TWI524991B - A laminated body, a method for producing a laminated body, and a method for manufacturing the flexible electronic device - Google Patents

Description

Laminate, method of manufacturing laminate, and method of manufacturing flexible electronic component

In the present invention, a flexible polymer film is temporarily fixed on a rigid temporary support inorganic substrate to form a laminate, and then a plurality of electronic components are formed on the polymer film, and then the polymer film is separated from the electronic component portion. A manufacturing technique of the flexible electronic component and the laminate are obtained.

As electronic components such as information communication equipment (playing equipment, mobile radio, 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. Or mounted on an inorganic substrate such as glass, germanium wafer or ceramic substrate. However, in recent years, it has been required to reduce the weight, size, thickness, and flexibility of electronic components, and attempts have been made to form various functional elements on polymer films.

It is preferable to form various functional elements on the surface of the polymer film by a so-called roll-to-roll process using flexibility of polymer film characteristics. However, in the semiconductor industry, the MEMS industry, the display industry, and the like, a process technology that targets a rigid planar substrate such as a wafer substrate or a glass substrate substrate has been mainstream. Therefore, in order to form various functional elements on the surface of the polymer film by using the existing basic structure, it is designed to bond the polymer film to a rigidity composed of inorganic materials (glass plate, ceramic plate, tantalum wafer, metal plate, etc.). The support is a process of stripping from the support after forming the desired component.

Generally, in the step of forming a functional element, a relatively high temperature is often employed. For example, a functional element such as a polycrystalline germanium or an oxide semiconductor is formed in a temperature range of about 200 to 500 °C. In order to dehydrogenate, it is necessary to heat a low temperature polycrystalline germanium film transistor at about 450 °C. Production The hydrogenated amorphous germanium film also requires a temperature range of about 200 to 300 °C. The temperature range exemplified herein is not too high a temperature for the inorganic material, but it is a relatively high temperature for the adhesive used for bonding the polymer film or the general polymer film. In the method of bonding a polymer film as described above to an inorganic substrate and performing peeling after forming a functional element, it is required to use a polymer film or an adhesive or adhesive for bonding, which is required to have sufficient heat resistance. The reason is that, in practical terms, the polymer film which is currently available in the high temperature region is limited, and the conventional bonding adhesive and the adhesive do not have sufficient heat resistance.

Since a heat-resistant adhesive method for temporarily attaching a polymer film to an inorganic substrate cannot be obtained, in this application, it is known to apply a solution of a polymer film or a precursor solution on an inorganic substrate, and dry it on an inorganic substrate. Thinning is carried out to use the technology for this purpose. However, since the polymer film obtained by this method is fragile and easily cracked, there are many cases where the functional element is broken 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 a yield that satisfies industrial demand.

In view of such a situation, the inventors of the present invention proposed a laminate of a polyimide film which is excellent in heat resistance, strong and thin, and which is bonded to a support (inorganic layer) made of an inorganic material via a coupling agent. The layer body is a laminate of a polymer film and a support for forming a functional element (Patent Documents 1 to 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-283262

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-011455

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-245675

According to the laminates described in the above Patent Documents 1 to 3, the polymer film and the inorganic substrate can be bonded without using an element such as an adhesive or an adhesive, and the laminate can be exposed to the laminate. The high temperature necessary for the production of the thin film element does not cause peeling of the polymer film. Therefore, by manufacturing the laminate directly on the substrate on which an inorganic material such as a glass plate or a germanium wafer is formed, an electronic component can be fabricated on the polymer film, and the polymer film can be removed from the polymer film. The inorganic substrate is peeled off to realize a flexible electronic component.

However, this technology still has the problems in industrial production as shown below.

Especially when producing high-definition electronic components, productivity is a problem. When a foreign matter is mixed between the polymer film and the inorganic substrate, a tent-like structure in which the foreign matter is compared as a pillar is generated on and around the foreign matter. This creates a void between the polymer film and the inorganic substrate, resulting in a portion that is not followed. The gas that is trapped in the gap is a cause of expansion defects (also referred to as foaming) due to swelling in a heated environment or a reduced pressure environment. Further, since the gap portion is not followed, when the strength is grasped on the giant view, the fluctuation of the strength becomes large.

In the vicinity of the foreign matter, the polymer film itself is in a state of bulging, and in particular, when patterning by photolithography or high-definition pattern such as microcontact printing is performed, it becomes a hindrance element, and it is impossible to perform good. The situation in which electronic components are formed.

The foreign matter can be reduced by the purification of the surface of the inorganic substrate and the surface of the polymer film, and the purification of the working environment. However, in the nature of the technical problem, foreign matter is sometimes caused by the decane coupling agent itself. In the prior art exemplified, an example in which a solvent solution of a decane coupling agent is directly applied to an inorganic substrate in a liquid state is described. The inventors of the present invention found that the decane coupling agent is affected by moisture or the like existing in the operating environment, and it is easy to form an aggregate. In the direct coating method exemplified, the non-intentionally formed decane is also applied to the inorganic substrate. As a result, the aggregate of the coupling agent is in a state in which the aggregate is dispersed as a foreign matter on the inorganic substrate together with the decane coupling agent. The negative effects caused by this foreign matter are as previously described.

The present invention has been made in view of the above-described circumstances, by fundamentally changing the coating method of the decane coupling agent, thereby preventing the aggregate of the decane coupling agent from adhering to the inorganic substrate, and providing the appearance quality excellent and high. A laminate in which the adhesion between the molecular film and the inorganic substrate is homogenized to solve problems in industrial production.

Furthermore, according to the present invention, the surface roughness of the inorganic substrate after the polymer film is peeled off is small, The decane coupling agent can be applied as a substrate after a simple cleaning operation, and the reproducibility of the inorganic substrate can be remarkably improved.

In order to solve the above problems, the inventors of the present invention have intensively reviewed and found that by applying a decane coupling agent to an inorganic substrate in a vapor phase, it is possible to provide a good laminate in which a foreign material is not inserted between the polymer film and the inorganic substrate. As a result, a high-fine-flexible electronic component having a good yield can be produced, and the reproducibility of the inorganic substrate can be improved, and the present invention has been completed.

In other words, the present invention includes the following constitution.

A laminate comprising a laminate of a polymer film and an inorganic substrate via a decane coupling agent layer, wherein the number of foreign matter having a major axis of 10 μm or more between the polymer film and the inorganic substrate is 3 pieces/cm ² or less, and the adhesive strength of the polymer film and the inorganic substrate is 1/2 or less of the breaking strength of the polymer film.

2. The laminate according to 1. wherein the foreign matter is a foreign matter containing a ruthenium atom.

3. The laminate according to 1. or 2. wherein the polymer film is a polyimide film having a thickness of 3 μm or more.

4. The laminate according to any one of the above aspects, wherein the inorganic substrate is a glass plate having an area of 1000 cm ² or more.

5. The laminate according to any one of 1 to 4, wherein the decane coupling agent is a chemical structure having one fluorene atom per molecule.

The laminate according to any one of the aspects of the present invention, wherein the polymer film and the inorganic substrate are bonded to each other via a layer of a decane coupling agent, wherein the polymer film and the inorganic substrate are provided. The good subsequent portions of the subsequent strengths are different from the easily peelable portions, and the good subsequent portions form a prescribed pattern with the easily peelable portions.

A method for producing a laminate, comprising the steps of (1) to (3): (1) forming a decane coupling agent on an inorganic substrate by exposing the inorganic substrate to a vaporized decane coupling agent. a step of layering; (2) a step of activating the polymer film on the overlapping surface of the decane coupling agent layer; (3) A step of heating both by heating and pressurization.

A method of producing a laminate, comprising the steps of (1) to (3): (1) forming a decane coupling agent on an inorganic substrate by exposing the inorganic substrate to a vaporized decane coupling agent. a step of layering; (2) a step of coating a polymer solution or a polymer precursor solution on the layer of the decane coupling agent; (3) drying ‧ heating the polymer solution or the polymer precursor solution to form a polymer The step of obtaining a laminate by a film.

9. The method for producing a laminate according to the above, wherein the step (1) is carried out at about atmospheric pressure.

10. The method for producing a laminate according to the above, wherein the step (1) is carried out under reduced pressure.

The method for producing a laminate according to any one of the above aspects, wherein the laminate has a good adhesion portion and an easy peeling strength between the polymer film and the inorganic substrate. And the good subsequent portion forms a prescribed pattern with the easily peelable portion.

12. The method for producing a laminate according to 11, wherein, when the decane coupling agent layer is formed, a part of the inorganic substrate is shielded, and the good adhesion portion and the easily peelable portion form a predetermined pattern.

13. The method for producing a laminate according to claim 11, wherein after the formation of the decane coupling agent layer, a part of the decane coupling agent layer is irradiated with an active energy ray, and the good adhesion portion and the easily peelable portion are formed into a predetermined specification. picture of.

A method for producing a flexible electronic component, characterized in that a laminate obtained by the production method according to any one of the items 7 to 10. is used to form an electron on the polymer film of the laminate. Element, and second, the polymer film is peeled off from the inorganic substrate together with the electronic component.

A method for producing a flexible electronic component, which is characterized in that the laminate obtained by the production method according to any one of the items 11. to 13 is used in a polymer film of the laminate. Forming an electronic component on a portion of the easy-peelable portion, and second, cutting the polymer film along a periphery of the easily peelable portion of the laminate The polymer film is peeled off from the inorganic substrate together with the electronic component.

According to the present invention, a good laminate in which foreign matter is not inserted between the polymer film and the inorganic substrate can be obtained, and as a result, the bonding strength between the polymer film and the inorganic substrate is homogenized.

Further, according to the present invention, a portion of the inorganic substrate may be masked in a predetermined pattern with respect to the decane coupling agent layer, or a part of the decane coupling agent layer may be formed after the formation of the decane coupling agent layer. The pattern is irradiated with active energy ray irradiation to intentionally obtain the presence/absence of the adhesion force, or strong/weak, and can be formed by using the desired pattern when the electronic component is formed, so that the polymer film does not occur during the component formation process. A good adhesion portion of the sufficient adhesion of the degree of peeling, and an easily peelable portion which can peel the polymer film relatively easily, and a slit is formed along the periphery of the easily peelable portion, and the functional element portion formed in the region can be peeled off.

Further, the surface of the inorganic substrate after the peeling of the polymer film of the present invention has a high degree of smoothness, and has an effect of being able to form a decane coupling layer by a relatively simple washing operation and using it as a material of the laminate.

More preferably, in the present invention, when a polymer film having high heat resistance is used, it can be bonded without using an adhesive or an adhesive having poor heat resistance, and when the functional element is formed, 180 ° C or higher, preferably 230 ° C or higher is used. Further, it is more preferably a high temperature of 260 ° C or higher to form an element. In general, since a semiconductor, a dielectric, or the like is capable of obtaining a film having a good film quality at a high temperature, it is expected to form a functional element having higher performance. According to the present invention, it is advantageous to manufacture a flexible electronic device that forms a dielectric element, a semiconductor element, a MEMS element, a display element, a light-emitting element, a photoelectric conversion element, a piezoelectric conversion element, a thermoelectric conversion element, and the like on a film substrate. element.

(Laminate and manufacturing method)

The laminated system of the present invention uses at least an inorganic substrate, a decane coupling agent, and a polymer film, and The laminate thus formed.

<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 material which can be used as a substrate made of an inorganic material, and examples thereof include a glass plate, a ceramic plate, a semiconductor wafer, a metal, and the like, and a laminate of these glass plates and ceramic plates. , a composite of a wafer, a metal, a dispersion of these, and the like, and the like.

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

The ceramic plate includes Al ₂ O ₃ , mullite, AlN, SiC, Si ₃ N ₄ , BN, crystallized glass, cordierite, spodumene, Pb-BSG+CaZrO ₃ +Al ₂ O ₃ , and crystallization. Ceramics for substrates such as glass + Al ₂ O ₃ , crystallized Ca-BSG, BSG + quartz, BSG + quartz, BSG + Al ₂ O ₃ , Pb + BSG + Al ₂ O ₃ , glass ceramics, and glass ceramics (zerodur) TiO ₂ , barium titanate, calcium titanate, magnesium titanate, alumina, MgO, stearite, BaTi ₄ O ₉ , BaTiO ₃ , BaTi ₄ +CaZrO ₃ , BaSrCaZrTiO ₃ , Ba(TiZr)O ₃ , Capacitor materials such as PMN-PT or PFN-PFW, PbNb ₂ O ₆ , Pb _0.5 Be _0.5 Nb ₂ O ₆ , PbTiO ₃ , BaTiO ₃ , PZT, 0.855PZT-95PT-0.5BT, 0.873PZT-0.97PT-0.3BT, Piezoelectric materials such as PLZT.

As the semiconductor wafer, a germanium wafer, a semiconductor wafer, a compound semiconductor wafer, or the like can be used, and in the case of a germanium wafer, a single crystal or a polycrystalline tantalum is processed on a thin plate, and doped with n-type or p. Types of wafers, intrinsic silicon wafers, etc., and also include germanium oxide or various thin films deposited on the surface of germanium wafers.矽-锗, gallium-arsenic, aluminum-gallium-indium, nitrogen-phosphorus-arsenic-tellurium, SiC, InP (indium germanium), InGaAs, Semiconductor wafers such as GaInNAs, LT, LN, ZnO (zinc oxide) or CdTe (cadmium telluride), ZnSe (zinc selenide), and compound semiconductor wafers.

The metal includes a single element metal such as W, Mo, Pt, Fe, Ni, or Au, Inconel, Monel, Nimonic, carbon copper, and Fe-Ni. Alloys such as invar steel alloys and super invar steel alloys. 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 or has properties such as non-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 P-V value of the surface roughness 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, but is preferably 10 mm or less, more preferably 3 mm or less, and still more preferably 1.3 mm or less from the viewpoint of workability. The appropriate value of the thickness is not particularly limited, and is suitably used in an amount of 0.07 mm or more, preferably 0.15 mm or more, more preferably 0.3 mm or more.

The area of the inorganic substrate is preferably a large area from the viewpoint of the production efficiency of the laminate or the flexible electronic component. More preferably, it is more preferably 1000 cm ² or more, more preferably 1500 cm ² , and still more preferably 2000 cm ² .

<decane 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 B Oxydecane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3- Glycidoxypropyltrimethoxydecane, 3-glycidoxy-n-methyldimethyldimethoxydecane, 3-glycidoxypropyltriethoxydecane, vinyltrichloromethane, Vinyl trimethoxy decane, vinyl triethoxy decane, 3-glycidoxypropyl trimethoxy decane, 3-glycidoxypropyl methyl diethoxy decane, 3-epoxy Propoxypropyltriethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxy Baseline, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane hydrochloride, 3-ureido Propyltriethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxyindole , 3-mercaptopropyltrimethoxydecane, bis(triethoxymethylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxydecane, gins-(3-trimethoxydecylpropyl) Isocyanurate, chloromethylphenethyltrimethoxydecane, chloromethyltrimethoxydecane, amine phenyltrimethoxydecane, amine phenethyltrimethoxydecane, amine phenylaminomethyl Phenylethyltrimethoxynonane, hexamethyldioxane, and the like.

As the decane coupling agent which can be used in the present invention, in addition to the above, n-propyltrimethoxydecane, butyltrichlorodecane, 2-cyanoethyltriethoxydecane, cyclohexyltrichlorodecane, fluorenyl group can also be used. Trichlorodecane, diethyl methoxy dimethyl decane, diethoxy dimethyl decane, dimethoxy dimethyl decane, dimethoxy diphenyl decane, dimethoxymethyl phenyl decane , dodecyltrichlorodecane, dodecyltrimethoxydecane, ethyltrichlorodecane, hexyltrimethoxydecane,octadecyltriethoxydecane,octadecyltrimethoxydecane, n-octyltrichloro Decane, n-octyltriethoxydecane, n-octyltrimethoxydecane, triethoxyethyldecane, triethoxymethyldecane, trimethoxymethylnonane, trimethoxyphenylnonane, pentane Triethoxy decane, pentyl trichloro decane, triethoxy methoxymethyl decane, trichlorohexyl decane, trichloromethyl decane, trichlorooctadecyl decane, trichloropropyl decane, trichlorotetradecane Base decane, trimethoxy propyl decane, allyl trichloro decane, allyl triethoxy decane, allyl tri Oxy decane, diethoxymethyl vinyl decane, dimethoxymethyl vinyl decane, trichlorovinyl decane, triethoxy vinyl decane, vinyl ginseng (2-methoxy ethoxy group) ) decane, trichloro-2-cyanoethyl decane, diethoxy (3-epoxypropyloxypropyl) methyl decane, 3-epoxypropyloxypropyl (dimethoxy) methyl Decane, 3-epoxypropyloxypropyl Trimethoxy decane and the like.

Among the decane coupling agents, a decane coupling agent which is suitably used in the present invention is preferably a decane coupling agent having a chemical structure of one fluorene 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-aminopropyltri Ethoxy decane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3 - glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, amine phenyltrimethoxy Base decane, amine phenethyl trimethoxy decane, amine phenylaminomethyl phenethyl trimethoxy decane, 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, the present invention may be used in combination with a phosphorus-based coupling agent, a titanate-based coupling agent, or the like.

<Coating method of decane coupling agent>

In the prior art, the coating of the decane coupling agent is carried out in a state in which the decane coupling agent is diluted with a solvent such as an alcohol. However, the present invention is characterized by the step of coating the decane coupling agent through a vapor phase. That is, the present invention is applied by exposing an inorganic 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 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, heating at 200 ° C or higher has a side effect 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, about normal pressure, or reduced pressure, and it is preferred to promote vaporization of the decane coupling agent at about atmospheric pressure or under reduced pressure. Since most of the decane coupling agents are flammable liquids, it is preferred to carry out the vaporization operation after replacing them with a non-reactive gas in a sealed container, preferably a container.

The time for exposing the inorganic substrate to the decane coupling agent is not particularly limited, but is within 20 hours, preferably within 60 minutes, further preferably within 15 minutes, and still more preferably within 1 minute.

Exposure of the inorganic substrate to the temperature of the inorganic substrate during the decane coupling agent, depending on the decane coupling agent A suitable temperature for controlling the type between the range of -50 ° C and 200 ° C and the thickness of the desired decane coupling agent layer is preferred.

The inorganic substrate exposed to the decane coupling agent is preferably heated to 70 ° C to 200 ° C after exposure, and more preferably heated to 75 ° C to 150 ° C. By this heating, a hydroxyl group or the like on the surface of the inorganic substrate is reacted with an alkoxy group or a decyl group of a decane coupling agent to complete the treatment with a 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 already 80 ° C or more, the subsequent heating can be omitted.

In the present invention, it is preferred that the decane coupling agent coated surface of the inorganic substrate is held downward to be exposed to the decane coupling agent vapor. In the conventional method of applying a solution of a decane coupling agent, since the coated surface of the inorganic substrate is always facing upward during and after the application, it is impossible to deny the possibility that the floating foreign matter in the working environment settles on the surface of the inorganic substrate. . However, in the present invention, since the inorganic substrate can be held downward, the adhesion of foreign matter in the environment can be greatly reduced.

Further, it is preferred to clean the surface of the inorganic substrate before the treatment with the decane coupling agent by short-wavelength UV/ozone irradiation or the like, or to purify it with a liquid detergent.

The coating amount and thickness of the coupling agent are theoretically sufficient as long as one molecular layer is sufficient, and a thickness which is negligible in mechanical design is sufficient. 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. the following. However, it is presumed that the coupling agent cannot be formed into a uniform coating film if it is calculated to fall below 5 nm, but it may be in the form of clusters, which is less preferable.

The film thickness of the coupling agent layer can be calculated from the ellipsometry method or the concentration and coating amount of the coupling agent solution at the time of coating.

<Patterning Processing on the Side of Inorganic Substrate>

In the present invention, the patterning treatment can be performed on the inorganic substrate side. Here, the patterning means an area in which the coating amount, activity, and the like of the operation coupling agent are intentionally produced. Thereby, the laminate has a good adhesion portion and an easily peelable portion in which the bonding strength between the inorganic substrate and the polymer film is different. And the good adhesion portion and the easily peelable portion can form a prescribed pattern. As the patterning treatment, a method of operating the coating of the decane coupling agent by using a mask prepared in a predetermined pattern in the case of applying the decane coupling agent can be exemplified. Further, the active energy ray may be irradiated onto the coated surface of the decane coupling agent, and at this time, patterning may be performed by a method such as masking or scanning operation. Here, the irradiation active energy ray includes an operation of irradiating an energy ray such as an ultraviolet ray, an electron beam, or an X-ray, and further includes an ultraviolet ray irradiation effect such as an ultraviolet ray irradiation treatment of a very short wavelength, and simultaneously occurring in the vicinity of the irradiation surface. Ozone gas exposure effect. Further, in addition to these, patterning treatment may be performed by corona treatment, vacuum plasma treatment, normal piezoelectric slurry treatment, sandblasting treatment, or the like.

<Polymer film>

As the polymer film of the present invention, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, wholly aromatic polyester, and the like can be used. Polymeric polyester, polymethyl methacrylate, other copolymerized acrylates, polycarbonates, polyamines, polyfluorenes, polyether oximes, polyether ketones, polyamidoximines, polyether oximines, aromatics Polyimine, alicyclic polyimine, fluorinated polyimine, cellulose acetate, nitrocellulose, aromatic polyamine, polyvinyl chloride, polyphenol, polyaryl ester, polyphenylene sulfide , polyphenylene ether, polystyrene and other films. The effect of the present invention is particularly remarkable. A useful one is a polymer having a heat resistance of 100 ° C or higher, that is, a film of a so-called engineering plastic. Here, heat resistance means a glass transition temperature or a heat distortion temperature.

In the polymer film of the present invention, among the polymer materials, a thermoplastic polymer material can be obtained by a melt extension method. Further, the non-thermoplastic polymer is mainly a solution film forming method. Further, as a specific example of the present invention, a method of applying a dried polymer material to an inorganic substrate or applying a solution of a dried precursor to thin the film may be employed.

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

The polymer film-based polyimine film which is particularly suitable for use in the present invention may be an aromatic polyimine, an alicyclic polyimine, a polyamidimide or a polyether quinone. When the present invention is particularly used for the manufacture of 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. , is not particularly limited to this.

In general, a polyimide film is a polyacrylamide (polyimine precursor) solution obtained by reacting a diamine with a tetracarboxylic acid in a solvent, and is applied to a support for producing a polyimide film. 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 heat-treated at a high temperature to carry out a dehydration ring-closure reaction, thereby obtaining.

The diamine constituting the polyamic acid is not particularly limited, and an aromatic diamine, an aliphatic diamine or an alicyclic diamine which is generally used for 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 exhibit high heat resistance, low heat shrinkage, and low linear expansion coefficient while exhibiting high heat resistance. The diamines may be used alone 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)benzo. 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 Azole)-4-(6-aminobenzone) 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 the 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] Bismuth, 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'-diamine Diphenylarylene, 3,4'-diaminodiphenylarylene, 4,4'-diaminodiphenylarylene, 3,3'-diaminodiphenylanthracene, 3, 4'-Diaminodiphenylphosphonium, 4,4'-diaminodiphenylanthracene, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Methane, bis[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-double [4] -(4-Aminophenoxy)phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,2-bis[4-(4-amine Phenoxy)phenyl]propane, 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)benzene 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-aminophenoxyl) Phenyl]-2-[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy) -3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane , 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4 , 4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]one, bis[4-(4-aminophenoxy)phenyl Thiol, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-amino) Phenoxy)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-aminophenoxyl) 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-amino group) Oxy) benzhydryl 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- Aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-α,α - dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-fluorophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4 -(4-Amino-6-methylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-cyanophenoxy) -α,α-dimethylbenzyl]benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'- Diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone , 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5' -phenoxybenzophenone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5 , 5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-linkage Phenoxybenzophenone, 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-biphenyl) Oxylbenzylidene)benzene, 1,3-bis(4-amino-5-biphenoxybenzylidene)benzene, 1,4-bis(4-amino-5-biphenoxy) Benzopyridyl)benzene, 2,6-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzonitrile, and an aromatic ring of the above aromatic diamine The carbon number of one or all of a hydrogen atom partially or wholly substituted with 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 is partially or wholly substituted with a halogen atom. A halogenated alkyl group or an alkoxy aromatic diamine or the like.

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 of the diamines. Better 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 all the diamines.

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

Examples of the alicyclic tetracarboxylic acid include a lipid such as cyclobutane tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 3,3',4,4'-dicyclohexyltetracarboxylic acid. a cyclotetracarboxylic acid, and an anhydride thereof. Among these, a dianhydride having two anhydride structures (for example, cyclobutane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3', 4, 4) '-Dicyclohexyltetracarboxylic dianhydride or the like) is preferred. 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, and still more preferably 95% by mass or more based on all the tetracarboxylic acids.

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 dianhydride. , 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2-bis[4-( 3,4-Dicarboxyphenoxy)phenyl]propane anhydride or 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 polyimine film of the present invention has a glass transition temperature of 250 ° C or higher, preferably 300 ° C or higher, more preferably 350 ° C or higher, or preferably no glass transition point is observed in 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 -5 ppm/K to +15 ppm/K, still more preferably 1 ppm/K to +10 ppm/ K. If the CTE is in the above range, the difference in linear expansion coefficient from the general support can be kept to a small value, and even if the heating is applied, the polyimide film can be prevented from peeling off from the support composed of the inorganic material.

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 burst strength is not limited, but is actually less than about 1000 MPa. Here, the breaking strength of the polymer film refers to the average value of the longitudinal direction and the transverse direction of the polymer film.

The bonding strength between the polymer film of the present invention and the inorganic substrate must be 1/2 or less of the breaking strength of the polymer film.

It is assumed that in the laminate of the present invention using a film having a thickness of 10 μm, the film has a bonding strength of 0.5 N/cm.

The breaking force applied to the film having a width of 10 mm was 0.5 N / (10 μm × 10 mm) = 0.5 N / 0.1 mm ² = 5 MPa. At this time, if the film has a fracture strength of about 10 times, that is, 50 MPa or more, the peeling operation can be performed without any hindrance when the film is peeled off.

The bonding strength is preferably 1/3 or less, more preferably 1/4 or less, of the breaking strength of the polymer film.

A good adhesive portion of the present invention refers to a portion having a stronger bonding strength between the inorganic substrate and the polyimide film, and the easily peelable portion of the present invention means a portion having a weaker bonding strength between the inorganic substrate and the polyimide film. The adhesion strength of the easily peelable portion is preferably 1/2 or less of the adhesion strength of the good adhesion portion, more preferably 1/3 or less, still more preferably 1/4 or less. The lower limit of the strength is not particularly limited, and is preferably 0.5 N/cm or more in the above-mentioned good adhesion portion and 0.01 N/cm or more in the above-mentioned easily peelable portion.

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 greater than 20%, then there is It is difficult to apply to the tendency of the narrow part. Further, the thickness of the film may not be measured by, for example, a contact film thickness gauge from a position where the film to be measured is randomly drawn at about 10 o'clock, and the film thickness is measured, and is obtained based on the following formula.

Film thickness unevenness (%) = 100 × (maximum film thickness - minimum film thickness) ÷ average film thickness

The polymer film of the present invention is preferably obtained by winding into a long polyimine film having a width of 300 mm or more and a length of 10 m or more at the time of production, and is obtained by winding on a winding core into a roll. The form of the polyimine film is more preferred.

In the polymer film, in order to ensure handleability and productivity, it is preferable to add ‧ a lubricating material (particles) to the film to impart fine unevenness on the surface of the polymer film to ensure slidability. The lubricating material (particles) is preferably a fine particle composed of an inorganic material, 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, a clay, or the like. Particles composed of clay minerals, etc. Preferred are metal oxides, phosphates, and carbonates such as cerium oxide, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, calcium carbonate, and glass filler. The lubricating material may be used alone or in combination of two or more.

The volume average particle diameter of the lubricating 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 measured value obtained by the light scattering method. When the particle diameter is less than the lower limit, the 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 may cause practical trouble.

The amount of the lubricating material to be added is 0.02 to 50% by mass, preferably 0.04 to 3% by mass, and more preferably 0.08 to 1.2% by mass, based on the amount of the polymer component in the polymer film. When the amount of the lubricating material added is too small, it is difficult to expect the effect of adding the lubricating material, and the slidability may not be sufficiently ensured, which may hinder the production of the polymer film. If the amount is too large, the surface unevenness of the film may become excessively large, and even if the sliding is ensured Sex also causes smoothness and high scores The problem that the fracture strength or the elongation at break of the sub-film is lowered, causing a rise in CTE or the like.

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

When the multilayer polymer film is a film produced by a melt-stretch film forming method, for example, it can be formed by first using a polymer film material containing no lubricating material, and at least one side of the film is coated in the middle of the step. It is obtained by lubricating the resin layer of the material. Alternatively, conversely, a thin film of a polymer film material containing a lubricating material may be used, and in the middle of the step or after the film formation, the polymer film material containing no lubricating material may be applied to obtain a film.

The same applies to the polymer film obtained by the solution film forming method, such as a polyimide film, for example, as a polyaminic acid solution (precursor solution of polyimine), which can be used in a polyamic acid solution. The polymer solid component contains a lubricating 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 proline acid solution and the non-lubricating material or a small amount thereof (preferably less than 0.02% by mass, more preferably less than 0.01% by mass relative to the polymer solid content in the polyaminic acid solution) Manufactured by a proline solution.

The method of laminating (layering) the multilayer polymer film is not particularly limited as long as the adhesion between the two layers is not problematic, and it is only required to be adhered without interposing an adhesive layer or the like.

In the case of a polyimide film, for example, i) a method in which another polyaminic acid solution is continuously coated on the polyimide film after the preparation of one of the polyimide films, and the imidization is carried out ; ii) after casting one of the polyaminic acid solutions to form a poly-proline film, after continuously coating another poly-proline solution on the poly-proline film, the method of imidization ; iii) by co-extrusion method; iv) coating on a film formed of a polyamic acid solution containing no lubricating material or a small amount thereof, by spraying, T-die coating or the like to coat a large amount of lubrication a polylysine solution of the material The method of imidization and the like. The present invention is preferably a method using the above i) or the above ii).

The ratio of the thickness of each layer in the multilayer polymer film is not particularly limited, and a polymer layer containing a large amount of a lubricating material is (a) layer, and a polymer layer containing no lubricating material or a small amount thereof is used as ( b) layer, then (a) layer / (b) layer is preferably 0.05 ~ 0.95. If the layer (a)/(b) is larger than 0.95, the smoothness of the layer (b) is easily 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.

<Surface activation treatment of polymer film>

It is preferred that the polymer film used in the present invention is surface-activated. 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. As the dry treatment of the present invention, 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 may be employed. In the case of wet treatment, a treatment of bringing the surface of the film into contact with an acid or alkali solution can be exemplified. The surface activation treatment which is suitably used in the present invention is a plasma treatment and is a combination of a plasma treatment and a wet acid 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. Ion implantation treatment, treatment using PBII method, flame treatment exposed to hot plasma, 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 a plasma having a high chemical etching effect or an Ar plasma is applied to the surface of the polymer. The treatment by the plasma having a high physical etching effect is preferred. Further, it is also preferable to add a plasma such as CO ₂ , H ₂ or N ₂ or a mixed gas thereof or to further add water vapor. When the treatment for a short period of time is aimed at, the plasma having a high energy density of plasma and having high kinetic energy of ions in the plasma is preferable because the plasma having a high density of the active material is preferable. From this point of view, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation by ion source that is easy to inject high-energy ions, PBII method, and the like are also preferable.

This surface activation treatment purifies the surface of the polymer to further form an active functional group. The resulting functional group and the coupling agent layer are bonded by hydrogen bonding or chemical reaction, and the polymer film layer and the coupling agent layer can be firmly adhered.

The plasma treatment also has the effect of etching the surface of the polymer film. In particular, in a polymer film containing a large amount of lubricating material particles, protrusions caused by the lubricating material may hinder 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 further 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 may be applied to both sides. In the case of performing plasma treatment on one side, the polymer film may be contacted and disposed on one side of the electrode by plasma treatment using a parallel plate type electrode, and only for the side of the polymer film not connected to the electrode One side is applied with a plasma treatment. Further, when the polymer film is provided 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 completed by performing plasma treatment in a state in which a protective film is attached to one surface of the polymer film. Further, as the protective film, a PET film or an olefin film to which an adhesive is attached can be used.

<Patterning processing on the film side>

In the present invention, the patterning treatment can be performed on the polymer film side. Here, the patterning means an area in which the degree of activity of the surface activation treatment or the like is intentionally produced. Thereby, the laminate has a good adhesion portion and an easily peelable portion in which the bonding strength between the inorganic substrate and the polymer film is different, and the good adhesion portion and the easily peelable portion can form a predetermined pattern. As the patterning treatment, a method of operating the surface activation treatment amount by using a mask prepared in a predetermined pattern in advance when performing the surface activation treatment can be exemplified. Further, when the surface activation treatment is performed, patterning may be performed by a method such as masking or scanning operation. It can also be further processed by masking or scanning other active energy ray on the surface of the surface of the polymer film after activation. The strength of sexuality. Here, the active energy ray irradiation refers to an operation of irradiating an energy ray such as an ultraviolet ray, an electron beam, or an X-ray, and further includes an ultraviolet ray irradiation effect such as an ultraviolet ray irradiation treatment of a very short wavelength, and occurs in the vicinity of the irradiation surface at the same time. The ozone gas exposure effect. Further, in addition to these, patterning treatment may be performed by corona treatment, vacuum plasma treatment, normal piezoelectric slurry treatment, sandblasting treatment, or the like.

<Film lamination method>

In the present invention, an inorganic substrate in which a decane coupling agent layer film is formed in a predetermined pattern is used as a temporary support, and a laminate is obtained by laminating or drying a film-forming polymer film through a decane coupling agent layer. In the case of bonding a polymer film, a laminate is obtained by laminating a polymer film on a temporary supporting inorganic substrate on which a decane coupling agent layer is formed and heating the pressure-activated surface.

The pressurization and the heat treatment may be carried out by pressurization, lamination, roll lamination, or the like while heating, for example, under an atmospheric pressure atmosphere or in a vacuum. Further, a method of applying pressure heating in a state in which a flexible bag is placed may be applied. From the viewpoint of improving productivity and high productivity due to low productivity, it is preferred to pressurize or roll laminate in an atmospheric environment, especially by using a roll (roller layer). Combination) is preferred.

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 problem that the support body is broken; if the pressure is too low, there is a case where an unadhesive portion is generated and then becomes 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. The non-thermoplastic polyimide film is preferably treated at 150 ° C to 400 ° C, more preferably at 250 ° C to 350 ° C.

Further, the pressure heat treatment may be carried out in an atmospheric pressure atmosphere as described above, and it is preferred to carry out the vacuum under pressure in order to obtain a comprehensive stability. In this case, the degree of vacuum generated by the general oil rotary pump is sufficient for the degree of vacuum, and it is sufficient as long as 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 a well element can be used for pressurization in a vacuum, or by thin film laminator in a vacuum or after being vacuumed. The rubber film is vacuum laminated such as a film laminator that applies pressure to the glass in one go, and for example, "MVLP" manufactured by a famous machine can be used.

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

<Using solution coating ‧ drying to form a polymer film layer>

As a method for producing a laminate of the present invention, a polymer film layer can be formed by coating a polymer solution or a polymer precursor solution on a inorganic substrate on which a decane coupling agent layer is formed and drying the film. As a coating method of the solution, a well-known method such as dip coating, spin coating, curtain coating, or slit casting coating can be employed.

In the polyimide-based resin, a polyamine liquid solution obtained by polycondensing a diamine of a raw material of a polyimide resin with a tetracarboxylic acid or an anhydride thereof in a solution is applied in a predetermined thickness. The inorganic substrate for temporary support of the present invention is subjected to drying, heat treatment or chemical imidization treatment to form a polyimide film on the temporary support inorganic substrate. In this case, a preferable film thickness is in the range of 7 to 100 μm, more preferably 15 to 80 μm, still more preferably 23 to 45 μm.

In general, the polyimine resin layer obtained by such a method is relatively fragile, and tearing occurs in the middle of peeling, and there are many cases where it is difficult to peel off from the inorganic substrate. However, in the present invention, it is present in decane. Since the coupling agent layer has a small amount of foreign matter or agglomerates, film tearing based on the disadvantage is less likely to occur, and as a result, the yield at the time of peeling is greatly improved.

<Method of Manufacturing Flexible Electronic Component>

When the laminate of the present invention is used, an electronic component can be formed on the polymer film of the laminate by using an existing device for manufacturing an electronic component, and the process can be separated from the laminate by the polymer film. Create flexible electronic components.

The electronic component of the present invention refers to an electronic circuit including a wiring board carrying an electric circuit, an active component such as a transistor or a diode, a passive component such as a resistor, a capacitor, an inductor, and the like, and sensing a pressure, a temperature, a light, and a humidity. Such as sensing elements, light-emitting elements, liquid crystal display, electrophoretic display, Image display elements such as self-luminous display, wireless, wired communication elements, arithmetic elements, memory elements, MEMS elements, solar cells, thin film transistors, and the like.

As a method of peeling a polymer film from a laminated body, the method of irradiating a strong light from an inorganic substrate side and thermally-decomposing or photo-decomposing the junction between an inorganic substrate and a polymer film, and the peeling- A method of removing a polymer film by a force of a limit value of an elastic strength of a polymer film; a method of exposing the bonding strength between an inorganic substrate and a polymer film to be peeled off by exposure to heated water, heating of a vapor, or the like.

In the present invention, when patterning is performed on the side of the inorganic substrate or the side of the polymer film or even on both sides, the area where the adhesion between the polymer film and the inorganic substrate is lowered by the patterning process (referred to as easy peeling) The electronic component is formed. Next, a slit is formed in the peripheral portion of the region, and a region in which the electronic component of the polymer film is formed is peeled off from the inorganic substrate, whereby a flexible electronic component can be obtained. By this method, peeling of a polymer film and an inorganic substrate becomes easier.

A method of cutting a polymer film along a periphery of an easily peelable portion of the laminate, and cutting the polymer film by a cutting tool such as a cutter; by using the laser to face the laminate a method of cutting a polymer film by scanning; a method of cutting a polymer film by scanning a water jet and a laminate; and cutting a polymer film by cutting a semiconductor wafer into a portion of the glass layer Method and so on. Further, a combination of these methods may be suitably employed; or a method in which the cutting tool overlaps the ultrasonic wave and increases the cutting performance by increasing the back and forth motion or the up and down motion.

When a slit is formed in the polymer film on the periphery of the easily peelable portion of the laminate, the position at which the slit is cut may include at least a part of the easily peelable portion, and may be cut according to a predetermined pattern, and may be absorbed according to an error. The production viewpoint can be judged appropriately.

The method of peeling the polymer film from the support is not particularly limited, and a method of winding up from the edge by a tweezers or the like may be employed. After the adhesive tape is attached to one side of the slit portion of the polymer film with the element, A method of partially rolling up the tape; a method of vacuum-adsorbing one side of the slit portion of the polymer film to which the element is attached, and rolling up from the portion. In addition, when peeling off, if When the slit portion of the polymer film with the element is bent to have a small curvature, stress is applied to the element of the portion to break the element, and therefore it is preferable to remove it with the curvature as large as possible. For example, it is preferable to wind up while winding on a roll having a large curvature, or to wind up a machine in which a roller having a large curvature is located in a peeling portion.

Further, it is also useful that the peeled portion is attached to other reinforcing substrates in advance, together with the method of peeling the reinforcing substrate. 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.

<Regeneration of inorganic substrate>

In the present invention, the inorganic substrate can be reused by completely removing the remaining polymer film from the support substrate after the target electronic component is removed, and performing a simple cleaning treatment or the like. In the case where a decane coupling agent layer is formed by liquid coating, the thickness of the uneven or decane coupling agent layer exists on the surface of the inorganic substrate after the polymer film is peeled off due to the adhesion of the argon coupling agent or other foreign matter. Inequality, the surface layer of the inorganic substrate must be ground for reuse to ensure a flat surface. According to the coating method of the present invention, the surface quality of the surface of the inorganic substrate after the peeling of the polymer film is good without re-grinding.

[Examples]

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

<Reductive viscosity of poly-proline solution>

A solution of N,N-dimethylacetamide dissolved in a polymer concentration of 0.2 g/dl was measured 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.).

<The thickness of the polymer film is uneven>

The thickness unevenness of the polymer film was measured by a micrometer ("Millitron 1245D" manufactured by Feinpruf Co., Ltd.), and the thickness of the film was measured by randomly extracting 10 points from the film to be measured, and the maximum value (maximum film thickness) of the obtained 10 values, The minimum value (minimum film thickness) and the average value (average film thickness) were calculated based on the following formula.

Film thickness unevenness (%) = 100 × (maximum film thickness - minimum film thickness) ÷ average film thickness

<Tensile modulus, tensile strength and tensile elongation at break of polymer film>

A test piece of a strip shape in which the flow direction (MD direction) and the width direction (TD direction) of the measurement target were 100 mm × 10 mm, respectively, and a tensile tester ("Autograph (registered trademark) manufactured by Shimadzu Corporation) was used. ); the model name AG-5000A"), the tensile modulus, the tensile strength, and the tensile elongation at break were measured for the MD direction and the TD direction under the conditions of a tensile speed of 50 mm/min and a distance between the clamps of 40 mm.

<Linear expansion coefficient (CTE) of polymer film>

The expansion ratio of the polymer film to be measured in the flow direction (MD direction) and the width direction (TD direction) was measured under the following conditions, and the interval of 15 ° C was measured (30 ° C to 45 ° C, 45 ° C to 60 ° C, ... The expansion ratio/temperature of the measurement was performed until 300 ° C, and the average value of all the measured values measured in the MD direction and the TD direction was calculated as the linear expansion coefficient (CTE).

Machine name: "TMA4000S" made by MAC Science

Sample length: 20mm

Sample width: 2mm

Heating start temperature: 25 ° C

Temperature rise temperature: 400 ° C

Heating rate: 5 ° C / min

Gas environment: argon

Initial load: 34.5g/mm ²

<glass transition temperature>

Using a DSC differential thermal analysis device, the range from room temperature to 500 ° C is caused by the knot The presence or absence of the absorption and exothermic change of the structure changes the glass transition temperature of the polymer film.

<Evaluation of polymer film: slidability>

The two polymer films are superposed on each other with different faces (ie, the non-identical faces, but the wound outer side when the film roll is wound and the inner side of the winding), and the overlapping of the thumb and the index finger When the imine film was lightly folded, the case where the polymer film and the polymer film were slid was evaluated as "○" or "good", and the case where the film was not slipped was evaluated as "x" or "poor". Further, although the outer side surface of the winding and the outer side surface of the winding, or the inner side surface of the winding and the inner side surface of the winding do not slide, it is not an evaluation item.

<thickness of coupler layer>

The thickness (nm) of the coupling agent layer (SC layer) was prepared by applying a dry coupling agent to the separately cleaned Si wafer in the same manner as in each of the examples and the comparative examples, and the Si wafer was formed on the Si wafer. The film thickness of the upper coupling agent layer was measured by an ellipsometry method using a spectroscopic ellipsometer ("FE-5000" manufactured by Photal Co., Ltd.) under the following conditions.

Reflecting angle range: 45°~80°

Wavelength range: 250nm~800nm

Wavelength decomposition energy: 1.25nm

Dot diameter: 1mm

TanΨ: measurement accuracy ±0.01

Cos△: Measurement accuracy ±0.01

Measuring method: rotary analyzer

Polarizer angle: 45°

Incidence angle: fixed at 70°

Polarization mirror: 0~360° every 11.25°

Wavelength: 250nm~800nm

The film thickness was calculated by fitting with a nonlinear least squares method. At this time, the model of Air/film/Si was used as a model, and the wavelength correlation C1 to C6 was obtained by the following equation.

n=C3/λ4+C2/λ2+C1

k=C6/λ4+C5/λ2+C4

<Continue strength>

The decane coupling agent is applied to the inorganic substrate for temporary support by a predetermined method, and the polymer film is laminated by a predetermined process, and the inorganic substrate for temporary support is measured under the following conditions according to the 180-degree peeling method described in JIS C6471. The strength of the bond with the polymer film. In addition, the sample to be subjected to the measurement was masked by half a 60 mm × 120 mm on a square substrate of 120 mm × 120 mm, and film processing was performed in one of the remaining half areas to prepare an inorganic substrate for temporary support for evaluation. Further, when the polymer film is laminated, the size of the film is set to 110 mm × 200 mm, and the unbonded portion of the polyimide film is provided on one side, and the portion is used for "exposed core" in the measurement sample. The film portion was cut with a cutter and measured in such a manner that the width was 10 mm.

Device name: "Autograph (registered trademark) AG-IS" manufactured by Shimadzu Corporation

Measuring temperature: room temperature

Peeling speed: 50mm/min

Gas environment: atmosphere

Measuring sample width: 10mm

<Appearance>

Regarding the appearance quality, the result of the entire laminate was visually inspected.

<foreign density>

The area of 30 mm × 30 mm was sampled, and the sampling area was observed with a microscope having a function of measuring the length of 100 times magnification. The foreign matter confirmed by 100-fold observation was further set to a magnification of 400 times, and the length of the long diameter was measured, and 10 μm was measured. The number of the above is taken as a coefficient divided by the observed area as the foreign matter density.

<Manufacture of Polyimine Film> [Manufacturing Example 1] (Preparation of poly-proline solution)

After substituting nitrogen gas in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 398 parts by mass of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine ( PDA) 147 parts by mass dissolved in 4,600 parts by mass of N,N-dimethylacetamide and added as a colloidal material for lubricating materials A dispersion of cerium oxide dispersed in dimethylacetamide ("Snowtex (registered trademark) DMAC-ST30" manufactured by Nissan Chemical Industries Co., Ltd.) with cerium oxide (lubricating material) relative to a polymer in a polyaminic acid solution The total amount of the solid content was 0.15 mass%, and the mixture was stirred at a reaction temperature of 25 ° C for 24 hours to obtain a brown viscous polyaminic acid solution V1 having the reduced viscosity shown in Table 1.

(Production of polyimine film)

The polyamic acid solution V1 obtained above was applied to a polyester film having a width of 1050 mm by a slit casting method so that the final film thickness (film thickness after yttrium imidation) was 25 μm (Toyobo Co., Ltd. limited) The smooth surface (non-lubricated material surface) of the company "A-4100") was dried at 105 ° C for 20 minutes, and then peeled off from the polyester film to obtain a self-supporting polyglycolic acid film having a width of 920 mm.

Next, the obtained self-supporting poly-proline film is heated stepwise in a temperature range of 150 ° C to 420 ° C by a pin comb tenter (first segment 180 ° C × 5 minutes, second segment 270 ° C × 10 minutes, 3rd stage 420 ° C × 5 minutes) and heat treatment to imidize the yttrium, and remove the needle comb holding portions at both ends with a slit to obtain a long polyimine film F1 (1000 m roll) having a width of 850 mm. ). The characteristics of the obtained film F1 are shown in Table 1.

[Manufacturing Example 2] (Preparation of poly-proline solution)

Adding 5-amino-2-(p-aminophenyl)benzene to a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, followed by nitrogen substitution 223 parts by mass of azole (DAMBO), and 4416 parts by mass of N,N-dimethylacetamide, and completely dissolved, and secondly, a colloidal cerium oxide as a lubricating material is dispersed in dimethylacetamide. The dispersion ("Snowtex (registered trademark) DMAC-ST30" manufactured by Nissan Chemical Industries Co., Ltd.) has a cerium oxide (lubricating material) of 0.12% by mass based on the total amount of the polymer solid content in the polyaminic acid solution. It was added together with 217 parts by mass of pyromellitic dianhydride (PMDA), and stirred at a reaction temperature of 25 ° C for 24 hours to obtain a brown viscous polyamine solution V2 having the reduced viscosity shown in Table 1.

(Production of polyimine film)

Instead of the polyaminic acid solution V1, the polyamic acid solution V2 obtained above was used, and the needle carding machine was used (the first stage 150 ° C × 5 points, the second stage 220 ° C × 5 points, the third stage 485 ° C ×10 minutes) The heat treatment was carried out to imidize the oxime, and the needle-clamping portions at both ends were removed by slits to obtain a polyimide film F2 (1000 m roll) having a width of 850 mm. The properties of the obtained film F2 are shown in Table 1.

[Manufacturing Example 3] (Preparation of poly-proline solution)

In the production example 2, except that a dispersion in which colloidal cerium oxide was dispersed in dimethylacetamide ("Snowtex (registered trademark) DMAC-ST30" manufactured by Nissan Chemical Industries, Ltd.) was added, the same operation was carried out. Polylysine solution V3.

(Production of polyimine film)

The polyamic acid solution V3 obtained above was applied to a width of 1050 mm by a comma coater so that the final film thickness (film thickness after yttrium imidation) became 5 μm. On the smooth surface (non-lubricated material surface) of the polyester film ("A-4100" manufactured by Toyobo Co., Ltd.), the polyether acid was applied to the final film thickness so that the V3 system became 38 μm in the final film thickness. The solution V2 was dried at 105 ° C for 25 minutes, and then peeled off from the polyester film to obtain a self-supporting polyglycolic acid film having a width of 920 mm. Next, the obtained self-supporting polyglycolic acid film was heat-treated by a needle card tenter (first stage 180 ° C × 5 minutes, second stage 220 ° C × 5 minutes, third stage 495 ° C × 10 minutes) Further, the oxime was imidized, and the needle-clamping portions at both ends were removed by slits to obtain a polyimine film F3 (1000 m roll) having a width of 850 mm. The properties of the obtained film F3 are shown in Table 1.

<Manufacture of plasma treated film>

A vacuum plasma treatment was applied to one surface of the polyimide film F1 obtained in Production Example 1 to obtain a plasma-treated polyimide film P1. The characteristics of the obtained film P1 are shown in Table 2.

As a vacuum plasma treatment, nitrogen gas was introduced into a vacuum chamber by a RIE mode using an electrode of a parallel plate type, and treated with RF plasma, and high frequency electric power of 13.54 MHz was introduced, and the treatment time was set to 3 minutes.

The plasma-treated polyimide film P2 was obtained in the same manner except that the polyimide film F1 was replaced with the polyimide film F2 obtained in Production Example 2. Further, plasma treatment was performed on the single side of the layer side of the film F3 containing no lubricating material in the same manner to form a film P3.

A polyimide film F4 was obtained by using a polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm instead of the polyimide film F1.

In the same manner, the polyimine film F1 was replaced, and a polyethylene naphthalate film "Teonex" (manufactured by Teijin Co., Ltd.) having a thickness of 100 μm was used to obtain a plasma-treated film P5.

The polyimine film P2 was treated with a plasma obtained by using a polyimide film F2, and a predetermined mask made of a stainless steel plate having a thickness of 1 mm was placed thereon, and a UV/ozone irradiation device manufactured by LAN TECHNICAL SERVICE Co., Ltd. was used for 120 seconds. UV/ozone irradiation gave a patterned plasma treated film PP2.

The properties of the obtained plasma-treated film and patterned plasma-treated film are shown in Table 2.

<Formation of a coupling layer to an inorganic substrate> <Coating Example 1>

The coating of the decane coupling agent to the inorganic substrate was carried out under the following conditions using a vacuum chamber having a hot plate.

100 parts by mass of a decane coupling agent ("KBM-903": 3-aminopropyltrimethoxydecane manufactured by Shin-Etsu Chemical Co., Ltd.) was filled in a petri dish and placed on a hot plate. At this time, the temperature of the hot plate was 25 °C. Next, at a distance of 300 mm from the liquid surface perpendicular to the liquid surface of the decane coupling agent, the PYREX glass plate of 300 mm × 350 mm × 0.7 mmt was horizontally held, the vacuum chamber was closed, nitrogen gas was introduced at atmospheric pressure until the oxygen concentration became 0.1% or less, and then the nitrogen gas was stopped to make the cavity The pressure is reduced to 3×10 ^-4 Pa in the room, and the temperature of the heating plate is raised to 120 ° C for 10 minutes to expose the vapor of the decane coupling agent. Thereafter, the temperature of the heating plate is lowered while quietly introducing the purity into the vacuum chamber. Nitrogen gas is returned to atmospheric pressure, the glass plate is taken out, and placed in a clean environment with a decane coupling agent coated face up on a hot plate at 100 ° C for about 3 minutes to obtain an inorganic layer forming a decane coupling agent layer. Substrate S1.

<Coating Example 2>

The coating of the decane coupling agent to 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 filled in a petri dish, and placed in a capped state. On the hot plate in the gas test bench, the heating plate was heated to 160 °C. Next, hold a 100 mm × 100 mm × 1.0 mmt soda lime glass plate horizontally at a distance of 100 mm from the liquid surface of the decane coupling agent, and open the lid of the culture dish for 15 minutes to expose the vapor of the decane coupling agent. Thereafter, The glass plate was placed on a hot plate at 100 ° C with the decane coupling agent coated upward, and heat-treated for about 3 minutes to obtain an inorganic substrate S2 on which a decane coupling agent layer was formed.

<Coating Example 3>

0.5 parts by mass of "cyclohexane coupling agent" (KBM-903: 3-aminopropyltrimethoxydecane) and 99.5 parts by mass of isopropyl alcohol were stirred and mixed in a clean glass vessel to prepare decane. Coupler solution. On the other hand, a PYREX glass plate of 300 mm × 350 mm × 0.7 mmt was placed in a spin coater manufactured by Japan Create Co., Ltd., first, 50 ml of isopropyl alcohol was dropped to the center of the glass, and washed by pulverizing at 500 rpm, and secondly, Prepared decane coupling agent solution About 30 ml was dropped into the center of the glass plate, rotated at 500 rpm for 10 seconds, and then the rotation speed was increased to 1500 rpm for 20 seconds, and the decane coupling agent solution was removed. Next, the glass plate was taken out from the spin coater which was stopped, and placed on a hot plate at 100 ° C in a pure environment with the coating side of the decane coupling agent applied thereto, and heat treatment was performed for about 3 minutes to obtain an inorganic layer forming a decane coupling agent layer. Substrate S3.

<Coating Example 4>

In the same manner as in Coating Example 3, a decane coupling agent layer was formed on a soda lime glass plate of 100 mm × 100 mm × 1.0 mmt by a spin coater to obtain an inorganic substrate S4.

<Coating Example 5> Patterning

A predetermined mask made of a stainless steel plate having a thickness of 1 mm was placed on the inorganic substrate S1 obtained in the coating example 1 and subjected to UV/ozone irradiation for 120 seconds using a UV/ozone irradiation apparatus manufactured by LAN TECHNICAL SERVICE to obtain a patterned inorganic substrate. SP1.

The obtained inorganic substrate is shown in Table 3.

<Example 1>

The plasma-treated surface of the rectangular plasma-treated film P1 which was trimmed to 280 mm × 330 mm was superposed on the decane coupling agent layer side of the obtained inorganic substrate S1 so as to expose the inorganic substrate surface by 10 mm, and laminated by Climb Products Co., Ltd. The machine was temporarily laminated at a temperature of 100 ° C on the inorganic substrate side, a roll pressure of 5 kg/cm ² at the time of lamination, and a roll speed of 5 mm/sec. The polymer film which is temporarily laminated is not peeled off by the weight of the film itself, but if it is lightly scraped, the edge of the film is easily peeled off. Thereafter, the obtained temporarily 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 laminate L1 of the present invention. The properties of the obtained laminate are shown in Table 4.

<Examples 2 to 5>

Hereinafter, a laminate is produced using the inorganic substrate S1 and the plasma-treated film shown in the table. Further, in the case of the plasma treatment film P4, the heating temperature of the clean oven was set to 140 ° C, and the case of the plasma treatment film P5 was set to 175 °C. The properties of the obtained laminate are shown in Table 4.

<Example 6>

The obtained inorganic substrate S1 and the patterned plasma-treated film PP2 were used in the same manner to obtain a laminate L6. In the laminate L6, a portion where the patterned plasma-treated film was not subjected to UV/ozone irradiation was used as a normal portion, and a portion to be irradiated was evaluated as an easily peelable portion.

(Comparative Example 1)

The plasma-treated surface of the rectangular plasma-treated film P1 having a thickness of 280 mm × 330 mm was superimposed on the decane coupling agent layer of the obtained inorganic substrate S1C so that the inorganic substrate surface was exposed by 10 mm, and a layer made of Climb Products Co., Ltd. was used. The machine was temporarily laminated at a temperature of 100 ° C on the inorganic substrate side, a roll pressure of 5 kg/cm ² at the time of lamination, and a roll speed of 5 mm/sec. The polymer film which is temporarily laminated is not peeled off by the weight of the film itself, but if it is lightly scraped, the edge of the film is easily peeled off. Thereafter, the obtained temporarily 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 laminate C1 of the present invention. The properties of the obtained laminate are shown in Table 4.

<Examples 7 to 11>

The plasma-treated surface of the rectangular plasma-treated film P1 having a thickness of 90 mm × 90 mm was superimposed on the side of the arsenal coupling agent layer of the inorganic substrate S2 so that the edge of the inorganic substrate surface was exposed by 5 mm, and was vacuum-pressed at the well manufacturing facility. In the machine, the cushioning material consisting of a carbon sheet was sandwiched between the upper and lower sides, and the temperature of the hot plate was set to 300 ° C under vacuum for 20 minutes, and the mixture was cooled to room temperature to obtain a laminate L7. Further, the plasma-treated films P2 to P5 were similarly used, and a laminate was obtained in the same manner. Further, in the case of the plasma-treated film P4, the vacuum pressure temperature was set to 140 ° C, and the plasma treatment film P5 was set to 175 °C. The properties of the obtained laminate are shown in Table 4.

<Comparative Example 2>

The laminate C2 was obtained in the same manner as in Example 7 except that the inorganic substrate S4 was used. The properties of the obtained laminate are shown in Table 4.

<Example 12>

Using the patterned inorganic substrate SP1 and the plasma-treated film P2, the laminate L12 was obtained in the same manner as in Example 1 below. In the laminate L6, a portion where the patterned inorganic plate was not subjected to UV/ozone irradiation was used as a normal portion, and a portion to be irradiated was evaluated as an easily peelable portion.

<Example 13>

The patterned inorganic substrate SP1 and the patterned plasma-treated film PP2 were used in the same manner as in Example 1 to obtain a laminate L13. Further, the mask for the patterning treatment on the inorganic sheet side has the same shape as the mask used for the patterning treatment on the side of the plasma processing film, and is disposed such that the portions processed together are overlapped with each other. In the laminate L13, a portion where no UV/ozone irradiation was performed was used as a normal portion, and a portion to be irradiated was evaluated as an easily peelable portion. The results are shown in Table 4.

<Example 14>

In the patterned inorganic substrate SP1, the polyamic acid solution obtained in Production Example 2 was applied by a mold coater so that the final film thickness became 25 μm, and placed in an explosion-proof oven and dried at 80 ° C for 100 minutes, and then dried at 5 ° C for 5 minutes. °C / min to 200 ° C, hold at 200 ° C for 60 minutes, followed by 10 ° C / min to 480 ° C and 480 ° C for 5 minutes, then cooled to 100 ° C at 30 ° C / min, open the oven door to cool to the chamber A laminate L14 in which a polymer film layer is directly formed on the surface of the inorganic substrate is obtained in the vicinity of the temperature. The results are shown in Table 4.

(Application example 1)

Using the laminates obtained in Examples 1 to 6, Example 12, Example 13, Example 14, and Comparative Example 1, a bottom gate type thin film transistor array was tried in accordance with the following procedure.

Gas barrier formation

A 100 nm gas barrier film made of SiON was formed on the polymer film side by a reactive sputtering method. Next, an aluminum layer having a thickness of 80 nm was formed by a sputtering method, and a gate wiring and a gate electrode were formed by photolithography. Next, an epoxy-based gate insulating film (thickness: 80 nm) was formed by a slit die coater. Further, a 5 nm chromium layer and a 40 nm gold layer were formed by a sputtering method, and a source electrode and a drain electrode were formed by photolithography. Next, an epoxy resin of an insulating layer and a dam layer was applied by a slit die coater, and an inclusion source was formed by ablation by a UV-YAG laser to form a circular shape having a diameter of 100 μm. The dam layer having a thickness of 250 nm for the semiconductor layer of the pole electrode and the drain electrode is also formed by the through hole at the connection point with the upper electrode. Next, the polythiophene of the organic semiconductor was discharged into the dam by an inkjet printing method, a silver paste was buried in the via hole portion, and an aluminum wiring was further formed as an upper electrode to form a thin film transistor array having 640 × 480 pixels.

Using the obtained thin film transistor array as a substrate, a display element was formed by superposing an electrophoretic display medium on a front plate, and the yield and display performance of the transistor were determined by ON/OFF of each pixel. As a result, the thin film transistor array obtained in the examples exhibited good display properties. On the other hand, in the laminate C1 of the comparative example, the display of 12 lines in the longitudinal direction and 5 lines in the horizontal direction became defects.

Further, in the pixel which was defective in Comparative Example C1, the disconnection of the gate wiring or the disconnection of the upper electrode occurred. A foreign matter having a long diameter of 10 μm or more is observed on the bottom surface of the polymer film corresponding to the broken portion, that is, on the surface of the glass plate, suggesting that the disconnection is inhibited from exposure by the photo-etching step due to foreign matter. The composition analysis of the foreign matter caused by the disconnection was carried out, and as a result, Si element accounted for 25% or more of the foreign matter, and it was judged to be a decane coupling agent agglomerate.

Regarding the patterning of L6, L12, L13, and L14, after the front plate is overlapped, the polymer film portion is burned by a UV-YAG laser along the periphery of the patterning portion to take advantage of the blade on the thin razor. The method of peeling off can be easily peeled off from the edge of the break, and a flexible electrophoretic display element can be obtained.

Regarding other laminates which are not subjected to patterning, YAG Ray is scanned from the side of the glass substrate In the state where the radiation of the polymer film and the glass plate is weakened, the peeling operation is performed in the same manner as the thin blade is lifted, and the flexible electrophoretic display element is obtained in the same manner.

The obtained flexible electrophoretic display element was found to have a display performance which was not deteriorated even when it was obtained by a cylinder having a diameter of 3 mm, and it was confirmed that the flexible electrophoretic display element had sufficient practical flexibility. The flexible electrophoretic display element obtained from L14 has no problem when wound around a cylinder having a diameter of 5 mm, but when wound around a cylinder having a diameter of 3 mm, cracks occur at the edges of the polymer film. This is because the polymer film itself is quite fragile.

<Application Example 2>

In the laminate L1 obtained in Example 1, after peeling off the flexible electrophoretic display device in Application Example 1, the PYREX glass plate of the original substrate was immersed in a 10% aqueous sodium hydroxide solution at room temperature for 20 hours, followed by After washing with water, the liquid crystal substrate was cleaned and washed with a glass cleaning device. The glass plate after washing was used in the same manner as in Example 1, and a decane coupling agent layer was formed on the same surface as that used in Example 1, and a laminate was obtained in the same manner as below. The obtained laminate was excellent in appearance quality, and had a foreign matter density of 0.5 / cm ² , and was sufficiently reproducibly used.

<Comparative application example>

In the laminate C1 obtained in the comparative example, after the flexible electrophoretic display element was peeled off in the same manner as in Application Example 2, the cleaning operation was performed in the same manner, and the laminate was formed in the same manner, and the foreign matter density was increased to 46. /cm ² , confirming that the appearance quality is significantly reduced.

(Application Example 3)

The laminates obtained in Examples 7 to 11 and Comparative Example 2 were covered with a stainless steel frame having an opening and fixed to a substrate holder in the thermal spraying apparatus. The substrate holder was fixed to the support of the laminate, and the temperature of the laminate was set by flowing a refrigerant into the substrate holder, and the temperature of the laminate was set to 2 °C. First, a plasma treatment is applied to the surface of the polymer film of the laminate. The plasma treatment conditions were set to argon gas at a frequency of 13.56 MHz, an output of 200 W, and a gas pressure of 1 × 10 ^-3 Torr. The temperature at the time of the treatment was 2 ° C, and the treatment time was 2 minutes. Next, using a target of nickel-chromium (chromium 10% by mass) alloy at a frequency of 13.56 MHz, an output of 450 W, and a pressure of 3 × 10 ^-3 Torr, by DC magnetron sputtering in an argon atmosphere, A nickel-chromium alloy film (base layer) having a thickness of 11 nm was formed at a rate of 1 nm/second. Next, the temperature of the laminate was set to 2 ° C, and thermal spraying was performed. Then, copper was vapor-deposited at a rate of 10 nm/sec to form a copper thin film having a thickness of 0.22 μm. Thus, a laminate having a film forming the underlying metal thin film was obtained from each of the laminates. Further, the thicknesses of the copper and NiCr layers were confirmed by a fluorescent X-ray method.

Next, a laminate from each film on which a film forming the underlying metal thin film is attached is fixed to a frame made of Cu, and immersed in an electrolytic plating solution (copper sulfate 80 g/liter, sulfuric acid 210 g/liter, HCl, using a copper sulfate plating bath). A small amount of the gloss agent) was formed by flowing an electric 1.5 A/dm ² to form a thick copper plating layer (thickness plating layer) having a thickness of 4 μm. Subsequently, heat treatment was performed at 120 ° C for 10 minutes and dried to form a copper foil layer on the surface of the polymer film of the laminate.

Each of the obtained metalized polyimide film ‧ support laminates was coated with a dry photoresist ("FR-200" manufactured by Shipley Co., Ltd.), and then subjected to non-contact exposure with a glass mask to further 1.2% by mass of KOH. Aqueous solution development. Next, etching was performed at an etching line of 40 ° C and 2 kgf / cm ² on an etching line containing copper chloride (II) of HCl and hydrogen peroxide to form a line array of line/space = 20 μm / 20 μm as a test pattern. Next, after applying a 0.5 μm thick electroless tin plating, annealing treatment was performed at 125 ° C for 1 hour to obtain a wiring pattern.

The obtained wiring pattern was observed with an optical microscope, and the test pattern was used to confirm the presence or absence of disconnection/short circuit. As a result, the wiring pattern obtained from the laminates of Examples 7 to 11 was not broken or short-circuited, and the pattern shape was also good. On the other hand, the wiring pattern obtained from the laminate of Comparative Example 2 was observed to be broken at a part. The wiring shape of the disconnection portion becomes a shape in which the wiring is thin and intermittent, and it is inferred that the exposure in the photoresist step is hindered. Further, the polymer film portion of the broken portion was in a convex state, and it was found that foreign matter was present between the polymer film and the glass substrate. As a result of analysis of the composition of the foreign body system, Si element accounts for 25% or more, and it is inferred that it is an agglomerate of a decane coupling agent.

Then, the polymer film was peeled from the glass plate in the same manner as in Application Example 1 to form a flexible wiring board. The flexibility of the obtained flexible wiring board was good.

According to the above results, the laminate of the present invention is suitable for producing a flexible electronic component and exhibits excellent characteristics in terms of reproducibility of the substrate.

[Industrial availability]

The laminate of the present invention can easily peel off the polymer film with the electronic component from the inorganic substrate after the electronic component is formed, and at the same time, can provide decane coupling for preventing the subsequent laminate. A laminate in which the aggregate of the agent adheres to the inorganic substrate and has excellent appearance quality and homogenizes the adhesion between the polymer film and the inorganic substrate contributes greatly to the industry.

Further, according to the present invention, the surface roughness of the inorganic substrate after the peeling of the polymer film can be reduced, and the decane coupling agent can be applied as a substrate after a simple cleaning operation, and the reproducibility of the inorganic substrate can be remarkably improved.

Claims (15)

A laminate obtained by bonding a polymer film and an inorganic substrate via a decane coupling agent layer, wherein the number of foreign matters having a long diameter of 10 μm or more between the polymer film and the inorganic substrate is 3/cm ² or less, and the adhesive strength of the polymer film and the inorganic substrate is 1/2 or less of the breaking strength of the polymer film. The laminate according to claim 1, wherein the foreign matter is a foreign matter containing a ruthenium atom. The laminate according to claim 1 or 2, wherein the polymer film is a polyimide film having a thickness of 3 μm or more. The laminate according to any one of claims 1 to 2, wherein the inorganic substrate is a glass plate having an area of 1000 cm ² or more. The laminate according to any one of claims 1 to 2, wherein the decane coupling agent is a chemical structure having one fluorene atom per molecule. The laminate according to any one of claims 1 to 2, wherein the polymer film is bonded to the inorganic substrate via a layer of a decane coupling agent, and has a bonding strength between the polymer film and the inorganic substrate. A distinct good subsequent portion and an easily peelable portion, and the good succeeding portion and the easily peelable portion form a prescribed pattern. A method for producing a laminate, characterized by having the following steps (1) to (3): (1) forming a decane coupling agent layer on an inorganic substrate by exposing the inorganic substrate to a vaporized decane coupling agent; (2) a polymer film which is activated on the surface of the decane coupling agent layer to be activated; (3) both are heated and pressurized to follow the two. A method for producing a laminate, characterized by having the following steps (1) to (3): (1) forming a decane coupling agent layer on an inorganic substrate by exposing the inorganic substrate to a vaporized decane coupling agent; (2) coating a polymer solution or a polymer precursor solution on the decane coupling agent layer; (3) drying ‧ heating the polymer solution or the polymer precursor solution to form a polymer film to obtain a laminate . The method for producing a laminate according to any one of claims 7 to 8, wherein the step (1) is carried out at about atmospheric pressure. The method for producing a laminate according to any one of claims 7 to 8, wherein the step (1) is carried out under reduced pressure. The method for producing a laminate according to any one of claims 7 to 8, wherein the laminate has a good adhesion portion and an easily peelable portion having different bonding strength between the polymer film and the inorganic substrate. And the good subsequent portion forms a prescribed pattern with the easily peelable portion. The method for producing a laminate according to claim 11, wherein a part of the inorganic substrate is shielded by forming the decane coupling agent layer so that the good adhesion portion and the easily peelable portion form a predetermined pattern. The method for producing a laminate according to claim 11, wherein after the decane coupling agent layer is formed, a part of the decane coupling agent layer is irradiated with an active energy ray to form the good adhesion portion and the easily peelable portion. The prescribed pattern. A method of producing a flexible electronic component, comprising: using the laminate obtained by the method for producing a laminate according to any one of claims 7 to 10, the polymer in the laminate An electronic component is formed on the film, and second, the polymer film is peeled off from the inorganic substrate together with the electronic component. A method of producing a flexible electronic component, comprising: a laminate obtained by the method for producing a laminate according to any one of claims 11 to 13; a polymer film in the laminate Forming an electronic component on a portion corresponding to the easily peelable portion, and second, making a slit in the polymer film along the periphery of the easily peelable portion of the laminate, and the polymer film together with the electronic component from the inorganic substrate Stripped.