the state which stuck. However, for example, when pressing or laminating under conditions exceeding 130 ° C., or when each treatment is performed directly on the surface of the polyimide film, each operation was performed after the protective film A was peeled off.

<< Film Production Example 2 >>
The coating amounts of the polyamic acid solutions A1 and A3 are the final thicknesses (thicknesses when finally becoming polyimide films) of “(a layer) thickness” or “(b layer)” shown in Table 3, respectively. A polyimide film 2 was obtained in the same manner as the film production example 1 except that the thickness was changed to be “thickness” (the thickness of the layer formed with each solution). Table 3 shows the properties of the obtained polyimide film.

<< Film Production Example 3 >>
The order of application of the polyamic acid solutions A1 and A3 is changed (that is, the b layer is formed of the polyamic acid solution A3 and the a layer is formed of the polyamic acid solution A1), and the application amounts of the polyamic acid solutions A1 and A3 are respectively determined. The final film thickness (film thickness when finally becoming a polyimide film) is shown in Table 3 as “(a layer) thickness” or “(b layer) thickness” (the thickness of the layer formed by each solution). The polyimide film 3 was obtained in the same manner as in the film production example 1 except that the change was made. Table 3 shows the properties of the obtained polyimide film.

<< Film Production Example 4 >>
The coating amounts of the polyamic acid solutions A1 and A3 are the final thicknesses (thicknesses when finally becoming polyimide films) of “(a layer) thickness” or “(b layer)” shown in Table 3, respectively. A polyimide film 4 was obtained in the same manner as in Film Production Example 1 except that the thickness was changed to be “thickness” (the thickness of the layer formed with each solution). Table 3 shows the properties of the obtained polyimide film.

<< Film Production Example 5 >>
The polyamic acid solution A3 is not applied (that is, the a layer is not formed), and the coating amount of the polyamic acid solution A1 is shown in Table 4 as the final film thickness (final film thickness when finally becoming a polyimide film). A polyimide film 5 was obtained in the same manner as in Film Production Example 1 except that the thickness was changed to “the thickness of (b layer)”. Table 4 shows the properties of the obtained polyimide film.

<< Film Production Example 6 >>
When the polyamic acid solution A3 is not applied (that is, the a layer is not formed), the polyamic acid solution A1 is changed to A2, and the coating amount of the polyamic acid solution A2 is changed to the final film thickness (finally a polyimide film) The polyimide film 6 was obtained in the same manner as in the film production example 1 except that the film thickness was changed to the “thickness of the (b layer)” shown in Table 4. Table 4 shows the properties of the obtained polyimide film.

<< Film Production Example 7 >>
The polyamic acid solution A1 is changed to B1, the polyamic acid solution A3 is changed to B2, and the coating amounts of the polyamic acid solutions B1 and B2 are set to final film thicknesses (film thicknesses when finally becoming polyimide films), respectively. Film production example 1 except that “(a layer) thickness” or “(b layer) thickness” (layer thickness formed by each solution) shown in Table 4 is changed. Similarly, a polyimide film 7 was obtained. Table 4 shows the properties of the obtained polyimide film.

<< Film Processing Examples 1 to 4 >>
With respect to the films 1 to 4, the surface of the polyimide side (layer side formed with the polyamic acid solution A3) containing no lubricant for each polyimide film was subjected to vacuum plasma treatment. As the vacuum plasma processing, RIE mode using parallel plate type electrodes and RF plasma processing are adopted, O ₂ gas is introduced into the vacuum chamber, high frequency power of 13.56 MHz is introduced, and processing time is increased. Was 3 minutes. Table 5 shows the properties of the obtained polyimide films after the treatment. In addition, since the acid treatment (HF process) was not given to each polyimide film after a process obtained here, the crater was not observed.

<< Film Processing Examples 5 to 7 >>
The films 3 to 5 were subjected to vacuum plasma treatment on both surfaces of each polyimide film, and subsequently acid-treated on both surfaces, then air-dried and dehydrated by placing on a 110 ° C. hot plate for 1 hour. . As the vacuum plasma processing, RIE mode using parallel plate type electrodes and RF plasma processing are adopted, O ₂ gas is introduced into the vacuum chamber, high frequency power of 13.54 MHz is introduced, and processing time is increased. Was 3 minutes. The subsequent acid treatment was performed by immersing in a 10% by mass HF aqueous solution for 1 minute, and then washing and drying. Table 6 shows the properties of the obtained polyimide films after the treatment.

<< Film Processing Examples 8 and 9 >>
The films 6 and 7 were subjected to vacuum plasma treatment in the same manner as in the above film treatment example 1. At this time, in the case of the film 6, the vacuum plasma treatment is applied to the surface containing the lubricant (the surface formed with the polyamic acid solution A2), and in the case of the film 7, the polyimide side not containing the lubricant (polyamide acid). It was applied to the surface of the layer side formed with the solution B2. Table 6 shows the properties of the obtained polyimide films after the treatment. In addition, since the acid treatment (HF process) was not given to each polyimide film after a process obtained here, the crater was not observed.

<< Example 10 of film processing >>
Except that both the surfaces of the film 6 (both surfaces formed with the polyamic acid solution A2) were subjected to the plasma treatment with the vacuum plasma treatment and the acid treatment, the vacuum plasma treatment, the acid treatment were performed in the same manner as the film treatment example 5 described above. Treated, air-dried and dehydrated. Table 7 shows the properties of the obtained polyimide films after the treatment.

(Examples 1-4)
While flowing nitrogen gas in a nitrogen-substituted glove box, 3-aminopropyltrimethoxysilane, which is a silane coupling agent (SC agent), is diluted to 0.5% by mass with isopropyl alcohol, and then a support made of an inorganic substance ( Glass (Corning EAGLE XG manufactured by Corning); 100 mm × 100 mm × 0 previously cleaned separately as a substrate) (ultrasonic cleaning with pure water 5 min, ultrasonic cleaning 5 min with ethanol, ultrasonic cleaning 5 min with pure water) .7 mm thickness) on a spin coater, isopropyl alcohol is dropped and the liquid is shaken off and dried at 1000 rpm. Then, the above-mentioned coupling agent diluted solution is dropped at the center of the rotation, and at 500 rpm first. Then rotate to 2500 rpm over 15 seconds Then spun at 15 seconds 2500 rpm, followed by stopping the rotation over 15 seconds, and a dry state after wetting the entire surface. This was heated for 1 minute on a hot plate heated to 105 ° C. placed in a clean bench to obtain a coupling agent-treated support having a coupling treatment layer having a thickness of 8 nm.

Next, a polyimide film cut out in a 70 mm × 70 mm (□ 70 mm) pattern was placed as a mask on the coupling treatment layer surface of the support provided with the coupling treatment layer obtained above, and a laminate (glass) of UV irradiation treatment was performed within a range of 70 mm × 70 mm (□ 70 mm), leaving 15 mm around each periphery.
The UV irradiation was performed by using a UV / O ₃ cleaning and reforming apparatus (“SKB1102N-01”) and a UV lamp (“SE-1103G05”) manufactured by Run Technical Service Co., Ltd., and separated from the UV lamp by about 3 cm. 4 minutes 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 capable of generating ozone that promotes inactivation treatment) and a wavelength of 254 nm. At this time, the illuminance is about 20 mW / cm ² (illuminance meter (“ORC UV− M03AUV ") at a wavelength of 254 nm.

Next, the coupling agent-treated / UV-irradiated treated surface of the support after UV irradiation treatment and each treated surface of the treated polyimide film obtained in Film Processing Examples 1 to 4 (polyamides in Examples 1 to 4). The surface of the layer formed with the acid solution A3) is opposed to each other, and the roll is laminated at the front and back using a roll laminator at 150 ° C. After laminating without moving, the laminate was pressed at a pressure of 10 MPa at 300 ° C. for 10 minutes to obtain a laminate of the present invention.
Table 8 shows the evaluation results of the obtained laminate.
Separately, the coupling agent-treated surface of the support provided with the coupling treatment layer obtained above, and each treated surface of the polyimide film after treatment obtained in Film Processing Examples 1 to 4 (in Examples 1 to 4). Layered with the polyamic acid solution A3 so as to face each other, and subjected to the same pressure and heat treatment (lamination using a roll and pressing in an atmospheric pressure) as above, and UV non-irradiation A sample for measuring the peel strength of the part was prepared.
The evaluation result is also obtained when the pressure and heat treatment is performed by vacuum pressing with a rotary pump at a pressure of 10 ⁺² Pa or less at a pressure of 10 MPa at 300 ° C. for 10 minutes. Was almost equivalent

(Example 5)
A laminate of the present invention was obtained in the same manner as in Example 2 except that a silicon wafer (Si wafer) having a thickness of 0.725 mm was used as the support (substrate) made of an inorganic substance.
Table 8 shows the evaluation results of the obtained laminate.
In addition, each Example (Examples 1, 3, and 4) other than Example 2 was performed in the same manner except that a silicon wafer was used instead of glass as a support made of an inorganic material, and a laminate was obtained. The evaluation results of the obtained laminate were almost the same as when the glass was used as the support.

(Examples 6 to 8)
Using the treated polyimide film obtained in Treatment Examples 5 to 7 as the polyimide film after film treatment to be superimposed on the support, the coupling agent treated surface of the coupling agent treated glass and each treatment of the treated polyimide film A laminated body of the present invention was obtained in the same manner as in Example 1 except that the surfaces (the surfaces on the layer side formed with the polyamic acid solution A1 in Examples 6 to 8) were opposed to each other. .
Table 9 shows the evaluation results of the obtained laminate.
In addition, about Example 6-8, it carried out similarly except using a silicon wafer instead of glass as a support body which consists of an inorganic substance, and obtained the laminated body, but all the evaluation results of the obtained laminated body are respectively It was almost the same as when glass was used as the support.

Example 9
Same as Example 2 except that n-propyltrimethoxysilane (n-PS) was used as a coupling agent, and that the UV irradiation treatment area was 15 mm around the glass. Thus, a laminate of the present invention was obtained.
Table 9 shows the evaluation results of the obtained laminate.
In addition, as the polyimide film after the film treatment to be overlapped with the support, the layer-side surface formed with the polyamic acid solution A3 of the film using the treated polyimide film obtained in Treatment Example 5 (only plasma treatment was performed). The surface (surface treated with plasma treatment and acid treatment) formed with the polyamic acid solution A2 of the post-treatment polyimide film obtained in Treatment Example 10 is used for the glass. A laminated body was obtained in the same manner except that the overlapping was performed. The evaluation results of the obtained laminated body were almost the same as those of Example 9.

(Examples 10 and 11)
A laminate of the present invention was obtained in the same manner as in Example 2 or Example 3 except that instead of the UV irradiation treatment, an active gas treatment with ozone gas was performed.
The active gas treatment with ozone uses a “PSA ozonizer” manufactured by Sumitomo Precision Industries, Ltd., the ozone concentration is 120 mg / L (standard conditions), the ozone gas flow rate is 2 slm, the inner diameter of the ozone gas discharge port is 3.7 cm, The distance between the ozone gas outlet and the sample was 8 cm, and the ozone gas was blown for 5 minutes in a 4 L reaction vessel. The exhaust was passed through an O ₃ decomposer and exhausted by a pump.
Table 10 shows the evaluation results of the obtained laminate. However, in Table 10, “UV irradiation part peeling strength” and “UV non-irradiation part peeling strength” of Examples 10 and 11 are read as “ozone gas spraying part peeling strength” and “ozone gas non-blowing part peeling strength”, respectively. And
In addition, as the polyimide film after the film treatment to be overlapped with the support, the layer-side surface formed with the polyamic acid solution A3 of the film using the treated polyimide film obtained in Treatment Example 5 (only plasma treatment was performed). The surface (surface treated with plasma treatment and acid treatment) formed with the polyamic acid solution A2 of the post-treatment polyimide film obtained in Treatment Example 10 is used for the glass. A laminated body was obtained in the same manner except that the overlapping was performed, but the evaluation results of the obtained laminated body were almost the same as those of Example 10 or 11.

(Comparative Examples 1-3)
Use each film No. 1, 2 and 7 film (polyimide film not subjected to plasma treatment) obtained in Film Preparation Examples 1, 2, and 7 and face each side that does not contain a lubricant to the glass. A laminate for comparison was obtained in the same manner as in Example 1 except that they were superposed.
Table 11 shows the evaluation results of the obtained laminate. In the table, “impossible to measure” refers to the case where the polyimide film has been peeled off during processing or measurement.

(Comparative Examples 4-5)
Example 1 except that the support was not treated with a coupling agent, and the post-treatment polyimide film obtained in Treatment Example 2 or 9 was used as the polyimide film after film treatment to be superimposed on the support. In the same manner as above, a comparative laminate was obtained.
Table 11 shows the evaluation results of the obtained laminate. In the table, “impossible to measure” refers to the case where the polyimide film has been peeled off during processing or measurement.

(Comparative Examples 6-7)
The treated polyimide obtained in Treatment Example 2 or 9 was used as a polyimide film after the film treatment to be applied with the coupling agent treatment but without the UV irradiation treatment and to be superposed on the support. A comparative laminate was obtained in the same manner as in Example 1 except that the film was used.
Table 12 shows the evaluation results of the obtained laminate. In the table, “impossible to measure” refers to the case where the polyimide film has been peeled off during processing or measurement.
With respect to this laminate, a cut was made in the polyimide film and the film was peeled off from the support.

(Comparative Examples 8 and 9)
Except for using the same glass as in Example 1 with sandblasting within a range of 70 mm × 70 mm (□ 70 mm) leaving 15 mm perimeter, the same as in Examples 2 and 11. Thus, a comparative laminate was obtained.
Table 12 shows the evaluation results of the obtained laminate. In the table, “impossible to measure” refers to the case where the polyimide film has been peeled off during processing or measurement.
In addition, the obtained laminate is a product in which a depression (irregularity) along the shape of the sandblast is generated on the surface of the polyimide film in the sandblasted portion, the flatness of the polyimide film is significantly impaired, and it is used for manufacturing a device. It became a difficult laminate.

(Comparative Example 10)
A glass coating (“Corning EAGLE XG” manufactured by Corning; 100 mm × 100 mm × 0.7 mm thickness) was placed on a spin coater with a protective film made of a circular PET film having a diameter of 80 mm attached to the spin coater. The same silane coupling agent was dropped onto the center of rotation and rotated at 500 rpm, and then rotated at 2000 rpm so that the entire surface of the support was wetted, and then dried. This was heated for 1 minute on a hot plate heated to 110 ° C. placed in a clean bench, and then the protective film was peeled off to obtain a glass substrate coated only with the silane coupling agent.
Next, the treated surface of the polyimide film after the treatment obtained in the film treatment example 1 is overlaid on the silane coupling agent-coated surface, and the degree of vacuum is 10 ⁺² Pa or less with a rotary pump at a pressure of 10 MPa at 300 ° C. A pressure heat treatment was performed by vacuum pressing for 10 minutes to obtain a comparative laminate. Here, UV irradiation is not performed.
The adhesive strength of the silane coupling agent-treated part of the obtained laminate was 2.1 N / cm, which is equivalent to the UV-irradiated part of Example 1. The uncoated portion of the silane coupling agent at the center of the glass substrate was not adhered at all. Moreover, when the heat resistance peel strength test of this laminated body was done, the film / glass space of the center part of the laminated body swelled greatly. Similarly, in the acid resistance peel strength test and the alkali resistance peel strength test, blisters were generated between the film and the glass.

(Measurement examples 1 to 5)
After preparing 5 sheets of Si wafers cut into 50 mm × 50 mm (□ 50 mm) as a support (substrate), and thoroughly washing them, after applying a silane coupling agent in the same manner as in Example 1. Heating was performed with a hot plate at 110 ° C. to form a 11 nm-thick coupling treatment layer. Next, 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 obtained sample was measured. The results are shown in Table 13. Note that the nitrogen surface composition ratio is a percentage of the atomic percent (%) of nitrogen after UV irradiation, with the nitrogen atomic percent before UV irradiation (Measurement Example 1) being 100%.

(Application 1)
Each laminated body obtained in Examples 1 to 11 and Comparative Examples 1 to 10 was covered with a stainless steel frame having an opening and fixed to a substrate holder in the sputtering apparatus. By fixing the substrate holder and the support of the laminate so that they are in close contact with each other and flowing a coolant through the substrate holder, the temperature of the laminate film can be set, and the temperature of the laminate film is set to 2 ° C. Set. First, plasma treatment was performed on the film surface. The plasma treatment conditions were as follows: argon gas, frequency 13.56 MHz, output 200 W, gas pressure 1 × 10 ⁻³ Torr, treatment temperature 2 ° C., treatment time 2 minutes. Next, under the conditions of a frequency of 13.56 MHz, an output of 450 W, and a gas pressure of 3 × 10 ⁻³ Torr, a nickel-chromium (chromium 10 mass%) alloy target is used to form a 1 nm film by DC magnetron sputtering in an argon atmosphere. A nickel-chromium alloy film (underlayer) having a thickness of 11 nm was formed at a rate of / sec. Next, the back surface of the sputtering surface of the substrate is brought into contact with the SUS plate of the substrate holder in which a coolant whose temperature is controlled to 3 ° C. is flown, so that the temperature of the film of the laminate is set to 2 ° C., and sputtering is performed. went. Then, copper was vapor-deposited at a rate of 10 nm / second to form a copper thin film having a thickness of 0.22 μm. Thus, the laminated board with a base metal thin film formation film was obtained from each laminated body. The thicknesses of the copper and NiCr layers were confirmed by the fluorescent X-ray method.

Next, a laminated board with a base metal thin film forming film from each film is fixed to a Cu frame, and an electroplating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, gloss, using a copper sulfate plating bath). A thick copper plating layer (thickening layer) having a thickness of 4 μm was formed by immersing in a small amount of the agent and flowing 1.5 Adm ^{2 of} electricity. Subsequently, it was heat-treated at 120 ° C. for 10 minutes and dried to obtain a metallized polyimide film / support laminate.

After applying and drying a photoresist (“FR-200” manufactured by Shipley Co., Ltd.) to each metallized polyimide film / support laminate, the resulting metallized polyimide film / support laminate was subjected to contact exposure with a glass photomask, and further 1.2 mass% KOH. Developed with an 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, after electroless tin plating was applied to a thickness of 0.5 μm, annealing treatment was performed at 125 ° C. for 1 hour. Then, the formed pattern was observed with an optical microscope, and the presence or absence of drool, pattern residue, pattern peeling, etc. was evaluated.

When the polyimide film laminated body of each Example was used, the favorable pattern without a sagging, pattern remaining, pattern peeling, etc. was obtained. Further, after the temperature is increased to 400 ° C. at a rate of temperature increase of 10 ° C./min in a muffle furnace further substituted with nitrogen, swelling and peeling occur even if the temperature is kept at 400 ° C. for 1 hour and then naturally cooled. There was nothing.
On the other hand, when the polyimide film laminated body of each comparative example was used, film peeling occurred and a good pattern was not obtained.

  From the results of the application example 1 described above, the laminate in which the peel 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. It was confirmed that a good pattern can be formed also in pattern production.

(Application example 2)
As an example of manufacturing a display device (display panel) which is an example of the device structure of the present invention, a TFT substrate was manufactured. FIG. 9A shows a schematic cross-sectional view of the TFT substrate, and FIG. 9B shows a top view thereof.
First, the laminate of the present invention obtained in Example 1 was used as a substrate 101, and Al (aluminum) was formed on the UV irradiation region (region subjected to UV irradiation treatment at the time of polyimide film preparation) on the polyimide film surface of the laminate. 102 was patterned and deposited by 200 nm sputtering to form a gate wiring bus line 111, a gate electrode (not shown), and a gate wiring 109. At this time, each gate wiring 109 is connected to the gate wiring bus line 111, and this gate wiring bus line 111 is used as a power supply line during anodization. Next, 3 μm of photoresist was applied, and the TFT portion (region A) and the wiring intersection (region B) were removed by a photoetching process. In this state, the entire substrate 101 is immersed in a chemical conversion solution (a solution adjusted to PH 7.0 by diluting a 3% tartaric acid solution with ethylene glycol and adding ammonia water), and a voltage of +72 V is applied to the gate wiring bus line 111. By adding for 30 minutes, 70 nm of Al in the regions A and B was changed to Al ₂ O _3, and an Al ₂ O ₃ film (anodized film) 103 of about 100 nm was formed. After removing the resist, the leakage current of the Al ₂ O ₃ film 103 was reduced by heating in the atmosphere at 200 ° C. for 1 hour. Next, a 300 nm first silicon nitride film 104 is formed on the Al ₂ O ₃ film 103 by plasma CVD, followed by 100 nm hydrogenated amorphous silicon (a-Si) 105 and 200 nm second nitride film. Silicon 106 was formed. At this time, the temperature of the substrate 101 was 380 ° C. Thereafter, the second silicon nitride 106 was patterned so that only the wiring intersections were formed on the TFT channels. Next, an amorphous silicon n layer 107 doped with about 2% phosphorus was deposited to 50 nm and then patterned to leave only the source / drain portion of the TFT. At this time, hydrogenated amorphous silicon (a-Si) 105 was also removed. Next, after depositing 100 nm of Cr (chromium) and 500 nm of Al (aluminum) by sputtering to form a Cr / Al layer 108, patterning is performed, and then signal lines 110, TFT drains, and source wires (not shown) are formed. Etc.). Here, the previously formed gate wiring bus line 111 was removed, and each gate wiring 109 was separated. Thereafter, 100 nm ITO is formed as a transparent electrode 112 by sputtering to form pixel electrodes, terminals and the like. Finally, about 1 μm of silicon nitride is deposited by plasma CVD, and silicon nitride on the terminal portion is formed by a photoetching process. Was removed.
As described above, after mounting a device (TFT) on the UV irradiation area of the polyimide film surface of the laminate of the present invention, the protective film covers the UV irradiation area of the polyimide film surface in order to protect it. (Polyester film) is pasted, and then a cut is made in the boundary line between the UV irradiation region and the UV non-irradiation region, and the TFT portion (device mounting portion) of the polyimide film is peeled off from the support. Obtained. At the time of peeling, the polyimide film was not torn and the TFT portion was not damaged, and it was able to peel well.
Next, a polyimide film cut out in a 70 mm × 70 mm (□ 70 mm) pattern was placed as a mask on the coupling treatment layer surface of the support provided with the coupling treatment layer obtained above, and a laminate (glass) of UV irradiation treatment was performed within a range of 70 mm × 70 mm (□ 70 mm), leaving 15 mm around each periphery.

In addition, as a manufacturing example of a display device (display panel) which is an example of the device structure of the present invention, a display device using an organic EL element was manufactured. FIG. 10 is a schematic sectional view of a display device using organic EL elements.
First, the laminate of the present invention obtained in Example 1 was used as a substrate 201, and a pixel electrode was formed on the UV irradiation region (region subjected to UV irradiation treatment at the time of polyimide film production) on the polyimide film surface of the laminate. After forming one electrode 202 by sputtering using molybdenum, a light emitting layer 203 was formed on the first electrode 202. The light emitting layer 203 was formed by forming a partition wall 205 on the first electrode 202 and then printing an organic layer containing poly (para-phenylene vinylene) which is not doped as a light emitting material by a screen printing method. At this time, the maximum temperature reached during film drying was 180 ° C. Next, ITO was sputtered on the light emitting layer 203 as the second electrode 204, and then a fluororesin layer was coated as the protective film 206. In the above manufacturing process, the highest reached temperature of heat applied to the substrate (laminated body) was 350 ° C. After that, as in Application Example 2, a cut is made at the boundary between the UV irradiation region and the UV non-irradiation region, the light emitting portion mounting portion (device mounting portion) of the polyimide film is peeled off from the support, and the organic EL element is used. A display device (self-luminous display device) was obtained. At the time of peeling, the polyimide film could be peeled off satisfactorily without tearing or damaging the light emitting part.
When an alternating voltage of 60 V and 1000 Hz was applied peak-to-peak to the display device using an organic EL element using the laminate of Example 1 described above, light was emitted in vivid green.
Further, display devices using organic EL elements using the laminates of the other examples were also produced in the same manner as described above, and when a voltage was applied in the same manner as above, good light emission was obtained. On the other hand, when a display device using an organic EL element using the laminate of each comparative example was produced in the same manner as described above and a voltage was applied in the same manner as described above, sufficient light emission was not obtained. This is presumably because the planarity of the polyimide film of the laminate was impaired by the heat applied during the process of manufacturing the display device, and the conductive layer, particularly the transparent conductive layer, was damaged.

  The laminated body obtained by the production method of the present invention can be easily peeled from the support by cutting out the polyimide film at the easy peeling portion when the devices are laminated. Moreover, these laminates can withstand a process such as metallization, and a good pattern can be obtained in subsequent pattern fabrication. Therefore, the laminate of the present invention can be used effectively in the production process of a device structure on an ultra-thin polyimide film, on an ultra-thin polymer film excellent in insulation, heat resistance, and dimensional stability. Circuits and devices can be formed with high accuracy. Therefore, in the manufacture of device structures such as 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 solar cells using them. It is useful and greatly contributes to the industry.

1: Glass substrate 2: Coupling treatment layer 3: UV light blocking mask 4: Coupling treatment layer UV non-irradiated part 5: Coupling treatment layer UV irradiation part 6: Polyimide film 7: Coupling treatment layer on UV irradiation part Polyimide film 8: Device 10: Good adhesion part 20: Easy peeling part 101: Laminate (substrate)
102: Al
103: Anodized film (Al ₂ O ₃ )
104: first silicon nitride 105: hydrogenated amorphous silicon 106: second silicon nitride 107: amorphous silicon n layer 108: Cr / Al layer 109: gate wiring 110: signal line 111: gate wiring bus line 112: Transparent electrode 201: laminate (substrate)
202: First electrode 203: Light emitting layer 204: Second electrode 205: Partition 206: Protective film

Claims (10)

A method for producing a laminate comprising at least a support and a polyimide film,
As the polyimide film, at least a film subjected to plasma treatment on the surface facing the support,
Using at least one of the surfaces where the support and the polyimide film face each other, a coupling agent is used to form a well-bonded portion and an easily-peelable portion having different adhesive peel strengths and substantially identical surface roughness After that, the support and the polyimide film are overlaid and subjected to pressure and heat treatment,
The polyimide film is a film obtained by a reaction between a diamine having an aromatic diamine as a main component and a tetracarboxylic acid having an aromatic tetracarboxylic acid as a main component, and 70 mol of the aromatic diamine. % Or more is an aromatic diamine having a benzoxazole structure.   The patterning treatment is performed by performing a coupling agent treatment to form a coupling treatment layer, and then performing a deactivation treatment on a part of the coupling treatment layer to form a predetermined pattern. The manufacturing method of the laminated body of description.   3. The 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 is performed as the inactivation treatment. The manufacturing method of the laminated body.   The manufacturing method of the laminated body of Claim 3 which performs at least UV irradiation process as said inactivation process.   The said pressurization heat processing is a manufacturing method of the laminated body in any one of Claims 1-4 performed in an atmospheric pressure atmosphere using a roll.   The pressure heating treatment is performed separately in a pressure process and a heating process, and after pressurizing at a temperature of less than 120 ° C, heating is performed at a low pressure or a normal pressure at a temperature of 120 ° C or higher. The manufacturing method of the laminated body in any one.   The manufacturing method of the laminated body in any one of Claims 1-6 using the film which gave the acid treatment after the said plasma treatment as the said polyimide film.   A laminate in which a support and a polyimide film are laminated via a coupling treatment layer, and having a good adhesion portion and an easy peel portion having different peel strengths between the support and the polyimide film And the good adhesion portion and the easily peelable portion form a predetermined pattern.   The 180-degree peel strength between the support and the polyimide film in the easily peelable portion is ½ or less of the 180-degree peel strength between the support and the polyimide film in the good adhesion portion. Laminated body.   A method for producing a structure in which a device is formed on a polyimide film, wherein the laminate according to claim 8 or 9 having a support and a polyimide film is used, and on the polyimide film of the laminate After the device is formed on the substrate, a method for producing a device structure is provided, in which a polyimide film at an easily peelable portion of the laminate is cut to peel the polyimide film from the support.