TW201702287A - Peeling layer forming composition - Google Patents

Abstract

A peeling layer forming composition is provided which contains polyamic acid, a carbon-based filler, and an organic solvent.

Description

Release layer forming composition

The present invention relates to a composition for forming a release layer, and is a composition for forming a release layer for forming a release layer provided on a substrate, as described in detail.

In recent years, electronic devices have been required to have a function of bending, thinning, and weight reduction. Based on this, it is required to replace a glass substrate which is heavy and fragile and cannot be bent, and a lightweight flexible plastic substrate is used. Further, in the new generation of displays, development of an automatic full-color TFT display panel using a lightweight flexible plastic substrate is required. For this reason, various methods for manufacturing an electronic device using a resin film as a substrate have been invented, and in a new-generation display, manufacturing is progressed by a process of converting an existing TFT device.

Patent Documents 1, 2, and 3 disclose that an amorphous germanium film layer is formed on a glass substrate, and a plastic substrate is formed on the film layer, and then the laser is irradiated from the glass surface side by crystallization of the amorphous germanium. A method of separating the plastic substrate from the glass substrate by the generated hydrogen gas. Further, Patent Document 4 discloses that the peeled layer is used by the technique disclosed in Patent Documents 1 to 3. A method in which the "transferred layer" is attached to a plastic film to complete a liquid crystal display device is described.

However, in the methods disclosed in Patent Documents 1 to 4, in particular, the method disclosed in Patent Document 4 is required to use a substrate having high light transmittance, and to sufficiently release hydrogen contained in the amorphous crucible through the substrate. Energy, but must be irradiated with a large amount of laser light, and there is a problem of damage to the peeled layer. Further, it takes a long time for the laser treatment to be performed, and it is difficult to peel off the peeled layer having a large area. Therefore, it is difficult to improve the productivity of the device production.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-125929

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-125931

[Patent Document 3] International Publication No. 2005/050754

[Patent Document 4] Japanese Patent Laid-Open No. Hei 10-125930

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a composition for forming a release layer which can be peeled off without causing damage to a resin substrate of a flexible electronic device.

As a result of intensive efforts to solve the above problems, the present inventors have found that a composition containing polyglycine, a carbon-based filler, and an organic solvent can have excellent adhesion to a substrate and can be used. The present invention has been completed by a moderate adhesion of a resin substrate of a flexible electronic device and a peeling layer of a moderate releasability.

In other words, the present invention provides a composition for forming a release layer, comprising a poly-proline, a carbon-based filler, and an organic solvent; 2. The composition for forming a release layer according to 1, wherein the polycondensation The amine acid is a polyamine acid obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride; 3. The composition for forming a release layer according to 2, wherein the aromatic diamine contains 1 to 5 benzenes. The aromatic diamine of the core; 4. The composition for forming a release layer according to 2 or 3, wherein the aromatic tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride having 1 to 5 benzene nuclei; The composition for forming a release layer according to any one of the above 1 to 4, wherein the carbon-based filler is a carbon nanotube or graphene; and 6. a release layer which is peeled off using any one of 1 to 5 a layer forming composition; 7. A method of manufacturing a flexible electronic device comprising a resin substrate, characterized by using a peeling layer of 6, wherein the resin substrate is a polymer. A substrate composed of quinone imine.

By using the composition for forming a release layer of the present invention, it is possible to obtain a film having excellent adhesion to the substrate and appropriate adhesion to the resin substrate and moderate peelability. By using such a composition, in the manufacturing process of the flexible electronic device, it is possible to damage the resin substrate formed on the substrate or the circuit provided thereon, and the resin substrate and the circuit. And so on together from the substrate. Therefore, the composition for forming a release layer of the present invention can contribute to simplification of the manufacturing process of the flexible electronic device including the resin substrate, improvement of the yield thereof, and the like.

Hereinafter, the present invention will be described in more detail.

The composition for forming a release layer of the present invention contains polyamic acid, a carbon-based filler, and an organic solvent. Here, the release layer of the present invention refers to a layer which is disposed directly above the glass substrate for a predetermined purpose, and as a typical example thereof, in the manufacturing process of the flexible electronic device, in the substrate and the polymerization The resin substrate of the flexible electronic device comprising the imide resin is provided for fixing the resin substrate in a predetermined process, and after forming an electronic circuit or the like on the resin substrate, the resin substrate is formed. The provided release layer can be easily peeled off from the substrate.

The polyamic acid to be used in the present invention is not particularly limited, and may be a reaction between a diamine and a tetracarboxylic dianhydride, but the function of the obtained film as a release layer is improved. Preferably aromatic Polylysine obtained by reacting a diamine with an aromatic tetracarboxylic dianhydride.

The aromatic diamine is not particularly limited as long as it has two amine groups in the molecule and has an aromatic ring, but is preferably an aromatic diamine containing 1 to 5 benzene nucleuses.

Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), and 1,2-diaminobenzene (o). -phenylenediamine), 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5 - dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6 -tetramethyl-p-phenylenediamine, m-nonanediamine, p-nonanediamine, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2- a diamine having a benzene nucleus such as diamine or 3,5-bis(trifluoromethyl)benzene-1,2-diamine; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1 , 4-naphthalenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine, 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2,3-naphthalenediamine, 2,6 -naphthalenediamine, 4,4'-biphenyldiamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl-4, 4'-Diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4' -diaminodiphenylmethane, 4,4'-diaminobenzimidamide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethyl Benzyl aniline, 3,3'-diamine Diphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2 - bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4- Aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylarylene, 3,4'-diaminodiphenylarylene, 4,4'-Diaminodiphenylarylene, 3,3'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 3,3',5,5'-four Fluorine biphenyl-4,4'-diamine, 4,4'-diamino octafluorobiphenyl, 2-(3-aminophenyl)-5-aminobenzimidazole, 2-(4-amine a phenyl nucleus such as phenyl)-5-aminobenzoxazole is a diamine; 1,5-diamino fluorene, 2,6-diamino fluorene, 9,10-diamino fluorene 1,8-Diaminophenanthrene, 2,7-diaminophenanthrene, 3,6-diaminophenanthrene, 9,10-diaminophenanthrene, 1,3-bis(3-aminophenyl) Benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3 - bis(3-aminophenyl sulfide) benzene, 1,3-bis(4-aminophenyl sulfide) benzene, 1,4-bis(4-aminophenyl sulfide) benzene, 1, 3-bis(3-aminophenylhydrazine)benzene, 1,3-bis(4-aminophenylphosphonium)benzene, 1,4-bis(4-aminophenylphosphonium)benzene, 1,3- Bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4 -Aminophenyl)isopropyl]benzene, 4,4"-diamino-p-biphenyl, 4,4"-diamino-m-biphenyl, etc. An amine or the like, but is not limited thereto. These may be used alone or in combination of two or more.

Among them, from the viewpoint of improving the functionality of the obtained release film as a release layer, it is preferred that the aromatic ring and the impurity which do not have a substituent such as a methyl group on the aromatic ring and the hetero ring to be condensed therewith are preferable. An aromatic diamine composed of an aromatic ring. Specifically, it is preferably p-phenylenediamine, m-phenylenediamine, 2-(3-aminophenyl)-5-aminobenzimidazole ring, 2-(4-aminophenyl)- 5-aminobenzoxazole, 4,4"-diamino-p-biphenyl and the like.

In the present invention, the amount of the aromatic diamine used is preferably less than 70% by mole, more preferably 80% by mole or more, still more preferably 90% by mole or more, and still more preferably, in the total diamine. It is 95% or more, and preferably 100% by mole. By adopting such usage, reproducibility is excellent A film having excellent adhesion to the substrate and moderate adhesion to the resin substrate and moderate peelability.

The aromatic tetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has an aromatic ring, but is preferably an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei.

Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, and naphthalene-1. 2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene-2,3, 5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, biphenyl-2,2', 3,3'-tetracarboxylic dianhydride, biphenyl-2,3,3',4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, hydrazine -1,2,3,4-tetracarboxylic dianhydride, indole-1,2,5,6-tetracarboxylic dianhydride, indole-1,2,6,7-tetracarboxylic dianhydride, hydrazine-1 , 2,7,8-tetracarboxylic dianhydride, indole-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,3,4-tetracarboxylic dianhydride, phenanthrene Phenanthrene)-1,2,5,6-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-four Carboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, phenathracene-2,3,5,6-tetracarboxylic dianhydride, phenanthrene-2, 3,6,7-tetracarboxylic dianhydride, phenanthrene-2,3,9,10-tetracarboxylic dianhydride, phenanthrene-3,4,5,6-tetracarboxylic dianhydride, Phenanthrene-3,4,9,10-tetracarboxylic dianhydride, etc. But is not limited thereto and the like. These may be used alone or in combination of two or more.

Among them, from the viewpoint of improving the functionality of the obtained film as a release layer, it is preferred that the benzene nucleus is one or two aromatic carboxylic acids. Diacid anhydride. Specifically, it is preferably an aromatic tetracarboxylic dianhydride represented by any one of the formulae (C1) to (C12), more preferably a formula (C1) to (C7) and (C9) to (C11). An aromatic tetracarboxylic dianhydride of any of the formulas.

In the present invention, the aromatic tetracarboxylic dianhydride is used in an amount of 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol%, based on the total tetracarboxylic dianhydride. More preferably, it is more than 95% by mole, and most preferably 100% by mole. By using such an amount of use, it is possible to obtain a film having excellent adhesion to a substrate, and an appropriate adhesion to a resin substrate and moderate peelability.

The polyamine contained in the composition for forming a release layer of the present invention can be obtained by reacting the above-described diamine with tetracarboxylic dianhydride.

The weight average molecular weight of the polyamic acid is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and more preferably 15,000 to 200,000 from the viewpoint of workability. Further, in the present invention, the weight average molecular weight is a standard polymerization by gel permeation chromatography (GPC). The average molecular weight obtained in terms of styrene.

The organic solvent to be used in such a reaction is not particularly limited as long as it does not adversely affect the reaction, but specific examples thereof include m-cresol, 2-pyrrolidone, and N-methyl-2-pyrrolidine. Ketone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 3-methoxy -N,N-dimethylpropyl decylamine, 3-ethoxy-N,N-dimethylpropyl decylamine, 3-propoxy-N,N-dimethylpropyl decylamine, 3-isopropoxy-N,N-dimethylpropyl decylamine, 3-butoxy-N,N-dimethylpropyl decylamine, 3-sec-butoxy-N,N-di Methyl propyl decylamine, 3-tert-butoxy-N,N-dimethylpropyl decylamine, γ-butyrolactone, and the like. Further, the organic solvent may be used singly or in combination of two or more kinds.

The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C. However, in order to prevent the imidization of the obtained polyglycine solution, the maintenance is maintained. The high content of the poly-proline unit is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and even more preferably about 0 to 50 ° C.

The reaction time is not always defined depending on the reaction temperature or the reactivity of the starting material, but it is usually about 1 to 100 hours.

The carbon-based filler used in the present invention is not particularly limited as long as it has a carbon atom as a main component, but is preferably a fibrous carbon material, a layered carbon material or a particulate carbon material. Further, these carbon-based fillers may be used singly or in combination of two or more kinds.

Specific examples of the fibrous carbon material include carbon nanotubes (CNT) and carbon nanofibers (CNF), but dispersibility and availability. From the viewpoint of the like, CNT is preferred. The CNT is generally produced by an arc discharge method, a chemical vapor deposition method (CVD method), a laser ablation method, or the like, but the CNT used in the present invention may be obtained by any method. In addition, the CNT has a single layer of CNT (hereinafter referred to as SWCNT) in which one carbon film (graphene sheet) is wound into a cylindrical shape, and two layers of CNTs in which two graphene sheets are wound into concentric circles (hereinafter In the present invention, the SWCNTs, the DWCNTs, and the MWCNTs may be used alone or in combination of a plurality of layers of CNTs (MWCNTs) which are concentrically wound into a plurality of graphene sheets.

Further, when SWCNT, DWCNT, and MWCNT are produced by the above method, since a catalyst metal such as nickel, iron, cobalt, or ruthenium may remain, it is necessary to perform purification for removing the impurities. In the removal of impurities, the acid treatment with nitric acid, sulfuric acid or the like is effective together with the ultrasonic treatment. However, in the acid treatment by nitric acid, sulfuric acid or the like, the π-conjugated CNTs constituting the CNT may be destroyed, and the original properties of the CNT may be impaired. Therefore, it is preferred to carry out purification under appropriate conditions. use.

Specific examples of the layered carbon material include graphite, graphene, and the like. There is no particular limitation on the graphite, and various commercially available graphites can be used. Graphene refers to a sheet of sp2 bonded carbon atoms having a thickness of 1 atom, and is a honeycomb-like hexagonal lattice structure formed by carbon atoms and a bond thereof, and has a thickness of about 0.38 nm. Further, in addition to commercially available graphene oxide, graphene oxide obtained by treating graphite by the Hummers method may also be used.

Specific examples of the particulate carbon material include carbon black such as furnace black, channel black, acetylene carbon, and thermal carbon black. The carbon black is not particularly limited, and various commercially available carbon blacks may be used, and the particle diameter thereof is preferably from 5 to 500 nm.

The ratio of the polyamic acid to the carbon-based filler in the composition for forming a release layer of the present invention is about 0.001 to 0.1, preferably 0.005, for the polyamine acid 1 in terms of a mass ratio. ~0.05 or so, more preferably about 0.01~0.02.

The composition for forming a release layer of the present invention contains an organic solvent. The organic solvent system is the same as the specific example of the reaction solvent of the above reaction. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylformamide are preferable in terms of uniformly dissolving polylysine and easily preparing a composition having high uniformity. N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ-butyrolactone, more preferably N-methyl- 2-pyrrolidone.

Further, even if it is a solvent which does not dissolve polylysine alone, it can be used for preparation of a composition as long as it does not precipitate in the case of poly-proline. In particular, it can be used for ethyl sirlo, butyl sirolimus, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol Alcohol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1 -monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, lactic acid Ethyl ester, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. The solvent of the force is moderately mixed. Thereby, it is known that the uniformity of the coating film is improved when the substrate is applied, and it can be suitably used in the present invention.

The preparation method of the composition for forming a release layer of the present invention is arbitrary. A preferred example of the preparation method is that a reaction solution containing polylysine which is obtained by the above-described method is filtered, and a carbon-based filler is added to the obtained filtrate to carry out the reaction. The method of dispersion processing. At this time, it is also possible to adjust the concentration, etc., and if necessary, dilute or concentrate the filtrate. By using such a method, not only the adhesion of the peeling layer produced from the obtained composition but also the cause of deterioration of adhesion, peeling, and the like can be reduced, and the composition for forming a release layer can be efficiently obtained. .

Examples of the dispersion treatment system include a wet treatment using a ball mill, a bead mill, a jet mill, or the like, or an ultrasonic treatment of a bus bar type or probe type ultrasonic oscillator. Although the time of the dispersion treatment is arbitrary, it is preferably from about 1 minute to 10 hours, more preferably from about 5 minutes to about 5 hours. Further, at the time of dispersion treatment, heat treatment may be performed as needed. Further, the solvent to be used for the dilution is not particularly limited, and specific examples thereof are the same as the specific examples of the reaction solvent of the above reaction. The solvent to be used for the dilution may be used singly or in combination of two or more.

The concentration of the polylysine in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, and the like, but is usually about 1 to 30% by mass. Good is about 1~20% by mass. Reproducible by setting it to such a concentration A peeling layer having a thickness of about 0.05 to 5 μm was obtained. The concentration of the polyaminic acid can be adjusted by adjusting the amount of the diamine and the tetracarboxylic dianhydride used as a raw material of the polyamic acid, and adjusting the amount and the like when the separated polylysine is dissolved in the solvent.

In addition, the viscosity of the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, and the like, in particular, a film having a thickness of about 0.05 to 5 μm is obtained with good reproducibility. The case is usually about 10 to 10,000 mPa ‧ at 25 ° C, preferably about 20 to 5,000 mPa ‧ s. Here, as the viscosity, a viscometer for viscosity measurement of a commercially available liquid can be used, for example, by measuring the temperature of the composition at 25 ° C in accordance with the procedure described in JIS K7117-2. Preferably, as the viscometer, a conical flat type (cone-plate type) rotational viscometer is used, preferably a viscometer of the same type and a 1° 34'×R24 is used as a standard conical rotor, and the temperature of the composition is 25° C. The conditions were measured. As such a rotary viscometer, for example, TVE-25L manufactured by Toki Sangyo Co., Ltd. can be cited.

In addition, the composition for forming a release layer of the present invention may contain, for example, a crosslinking agent or the like in order to increase the strength of the film, in addition to the polyamic acid and the organic solvent.

The peeling layer forming composition of the present invention described above is applied to a substrate, and the obtained coating film is heated to thermally amidize the polylysine, whereby excellent adhesion to the substrate can be obtained. A release layer composed of a polyimide film having an appropriate adhesion to a resin substrate and an appropriate peeling property.

Forming the peeling layer of the present invention on the substrate In this case, the release layer may be formed on a part of the surface of the substrate or may be formed in a comprehensive manner. A state in which a peeling layer is formed on a part of the surface of the substrate is formed by forming a peeling layer only in a predetermined range on the surface of the substrate, forming a dot pattern, a line and a space pattern on the surface of the substrate, and the like. The state of the peeling layer, and the like. Further, in the present invention, the base system means a composition for forming a release layer of the present invention, and is used in a manufacturer of a flexible electronic device or the like.

Examples of the substrate (base material) include glass and plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, For example, a norbornene-based resin, a metal (such as a ruthenium wafer), wood, paper, or slate, but in particular, the release layer of the present invention has a sufficient adhesion to the glass. . Further, the surface of the substrate may be composed of a single material or may be composed of two or more materials. As a form of the surface of the substrate composed of two or more kinds of materials, a certain range of the surface of the substrate is composed of a certain material, and the remaining surface is composed of other materials, and the entire surface of the substrate is located at a point pattern, a line and a space. A pattern-like material such as a pattern is a form existing in other materials.

The coating method is not particularly limited, and examples thereof include a coating method, a spin coating method, a knife coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, and a printing method. (embossing, gravure, lithography, screen printing, etc.), etc.

Although the heating temperature for the imidization is usually determined within the range of 50 to 550 ° C, it is preferably more than 150 ° C. 510 ° C. By setting the heating temperature in this manner, it is possible to prevent the obtained film from being weakened, and to sufficiently carry out the hydrazine imidization reaction. Although the heating time varies depending on the heating temperature, it cannot be specified, but it is usually 5 minutes to 5 hours. Further, the sulfhydrylation rate is only required to be in the range of 50 to 100%.

A preferred example of the heating state of the present invention is that after heating at 50 to 150 ° C for 5 minutes to 2 hours, the heating temperature is gradually increased in this state, and finally, the temperature exceeds 150 ° C to 510. °C is carried out for 30 minutes to 4 hours. In particular, it is preferably carried out at 50 to 150 ° C for 5 minutes to 2 hours, and then at 150 ° C to 350 ° C for 5 minutes to 2 hours, followed by more than 350 ° C to 450 ° C for 30 minutes to 4 hours, and finally Heating at temperatures in excess of 450 ° C to 510 ° C for 30 minutes to 4 hours.

Examples of the apparatus used for heating include a hot plate, an oven, and the like. The heating environment can be under air or under an inert gas, under normal pressure or under reduced pressure.

The thickness of the peeling layer is usually about 0.01 to 50 μm, and from the viewpoint of productivity, it is preferably about 0.05 to 20 μm. Further, the desired thickness is achieved by adjusting the thickness of the coating film before heating.

The release layer described above has excellent adhesion to a substrate, in particular, a substrate of glass, and an appropriate adhesion to a resin substrate and moderate peelability. Therefore, the release layer of the present invention can be suitably used in a manufacturing process of a flexible electronic device without causing damage to the resin substrate of the device, and the resin substrate and a circuit formed on the resin substrate are used. Peel off together from the substrate.

Hereinafter, an example of a method of manufacturing a flexible electronic device using the release layer of the present invention will be described.

Using the composition for forming a release layer of the present invention, a release layer is formed on the glass substrate by the above method. A resin solution for forming a resin substrate is applied onto the release layer, and the coating film is heated to form a resin substrate fixed to the glass substrate via the release layer of the present invention. At this time, the substrate was formed in an area larger than the area of the peeling layer so as to completely cover the peeling layer. The resin substrate is a resin substrate composed of a polyimide resin represented by a resin substrate of a flexible electronic device, and examples of the resin solution for forming the resin substrate include a polyimine solution or a polyamide. Acid solution. The method of forming the resin substrate may be carried out in accordance with a conventional method.

Next, a desired circuit is formed on the resin substrate which is fixed to the substrate via the peeling layer of the present invention, and thereafter, the resin substrate is cut along the peeling layer, for example, and the resin substrate is peeled off together with the circuit. The resin substrate is separated from the substrate by peeling. At this time, a part of the substrate may be cut together with the peeling layer.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

[1] Abbreviation of compound

p-PDA: p-phenylenediamine (Tokyo Chemical Industry Co., Ltd.)

DATP: 4,4"-diamino-p-bitriphenyl (Tokyo Chemical Industry Co., Ltd.)

ABO: 2-(4-aminophenyl)-5-aminobenzoxazole (manufactured by Changzhou Sunlight Pharmaceutical Co., Ltd.)

PMDA: pyromellitic dianhydride (Tokyo Chemical Industry Co., Ltd.)

CNT: carbon nanotube, product name NC7000 (manufactured by Nanocyl)

GRA: Graphene, product name iGurafen-α (made by iTEC)

NMP: N-methyl-2-pyrrolidone

<Measurement of Weight Average Molecular Weight and Molecular Weight Distribution>

The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polymer were measured using a GPC apparatus manufactured by JASCO Corporation (column: OHpak SB803-HQ manufactured by Showa Denko Co., Ltd., and OHpak SB804-HQ; Eluant: dimethylformamide _{/LiBr.H 2 O (29.6mM) / H} 3 PO 4 (29.6mM) / THF (0.1 mass%); flow rate: 1.0mL / min; column temperature: 40 deg.] C ; Mw: standard polystyrene equivalent value) (the same in the following examples and comparative examples).

[2] Preparation Example of Composition for Resin Substrate <Preparation Example 1-1 Synthesis of Polylysine>

20.3 g (188 mmol) of p-PDA and 12.2 g (47 mmol) of DATP were dissolved in 61. 7 g of NMP. The obtained solution was cooled to 15 ° C, and 50.1 g (230 mmol) of PMDA was added thereto, and the mixture was heated to 50 ° C under a nitrogen atmosphere to carry out a reaction for 48 hours. The resulting polymer has a Mw of 82,100, molecular The amount distribution is 2.7. In addition, the polylysine is not separated from the obtained reaction liquid, and the reaction liquid is used as a resin substrate-forming composition as it is.

[3] Modulation of filler dispersion <Modulation Example 2-1>

2.49 g (23.0 mmol) of p-PDA was dissolved in 63 g of NMP. Thereafter, 4.51 g (20.7 mmol) of PMDA was added, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. Then, 0.07 g of CNT was added to the obtained solution, and the mixture was further stirred at room temperature for 30 minutes, and then the resulting mixture was stirred for 10 minutes in an ultrasonic wave generating apparatus (UIP 1000 hd (manufactured by Transducer), the same below). The sound wave is processed to obtain a filler dispersion.

<Modulation Example 2-2>

1.72 g (15.9 mmol) of p-PDA and 1.03 g (3.97 mmol) of DATP were dissolved in 63 g of NMP. Thereafter, 4.25 g (19.5 mmol) of PMDA was added, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere.

Next, 0.07 g of CNT was added to the obtained solution, and the mixture was further stirred at room temperature for 30 minutes, and then the resulting mixture was subjected to ultrasonic treatment for 500 minutes in an ultrasonic generating apparatus while stirring for 10 minutes to obtain a filler dispersion liquid.

<Modulation Example 2-3>

ABO 3.59 g (15.9 mmol) was dissolved in 63 g of NMP. Thereafter, 3.40 g (15.6 mmol) of PMDA was added, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. Next, 0.07 g of CNT was added to the obtained solution, and the mixture was further stirred at room temperature for 30 minutes, and then the resulting mixture was subjected to ultrasonic treatment for 500 minutes in an ultrasonic generating apparatus while stirring for 10 minutes to obtain a filler dispersion liquid.

<Modulation Example 2-4>

ABO 3.59 g (15.9 mmol) was dissolved in 63 g of NMP. To the obtained solution, 3.40 g (15.6 mmol) of PMDA was added, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. Next, GRA 0.07 g was added to the obtained solution, and the mixture was further stirred at room temperature for 30 minutes, and then the resulting mixture was subjected to ultrasonic treatment for 500 minutes in an ultrasonic wave generating apparatus for 10 minutes while stirring to obtain a filler dispersion liquid.

[4] Modulation of composition for forming a release layer <Modulation Example 3-1>

10 g of the filler dispersion liquid prepared in Preparation Example 2-1 was mixed with NMP to obtain a composition for peeling formation having a solid concentration of 5 mass%. In addition, the solid content here means the one which mix|blends a poly lysine and a filler.

<Modulation example 3-2~3-4>

Instead of the dispersion obtained in Preparation Example 2-1, Preparation Example 2-2 was used. In the same manner as in Example 3-1, a composition for forming a release layer having a solid concentration of 5 mass% was obtained in the same manner as in Example 3-1.

[5] Formation of peeling layer <Example 1-1>

The peeling forming composition obtained in Preparation Example 3-1 was applied onto an alkali-free glass substrate of 100 mm × 100 mm using a spin coater (condition: rotation number: 3000 rpm × 30 seconds), and the obtained coating film was heated. It was heated at 80 ° C for 10 minutes.

Next, the obtained film was placed in a vacuum gas replacement furnace (KDF-900GL (manufactured by DENKEN-HIGHDENTAL)), and the inside of the furnace was depressurized at room temperature for 60 minutes, and then nitrogen substitution was performed.

Thereafter, the temperature was raised from room temperature to 300 ° C, followed by heating at 300 ° C for 30 minutes, 400 ° C for 60 minutes, and 500 ° C for 10 minutes, and a release layer having a thickness of about 0.1 μm was formed on the glass substrate.

Further, the temperature increase rate at room temperature to 300 ° C, 300 to 400 ° C, and 400 to 500 ° C was set to 10 ° C / min.

<Examples 1-2 to 1-4>

A release layer was formed in the same manner as in Example 1-1, except that the composition for forming a release layer obtained in Preparation Example 3-1 was used.

[6] Evaluation of the peeling layer

The function as a peeling layer was evaluated by the following method for the peeling layer produced.

<Evaluation of adhesion between glass substrate and release layer>

The peeling layer formed on the glass substrate was cross-cut (1 mm in the vertical and horizontal directions, the same applies hereinafter), and 100-cut. That is, by this cross-cutting, 100 meshes of 1 mm square are formed.

Next, an adhesive tape was attached to the 100-cut portion, and the tape was peeled off, and the degree of peeling was evaluated based on the following criteria (5B to 0B, B, A, AA).

5B: 0% peeling (no peeling)

4B: Peeling less than 5%

3B: 5~ less than 15% stripping

2B: 15~ less than 35% of the stripping

1B: 35~ less than 65% stripping

0B: 65~ not up to 80% peeling

B: 80~ less than 95% of the stripping

A: 95~ not up to 100% stripping

AA: 100% peeling (complete peeling)

<Evaluation of adhesion between peeling layer and resin substrate>

The resin substrate-forming composition obtained in Preparation Example 1-1 was applied onto the release layer obtained in Example 1-1 using a bar coater (gap: 250 μm). Thereafter, the obtained coating film was subjected to a hot plate at a temperature of 80 ° C for 30 minutes. The clock is heated.

Next, the obtained film was placed in a vacuum gas replacement furnace (KDF-900GL (manufactured by DENKEN-HIGHDENTAL)), and the inside of the furnace was depressurized at room temperature for 60 minutes, and then nitrogen substitution was performed.

Thereafter, the temperature was raised from room temperature to 300 ° C, and the mixture was heated at 300 ° C for 30 minutes, at 400 ° C for 30 minutes, and at 500 ° C for 60 minutes to form a resin substrate having a thickness of about 10 μm on the glass substrate.

Further, the temperature increase rate at room temperature to 300 ° C, 300 to 400 ° C, and 400 to 500 ° C was set to 10 ° C / min. In the same manner, a resin substrate was produced on the release layer obtained in Examples 1-2 to 1-4.

Then, by performing cross-cutting of the cross-cut of the resin substrate/release layer (the interval is 1 mm in the vertical and horizontal directions, the same applies hereinafter), 100-mesh cutting is performed, and the adhesive tape is attached to the 100-mesh cutting portion, and the tape is peeled off, according to the above. Benchmarks (5B~0B, B, A, AA), assess the extent of stripping.

The results of the peelability evaluation are shown in Table 1. As shown in Table 1, it was found that the release layer of the present invention is excellent in adhesion to a glass substrate and excellent in peelability from a resin substrate.

Claims (8)

A composition for forming a release layer comprising a polyphthalic acid, a carbon-based filler, and an organic solvent. The composition for forming a release layer according to claim 1, wherein the polyamic acid is a polyamic acid obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride. The composition for forming a release layer according to claim 2, wherein the aromatic diamine contains an aromatic diamine of 1 to 5 benzene nuclei. The composition for forming a release layer according to claim 2 or 3, wherein the aromatic tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride of 1 to 5 benzene nuclei. The composition for forming a release layer according to any one of claims 1 to 4, wherein the carbon-based filler is a carbon nanotube or graphene. A release layer formed using the composition for forming a release layer according to any one of claims 1 to 5. A method of producing a flexible electronic device comprising a resin substrate, characterized in that the release layer of claim 6 is used. The method of claim 7, wherein the resin substrate is a substrate made of polyimide.