TWI719965B - Layered body - Google Patents

Abstract

The present invention provides a composition for forming a release layer, which contains polyamide acid, a carbon-based filler, and an organic solvent.

Description

Layered body

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

In recent years, electronic devices are required to have the function of bending or the performance of thinner and lighter weight. Based on this, it is required to replace the heavy, fragile and inflexible glass substrate in the past and use a lightweight flexible plastic substrate. In addition, the development of an active full-color TFT display panel using a lightweight flexible plastic substrate is required in the new generation of displays. Therefore, various researches have been conducted on the manufacturing methods of electronic devices using resin films as substrates. In the new generation of displays, the manufacturing process can be converted to existing TFT devices.

Patent Documents 1, 2, and 3 disclose that an amorphous silicon thin film layer is formed on a glass substrate, and a plastic substrate is formed on the thin film layer. After that, a laser is irradiated from the glass surface side to form an amorphous silicon film. A method of peeling the plastic substrate from the glass substrate due to the generated hydrogen. In addition, Patent Document 4 discloses the use of the techniques disclosed in Patent Documents 1 to 3 to remove the peeled layer (in the patent It is described as "transferred layer" in Li Literature 4) is a method of attaching to a plastic film to complete a liquid crystal display device.

However, the methods disclosed in Patent Documents 1 to 4, especially the method disclosed in Patent Document 4, require the use of a substrate with high light transmittance, in order to pass through the substrate and thereby allow the hydrogen contained in the amorphous silicon to be released sufficiently. Energy, it must be irradiated with a larger laser light, and there is a problem of damage to the peeled layer. In addition, it takes a long time for laser processing, and it is difficult to peel off the peeled layer with a large area. Therefore, there is also a problem that it is difficult to improve the productivity of device manufacturing.

[Prior Technical Literature] [Patent Literature]

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

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

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

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

The present invention was made in view of the above circumstances, and its object is to provide a composition for forming a release layer that can be released without damaging the resin substrate of a flexible electronic device.

The inventors of the present invention have repeatedly studied to solve the above-mentioned problems and found that a composition containing polyamide acid, a carbon-based filler, and an organic solvent can be formed to have excellent adhesion to the substrate and to be used in The resin substrate of a flexible electronic device has a suitable adhesion and a suitable peelable peeling layer, and the present invention has been completed.

That is, the present invention provides 1. A composition for forming a peeling layer, which contains polyamide acid, a carbon-based filler, and an organic solvent; 2. The composition for forming a peeling layer according to 1, wherein the aforementioned polyamide Amino acid is a polyamide acid obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride; 3. The composition for forming a peeling layer as described in 2, wherein the aforementioned aromatic diamine contains 1 to 5 benzene Core aromatic diamine; 4. The composition for forming a peeling layer as 2 or 3, wherein the aforementioned aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei; 5. Such as the composition for forming a peeling layer of any one of 1 to 4, wherein the aforementioned carbon-based filler is carbon nanotube or graphene; 6. A peeling layer using any one of 1 to 5 7. A method for manufacturing a flexible electronic device with a resin substrate, characterized by using a peeling layer as described in 6; 8. The method of manufacturing as described in 7, wherein the resin substrate is made of poly Substrate composed of imine.

By using the composition for forming a release layer of the present invention, a film having excellent adhesion to the substrate and moderate adhesion to the resin substrate and moderate releasability can be obtained with good reproducibility. By using such a composition, in the manufacturing process of a flexible electronic device, the resin substrate formed on the substrate or the circuit provided on the substrate can be prevented from damaging the resin substrate and the circuit. Separate from the substrate together. Therefore, the composition for forming a release layer of the present invention can contribute to the simplification of the manufacturing process of the flexible electronic device with the resin substrate or the improvement of its yield.

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

The composition system for forming a release layer of the present invention contains polyamide acid, a carbon-based filler, and an organic solvent. Here, the peeling layer of the present invention refers to a layer that is set directly above the glass substrate for a predetermined purpose. As a typical example, it can be cited: in the manufacturing process of flexible electronic devices, the substrate and the polyamide Between the resin substrates of the flexible electronic device composed of imine resin, the resin substrate is fixed in a predetermined process, and after the electronic circuit is formed on the resin substrate, in order to make the resin substrate The provided release layer can be easily peeled from the substrate.

The polyamide acid used in the present invention is not particularly limited. Although it can be obtained by reacting diamine with tetracarboxylic dianhydride, from the viewpoint of improving the functionality of the resulting film as a release layer, It is better to make aromatic Polyamide acid obtained by the reaction of diamine and aromatic tetracarboxylic dianhydride.

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

Specific examples include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 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-diamine, p-diamine, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2- Diamines, 3,5-bis(trifluoromethyl)benzene-1,2-diamine, etc. whose benzene nucleus is one diamine; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1 ,4-Naphthalene diamine, 1,5-naphthalene diamine, 1,6-naphthalene diamine, 1,7-naphthalene diamine, 1,8-naphthalene diamine, 2,3-naphthalene diamine, 2,6 -Naphthalenediamine, 4,4'-diphenyldiamine, 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'-diaminobenzaniline, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethyl Benzidine, 3,3'-diaminodiphenylmethane, 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-hexa Fluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfene, 3,4 '-Diaminodiphenyl sulfene, 4,4'-diaminodiphenyl sulfene, 3,3'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 3, 3',5,5'-four Fluorobiphenyl-4,4'-diamine, 4,4'-diaminooctafluorobiphenyl, 2-(3-aminophenyl)-5-aminobenzimidazole, 2-(4-amine Phenyl)-5-aminobenzoxazole and other diamines with two benzene nuclei; 1,5-diaminoanthracene, 2,6-diaminoanthracene, 9,10-diaminoanthracene , 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-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1, 3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenyl)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-terphenyl, 4,4"-diamino-m-terphenyl, etc. The benzene nuclei are three diphenylene nuclei Amine etc., but it is not limited to these. These systems may be used alone or in combination of two or more types.

Among them, from the viewpoint of improving the functionality of the resulting film as a release layer, it is preferable to include only aromatic rings and heterocyclic rings that do not have substituents such as methyl groups on the aromatic ring and the heterocyclic ring condensed therewith. Aromatic diamine composed of aromatic ring. Specifically, p-phenylenediamine, m-phenylenediamine, 2-(3-aminophenyl)-5-aminobenzimidazole ring, 2-(4-aminophenyl)- 5-aminobenzoxazole, 4,4"-diamino-p-terphenyl, etc.

In the present invention, the amount of aromatic diamine used is the total diamine, preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably It is 95 mol% or more, and the best is 100 mol%. By using such a usage amount, the reproducibility is excellent To a film with excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate releasability.

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

Specific examples include: pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, 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, anthracene -1,2,3,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2,6,7-tetracarboxylic dianhydride, anthracene-1 ,2,7,8-tetracarboxylic dianhydride, anthracene-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-tetra 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 not limited to these. These systems may be used alone or in combination of two or more types.

Among them, from the viewpoint of improving the functionality of the resulting film as a release layer, an aromatic carboxylic acid having one or two benzene nuclei is preferred Dianhydride. Specifically, it is preferably an aromatic tetracarboxylic dianhydride represented by any one of formulas (C1) to (C12), and more preferably one of formulas (C1) to (C7) and (C9) to (C11) Aromatic tetracarboxylic dianhydride represented by any formula.

In the present invention, the amount of aromatic tetracarboxylic dianhydride used is in total tetracarboxylic dianhydride, preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% Above, more preferably 95 mol% or more, and most preferably 100 mol%. By using such a usage amount, a film with excellent adhesion to the substrate and moderate adhesion to the resin substrate and moderate releasability can be obtained with good reproducibility.

By reacting the diamine described above with tetracarboxylic dianhydride, the polyamide acid contained in the composition for forming a release layer of the present invention can be obtained.

The weight average molecular weight of the aforementioned polyamide acid is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and even more preferably 15,000 to 200,000 from the viewpoint of operability. In addition, in the present invention, the weight-average molecular weight is a standard polymerization method performed by gel permeation chromatography (GPC). Average molecular weight calculated from styrene.

The organic solvent used in such a reaction is not particularly limited as long as it does not adversely affect the reaction, but specific examples 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 Group-N,N-dimethylpropylamide, 3-ethoxy-N,N-dimethylpropylamide, 3-propoxy-N,N-dimethylpropylamide, 3-isopropoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-dimethylpropylamide, 3-sec-butoxy-N,N-di Methyl propyl amide, 3-tert-butoxy-N,N-dimethyl propyl amide, γ-butyrolactone, etc. In addition, the organic solvent system may be used alone or in combination of two or more kinds.

The reaction temperature should be appropriately set within the range from the melting point to the boiling point of the solvent used, and it is usually about 0 to 100°C. However, in order to prevent the imidization of the resulting polyamide acid solution, it is maintained The high content of the polyamide unit is preferably about 0 to 70°C, more preferably about 0 to 60°C, and still more preferably about 0 to 50°C.

The reaction time depends on the reaction temperature or the reactivity of the raw materials and cannot be specified, but it is usually about 1 to 100 hours.

Although the carbon-based filler used in the present invention is not particularly limited as long as it has carbon atoms as a main component, it is preferably a fibrous carbon material, a layered carbon material, and a particulate carbon material. In addition, these carbon-based filler systems may be used alone or in combination of two or more types.

Specific examples of fibrous carbon materials include carbon nanotubes (CNT), carbon nanofibers (CNF), etc., but in terms of dispersibility and availability From the viewpoint of others, CNT is preferred. CNTs are generally produced by arc discharge method, chemical vapor growth method (CVD method), laser ablation method, etc. However, the CNT used in the present invention can be obtained by any method. In addition, although CNT has a single carbon film (graphene sheet) rolled into a cylindrical single-layer CNT (hereinafter also referred to as SWCNT), two graphene sheets are rolled into a concentric two-layer CNT (hereinafter referred to as SWCNT). , Also abbreviated as DWCNT), and a multi-layered CNT (MWCNT) in which a plurality of graphene sheets are rolled into concentric circles. However, in the present invention, SWCNT, DWCNT, and MWCNT can be used individually or in combination.

In addition, when SWCNT, DWCNT, and MWCNT are produced by the above-mentioned method, since catalyst metals such as nickel, iron, cobalt, and yttrium may also remain, it may be necessary to perform purification to remove these impurities. In the removal of impurities, acid treatment with nitric acid, sulfuric acid, etc. together with ultrasonic treatment is effective. However, in acid treatment with nitric acid, sulfuric acid, etc., the π-conjugated system constituting the CNT may be destroyed, and the original characteristics of the CNT may be impaired. Therefore, it is better to purify under appropriate conditions. use.

As specific examples of the layered carbon material, graphite, graphene, etc. can be cited. There are no special restrictions on graphite, and various commercially available graphites can be used. Graphene refers to a sheet of sp2 bonded carbon atoms with a thickness of 1 atom, and is a honeycomb-like hexagonal lattice structure formed by carbon atoms and their bonds, and its thickness is about 0.38 nm. Moreover, in addition to commercially available graphene oxide, graphene oxide obtained by treating graphite by the Hummers method can also be used.

Specific examples of the particulate carbon material include carbon black such as furnace black, channel black, acetylene carbon, and thermal black. There are no special restrictions on carbon black, and various commercially available carbon blacks can be used, and the particle size is preferably 5 to 500 nm.

The ratio of the polyamide 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 for the polyamide acid 1 in terms of mass ratio, but is preferably 0.005 ~0.05 or so, more preferably 0.01~0.02 or so.

The composition for forming a release layer of the present invention contains an organic solvent. As this organic solvent system, the same thing as the specific example of the reaction solvent of the said reaction is mentioned. Among them, from the viewpoint of dissolving polyamide acid uniformly and easily preparing a composition with high uniformity, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, more preferably N-methyl- 2-pyrrolidone.

In addition, even if it is a solvent that does not dissolve polyamic acid when it is alone, it can be used for the preparation of a composition as long as it is in a range where polyamic acid does not precipitate. In particular, it can make ethyl siloxol, butyl siloxol, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propane 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, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. have low surface tension Strong solvents are mixed in moderately. Thereby, it is known that the uniformity of the coating film is improved when coating a substrate, and it can also be suitably used in the present invention.

The method of preparing the composition for forming a release layer of the present invention is arbitrary. A preferable example of the preparation method is: filtering the intended reaction solution containing polyamide acid obtained by the above-described method, and adding a carbon-based filler to the obtained filtrate to perform Distributed processing method. At this time, the purpose of concentration adjustment etc. can also be used, and if necessary, the filtrate may be diluted or concentrated. By adopting such a method, it is possible not only to reduce the mixing of impurities that may cause deterioration of adhesion, releasability, etc., in the peeling layer produced from the obtained composition, but also to efficiently obtain a composition for forming a peeling layer .

Examples of the dispersion treatment system include mechanical treatment, wet treatment using a ball mill, bead mill, jet mill, etc., or ultrasonic treatment using a bus-bar type or probe type ultrasonic oscillator. Although the time of the dispersion treatment is arbitrary, it is preferably about 1 minute to 10 hours, and more preferably about 5 minutes to 5 hours. In addition, in the case of dispersing treatment, heating treatment can also be performed as needed. In addition, the solvent used for dilution is not particularly limited, and specific examples thereof include those similar to the specific examples of the reaction solvent of the above-mentioned reaction. The solvent used for dilution can be used alone or in combination of two or more.

Although the concentration of polyamide acid 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, etc., it is usually about 1 to 30% by mass, which is relatively high. Preferably, it is about 1-20% by mass. By setting such a density, the reproducibility is good A peeling layer with a thickness of about 0.05~5μm is obtained. The concentration of polyamic acid can be adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride used as raw materials of polyamic acid, and adjusting the amount when dissolving the separated polyamic acid in a solvent.

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

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

The release layer forming composition of the present invention described above is applied to a substrate, and the resulting coating film is heated to thermally imidize polyamide acid, thereby obtaining excellent adhesion to the substrate It is a peeling layer made of polyimide film with proper adhesion to the resin substrate and proper peelability.

In such a case where the release layer of the present invention is formed on the substrate In some cases, the peeling layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface. As a form of forming a peeling layer on a part of the surface of the substrate, there are forms of forming a peeling layer only on a predetermined area on the surface of the substrate, and pattern formation such as dot pattern, line and space pattern on the whole surface of the substrate. The appearance of the peeled layer, etc. In addition, in the present invention, the base system means one that coats the release layer forming composition of the present invention on the surface thereof, and is used by manufacturers of flexible electronic devices and the like.

Examples of substrates (substrates) include glass, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, Norbornene resins, etc.), metals (silicon wafers, etc.), wood, paper, slate, etc., but especially from the viewpoint that the release layer of the present invention has sufficient adhesion to it, glass is preferred . In addition, the surface of the substrate may be composed of a single material, or may be composed of two or more materials. As the surface of the substrate is composed of two or more materials, a certain area of the surface of the substrate is composed of a certain material, and the rest of the surface is composed of other materials. The entire surface of the substrate is located in a dot pattern, line and space. Pattern-like materials such as patterns are patterns that exist in other materials.

Although the coating method is not particularly limited, for example, coating method, spin coating method, knife coating, dip coating method, roll coating method, bar coating method, die coating method, inkjet method, and printing method can be mentioned. (Relief, intaglio, lithography, screen printing, etc.) etc.

Although the heating temperature used for imidization is usually appropriately determined in the range of 50~550℃, it is preferably more than 150℃~ 510°C. By setting the heating temperature in this way, the fragility of the obtained film can be prevented, and the imidization reaction can proceed sufficiently. Although the heating time differs depending on the heating temperature, it cannot be specified, but it is usually 5 minutes to 5 hours. In addition, the imidization rate may be in the range of 50 to 100%.

As a preferable example of the heating aspect of the present invention, one can cite: after heating at 50 to 150°C for 5 minutes to 2 hours, the heating temperature is gradually increased in this state, and finally exceeds 150°C to 510°C. It is heated for 30 minutes to 4 hours at ℃. In particular, it is preferable to perform heating at 50 to 150°C for 5 minutes to 2 hours, then at a temperature exceeding 150°C to 350°C for 5 minutes to 2 hours, and then at a temperature exceeding 350°C to 450°C for 30 minutes to 4 hours, and finally Heat over 450℃~510℃ for 30 minutes to 4 hours.

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

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

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

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

Using the composition for forming a peeling layer of the present invention, a peeling layer is formed on a glass substrate by the above-mentioned method. By applying a resin solution for forming a resin substrate on this peeling layer, and heating the coating film, a resin substrate fixed to a glass substrate is formed via the peeling layer of the present invention. At this time, the substrate is formed in an area larger than the area of the release layer so as to completely cover the release layer. As the aforementioned resin substrate, a resin substrate made of polyimide represented by the resin substrate of a flexible electronic device can be cited, and as the resin solution used to form it, a polyimide solution or polyimide can be cited. Acid solution. The method of forming the resin substrate may be in accordance with a conventional method.

Next, on the resin substrate fixed to the base via the release layer of the present invention, a desired circuit is formed, and then, for example, the resin substrate is cut along the release layer, and the resin substrate is removed from the release layer together with the circuit. Peel off to separate the resin substrate from the base. At this time, a part of the base body may be cut together with the release layer.

[Example]

Hereinafter, although the present invention will be explained in more detail with examples, the present invention is not limited to these examples.

[1] Abbreviation of compound

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

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

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

PMDA: Pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

GRA: Graphene, product name iGurafen-α (manufactured 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 GPC equipment manufactured by JASCO Corporation (Column: Showa Denko Corporation OHpak SB803-HQ and OHpak SB804-HQ; Eluent: dimethylformamide _{/LiBr.H 2} O (29.6mM)/H ₃ PO ₄ (29.6mM)/THF (0.1% by mass); flow rate: 1.0mL/min; column temperature: 40°C ; Mw: standard polystyrene conversion value) (the same in the following examples and comparative examples).

[2] Preparation example of composition for resin substrate <Preparation Example 1-1 Synthesis of Polyamide Acid>

20.3g (188mmol) of p-PDA and 12.2g (47mmol) of DATP were dissolved in 617.4g of NMP. The resulting solution was cooled to 15°C, 50.1 g (230 mmol) of PMDA was added thereto, and the temperature was raised to 50°C under a nitrogen atmosphere, and the reaction was carried out for 48 hours. The Mw of the obtained polymer is 82,100, the molecule The quantity distribution is 2.7. In addition, the polyamic acid was not separated from the obtained reaction liquid, and the reaction liquid was used as a composition for forming a resin substrate as it was.

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

Dissolve 2.49 g (23.0 mmol) of p-PDA in 63 g of NMP. After that, 4.51 g (20.7 mmol) of PMDA was added, and stirring was performed at room temperature under a nitrogen environment for 24 hours. Next, 0.07 g of CNT was added to the resulting solution, and after further stirring for 30 minutes at room temperature, the resulting mixture was stirred with an ultrasonic generator (UIP1000hd (manufactured by Transducer), the same below) for 10 minutes at 500w. Acoustic treatment to obtain a filler dispersion.

<Modulation example 2-2>

Dissolve 1.72 g (15.9 mmol) of p-PDA and 1.03 g (3.97 mmol) of DATP in 63 g of NMP. After that, 4.25 g (19.5 mmol) of PMDA was added, and stirring was performed at room temperature under a nitrogen environment for 24 hours.

Next, 0.07 g of CNT was added to the resulting solution, and after further stirring for 30 minutes at room temperature, the resulting mixture was subjected to ultrasonic treatment with an ultrasonic generator for 10 minutes and 500w while stirring, to obtain a filler dispersion.

<Modulation example 2-3>

Dissolve 3.59 g (15.9 mmol) of ABO in 63 g of NMP. After that, 3.40 g (15.6 mmol) of PMDA was added, and stirring was performed at room temperature under a nitrogen environment for 24 hours. Next, 0.07 g of CNT was added to the resulting solution, and after further stirring for 30 minutes at room temperature, the resulting mixture was subjected to ultrasonic treatment with an ultrasonic generator for 10 minutes and 500w while stirring, to obtain a filler dispersion.

<Modulation example 2-4>

Dissolve 3.59 g (15.9 mmol) of ABO in 63 g of NMP. To the resulting 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 environment. Next, 0.07 g of GRA was added to the resulting solution, and after further stirring for 30 minutes at room temperature, the resulting mixture was subjected to 500w ultrasonic treatment for 10 minutes with an ultrasonic generator while stirring, to obtain a filler dispersion.

[4] Preparation of composition for forming peeling layer <Modulation example 3-1>

10 g of the filler dispersion obtained in Preparation Example 2-1 was mixed with NMP to obtain a releasable forming composition having a solid content of 5% by mass. In addition, the solid content here means a mixture of polyamide acid and filler.

<Modulation example 3-2~3-4>

In place of the dispersion obtained in Preparation Example 2-1, Preparation Example 2-2 was used respectively Except for the dispersion liquid obtained in ~2-4, a composition for forming a peeling layer having a solid content of 5% by mass was obtained by the same method as in Example 3-1.

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

Using a spin coater (condition: rotation number 3000 rpm × 30 seconds), the peeling-forming composition obtained in Preparation Example 3-1 was coated on a 100 mm × 100 mm alkali-free glass substrate, and the resulting coating film was used on a hot plate Heating was performed at 80°C for 10 minutes.

Next, the obtained membrane was put into a vacuum gas displacement furnace (manufactured by KDF-900GL (DENKEN-HIGHDENTAL) (manufactured by DENKEN-HIGHDENTAL)), the furnace was depressurized at room temperature for 60 minutes, and then nitrogen displacement 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 to form a release layer with a thickness of about 0.1 μm on the glass substrate.

In addition, the heating rate of room temperature to 300°C, 300 to 400°C, and 400 to 500°C is set to 10°C/min.

<Examples 1-2~1-4>

Except for using the composition for forming a peeling layer obtained in Preparation Example 3-1, a peeling layer was formed in the same manner as in Example 1-1.

[6] Evaluation of the peeling layer

For the produced peeling layer, the function of the peeling layer was evaluated by the following method.

<Evaluation of adhesion between glass substrate and peeling layer>

Cross-cutting (1mm interval in vertical and horizontal, the same below) of the peeling layer formed on the glass substrate and 100-cell cutting were performed. That is, by this cross cutting, 100 1mm square meshes are formed.

Then, stick the adhesive tape on the 100-cell cut part, peel off the tape, and evaluate the degree of peeling according to the following standards (5B~0B, B, A, AA).

5B: 0% peeling (no peeling)

4B: Stripping less than 5%

3B: 5 to less than 15% peeling

2B: 15 to less than 35% peeling

1B: 35 to less than 65% peeling

0B: 65 to less than 80% peeling

B: 80~95% peeling

A: 95 to less than 100% peeling

AA: 100% peeling (complete peeling)

<Evaluation of adhesion between peeling layer and resin substrate>

Using a bar coater (gap: 250 μm), the resin substrate forming composition obtained in Preparation Example 1-1 was applied on the release layer obtained in Example 1-1. After that, the obtained coating film was heated at 80°C for 30 minutes using a hot plate Bell heating.

Next, the obtained membrane was put into a vacuum gas displacement furnace (manufactured by KDF-900GL (DENKEN-HIGHDENTAL) (manufactured by DENKEN-HIGHDENTAL)), the furnace was depressurized at room temperature for 60 minutes, and then nitrogen displacement 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 30 minutes, and 500°C for 60 minutes to form a resin substrate with a thickness of about 10 μm on the glass substrate.

In addition, the heating rate of room temperature to 300°C, 300 to 400°C, and 400 to 500°C is set to 10°C/min. In the same manner, a resin substrate was fabricated on the peeling layer obtained in Examples 1-2 to 1-4.

Next, by performing cross cutting of resin substrate/peeling layer cross cutting (1mm in vertical and horizontal length, the same below), a 100 grid cut is performed, and an adhesive tape is attached to the 100 grid cut part, and the tape is peeled off according to the above Benchmark (5B~0B, B, A, AA) to evaluate the degree of peeling.

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

Claims (8)

A laminate having a substrate, a release layer formed on the substrate, and a resin substrate formed on the release layer, the release layer being formed of a release layer containing polyamide acid, a carbon-based filler, and an organic solvent Formed with composition. The laminate of claim 1, wherein the polyamide acid is a polyamide acid obtained by reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride. The laminate of claim 2, wherein the aforementioned aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei. The laminate according to claim 2 or 3, wherein the aforementioned aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei. The laminate according to any one of claims 1 to 3, wherein the aforementioned carbon-based filler is carbon nanotube or graphene. The laminate of claim 4, wherein the aforementioned carbon-based filler is carbon nanotube or graphene. A method for manufacturing a flexible electronic device, which uses a laminate as claimed in any one of claims 1 to 6. The method for manufacturing a flexible electronic device according to claim 7, wherein the resin substrate is a substrate made of polyimide.