TW201517220A - Method for producing flexible electronic device - Google Patents

Abstract

To provide a high-quality laminate for forming a flexible electronic device by laminating a polymer film such as a polyimide film or polyester film on an inorganic substrate and peeling the polymer film after device formation. Also, to provide a method for producing the laminate and flexible electronic device. Provided is a method for producing a flexible electronic device, in which a polymer film is adhered to an inorganic substrate to form a multilayered substrate, an electronic device is formed on the polymer film of the multilayered substrate, and then the polymer film is peeled from the inorganic substrate, wherein the method is characterized in that the polymer film is adhered to the inorganic substrate so that the film is divided into at least two sections.

Description

Method for manufacturing flexible electronic component

In the present invention, a flexible polymer film is temporarily fixed to a rigid temporary supporting inorganic substrate to form a laminate, and secondly, various electronic components are formed on the polymer film, and then the polymer film is peeled off together with the electronic component portion. Manufacturing technology for flexible electronic components.

As electronic components such as information communication equipment (playing equipment, mobile wireless, mobile communication equipment, etc.), radar, and high-speed information processing equipment, functional components (components) such as semiconductor components, MEMS components, and display components are used. It is formed or loaded on an inorganic substrate such as glass, germanium wafer or ceramic substrate. However, in recent years, as electronic components are required to be lighter, smaller, thinner, and flexible, attempts have been made to form various functional elements on a polymer film.

It is desirable to form various functional elements on the surface of the polymer film by utilizing the flexibility of the properties of the polymer film, that is, by a roll-to-roll process. However, in the semiconductor industry, the MEMS industry, the display industry, and the like, process technology for rigid planar substrates such as wafer-based or glass-based substrates has hitherto been the mainstream. Therefore, in order to form various functional elements on the surface of the polymer film by using the existing basic structure, the polymer film is first bonded to an inorganic material (glass plate, ceramic plate, tantalum wafer, metal plate, etc.). The rigid support is a process of peeling from the support after forming the desired component.

Generally, higher temperatures are used in the steps of forming functional elements. For example, in the formation of functional elements such as polycrystalline germanium or an oxide semiconductor, a temperature range of about 120 to 500 ° C is used. In the production of a low-temperature polycrystalline germanium film transistor, there is a case where heating at about 450 ° C is required for dehydrogenation. A temperature range of about 150 to 250 ° C is also required in the production of a hydrogenated amorphous germanium film. In the temperature range exemplified herein, although the temperature is not too high for the inorganic material, it is a relatively high temperature for the polymer film or the adhesive generally used for bonding the polymer film. . Therefore, in the method of bonding a polymer film to an inorganic substrate as described above and performing peeling after formation of a functional element, it is required to be sufficient for the polymer film to be used or the adhesive or adhesive for bonding. Heat resistance, however, in terms of practical problems, a polymer film which can practically withstand such a high temperature range is limited. In addition, as for the conventional bonding adhesives and adhesives, there are few cases in which sufficient heat resistance is present.

Since a heat-resistant bonding means for temporarily attaching a polymer film to an inorganic substrate is not obtained, in this application, a solution of a polymer film or a precursor solution is applied onto an inorganic substrate to dry and harden the inorganic substrate. The technology used for this purpose, which is thinned, is well known. However, the polymer film obtained by this means is weak and easily broken, and the functional element is often damaged when peeled off from the inorganic substrate. In particular, it is extremely difficult to peel off a large-area component, and it is almost impossible to obtain an industrially advantageous yield. In view of such circumstances, the present inventors have proposed a laminate in which a polyimide film having excellent heat resistance, strength, and film properties can be bonded to a support (inorganic layer) made of an inorganic material via a coupling agent. The laminate is a laminate of a polymer film and a support for forming a functional element (Patent Documents 1 to 3).

The polymer film is originally a soft material that is slightly stretchable or bendable and is unobstructed. On the other hand, in many cases, the electronic component formed on the polymer film has a fine structure in which a conductor composed of an inorganic material and a semiconductor are combined in a specific pattern, and the structure is slightly stressed by stretching or bending. Damaged, loss as a characteristic of the component. This stress is easily generated when the electronic component is peeled off together with the polymer film from the inorganic substrate. Therefore, the inventors of the present invention have continually further improved, and proposed to partially inactivate the inorganic substrate subjected to the coupling agent treatment to form a portion having a high activity of the coupling agent and a low portion, and to laminate the polymer film. When making a good adhesion part which is difficult to peel off, and an easily peelable part which is easy to peel off, an electronic component is formed in the easily peelable portion, and an incision is made at the boundary of the polymer film with the easy peeling portion/good adhesion portion. A technique in which only the easily peelable portion is peeled off, whereby the stress applied to the electronic component is reduced, (Patent Document 4). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-245675 (Patent Document 3) JP-A-2011-245675 (Patent Document 4) JP-A-2013-010342 Bulletin

[Problems to be solved by the invention]

According to the laminated body described in the above Patent Documents 1 to 4, the polymer film and the inorganic substrate can be bonded without using an element such as an adhesive or an adhesive, and the laminate is exposed to a film element. The high temperature required does not cause peeling of the polymer film. Therefore, the laminated body can be provided in a process of directly forming an electronic component on a substrate of an inorganic material such as a glass plate or a tantalum wafer. However, the inventors of the present invention have found that even in this technique, when the size of the inorganic substrate becomes larger than a certain range, problems in industrial production will rise to the surface.

In a rectangular or large-area polymer film, there is a potential for a property inhomogeneity in the width direction of a film generally referred to as a bowing. This is because the deformation of the central portion in the width direction is first performed compared to the deformation of the end portion in the width direction of the film; or the deformation at the central portion in the width direction is delayed as compared with the deformation of the end portion in the width direction of the film, and strain is left inside the film. phenomenon. This strain is called a tortuous strain.

The tortuous strain system appears, for example, in the form of anisotropy of the thermal shrinkage of the film and anisotropy of the linear expansion coefficient. The anisotropy is a problem that when the size of the inorganic substrate is small, that is, when the size of the polymer film is small, it does not become too large. However, in particular, when the size of the inorganic substrate is increased, specifically, when the rectangular side becomes larger than 700 mm, it becomes a problem. For example, the polymer film portion of the inorganic substrate/polymer film laminate is stretched and contracted due to high-temperature exposure during processing of the electronic component, and thus warp is generated in the entire laminate. When the expansion and contraction due to heating is uniform, the warpage itself can be sufficiently predicted, and therefore, in the actual manufacturing step, the amount of warpage can be assumed in advance, and the condition setting and operation mode can be determined. However, in actuality, the expansion and contraction and the shrinkage are not homogeneous due to the tortuosity phenomenon, but the anisotropy is biased in a specific direction, so that it is accompanied by twisting or bending, resulting in an unpredictable deformation.

In the processing of the flexible electronic component as an object of the present invention, it is required to highly combine high-precision component processing techniques such as printing technology and photolithography. In general, such high-precision processing is carried out in an environment of extremely high cleanliness, with the elimination of manpower as much as possible, using an automatic transport device. What is necessary here is the flatness of the inorganic substrate/polymer film laminate. The laminated body which is complicatedly deformed by bending has many problems in automatic transportation, and it may occur in the opening portion, or the substrate surface contacts one part of the machine, or the vacuum adsorption cannot be smoothly performed, and the coating of the liquid photoresist material is hindered. Sexuality, inability to focus when exposed, and many other problems, and it is difficult to perform high-precision processing of the purpose. [Means to solve the problem]

The method for producing a flexible electronic component by temporarily fixing a polymer film to an inorganic substrate to perform element processing and peeling off the polymer film from the inorganic substrate will be described. The method of temporarily fixing the polymer film for processing is an excellent method for producing a flexible electronic component. However, particularly when the size of the inorganic substrate becomes large, the high-fine processing becomes difficult due to the heterogeneous influence of the strain due to the tortuosity of the film. In order to solve the above problems, the inventors of the present invention have intensively studied and found that a polymer film is divided into a plurality of layers to bond with an inorganic substrate, thereby solving the problem, and it has been found that a high-definition substrate can be produced even in a large-area substrate. The electronic component is completed to complete the present invention.

That is, the present invention encompasses the following constitution. (1) A method of producing a flexible electronic component in which an inorganic substrate is bonded to a polymer film to form a multilayer substrate, and an electronic component is formed on the polymer film of the multilayer substrate, and the high density is peeled off from the inorganic substrate. A method for producing a flexible electronic component of a molecular film, characterized in that the polymer film is divided into at least two or more blocks to be bonded to the inorganic substrate. (2) The method for producing a flexible electronic component according to the above aspect, wherein the polymer film has a thickness of 12 μm or more, a Young's modulus of 6 GPa or more, and a shrinkage ratio of 0.5% when heated at 400 ° C for 1 hour. the following. (3) The method for producing a flexible electronic component according to the above aspect, wherein the inorganic substrate has a substantially rectangular shape with an area of 4,900 cm ² or more and at least a short side of 700 mm or more. (4) The method for producing a flexible electronic device according to any one of the above aspects, wherein the inorganic substrate and the polymer film are bonded to each other by heat and pressure. The inorganic substrate is treated with a surface-activated polymer film. (5) The method for producing a flexible electronic component according to any one of (1) to (4), wherein an adhesive having a thickness of 5 μm or less is used for bonding the inorganic substrate to the polymer film. Adhesive. (6) The method for producing a flexible electronic component according to any one of (1) to (5), comprising at least the following steps (I) to (V): (I) on a protective film a step of bonding a polymer film at least divided into blocks of 2 or more to obtain a multilayer laminated film; (II) a step of bonding the inorganic substrate and the polymer film side of the multilayer laminated film to obtain a multilayer substrate; (III) a step of peeling off the protective film from the multilayer substrate; (IV) a step of forming an electronic component on the polymer film of the multilayer substrate; (V) a step of peeling the polymer film from the multilayer substrate. [Effect of the invention]

In the present invention, a polymer film is divided into a plurality of blocks and bonded to an inorganic substrate to obtain a laminate. By dividing the polymer film, a buffer region of thermal deformation (mainly stretching and contraction) of the polymer film can be obtained. Further, the film divided into a plurality of layers is arbitrarily or arbitrarily arranged in such a manner that the absolute amount of expansion and contraction and the contraction are offset to some extent, thereby suppressing deformation due to heating of the laminated body or inducing deformation thereof. The shape of the desire. The present invention is a protective film having a size or a width substantially the same as that of an inorganic substrate, and a polymer film is appropriately arranged as a laminated film which is temporarily bonded, and the polymer film side of the laminated film is attached to the inorganic substrate. The step of bonding can be saved.

The manufacturing method of the flexible electronic component of the present invention is an inorganic substrate, a polymer film, a protective film used as needed, a bonding means of an inorganic substrate and a polymer film, and a forming means for an electronic component of a polymer film surface. And a polymer film peeling means.

<Inorganic Substrate> In the present invention, an inorganic substrate is used as a support for the polymer film. The inorganic substrate may be a plate-like material that can be used as a substrate, and examples thereof include a glass plate, a ceramic plate, a semiconductor wafer, a metal, and the like, and a glass plate or a ceramic plate. A composite of a wafer or a metal, a laminate of these, a dispersion of these, and the like.

The glass plate includes quartz glass, perrhenic acid glass (96% cerium oxide), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (PYREX (registered trademark)), and borosilicate glass ( Non-alkali), borosilicate glass, aluminosilicate glass, and the like. Among them, it is preferable that the linear expansion coefficient is 5 ppm/K or less, and if it is a commercially available product, "Corning (registered trademark) 7059" or "Corning (registered trademark) manufactured by Corning Co., Ltd. for liquid crystal glass. 1737", "EAGLE", "AN100" manufactured by Asahi Glass Co., Ltd., "OA10" manufactured by Nippon Electric Glass Co., Ltd., "AF32" manufactured by SCHOTT Co., Ltd., etc. are preferable.

Examples of the ceramic plate, comprising _{Al 2 O 3, Mullite, AlN} , SiC, Si 3 N 4, BN, crystallized glass, Cordierite, Spodumene, Pb-BSG + CaZrO 3 + Al2O 3, Crystallized glass + Al 2 O 3, Crystallized Ca-BSG, BSG+Quartz, BSG+Quartz, BSG+Al ₂ O ₃ , Pb+BSG+Al ₂ O ₃ , Glass-ceramic, glass-ceramic (zerodur) materials, ceramics for substrates, TiO ₂ , titanic acid Barium, calcium titanate, magnesium titanate, alumina, MgO, steatite, BaTi ₄ O ₉ , BaTiO ₃ , BaTi ₄ +CaZrO ₃ , BaSrCaZrTiO ₃ , Ba(TiZr)O ₃ , PMN-PT or PFN -Pixel materials such as PFW, PbNb ₂ O ₆ , Pb _0.5 Be _0.5 Nb ₂ O ₆ , PbTiO ₃ , BaTiO ₃ , PZT, 0.855PZT-95PT-0.5BT, 0.873PZT-0.97PT-0.3BT, PLZT, etc. .

As the semiconductor wafer, a germanium wafer, a semiconductor wafer, a compound semiconductor wafer, or the like can be used. The germanium wafer is a single crystal or a polycrystalline germanium processed on a thin plate, and includes a doped n-type or p-type twin crystal. Round, intrinsic wafers, etc., and also include tantalum oxide layers or various thin films on the surface of germanium wafers. In addition to germanium wafers, germanium, germanium-tellurium, gallium-arsenic, Aluminum-gallium-indium, nitrogen-phosphorus-arsenic-bismuth, SiC, InP (indium phosphide), InGaAs, GaInNAs, LT, LN, ZnO (zinc oxide) or CdTe (cadmium telluride), ZnSe (zinc selenide) Such as semiconductor wafers, compound semiconductor wafers, and the like.

As the metal, a single element metal such as W, Mo, Pt, Fe, Ni, Au, etc., Inco, nickel, nickel nickel, nickel chromium, carbon copper, Fe-Ni type constant vane steel alloy, super constant steel alloy Alloys, etc. Further, a multilayer metal plate in which another metal layer or a ceramic layer is added to the metal is also included. At this time, if the CTE of the entire additional layer is low, Cu, Al, or the like may be used for the main metal layer. The metal to be used as the additional metal layer is not limited as long as it has a good adhesion to the polyimide film and has properties such as no diffusion, chemical resistance, or heat resistance. Chromium, nickel, TiN, and Cu containing Mo are preferred examples.

It is preferable that the planar portion of the inorganic substrate is sufficiently flat. Specifically, the surface roughness Ra is preferably 10 nm or less, preferably 3 nm or less, and further preferably 0.9 nm or less. Further, the surface roughness P-V値 is 50 nm or less, more preferably 20 nm or less, still more preferably 5 nm or less. If it is rough, the bonding strength between the polymer film and the inorganic substrate may be insufficient. The thickness of the inorganic substrate is not particularly limited, and from the viewpoint of workability, the thickness is preferably 10 mm or less, more preferably 3 mm or less, and still more preferably 1.3 mm or less. The degree of the thickness is not particularly limited, but is preferably 0.07 mm or more, preferably 0.15 mm or more, and more preferably 0.3 mm or more.

The inorganic substrate of the present invention preferably has a size of at least 4,900 cm ² or more. The inorganic substrate of the present invention is preferably a substantially rectangular shape having at least a short side of 700 mm or more. The present invention, preferred inorganic-based substrate area of 5000cm ² or more, and further 10000cm ² or more, further more of 18000cm ² is preferred. Further, it is preferable that the rectangular short side length of the present invention is 730 mm or more and 840 mm or more, and more preferably, it is more preferably 1000 mm or more. In addition, "substantially rectangular" herein means that the corner of the rectangle is allowed to have R, cut-off, notch, orientation plane, and the like. The present invention is also applicable to a glass substrate of 680×880 mm or 730×920 mm, which is called the fourth generation in the flat panel display industry, and a glass substrate called 1000×1200 mm, 1100×1250 mm, and 1300×1500 mm of the fifth generation. A glass substrate of 1370×1670mm or 1500×1800mm for the 6th generation, a glass substrate of 1870×2200mm called the 7th generation, a glass substrate called 2160×2460mm or 2200×2500mm of the 8th generation, called the 9th generation. A glass substrate of 2400 × 2800 mm, a glass substrate of 2,880 × 3,130 mm called the 10th generation, a glass substrate of 3,320 × 3,000 mm called the 11th generation, or a glass substrate having the above dimensions. However, the present invention does not limit the application of inorganic substrates smaller than the area, size, and rectangular short side length dimensions exemplified herein.

<Polymer film> As the polymer film of the present invention, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and wholly aromatic can be used. Polyester, other copolymerized polyester, polymethyl methacrylate, other copolymerized acrylate, polycarbonate, polyamide, polyfluorene, polyether oxime, polyether ketone, polyamidoximine, polyether Yttrium imine, aromatic polyimide, alicyclic polyimide, fluorinated polyimine, cellulose acetate, nitrocellulose, aromatic polyamine, polyvinyl chloride, polyphenol, polyarylate , polyphenylene sulfide, polyphenylene ether, polystyrene and other films. In the present invention, the effect is particularly remarkable. A useful one is a polymer having a heat resistance of 100 ° C or higher, and a film of an engineering plastic. Here, heat resistance refers to a glass transition temperature or a heat distortion temperature.

The Young's modulus (elastic modulus) of the polymer film of the present invention is preferably 6 GPa or more, more preferably 7.4 GPa or more, still more preferably 8.2 GPa or more, and still more preferably 9.1 GPa or more. Here, the Young's modulus is the Young's modulus obtained by stretching. When the Young's modulus does not satisfy this range, when the polymer film is peeled off from the inorganic substrate, the elongation of the polymer film becomes large, and the possibility that the electronic component is broken is increased. In the present invention, the upper limit of the Young's modulus is not particularly limited, but is practically about 15 GPa. The material with too high Young's modulus is often weak and easily broken, so it is not suitable as a substrate for flexible electronic components.

The lower limit of the thickness of the polymer film of the present invention is not particularly limited, and is preferably 4.5 μm or more in order to maintain the minimum mechanical strength of the substrate of the electronic component. The present invention is more preferably 12 μm or more, further preferably 24 μm or more, and still more preferably 45 μm or more. The upper limit of the thickness of the polymer film is not particularly limited, and is preferably 250 μm or less, more preferably 150 μm or less, and still more preferably 90 μm or less as a requirement of the flexible electronic component.

The polymer film-based polyimine film which is particularly suitable for the present invention may be an aromatic polyimine, an alicyclic polyimine, a polyamidimide or a polyetherimine. In particular, when the present invention is used to manufacture a flexible display element, it is preferable to use a polyimide film having colorless transparency, and when forming a back surface element of a reflective or self-luminous type display, This restriction is not specifically limited.

In general, a polyimide film is coated on a polyimide film by supporting a solution of a polyaminic acid (polyimine precursor) obtained by reacting a diamine with a tetracarboxylic acid in a solvent. The body is dried to form a green film (also referred to as "precursor film" or "poly-proline film"), and further on the support for producing a polyimide film or in a state of being peeled off from the support The green film is subjected to a high temperature heat treatment to carry out a dehydration ring closure reaction.

The diamine constituting the polyamic acid is not particularly limited, and an aromatic diamine, an aliphatic diamine or an alicyclic diamine which is usually used in the synthesis of polyimine can be used. From the viewpoint of heat resistance, aromatic diamines are preferred, and among aromatic diamines, benzo has The aromatic diamines of the azole structure are more preferred. If using benzo The aromatic diamines of the azole structure may exhibit high heat resistance and high elastic modulus, low heat shrinkage, and low linear expansion coefficient while exhibiting high heat resistance. The diamines may be used singly or in combination of two or more.

Benzene The aromatic diamine of the azole structure is not particularly limited, and examples thereof include 5-amino-2-(p-aminophenyl)benzene. Azole, 6-amino-2-(p-aminophenyl)benzo Azole, 5-amino-2-(m-aminophenyl)benzo Azole, 6-amino-2-(m-aminophenyl)benzo Azole, 2,2'-p-phenylene bis(5-aminobenzo) Oxazole), 2,2'-p-phenylene bis(6-aminobenzo) Oxazole), 1-(5-aminobenzophenone Oxazo)-4-(6-aminobenzophenone Azolo)benzene, 2,6-(4,4'-diaminodiphenyl)benzo[1,2-d:5,4-d'] Azole, 2,6-(4,4'-diaminodiphenyl)benzo[1,2-d:4,5-d'] Azole, 2,6-(3,4'-diaminodiphenyl)benzo[1,2-d:5,4-d'] Azole, 2,6-(3,4'-diaminodiphenyl)benzo[1,2-d:4,5-d'] Azole, 2,6-(3,3'-diaminodiphenyl)benzo[1,2-d:5,4-d'] Azole, 2,6-(3,3'-diaminodiphenyl)benzo[1,2-d:4,5-d'] Oxazole and the like.

Benzene as described above Examples of the aromatic diamines other than the aromatic diamines of the azole structure include 2,2'-dimethyl-4,4'-diaminobiphenyl and 1,4-bis[2-(4- Aminophenyl)-2-propyl]benzene (diphenylamine), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, 2,2'-ditrifluoromethyl -4,4'-diaminobiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, double [ 4-(3-Aminophenoxy)phenyl]one, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl碸, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1, 1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3' -diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3 , 3'-diaminodiphenylarylene, 3,4'-diaminodiphenylarylene, 4,4'-diaminodiphenylarylene, 3,3'-diaminodi Phenylhydrazine, 3,4'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylanthracene, 3,3'-diaminobenzophenone, 3,4'-diamine Benzophenone, 4, 4 '-Diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, double [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)benzene 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]one, bis[4-(4-aminophenoxy)phenyl] Thioether, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminobenzene) Oxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,3-bis[4-(4-aminophenoxy)benzylidene]benzene, 1,3-bis[4-(3-aminophenoxy)benzylidene]benzene, 1,4-bis[4-(3-aminophenoxy)benzylidene]benzene, 4, 4'-bis[(3-aminophenoxy)benzylidene]benzene, 1,1-bis[4-(3-aminophenoxy)phenyl]propane, 1,3-double [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]arene, 4 , 4'-bis[3-(4-aminophenoxy)benzylidene]diphenyl ether, 4,4'-bis[3-(3-aminobenzene) Benzobenzyl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4' - bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylanthracene, bis[4-{4-(4-aminophenoxy)phenoxy} Phenyl]anthracene, 1,4-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amine Phenoxy)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-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-cyanophenoxy)- α,α-Dimethylbenzyl]benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-di Phenoxybenzophenone, 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'-diphenoxybenzophenone, 4,4'-diamino- 5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4- Biphenyloxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3 , 4'-diamino-5'-biphenoxybenzophenone, 1,3-bis(3-amino-4-phenoxybenzylidene)benzene, 1,4-bis(3) -amino-4-phenoxybenzhydryl)benzene, 1,3-bis(4-amino-5-phenoxybenzylidene)benzene, 1,4-bis(4-amino- 5-phenoxybenzhydryl)benzene, 1,3-bis(3-amino-4-biphenoxybenzylidene)benzene, 1,4-bis(3-amino-4-linked Phenoxybenzhydryl)benzene, 1,3-bis(4-amino-5-biphenoxybenzylidene)benzene, 1,4-bis(4-amino-5-biphenyloxy) Benzobenzyl)benzene, 2,6-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzonitrile, and the aromatic ring of the above aromatic diamine The carbon number of one or all of the hydrogen atoms partially or wholly via a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, a cyano group, or a hydrogen atom of an alkyl group or an alkoxy group substituted by a halogen atom. An aromatic diamine substituted with a halogenated alkyl group or an alkoxy group .

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane. 1,8-diaminooctane and the like. Examples of the alicyclic diamines include 1,4-diaminocyclohexane and 4,4′-methylenebis(2,6-dimethylcyclohexylamine). The total amount of the diamines (aliphatic diamines and alicyclic diamines) other than the aromatic diamines is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total diamines. More preferably, it is 5% by mass or less. In other words, the aromatic diamine is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more based on the total diamine.

As the tetracarboxylic acid constituting the polyamic acid, an aromatic tetracarboxylic acid (including an acid anhydride thereof), an aliphatic tetracarboxylic acid (including an acid anhydride thereof), or an alicyclic tetracarboxylic acid which are generally used for synthesizing polyimine can be used. (including its anhydride). Among them, aromatic tetracarboxylic anhydrides and alicyclic tetracarboxylic anhydrides are preferred, and from the viewpoint of heat resistance, aromatic tetracarboxylic anhydrides are more preferable, and from the viewpoint of light transmittance, The alicyclic tetracarboxylic acid is more preferred. When these are anhydrides, they may have one or two anhydrate structures in the molecule, and preferably have two anhydrate structures (dianhydrides). The tetracarboxylic acids may be used singly or in combination of two or more.

Examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 3,3',4,4'-dicyclohexyltetracarboxylic acid. An alicyclic tetracarboxylic acid, and an anhydride thereof. Among these, a dianhydride having two anhydrate structures (for example, cyclobutane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3', 4) It is preferred that 4'-dicyclohexyltetracarboxylic dianhydride or the like). Further, the alicyclic tetracarboxylic acids may be used singly or in combination of two or more. When the transparency is important, the alicyclic tetracarboxylic acid is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, based on the total tetracarboxylic acid.

The aromatic tetracarboxylic acid is not particularly limited, and a pyromellinic acid residue (that is, a structure having a structure derived from pyromellitic acid) is preferred, and an acid anhydride thereof is more preferable. Examples of such an aromatic tetracarboxylic acid include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 4,4'-oxydiphthalic acid dianhydride. 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2-bis[4-(3 , 4-dicarboxyphenoxy)phenyl]propionic anhydride, and the like. When the heat resistance is emphasized, the aromatic tetracarboxylic acid is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, based on the total tetracarboxylic acid.

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

The linear expansion coefficient (CTE) of the polymer film of the present invention is preferably -5 ppm/K to +20 ppm/K, more preferably from -5 ppm/K to +15 ppm/K, still more preferably from 1 ppm/K to +10 ppm. /K. When the CTE is in the above range, the difference in the coefficient of linear expansion from the general support can be kept small, and even if it is provided in the heating process, the peeling of the polyimide film and the support composed of the inorganic material can be avoided.

The polymer film of the present invention has a breaking strength of 60 MPa or more, preferably 120 MP or more, and more preferably 240 MPa or more. The upper limit of the breaking strength is not limited, but is actually less than about 1000 MPa. Further, the breaking strength of the polymer film herein means the average enthalpy in the longitudinal direction and the transverse direction of the polymer film.

The heat shrinkage rate of the polymer film of the present invention is preferably 0.5% or less when heated at 400 ° C for 1 hour. This property can be achieved by using 50 mol% or more of pyromellitic acid as a tetracarboxylic dianhydride in the raw material of the polyimide film, while using p-phenylenediamine or having benzoic acid. The diamine having an azole structure is 50 mol% or more; or a tetracarboxylic acid anhydride having one or two aromatic rings and 85 mol% or more of p-phenylenediamine as a diamine component are used.

The thickness unevenness of the polymer film of the present invention is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. If the thickness unevenness is more than 20%, it tends to be difficult to apply to a narrow portion. Further, the thickness of the film may not be determined, for example, by taking a position of about 10 o'clock from the film to be measured by a contact type film thickness gauge to measure the film thickness, and is obtained based on the following formula. Film thickness unevenness (%) = 100 × (maximum film thickness - minimum film thickness) ÷ average film thickness

In the polymer film, in order to ensure operability and productivity, it is preferable to add and contain a sliding material (particles) to the film, and to provide fine unevenness on the surface of the polymer film to ensure slidability. The above-mentioned sliding material (particle) means a fine particle preferably composed of an inorganic substance, and may be used of a metal, a metal oxide, a metal nitride, a metal carbide, a metal salt, a phosphate, a carbonate, a talc, a mica, or a clay. And other clay minerals and other particles. Metal oxides, phosphates, and carbonates such as cerium oxide, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, apatite, calcium carbonate, and glass filler are preferably used. The sliding material may be one type or two or more types.

The volume average particle diameter of the sliding material (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 the measurement enthalpy obtained by the light scattering method. When the particle diameter is less than the lower limit, industrial production of the polymer film becomes difficult, and if it is larger than the upper limit, the unevenness of the surface becomes excessively large and the adhesion strength becomes weak, which causes a practical obstacle.

The amount of the sliding material added is 0.02 to 5% by mass, preferably 0.04 to 1% by mass, and more preferably 0.08 to 0.4% by mass, based on the amount of the polymer component in the polymer film. When the amount of the sliding material added is too small, it is difficult to expect the effect of adding the sliding material, and the slidability is not sufficiently ensured, which may cause an obstacle to the production of the polymer film. If the amount of the sliding material is too large, the surface unevenness of the film becomes too large, even if it seems to ensure sliding. Sexuality causes a decrease in smoothness, and causes a decrease in the breaking strength or the elongation at break of the polymer film, and causes a problem such as an increase in CTE.

When a polymer film is added and a sliding material (particles) is contained, it can be used as a single-layer polymer film in which a sliding material is uniformly dispersed, and for example, one surface can be formed as a polymer film containing a sliding material, and the other side can be formed. A multilayer polymer film comprising a polymer film which does not contain a sliding material or contains a small amount of a sliding material. In such a multilayer polymer film, fine unevenness can be imparted to the surface of one layer (film) to ensure slidability in the layer (film), and good workability and productivity can be ensured.

When the multilayer polymer film is a film produced by a melt-stretch film formation method, for example, it can be formed by first using a polymer film raw material containing no slip agent, and at least one side of the film is coated in the middle of the step. A resin layer of a slip agent. On the contrary, in contrast, a polymer film raw material containing a slip agent may be used for film formation, and a polymer film raw material not containing a slip agent may be applied in the middle of the step or after the film formation is completed to obtain a film. When a polymer film obtained by a solution forming method such as a polyimide film is used, it can be similarly used, for example, as a polyaminic acid solution (polyimine precursor solution), in a solution of a polyamic acid solution. The polymer solid component contains a sliding material (preferably having an average particle diameter of about 0.05 to 2.5 μm) of 0.02% by mass to 50% by mass (preferably 0.04 to 3% by mass, more preferably 0.08 to 1.2% by mass). The polyaminic acid solution and the non-sliding material or a small amount thereof (preferably less than 0.02% by mass, more preferably less than 0.01% by mass based on the polymer solid content in the polyamido acid solution) Polylysine solution is used to make.

The method of multilayering (layering) the multilayer polymer film is not particularly limited as long as the adhesion of the two layers is not problematic, and may be any one that is not adhered by an adhesive layer or the like. In the case of a polyimide film, for example, i) by forming one polyimide film, the other polyimide solution is continuously applied to the polyimide film to carry out the ruthenium imidization. Method; ii) After casting a poly-proline solution to prepare a poly-proline film, continuously coating the other poly-proline solution on the poly-proline film, and then performing imidization Method; iii) by co-extrusion method; iv) spraying a polylysine solution containing a large amount of slip material on a film formed of a polyglycine solution containing no slip material or a small amount thereof, using A method of coating with a T film or the like to carry out hydrazine imidization or the like. The present invention is preferably a method using the above i) or the above ii).

The thickness ratio of each layer in the multilayer polymer film is not particularly limited, and a polymer layer containing a large amount of the sliding material is used as the layer (a), the layer containing no sliding material, or a small amount of the polymer layer as the layer (b). Preferably, the layer (a)/(b) is preferably 0.05 to 0.95. When the layer (a) or layer (b) is more than 0.95, the smoothness of the layer (b) is lost. On the other hand, when it is less than 0.05, the effect of improving the surface characteristics is insufficient and the slipperiness is lost.

The polymer film of the present invention is preferably obtained by winding an elongated film having a width of 300 mm or more and a length of 10 m or more at the time of production, and is wound around a winding axis. The shape of the amine film is better.

<Protective Film> The present invention can use a protective film as needed. The protective film is literally responsible for protecting the protected object of the main body from contamination and damage. In the present invention, it is further responsible for the integration of the divided polymer film and the step of bonding the inorganic substrate. The protective film of the present invention is composed of a base film and an adhesive. As the base film, in addition to the extremely general PET film, PEN film, polypropylene film, nylon film, etc., PPS film, PEEK film, aromatic polyamide film, polyimide film, polyfluorene can be used. Heat-resistant super engineering plastic film such as imine benzoxazole film. The substrate of the protective film suitable for use in the present invention is a PET film which is annealed to improve dimensional stability, a PEN film which is annealed in the same manner, and a polyimide film. As the adhesive to be used for the protective film of the present invention, a known adhesive such as a polyfluorene-based, acrylic, or urethane-based adhesive can be used. The protective film of the present invention protects the element forming surface of the polymer film of the substrate of the flexible electronic component. Therefore, an adhesive having a type in which the transfer of the adhesive component is extremely small or the transfer component is simply removed by dry or wet cleaning is preferred. In the present invention, for example, an adhesive having a side chain crystalline polymer having a property of reducing adhesion due to cooling can be used.

<Adhesive means for the inorganic substrate and the polymer film> As the bonding means of the inorganic substrate and the polymer film of the present invention, well-known adhesives such as polyoxyxylene resin, epoxy resin, acrylic resin, and polyester resin can be used. , adhesive. The present invention can be used, for example, by using an adhesive having a side chain crystalline polymer having a property of reducing adhesion due to cooling. The preferred bonding means of the present invention is preferably a bonding means for an extremely thin bonding/adhesive layer having a thickness of 5 μm or less, or preferably a bonding means for substantially not using an adhesive or an adhesive. In the present invention, an organic layer treatment such as a decane coupling agent treatment or a UV ozone treatment may be performed on the inorganic substrate side, and an activation treatment may be performed. Similarly, vacuum plasma treatment, atmospheric piezoelectric slurry treatment, corona treatment, and flame are also performed on the polymer film side. A bonding method in which an activation treatment such as treatment, ITRO treatment, UV ozone treatment, exposure to an active gas, or the like is performed, and both treatment surfaces are adhered to each other to perform pressurization and heat treatment.

<Centane Coupling Agent> The decane coupling agent of the present invention refers to a compound which is physically or chemically interposed between a temporary support and a polymer film and has an effect of improving the adhesion between the two. Preferred examples of the decane coupling agent include N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane and N-2-(aminoethyl)-3- Aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltri Ethoxy decane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane , 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, vinyl III Chlorodecane, vinyltrimethoxydecane, vinyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane , 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, p-styryltrimethoxydecane, 3-methylpropene oxime Propylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxyhydrazine Alkane, 3-methacryloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-( Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane hydrochloride, 3-ureidopropyltriethoxydecane, 3-chloropropyltrimethoxydecane, 3 - mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxymethylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxydecane, ginseng- (3-trimethoxymercaptopropyl)isocyanate, chloromethylphenethyltrimethoxydecane, chloromethyltrimethoxydecane, aminophenyltrimethoxydecane, aminophenylbenzene Trimethoxy decane, aminophenyl phenylaminomethyl phenethyl trimethoxy decane, hexamethyldioxane, and the like.

It is also possible to use n-propyltrimethoxydecane, butyltrichlorodecane, 2-cyanoethyltriethoxydecane, cyclohexyltrichlorodecane, decyltrichlorodecane, diethyl methoxy dimethyl decane. , diethoxydimethyl decane, dimethoxy dimethyl decane, dimethoxy diphenyl decane, dimethoxymethyl phenyl decane, dodecyl trichloro decane, dodecyl trimethoxy Baseline, ethyltrichlorodecane, hexyltrimethoxydecane, octadecyltriethoxydecane,octadecyltrimethoxydecane, n-octyltrichlorodecane, n-octyltriethoxydecane, n-octyl Trimethoxy decane, triethoxyethyl decane, triethoxymethyl decane, trimethoxymethyl decane, trimethoxyphenyl decane, pentyl triethoxy decane, pentyl trichloro decane, Triethoxymethyl decane, trichlorohexyl decane, trichloromethyl decane, trichlorooctadecyl decane, trichloropropyl decane, trichlorotetradecyl decane, trimethoxy propyl decane, allyl Trichlorodecane, allyltriethoxydecane, allyltrimethoxydecane, diethoxymethylvinylnonane, dimethoxy Methyl vinyl decane, trichlorovinyl decane, triethoxy vinyl decane, vinyl ginseng (2-methoxyethoxy) decane, trichloro-2-cyanoethyl decane, diethoxy (3-epoxypropyloxypropyl)methylnonane, 3-epoxypropyloxypropyl(dimethoxy)methylnonane, 3-epoxypropyloxypropyltrimethoxydecane Wait.

Among the decane coupling agents, the decane coupling agent preferably used in the present invention is preferably a decane coupling agent having a chemical structure of a ruthenium atom per molecule of the coupling agent. Preferred examples of the decane coupling agent in the present invention include N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane and N-2-(aminoethyl)-3. -Aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxy decane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, Amino Phenyltrimethoxydecane, aminophenethyltrimethoxydecane, aminophenylaminomethylphenethyltrimethoxydecane, and the like. When the process particularly requires high heat resistance, it is preferred to use an aromatic group to bond between Si and an amine group. Further, in the present invention, a phosphorus-based coupling agent, a titanate-based coupling agent, or the like may be used in combination as needed.

<Coating method of decane coupling agent> As a coating method of the decane coupling agent of the present invention, a coating method in a liquid phase or a coating method in a vapor phase can be employed. As a method of coating the liquid phase, a solution in which a decane coupling agent is diluted with a solvent such as an alcohol is used, and examples thereof include a spin coating method, a curtain coating method, a dip coating method, a slit die coating method, a gravure coating method, and a bar coating method. A general liquid coating method such as a notch wheel coating method, an applicator method, a screen printing method, or a spray coating method. When it is used in a liquid phase coating method, it is preferably dried at a temperature of about 100 ± 30 ° C for about several seconds to about 10 minutes after drying. By heat treatment, the decane coupling agent is bonded to the surface of the coated surface via a chemical reaction.

The present invention can coat a decane coupling agent by a vapor phase. The vapor phase coating is achieved by exposing the substrate to a vapor of a decane coupling agent, that is, a substantially gaseous decane coupling agent. The vapor of the decane coupling agent can be obtained by heating the liquid decane coupling agent to a temperature of about 40 ° C to the boiling point of the decane coupling agent. The boiling point of the decane coupling agent varies depending on the chemical structure, and is approximately in the range of 100 to 250 °C. However, the heating at 200 ° C or higher has a disadvantage of causing side reactions on the organic side of the decane coupling agent. The environment for heating the decane coupling agent may be any one under pressure, slightly under normal pressure and reduced pressure, and in the case of promoting vaporization of the decane coupling agent, it is preferably under a slight pressure or under reduced pressure. . Since most of the decane coupling agents are flammable liquids, it is preferred to carry out the gasification operation after replacing them in a sealed container, preferably with an inert gas in the container. The time for exposing the inorganic substrate to the decane coupling agent is not particularly limited, and is within 20 hours, preferably within 60 minutes, further preferably within 15 minutes, and still more preferably within 1 minute. The temperature of the inorganic substrate during exposure of the inorganic substrate to the decane coupling agent is preferably a temperature suitable to be controlled between -50 ° C and 200 ° C depending on the type of the decane coupling agent and the thickness of the desired decane coupling agent layer. The inorganic substrate exposed to the decane coupling agent is preferably heated to 70 ° C to 200 ° C, more preferably 75 ° C to 150 ° C after exposure. By this heating, the hydroxyl group or the like on the surface of the inorganic substrate is reacted with the alkoxy group or the decane-alkyl group of the decane coupling agent to complete the treatment with the decane coupling agent. The time required for heating is within 10 seconds or more and 10 minutes or less. When the temperature is too high or the time is too long, there is a case where the deterioration of the coupling agent occurs. Moreover, if it is too short, the processing effect cannot be obtained. Further, when the temperature of the substrate exposed to the decane coupling agent is 80 ° C or more, the subsequent heating may be omitted. In the present invention, it is preferred that the coating surface of the decane coupling agent of the inorganic substrate is kept downward to be exposed to the vapor of the decane coupling agent. Since the coating method of the liquid phase inevitably brings the coated surface of the inorganic substrate upward during and after the application, it is impossible to deny the possibility that the floating foreign matter or the like is deposited on the surface of the inorganic substrate in the working environment. However, since the inorganic substrate is kept downward by the vapor phase coating method, foreign matter adhesion in the environment can be greatly reduced. Further, it is a preferable operation to purify the surface of the inorganic substrate before the treatment of the decane coupling agent by means of short-wavelength UV/ozone irradiation or to purify the liquid detergent.

Regarding the coating amount and thickness of the coupling agent, theoretically, as long as one molecular layer is sufficient, it is sufficient to have a negligible thickness from the viewpoint of mechanical design. In general, it is preferably less than 400 nm (less than 0.4 μm) and 200 nm or less (0.2 μm or less), more preferably 100 nm or less (0.1 μm or less), more preferably 50 nm or less, still more preferably 10 nm or less. . However, if the area is 5 nm or less in the calculation, it is not preferable that the coupling agent is not formed as a uniform coating film but in the form of a cluster. The film thickness of the coupling agent layer can be calculated from the elliposimetry method or the concentration and coating amount of the coupling agent solution at the time of coating.

In the present invention, an inorganic substrate treated with a decane coupling agent or an untreated inorganic substrate can be used, and further, an inorganic substrate which has been subjected to a cleaning treatment by ultrapure water or the like can be used for UV ozone treatment, thereby being activated. Inorganic substrate. The UV ozone treatment of the present invention refers to a treatment in which ultraviolet rays having a wavelength of 270 nm or less, preferably 210 nm or less, more preferably 180 nm or less are irradiated at a relatively short distance in the presence of oxygen. Short-wavelength ultraviolet rays ozonize oxygen in the atmosphere, and the ultraviolet rays themselves attenuate. Therefore, if the distance between the light source and the object to be processed is too long, the effect cannot be obtained. In the present invention, the distance between the light source and the object to be processed is 30 mm or less, preferably 16 mm or less, more preferably 8 mm or less. In the present invention, when only the decane coupling agent is treated, the adhesion between the inorganic substrate and the polymer film becomes too strong, and the peeling is hindered. Although it can be adjusted by reducing the coating amount of the decane coupling agent, since treatment unevenness is likely to occur, the present invention proposes to perform UV ozone treatment or the like after the treatment with the decane coupling agent to carry out introduction by a decane coupling agent. The method of deactivation of functional groups.

<Surfacting Treatment of Polymer Film> The polymer film used in the present invention is preferably subjected to surface activation treatment. By the surface activation treatment, the surface of the polymer film is modified to a state in which a functional group is present (that is, in a state of being activated), and the adhesion to the inorganic substrate is improved. The surface activation treatment of the present invention refers to a dry or wet surface treatment. The dry treatment of the present invention can be used for surface treatment of active energy rays such as ultraviolet rays, electron beams, and X-rays, corona treatment, vacuum plasma treatment, normal piezoelectric slurry treatment, flame treatment, and ITRO treatment. As the wet treatment, a treatment of bringing the surface of the film into contact with an acid or an alkali solution can be exemplified. The surface activation treatment preferably used in the present invention is a combination of plasma treatment, plasma treatment and wet acid treatment, and UV ozone treatment.

The plasma treatment is not particularly limited, and there are RF plasma treatment, microwave plasma treatment, microwave ECR plasma treatment, atmospheric piezoelectric slurry treatment, corona treatment, etc. in a vacuum, and also includes fluorine gas treatment, using an ion source. The ion implantation treatment, the treatment using the PBII method, the flame treatment exposed to the hot plasma, the ITRO treatment, and the like. Among them, RF plasma treatment, microwave plasma treatment, and atmospheric piezoelectric slurry treatment in a vacuum are preferred.

As a suitable condition for the plasma treatment, a plasma having a high chemical etching effect such as a fluorine plasma such as oxygen plasma, CF ₄ or C ₂ F ₆ or the like, or a physical energy such as Ar plasma is imparted. The physical etching effect of the polymer surface is preferably performed by a high plasma. Further, a plasma such as CO ₂ , H ₂ or N ₂ , a mixed gas of these, or a further water vapor is also preferable. When the treatment is performed for a short period of time, it is preferable that the energy density of the plasma is high, the kinetic energy of the ions in the plasma is high, and the number density of the active species is high. From this point of view, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation of an ion source that is easy to inject high-energy ions, PBII method, and the like are also preferable.

In the present invention, a plurality of surface activation treatments may be combined to carry out. A preferred combination of the invention is a combination of vacuum plasma treatment and UV ozone treatment. This surface activation treatment purifies the surface of the polymer and further generates active functional groups. The resulting functional group and the coupling agent layer are bonded by hydrogen bonding or chemical reaction to bond the polymer film layer and the coupling agent layer. In the present invention, if only the plasma treatment is performed, the adhesion between the inorganic substrate and the polymer film becomes too strong, and the peeling is hindered. Although it can be adjusted by shortening the processing time of the plasma treatment, reducing the input power, etc., since the processing unevenness is likely to occur, the present invention proposes to change the plasma treatment effect by performing UV ozone treatment or the like after the plasma treatment. technique. In the plasma treatment, the effect of etching the surface of the polymer film can also be obtained. In particular, in a polymer film containing a large amount of the lubricant particles, there is a case where the protrusion caused by the lubricant hinders the adhesion of the film to the inorganic substrate. At this time, if the surface of the polymer film is thinly etched by the plasma treatment, a part of the lubricant particles is exposed and treated with hydrofluoric acid, the lubricant particles in the vicinity of the surface of the film can be removed.

The surface activation treatment may be applied to only one side of the polymer film or to both sides. In the case of performing plasma treatment on one side, the polymer film is placed in contact with the electrode on one side by plasma treatment with a parallel plate electrode, but only on the side not in contact with the electrode of the polymer film. Plasma treatment is applied to the surface. Further, when the polymer film is placed in a state in which the space between the two electrodes is electrically floated, the plasma treatment can be performed on both surfaces. Further, the single-sided treatment can be performed by performing plasma treatment in a state where the protective film is attached to one surface of the polymer film. Further, as the protective film, a PET film to which an adhesive is attached, a PEN film, an olefin film, a polyimide film, or the like can be used.

In the present invention, when the activation treatment is performed, a part of the mask may be applied, or the intensity of the activation treatment, the treatment time, and the like may be partially changed, and a portion having a strong adhesive force and a portion having a weak adhesion force may be deliberately made.

<Film Lamination Method> In the present invention, the surface of the activated inorganic substrate and the surface of the activated polymer film can be bonded by overlapping, heating, and pressurization. The pressurization and heat treatment may be performed by pressing, laminating, rolling, or the like while heating, for example, in an air atmosphere or in a vacuum. Further, it is also possible to apply a method of pressurizing and heating in a state where a flexible bag is placed. From the viewpoint of improving productivity and low processing cost due to high productivity, it is preferable to pressurize or roll under atmospheric conditions, in particular, using a roll (rolling pressure, etc.) ) is better.

The pressure at the time of the pressure heat treatment is preferably 1 MPa to 20 MPa, and more preferably 3 MPa to 10 MPa. If the pressure is too high, there is a possibility that the support is damaged; if the pressure is too low, there is a case where the portion is not dense, and the adhesion is insufficient. The temperature at the time of the pressure heat treatment is carried out in a range not exceeding the heat resistant temperature of the polymer film to be used. In the case of the non-thermoplastic polyimide film, it is preferably 150 to 400 ° C, more preferably 250 to 350 ° C. Further, the pressure heat treatment may be carried out in an atmosphere as described above, and in order to obtain a fully stable adhesive strength, it is preferably carried out under vacuum. In this case, the degree of vacuum of the ordinary rotary pump is sufficient, and it is sufficient if it is about 10 Torr or less. As a device which can be used for the pressurization and heat treatment, for example, "11FD" manufactured by Imoto Seiki Co., Ltd. can be used, and a roll type film laminator in vacuum or a thin rubber film can be used after vacuuming. For the vacuum lamination of a film laminator or the like which is applied to the glass at the same time, for example, "MVLP" manufactured by a famous machine can be used.

The aforementioned pressurized heat treatment can be carried out by separating into a pressurizing step and a heating step. At this time, first, the polymer film and the inorganic substrate are pressed at a relatively low temperature (for example, a temperature lower than 120 ° C, more preferably 95 ° C or lower) (preferably about 0.2 to 50 MPa) to ensure adhesion between the two. Thereafter, heating is carried out at a low pressure (preferably less than 0.2 MPa, more preferably 0.1 MPa or less) or a normal pressure at a relatively high temperature (for example, 120 ° C or higher, more preferably 120 to 250 ° C, still more preferably 150 to 230 ° C). Thereby, the chemical reaction of the adhesion interface can be promoted to laminate the polymer film and the temporary support inorganic substrate.

Further, in the present invention, it is preferred to control the moisture absorption rate of the polymer film when the polymer film and the inorganic substrate are bonded to 1.8% or less. The moisture absorption rate of the polymer film refers to the moisture absorption rate in a state in which the polymer film and the inorganic substrate are pressed. The moisture absorption rate of the polymer film depends on the temperature and humidity of the room in which the polymer film is placed. Further, since it takes time to absorb moisture and dehumidify, the measurement must be carried out under a certain condition for a sufficiently long period of time, at least 24 hours or more, and then evaluated. If the amount of the moisture absorbed moisture is too large, it may become a cause of blister when heated in the subsequent step. On the other hand, if the amount is too small, the adhesion to the inorganic substrate may be stabilized. That is, the chemical reaction between the polymer film and various surfaces of the inorganic substrate is affected by the moisture contained in the polymer film. The moisture absorption rate of the polymer film is preferably 1.5% or less and preferably 1.2% or less. Further, the lower limit of the moisture absorption rate is 0.1%, preferably 0.2%, and more preferably 0.4%.

<Adhesive Step of Polymer Film and Inorganic Substrate> The laminate of the inorganic substrate and the polymer film of the present invention is characterized in that the polymer film is at least divided into two or more blocks for bonding to one inorganic substrate. . As a method of obtaining such a laminate, the following method can be exemplified. (1) A method in which a polymer film of almost the same size is bonded to an inorganic substrate, and only a polymer film is divided by a laser or a mechanical cutting edge. At this time, the distribution of the tortuous strain existing in the production of the polymer film itself remains. However, by dividing the polymer film, even in the case where the polymer film is stretched and contracted, the tensile stress is covered in the divided portion. The stress applied to the inorganic substrate is subdivided, and the entire deformation can be suppressed. (2) The polymer film divided in advance is directly bonded to a predetermined position of the inorganic substrate. Since the polymer film can be divided and laminated at random or offset against the expected tortuous strain, the tensile stress caused by the expansion and contraction of the polymer film can be homogenized and dispersed throughout the inorganic substrate. Therefore, the deformation of the whole can be further suppressed. (3) arranging the polymer film which has been previously divided and attaching it to a predetermined position on an intermediate medium such as a protective film having an almost the same size as the inorganic substrate, and attaching it to the inorganic substrate while being placed in the intermediate medium, and then peeling off the intermediate medium. The method. Basically, as in the above item (2), since the step of bonding to the inorganic substrate is completed only once, the contamination of the surface of the inorganic substrate and the surface of the polymer film attached in advance can be avoided.

<Division Pattern> The form of the divided polymer film may be divided into two, three, four, or more with respect to the substrate size. The shape of each of the divided regions can be made into a shape similar to the shape of the inorganic substrate. For example, in the elongated inorganic substrate, as long as the vertical and horizontal divisions are equally divided, it is possible to divide into four divisions, nine divisions, and six divisions. It is not necessary to have the same shape and size of the entire region, and it may be arranged in such a manner that the shape and size of the flexible electronic component to be manufactured are small in design. A preferred film shape is a polygonal shape in which the shape is formed by a straight line, and a rectangle having a square shape, a rectangular shape, and particularly an aspect ratio of 4 to 3 or 16 to 9 is preferable. In the present invention, the polymer film may be elongated only in one direction, and may be arranged in a stripe shape on the inorganic substrate. In this case, the divided polymer film can be wound into a roll shape, and since the protective film can also be formed into a roll shape so that the two are continuously wound in a roll-to-roll type, the split polymer film is used for the protective film. The configuration becomes easy. That is, the flexible electronic component can be obtained by the following steps: (1) dispensing and laminating a plurality of polymer films divided into a plurality of laminated films on a protective film; (2) bonding the inorganic substrate a step of obtaining a multilayer substrate on the side of the polymer film of the multilayer laminated film; (3) a step of separating the protective film from the multilayer substrate to realize a state in which the divided polymer film is dispensed on the inorganic substrate; a step of forming an electronic component on the polymer film of the multilayer substrate; (5) a step of peeling the polymer film from the multilayer substrate.

The main idea of the present invention is to offset the tortuous strain of the polymer film by the drilling arrangement to suppress the deformation of the laminate formed of the polymer film/inorganic substrate, for example, the short side of the inorganic substrate. The plurality of polymer films produced by the narrower width are directly bonded to the inorganic substrate, or are laminated on the protective film, and bonded to the inorganic substrate, whereby even a narrow-width polymer film can be used. A large-sized inorganic substrate is used to form the element. At this time, it is preferable to bond the polymer film in a direction to cancel the tortuous strain.

Further, in order to secure the yield, of course, in the present invention, the gap between the divided polymer films is preferably as small as possible, preferably 5 mm or less, further 2 mm or less, and further 0.7 mm or less. It is better.

<Manufacturing means of the flexible electronic component> When the laminated body of the present invention is used, an electronic component can be formed on the polymer film of the laminated body by using an existing device for manufacturing an electronic component, and a process can be used, and the polymer film can be laminated together with the polymer film. The body is peeled off to produce a flexible electronic component. The electronic component of the present invention refers to an electronic circuit including a wiring substrate carrying a wiring, an active component such as a transistor or a diode, a passive component including a resistor, a capacitor, an inductor, and the like, and sensing pressure, temperature, light, humidity, and the like. Imaging elements such as sensing elements, light-emitting elements, liquid crystal displays, electrophoretic displays, self-luminous displays, wireless, wired communication elements, computing elements, memory elements, MEMS elements, solar cells, thin film transistors, and the like.

<Means for peeling the polymer film from the inorganic substrate> The means for peeling the polymer film from the support is not particularly limited, and a known method may be used. The method of peeling off a polymer film from a laminated body, the method of irradiating a strong light from an inorganic substrate side, and thermally-decomposing the bonding site between an inorganic substrate and a polymer film, or photo-decomposition and peeling is mentioned. A method of peeling off a polymer film with a force less than a limit of the elastic strength of the polymer film; a method of peeling off by heating the water, heating the vapor, or the like to weaken the bonding strength between the inorganic substrate and the polymer film. As a method of producing the "starting point" at the time of peeling, a method of rolling up from one end with a tweezers or the like may be employed; after attaching an adhesive tape to one side of the slit portion of the polymer film with the component, the portion is rolled up from the tape portion. a method of vacuum-adsorbing one side of a slit portion of a polymer film with a component, and rolling it from the portion; or by previously making a portion of the polymer film not bonded to the inorganic plate or the polymer A method in which one of the thin films protrudes from the inorganic substrate to obtain a grip portion.

In the present invention, the 90-degree peeling adhesion strength between the inorganic substrate and the polymer film is preferably within a predetermined range. When a thermoplastic film such as a PET film, a PEN film or the like is used as the polymer film, it is assumed that an amorphous germanium or an organic semiconductor is used as a semiconductor, adhesion after heat treatment at 140 ° C for 30 minutes; or when the present invention uses a polyimide film As the polymer film, it is assumed that the adhesion force after the dehydrogenation step of the amorphous germanium and the heat treatment at 420 ° C for 30 minutes in the polycrystallization step is less than 1.0 N/cm, preferably less than 0.6 N in the 90-degree peeling mode, respectively. More preferably, it is less than 0.4 N/cm, still more preferably less than 0.3 N/cm.

Further, in the present invention, the peeling angle at the time of peeling is preferably set to π/6 radian (30 degrees) or less, and it is more preferably π/12 radian (15 degrees) or less, and further set to π/24 radian (7.5 degrees). The following is further better. When the lower limit of the peeling angle is 0, it corresponds to natural peeling. At this time, in the electronic component processing step, problems such as foaming or film peeling easily occur. The lower limit of the peeling angle of the present invention is 1.0 degree, more preferably about 2 degrees.

In the present invention, a method of attaching another reinforcing substrate to the peeled portion in advance and peeling together with the reinforcing substrate is also useful. When the peeled flexible electronic component is the bottom plate of the display element, the front plate of the display element may be attached in advance, and after being integrated on the inorganic substrate, both are peeled off to obtain a flexible display element.

In the present invention, the patterning treatment can be performed on the inorganic substrate side, the polymer film side, or both. The patterning of the present invention refers to controlling the degree of surface treatment of a polymer film, or an inorganic substrate, or both, and making a portion having a strong adhesive force and a weak portion. In the present invention, an electronic component can be formed in a region where the adhesion between the polymer film and the inorganic substrate is low (referred to as an easily peelable portion) by patterning, and second, a slit is cut out at a peripheral portion of the region. The region in which the electronic component of the polymer film is formed is peeled off from the inorganic substrate, whereby a flexible electronic component is obtained. By this method, peeling of the polymer film and the inorganic substrate becomes easier.

As a method of cutting a slit into a polymer film along the periphery of the easily peelable portion of the laminate, a method of cutting the polymer film by a cutter such as a blade can be used, and the laser and the laminate are relatively scanned. A method of cutting a polymer film, a method of cutting a polymer film by relatively scanning a water jet and a laminate, and a method of cutting a polymer film by cutting a semiconductor layer by a semiconductor wafer cutting device Wait. Further, it is also possible to suitably use a combination of these methods, superimpose ultrasonic waves on the cutting tool, add back and forth motion, or move up and down to improve the cutting performance.

When the slit is cut in the polymer film on the periphery of the easily peelable portion of the laminate, the position at which the slit is cut may be at least a part of the easily peelable portion, and basically it may be cut along a predetermined pattern, and the error may be Appropriate judgments such as absorption and productivity.

Hereinafter, the present invention will be described using the drawings. 1, 2, 3, and 4 are examples of division of the polymer film of the present invention. Fig. 1 shows an example in which two divisions are performed vertically and horizontally, and all four divisions are made. Fig. 2 shows an example in which three divisions are performed vertically and horizontally, and all nine divisions are made. Fig. 3 is an example of division of regions in which sizes are set. Fig. 4 shows an example in which two divisions are simply performed. The diagram is a schematic diagram that emphasizes the gap between the divided regions. In reality, the gap is generally as small as possible. 5 and 6 show an example in which an adhesive film is attached to an inorganic substrate using an adhesive. In FIG. 5, a case where an adhesive is applied or laminated on the side of the inorganic substrate, and the divided polymer film is attached thereto is exemplified. Fig. 6 is a view showing a case where the polymer film side is coated or laminated with an adhesive, and thereafter bonded to an inorganic substrate.

Fig. 7 is a schematic view showing a state in which a two-part polymer film is continuously attached to a protective film wound in a roll shape. The laminated film composed of the bonded polymer film and the protective film can be wound into a roll again.

FIG. 8, FIG. 9, and FIG. 10 are schematic views showing a state in which the divided polymer film is attached to the inorganic substrate via a protective film. Fig. 8 is a schematic view showing a state in which a split polymer film is attached to a protective film and rolled again into a roll shape. For convenience of illustration, the polymer film is divided in the longitudinal direction of the roller. However, the direction of division is not limited, and it may be divided in the width direction as illustrated in FIG. 7 . Fig. 9 is a view showing a state in which a polymer film is attached to an inorganic substrate provided with an adhesive layer via a protective film wound in a roll shape. As long as the protective film is cut immediately after lamination, it can be operated in a sheet state in which the inorganic substrate is used as a support in the subsequent step. Fig. 10 shows the case where the protective film is peeled off. Although the example in which the peeled protective film is wound into a roll shape is shown here, it does not have to be wound into a roll shape. [Examples]

The present invention will be more specifically described by the following examples and comparative examples, but the present invention is not limited by the following examples. Further, the physical property evaluation methods of the following examples are as follows.

<Reduction viscosity of polyproline solution> A solution prepared by dissolving N,N-dimethylacetamide in a polymer concentration of 0.2 g/dl, and measuring at 30 ° C using a Ubbelt type viscosity tube. .

<Thickness of Polymer Film> The thickness of the polymer film was measured using a micrometer ("Millitron 1245D" manufactured by Feinpruf Co., Ltd.).

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

<Linear expansion coefficient (CTE) of the polymer film> The expansion ratio was measured in the flow direction (MD direction) and the width direction (TD direction) of the polymer film to be measured, and the measurement was performed at intervals of 15 ° C ( 30 ° C ~ 45 ° C, 45 ° C ~ 60 ° C, ...) expansion ratio / temperature, the measurement is carried out until 300 ° C, the average measured enthalpy measured in the MD direction and TD direction as the coefficient of linear expansion (CTE) And calculate. Machine name: "TMA4000S" manufactured by MAC Science Co., Ltd. Sample length: 20 mm Sample width: 2 mm Temperature rise temperature: 25 °C Temperature rise temperature: 400 °C Temperature increase rate: 5 °C / minute gas atmosphere: Argon initial load: 34.5 g/mm ²

<Thermal shrinkage rate of the polymer film> The measurement was carried out by the heating method under the conditions specified in IEC 61189-2 and Test 2X02 at 400 ° C for 1 hour.

<The moisture absorption rate of the polymer film> The measurement was carried out in accordance with the A method defined in JIS K7251.

<warpage of the laminated body> The rectangular laminated body is placed on the fixed plate so that the warping is upward and the concave shape is formed, and the height of the corner portion from the fixed plate is measured by a carpenter's square, and each corner is obtained. Height and average 値. <Transportability> Comprehensive evaluation of the transportability of automatic transport machines for the manufacture of liquid crystal displays. The evaluation criteria are as follows. ○: It can be transported under standard conditions without problems. △: There are some problems in transportation, but it can be matched by changing the condition of the device. ×: Unable to transport.

<Adhesive strength 90-degree peeling method> A 100 mm square portion of the laminate was cut out from the laminate, and the adhesion strength between the inorganic substrate and the polymer film was measured under the following conditions according to the 90-degree peeling method described in JIS C6481. Device name: "Autograph (registered trademark) AG-IS" manufactured by Shimadzu Corporation. Measurement temperature: room temperature Peeling speed: 50 mm/min Gas environment: Atmosphere Measuring sample width: 10 mm

<Production of Polyimine Film> [Production Example 1] (Preparation of Polyproline Solution) After nitrogen substitution in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 3, 3', 4, 398 parts by mass of 4'-biphenyltetracarboxylic dianhydride (BPDA), and 147 parts by mass of p-phenylenediamine (PDA) were dissolved in 4,600 parts by mass of N,N-dimethylacetamide, and added as cerium oxide. (Sliding material) A dispersion obtained by dispersing a colloidal cerium oxide as a sliding material in dimethyl acetamide (Nissan) is added to a total amount of the polymer solid content in the polyaminic acid solution to be 0.08% by mass. "SNOWTEX (registered trademark) DMAC-ST30" manufactured by Chemical Industry Co., Ltd. was stirred at a reaction temperature of 25 ° C for 24 hours to obtain a brown and viscous polyamine acid solution V1 having the reduced viscosity shown in Table 1.

(Production of Polyimide Film) The final film thickness was obtained on a smooth surface (no sliding material surface) of an elongated polyester film ("A-4100" manufactured by Toyobo Co., Ltd.) having a width of 1500 mm using a slit die ( The polyamic acid solution V1 obtained above was applied to a film having a thickness of 25 μm, and dried at 105 ° C for 20 minutes, and then peeled off from the polyester film to obtain a self-supporting polyamine film having a width of 1420 mm. . Next, the obtained self-supporting polyglycolic acid film was stretched by 1.1 times in the longitudinal direction by the speed difference of the transporting rolls, and secondly, it was stretched by 1.05 times in the width direction by a pin tenter, and at 150 ° C. In a temperature range of ～420° C., the stage temperature is increased (the first stage is 180° C.×5 minutes, the second stage is 270° C.×10 minutes, and the third stage is 420° C.×5 minutes), and heat treatment is performed to imidize the oxime. The needle plate holding portions at both ends were removed by slits to obtain an elongated polyimine film F1 (1000 m roll) having a width of 1290 mm. The properties of the obtained film F1 are shown in Table 2.

[Production Example 2] (Preparation of Polyproline Solution) After a nitrogen substitution in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 5-amino-2-(p-aminophenyl)benzene was added. and 223 parts by mass of azole (DAMBO) and 4416 parts by mass of N,N-dimethylacetamide were completely dissolved, and secondly, 217 parts by mass of pyromellitic dianhydride (PMDA) was added while cerium oxide (sliding) A dispersion obtained by dispersing colloidal cerium oxide as a sliding material in dimethylacetamide in a manner of 0.09% by mass based on the total amount of the polymer solid content in the polyaminic acid solution (Nissan Chemical Co., Ltd.) Industrial product "SNOWTEX (registered trademark) DMAC-ST30") was stirred at a reaction temperature of 25 ° C for 36 hours to obtain a brown and viscous polyamine acid solution V2 having the reduced viscosity shown in Table 1.

<Preparation of Polyimine Film> The poly-proline solution V1 was used, and the polyamic acid solution V2 obtained above was used to form an elongated polyester film having a width of 800 mm using a slit die ("A-Nippon Co., Ltd." 4100") smooth surface (no slip surface), coated with a final film thickness (film thickness after yttrium imidation) of 38 μm, dried at 105 ° C for 25 minutes, and then peeled off from the polyester film, by The needle plate tenter is heat-treated in the first stage at 150 ° C × 5 minutes, the second stage at 220 ° C × 5 minutes, and the third stage at 495 ° C × 10 minutes to imidize the yttrium, and the needles at both ends are removed by slits. The plate was gripped to obtain a long polyimine film F2 (1000 m roll) having a width of 645 mm. The properties of the obtained film F2 are shown in Table 2.

[Table 1] <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Manufacturing Example 1 </td><td> Production Example 2 </td></tr><tr><td> Polyglycine solution</td><td> V1 </td><td> V2 </td></tr><tr>< Td> tetracarboxylic anhydride </td><td> PMDA </td><td> mass fraction </td><td> - </td><td> 217 </td></tr><tr> <td> BPDA </td><td> 398 </td><td> - </td></tr><tr><td> Diamines </td><td> PDA </td>< Td> 147 </td><td> - </td></tr><tr><td> DAMBO </td><td> - </td><td> 223 </td></tr> <tr><td> 矽 矽</td><td> [%] </td><td> 0.08 </td><td> 0.09 </td></tr><tr><td> reduction viscosity </td><td> ηsp/c </td><td> </td><td> 3.8 </td><td> 3.7 </td></tr></TBODY></TABLE>

<Production of the surface-activated film> The both sides of the polyimide film F1 obtained in the production example 1 were subjected to vacuum plasma treatment, and further subjected to UV ozone treatment on both surfaces to obtain a surface-treated film P1. In the vacuum plasma treatment, the RIE mode of the parallel plate type electrode was used, and nitrogen gas was introduced into the vacuum chamber by the treatment of RF plasma, and high frequency power of 13.54 MHz was introduced, and the treatment time was set to 3 minutes. The UV ozone treatment system uses a UV/O ₃ cleaning and upgrading device ("SKB1102N-01") manufactured by LANTECHNICAL SERVICE Co., Ltd. and a UV lamp ("SE-1103G05"), and is carried out at a distance of about 20 mm from the UV lamp. minute. At the time of irradiation, a special gas was not introduced into the UV/O ₃ cleaning and reforming apparatus, and the UV irradiation was performed in an atmospheric environment at room temperature. In addition, the UV lamp emits a light beam of 185 nm (a short wavelength capable of generating ozone for inactivating treatment) and a wavelength of 254 nm, and the illuminance is an illuminance meter "UV-M03AUV (measured at a wavelength of 254 nm) manufactured by ORC Corporation". It is 20mW/cm ² .

The surface-activated polyimine film P2 was obtained by performing the same operation except for the polyimine film F1 except the polyimine film F1. Further, a commercially available polyimide film: Kapton H (manufactured by Toray DuPont Co., Ltd.), a commercially available PEN film (manufactured by Teijin DuPont Co., Ltd.), and a commercially available wholly aromatic polyester film (LCP, manufactured by Sumitomo Chemical Co., Ltd.) The surface treatment was carried out in the same manner. The results are shown in Table 2 and Table 3.

[Table 2] <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Film</td><td> F1 </td><td> F2 </td><td> Kapton H </td><td> PEN </td></tr><tr><td> Polyglycine solution</td><td> V1 </td><td > V2 </td><td> - </td><td> - </td></tr><tr><td> Film thickness</td><td> μm </td><td> 25 </td><td> 38 </td><td> 50 </td><td> 50 </td></tr><tr><td> film thickness unevenness</td><td> % </td><td> 1.7 </td><td> 1.2 </td><td> 1.5 </td><td> 1.5 </td></tr><tr><td> CTE </td ><td> ppm/°C </td><td> 12.0 </td><td> 2.5 </td><td> 35 </td><td> 13 </td></tr><tr> <td> Tensile modulus of elasticity (MD/TD) </td><td> GPa </td><td> 9.8/9.4 </td><td> 8.4/8.6 </td><td> 3.8/ 4.0 </td><td> 12 </td></tr><tr><td> tensile strength at break (MD/TD) </td><td> MPa </td><td> 340/320 </td><td> 380/390 </td><td> 320/350 </td><td> 350/360 </td></tr><tr><td> tensile elongation at break ( MD/TD) </td><td> % </td><td> 47/52 </td><td> 42/40 </td><td> 70/85 </td><td> 140 /130 </td></tr><tr><td> Moisture absorption rate</td><td> % </td><td> 0.42 </td><td> 1.15 </td><td> 0.9 </td><td> 0.35 </td></tr><tr><td> heat shrinkage rate (400°C for 1 hour) </td><td> % </td><td> 0.45 </td ><td> 0.09 </td><td> 1.2 </td><td> Not evaluated</td></tr></TBODY></TABLE>

[Table 3] <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Surface-activated film</td><td> P1 </td> <td> P2 </td><td> P3 </td><td> P4 </td><td> P5 </td></tr><tr><td> Thin film</td><td> F1 </td><td> F2 </td><td> Kapton H </td><td> PEN </td><td> LCP </td></tr><tr><td> Processing </td><td> processing time (minutes) </td><td> 3 </td><td> 3 </td><td> 3 </td><td> - </td>< Td> - </td></tr><tr><td> UV ozone treatment</td><td> Processing time (minutes) </td><td> 5 </td><td> 5 </ Td><td> 5 </td><td> 3 </td><td> 3 </td></tr></TBODY></TABLE>

<Finishing of Protective Film and Polymer Film> 25 m of the surface-treated film P1 was cut into four in the width direction and rolled up to have a width of 322.5 mm. Further, the obtained four rolls were set to P1a, P1b, P1c, and P1d from the left side in the film forming direction at the time of film formation. A protective film having a width of 1300 mm was provided on the winding portion of the film laminator having two pairs of polyoxyethylene rubber rolls. The protective film to be used was a PET film E5100 manufactured by Toyobo Co., Ltd., which was annealed at 150 ° C and a thickness of 50 μm, and was coated on a single side with a polyoxynoxy adhesive having a thickness of 10 μm. In the other winding portion of the film laminator, the polyimide film having a width of 322.5 mm in advance is cut into the order of P1b, P1d, P1a, and P1c from the left side in the direction in which the protective film is wound out, and the film gap becomes 2 mm. Way of configuration. Next, the protective film was bonded to the polyimide film and rolled again into a roll shape. The line speed of the laminated layer was 5 m/min, and the tension between the protective film side and the polyimide film side was equal, and the roll temperature was set to room temperature. In the same manner, for the protective film having a width of 1300 mm, the surface-activated film P2 was arranged in two rows in the width direction with a gap of 1 mm in the width direction, and laminated, and wound into a roll shape.

<Surfacting Treatment of Inorganic Substrate> The surface treatment of the inorganic substrate was carried out by a gas phase coating of a decane coupling agent treatment and a UV ozone treatment. Further, Lotus Glass manufactured by Corning Incorporated, 1300 × 1500 mm, was used as the inorganic substrate. <Copolymer coupling agent coating> The decane coupling agent coating on the inorganic substrate was carried out under the following conditions. 100 parts by mass of a decane coupling agent ("KBM-903": 3-aminopropyltrimethoxydecane manufactured by Shin-Etsu Chemical Co., Ltd.) was introduced into an evaporation tank in a chamber, and nitrogen gas was introduced at atmospheric pressure until the oxygen concentration became 0.1% or less. Next, the nitrogen gas was stopped, the pressure in the chamber was reduced to 3 × 10 ^-4 Pa, and the temperature of the tank in which the decane coupling agent was charged was raised to 120 °C. Next, for a liquid crystal display of 1300 × 1500 mm, the glass "G0" was kept at a level of 100 mm from the vertical direction of the liquid surface of the decane coupling agent, and the vapor of the decane coupling agent was exposed at a speed of 7 mm/sec. The pure nitrogen gas is gradually introduced into the vacuum chamber to return to the atmospheric pressure, and the glass temperature is controlled between 95 ° C and 105 ° C by far infrared ray heating, and heat treatment is performed for about 3 minutes to obtain a coated decane coupling agent as a substrate for surface activation treatment. "G1".

Using a UV/O ₃ cleaning and upgrading apparatus manufactured by LANTECHNICAL SERVICE Co., Ltd., the obtained decane coupling agent-coated substrate G1 was irradiated with UV for 5 minutes in a distance of about 20 mm from the UV lamp in an atmosphere. The substrate G2 is surface-activated. In addition, the UV lamp emits a light beam of 185 nm (a short wavelength capable of generating ozone for inactivating treatment) and a wavelength of 254 nm, and the illuminance is an illuminance meter "UV-M03AUV (measured at a wavelength of 254 nm) manufactured by ORC Corporation". It is 20mW/cm ² .

(Comparative Example 1) <Evaluation of the production of the laminate and the initial characteristics> The surface of the surface-activated film P1 and the surface of the surface-activated substrate G1 were opposed to each other, and a roll press machine manufactured by MCK Co., Ltd. was used as the inorganic substrate. Temporary lamination was carried out at a side temperature of 100 ° C, a roll pressure of 5 kg/cm ² , and a roll speed of 5 mm/sec. The polymer film which is temporarily laminated has a degree of adhesion which is not peeled off by the weight of the film itself, but which is easily peeled off when scratching the film end. Thereafter, the obtained temporary laminated substrate was placed in a clean oven, heated at 200 ° C for 30 minutes, and then left to cool to room temperature to obtain a layered product L1. The appearance of the obtained laminate was observed, the warpage was measured, and the 90-degree peel adhesion strength of the film and the substrate was further evaluated for the 90-degree peel adhesion strength and warpage after treatment at 420 ° C for 30 minutes. . The results are shown in Table 4. Further, the production of the laminate was carried out in a laboratory maintained at a temperature of 25 ° C ± 2 ° C and a humidity of 55% ± 3%, and the surface-activated film was laminated in the laboratory for 24 hours or more.

(Example 1) The surface-activated films P1a, P1b, P1c, and P1d which were subjected to four divisions and attached to a protective film and wound into a roll shape were placed on a laminator together with a protective film, and laminated on the surface-activated substrate G1 in the same manner. For temporary bonding. Next, the obtained temporary laminated substrate was placed in a clean oven, heated at 150 ° C for 180 minutes, left to cool to room temperature, and the protective film was peeled off cautiously to obtain a layered product L2 of the present invention. The evaluation results are shown in Table 4.

(Example 2) The surface-activated film P2 which was attached in two rows in parallel was placed in a laminator in the same manner as the roll formed of the protective film, and was laminated on the surface-activated substrate G1 in the same manner for temporary bonding. Next, the obtained temporary laminated substrate was placed in a clean oven, heated at 150 ° C for 180 minutes, and then left to cool to room temperature, and the protective film was peeled off cautiously to obtain a layered product L3 of the present invention. The evaluation results are shown in Table 4. The layered body L3 is in the form illustrated in Figs. 4 and 7 . At this time, it can be understood that even a polymer film which does not have a width of a minimum width of the glass substrate can be bonded by using such a method; and the polymer film containing a chemical structure having a rigidity can maintain the deformation of the substrate at at the lowest limit. (Comparative Example 2) In the same manner as in Comparative Example 1, the surface-activated film P3 and G1 were bonded together to obtain L4. The evaluation results are shown in Table 4.

(Example 3) The surface-activated film P3 was divided into three dimensions, the vertical and horizontal directions of the inorganic substrate, and the gap was 1.0 mm. The protective film was randomly arranged to form a bonded roll, and was similarly placed on the laminator. Similarly, the surface-activated substrate G1 is laminated to temporarily bond. Next, the obtained temporary laminated substrate was placed in a clean oven, heated at 150 ° C for 120 minutes, left to cool to room temperature, and the protective film was peeled off cautiously to obtain a layered product L5 of the present invention. The evaluation results are shown in Table 4. (Comparative Example 3) An acrylic pressure-sensitive adhesive was applied to the surface of the untreated glass plate G0, and the surface-activated film P4 was laminated to obtain a layered product L6. The evaluation results are shown in Table 4. Further, since the film did not have heat resistance at 420 ° C, no heating test was performed.

(Example 4) An acrylic pressure-sensitive adhesive was applied to the surface of the untreated glass plate G0, and the surface-activated film P4 was subjected to 3 × 3 division in the same manner as in Example 3, and laminated on G0 to obtain a layered product L7. The evaluation results are shown in Table 4. Further, since the film did not have heat resistance at 420 ° C, no heating test was performed. (Comparative Example 4) A layered product L8 was obtained in the same manner as in Comparative Example 3, using the surface-active film P5. The evaluation results are shown in Table 4. Further, since the film did not have heat resistance at 420 ° C, no heating test was performed. (Example 5) Using the surface-activated film P5, in the same manner as in Comparative Example 3, the number of divisions was 4 × 4, and the arrangement was random to obtain a layered product L9. The evaluation results are shown in Table 4. Further, since the film did not have heat resistance at 420 ° C, no heating test was performed.

【Table 4】 [Industrial availability]

According to the method for producing a flexible electronic component of the present invention, after the electronic component is formed on the polymer film temporarily fixed to the temporary supporting inorganic substrate, the electronic component is peeled off from the inorganic substrate so as not to stress the electronic component. Polymer films, especially in the manufacture of flexible electronic components, have contributed greatly to the industry.

1‧‧‧Inorganic substrate
2‧‧‧ polymer film
3‧‧‧Adhesive
4‧‧‧Protective film

Fig. 1 is a cross-sectional example 1 of a polymer film. Fig. 2 is a division example 2 of a polymer film. Fig. 3 is a division example 3 of a polymer film. Fig. 4 is a division example 4 of a polymer film. Fig. 5 shows an arrangement example 1 of an inorganic substrate, an adhesive, and a polymer film. Fig. 6 shows an arrangement example 2 of an inorganic substrate, an adhesive, and a polymer film. Fig. 7 shows an example of attachment of a protective film and a polymer film. [Fig. 8] A step of attaching a polymer film to a protective film. [Fig. 9] A step of attaching a protective film/polymer film laminate to an inorganic substrate. Fig. 10 is a step of peeling off a protective film to form a laminate comprising a polymer film/adhesive/inorganic substrate.

no.

Claims (6)

A method for producing a flexible electronic component, wherein an inorganic substrate is bonded to a polymer film to form a multilayer substrate, and an electronic component is formed on the polymer film of the multilayer substrate, and the polymer film is peeled off from the inorganic substrate. The polymer film is divided into at least two or more blocks and bonded to the inorganic substrate. The method for producing a flexible electronic component according to the first aspect of the invention, wherein the polymer film has a thickness of 12 μm or more, a Young's modulus of 6 GPa or more, and a shrinkage ratio of 0.5% or less when heated at 400 ° C for 1 hour. The method for producing a flexible electronic component according to claim 1 or 2, wherein the inorganic substrate has a substantially rectangular shape with an area of 4,900 cm ² or more and at least a short side of 700 mm or more. The method for producing a flexible electronic device according to the first or second aspect of the invention, wherein the inorganic substrate and the polymer film are bonded to each other by an inorganic substrate and a surface treated by heating and pressurization. The surface-activated polymer film is used for the surface treatment. The method for producing a flexible electronic component according to the first or second aspect of the invention, wherein the inorganic substrate and the polymer film are bonded together with an adhesive or a binder having a thickness of 5 μm or less. The method for producing a flexible electronic component according to claim 1 or 2, comprising at least the following steps (1) to (5): (1) bonding at least one of the protective films to at least 2 or more a step of obtaining a multilayer laminated film by the polymer film of the block; (2) a step of bonding the inorganic substrate and the polymer film side of the multilayer laminated film to obtain a multilayer substrate; (3) peeling off the protective film from the multilayer substrate Step (4) a step of forming an electronic component on the polymer film of the multilayer substrate; (5) a step of peeling the polymer film from the multilayer substrate.