JPWO2016140238A1 - Release layer forming composition - Google Patents

Abstract

A release layer forming composition comprising a polyamic acid, a carbon-based filler, and an organic solvent is provided.

Description

  The present invention relates to a release layer forming composition, and more particularly, to a release layer forming composition for forming a release layer provided on a substrate.

  In recent years, electronic devices have been required to have the functions of bending, thinning and lightening. For this reason, it is required to use a lightweight flexible plastic substrate in place of the conventional glass substrate that is fragile and cannot be bent. In the new generation display, development of an active full-color TFT display panel using a lightweight flexible plastic substrate is required. Therefore, various methods for manufacturing electronic devices using a resin film as a substrate are being studied, and in the new generation display, manufacturing studies are being carried out in a process that can divert existing TFT equipment.

  In Patent Documents 1, 2, and 3, an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side to accompany crystallization of amorphous silicon. A method of peeling a plastic substrate from a glass substrate with generated hydrogen gas is disclosed. Patent Document 4 discloses a method for attaching a layer to be peeled (described as “transfer target layer” in Patent Document 4) to a plastic film by using the techniques disclosed in Patent Documents 1 to 3 to complete a liquid crystal display device. Is disclosed.

  However, in the methods disclosed in Patent Documents 1 to 4, particularly the method disclosed in Patent Document 4, it is essential to use a substrate having high translucency, and hydrogen contained in amorphous silicon is allowed to pass through the substrate. In order to give energy sufficient to emit, there is a problem that irradiation with a relatively large laser beam is required and the layer to be peeled is damaged. In addition, since laser treatment takes a long time and it is difficult to peel off a layer to be peeled, there is a problem that it is difficult to increase the productivity of device fabrication.

Japanese Patent Laid-Open No. 10-125929 Japanese Patent Laid-Open No. 10-125931 International Publication No. 2005/050754 Japanese Patent Laid-Open No. 10-125930

  This invention is made | formed in view of the said situation, and it aims at providing the composition for peeling layer formation which can peel without damaging the resin substrate of a flexible electronic device.

  As a result of intensive studies to solve the above problems, the present inventors have used a composition containing polyamic acid, a carbon-based filler, and an organic solvent for excellent adhesion to a substrate and a flexible electronic device. The present invention has been completed by finding that a release layer having appropriate adhesion to a resin substrate to be obtained and appropriate release properties can be formed.

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

  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, moderate adhesion to the resin substrate, and moderate peelability with good reproducibility. By using such a composition, in the manufacturing process of the flexible electronic device, the resin substrate formed on the substrate, and further, the resin substrate together with the circuit, etc. without damaging the circuit provided on the substrate. Can be separated from the substrate. Therefore, the composition for forming a release layer of the present invention can contribute to simplification of the production process of a flexible electronic device including a resin substrate, improvement of its yield, 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 a polyamic acid, a carbon-based filler, and an organic solvent. Here, the release layer in the present invention is a layer provided immediately above a glass substrate for a predetermined purpose. As a typical example, in a manufacturing process of a flexible electronic device, a flexible electronic made of a substrate and a resin such as polyimide is used. Provided between the device resin substrate and the resin substrate in a predetermined process, and after the electronic circuit or the like is formed on the resin substrate, the resin substrate can be easily peeled from the substrate. For example, a release layer may be used.

  The polyamic acid used in the present invention is not particularly limited and can be obtained by reacting diamine with tetracarboxylic dianhydride, but improves the functionality of the resulting film as a release layer. The polyamic acid obtained by making an aromatic diamine and aromatic tetracarboxylic dianhydride react is preferable from the viewpoint of making it.

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

  Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), and 2,4-diamino. Toluene, 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-xylylenediamine, p-xylylenediamine, 5-trifluoromethylbenzene-1 , 3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5-bis (trifluoromethyl A diamine having a single benzene nucleus such as 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'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3 -Dimethylbenzidine, 2,2'-dimethylbenzidine, 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-hexafluoropropane, 2,2-bis (4-aminophenyl) ) -1,1,1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′- Bis (trifluoromethyl) biphenyl-4,4′-diamine, 3,3 ′, 5,5′-tetrafluorobiphenyl-4,4′- Diamine, 4,4'-diaminooctafluorobiphenyl, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzooxol, and other benzene nuclei have two diamines 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-aminophenyl sulfide) benzene, 1,3-bis (4 Aminophenylsulfide) benzene, 1,4-bis (4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1, 4-bis (4-aminophenylsulfone) 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., benzene nucleus having three diamines, etc. Although not limited to these, it is not limited to these. These can be used alone or in combination of two or more.

  Among these, from the viewpoint of improving the functionality of the resulting film as a release layer, it is composed only of aromatic rings and heteroaromatic rings that do not have a substituent such as a methyl group on the aromatic ring and the heterocyclic ring condensed thereto. Aromatic diamines are preferred. Specifically, p-phenylenediamine, m-phenylenediamine, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzooxol, 4,4 ′ '-Diamino-p-terphenyl and the like are preferred.

  In the present invention, the amount of aromatic diamine used is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably in all diamines. Is 100 mol%. By adopting such a use amount, it is possible to obtain a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate peelability with good reproducibility.

  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 an aromatic carboxylic acid containing 1 to 5 benzene nuclei. Group tetracarboxylic dianhydrides are preferred.

  Specific examples thereof 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'-tetra Carboxylic dianhydride, anthracene-1, , 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-1 , 2,5,6-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene- 1,2,9,10-tetracarboxylic dianhydride, phenanthracene-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 Although an anhydride etc. can be mentioned, it is not limited to these. These can be used alone or in combination of two or more.

  Among them, an aromatic carboxylic dianhydride having one or two benzene nuclei is preferable from the viewpoint of improving the functionality of the obtained film as a release layer. Specifically, an aromatic tetracarboxylic dianhydride represented by any one of formulas (C1) to (C12) is preferable, and any one of formulas (C1) to (C7) and (C9) to (C11) The aromatic tetracarboxylic dianhydride shown is more preferred.

  In the present invention, the amount of aromatic tetracarboxylic dianhydride used is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, in the total tetracarboxylic dianhydride. More preferably, it is 95 mol% or more, and most preferably 100 mol%. By adopting such a use amount, it is possible to obtain a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate peelability with good reproducibility.

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

  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 even more preferably 15,000 to 200,000 from the viewpoint of handling properties. In the present invention, the weight average molecular weight is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (GPC) analysis.

  The organic solvent used in such a reaction is not particularly limited as long as it does not adversely affect the reaction. Specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N- Ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropyl Amide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethyl And propylamide, 3-tert-butoxy-N, N-dimethylpropylamide, and γ-butyrolactone. . In addition, you may use an organic solvent individually by 1 type or in combination of 2 or more types.

  What is necessary is just to set reaction temperature suitably in the range from melting | fusing point to the boiling point of the solvent to be used, and it is about 0-100 degreeC normally, However, Imidation in the solution of the obtained polyamic acid is prevented and high content of a polyamic acid unit is contained. In order to maintain the amount, the temperature is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.

  Although the reaction time depends on the reaction temperature and the reactivity of the raw material, it cannot be defined unconditionally, but is usually about 1 to 100 hours.

  The carbon-based filler used in the present invention is not particularly limited as long as it contains carbon atoms as a main component, but a fibrous carbon material, a layered carbon material, and a particulate carbon material are preferable. These carbon-based fillers can be used alone or in combination of two or more.

  Specific examples of the fibrous carbon material include carbon nanotubes (CNT) and carbon nanofibers (CNF), and CNTs are preferable from the viewpoint of dispersibility and availability. CNTs are generally produced by arc discharge, chemical vapor deposition (CVD), laser ablation, etc., but the CNTs used in the present invention may be obtained by any method. . In addition, a single-layer CNT (hereinafter also abbreviated as SWCNT) in which a single carbon film (graphene sheet) is wound in a cylindrical shape and two layers in which two graphene sheets are wound in a concentric shape. There are CNT (hereinafter abbreviated as DWCNT) and multi-layer CNT (MWCNT) in which a plurality of graphene sheets are concentrically wound. Can be used in combination.

  When SWCNT, DWCNT or MWCNT is produced by the above method, catalyst metals such as nickel, iron, cobalt, yttrium may remain, so that purification for removing these impurities is necessary. There is. In order to remove impurities, ultrasonic treatment is effective together with acid treatment with nitric acid, sulfuric acid and the like. However, acid treatment with nitric acid, sulfuric acid, or the like destroys the π-conjugated system constituting CNT and may impair the original characteristics of CNT. Therefore, it is desirable to purify and use under appropriate conditions.

  Specific examples of the layered carbon material include graphite and graphene. The graphite is not particularly limited, and various commercially available graphites can be used. Graphene is a sheet of sp2-bonded carbon atoms with a thickness of 1 atom, and has a hexagonal lattice structure like a honeycomb made of carbon atoms and their bonds, and its thickness is about 0.38 nm. It is said. In addition to commercially available graphene oxide, graphene oxide obtained by processing graphite by the Hummers method may be used.

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

  The ratio of the polyamic acid to the carbon-based filler in the composition for forming a release layer according to the present invention is a mass ratio of about 0.001 to 0.1 carbon-based filler with respect to polyamic acid 1, but preferably 0. About 0.005 to 0.05, more preferably about 0.01 to 0.02.

  The composition for forming a release layer of the present invention contains an organic solvent. As this organic solvent, the same thing as the specific example of the reaction solvent of the said reaction is mentioned. Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-, which dissolve polyamic acid well and is easy to prepare a highly uniform composition. 2-Imidazolidinone, N-ethyl-2-pyrrolidone and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred.

  In addition, even if it is a solvent which does not dissolve polyamic acid alone, it can be used for the preparation of the composition as long as polyamic acid does not precipitate. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 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-ethoxy Propoxy) A solvent having a low surface tension such as propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and the like can be mixed appropriately. Thereby, it is known that the coating film uniformity is improved at the time of application to the substrate, and can be suitably used in the present invention.

  The method for preparing the composition for forming a release layer of the present invention is arbitrary. A preferable example of the preparation method is a method of filtering the reaction solution containing the target polyamic acid obtained by the above-described method, and adding a carbon-based filler to the obtained filtrate to perform a dispersion treatment. At this time, the filtrate may be diluted or concentrated if necessary for the purpose of adjusting the concentration. By adopting such a method, it is possible not only to reduce the contamination of impurities that can cause deterioration in the adhesion, peelability, etc. of the release layer produced from the resulting composition, but also to efficiently form a release layer forming composition. Can be obtained.

  Examples of the dispersion treatment include mechanical treatment, wet treatment using a ball mill, bead mill, jet mill, or the like, and ultrasonic treatment using a bath type or probe type sonicator. The time for the dispersion treatment is arbitrary, but is preferably about 1 minute to 10 hours, and more preferably about 5 minutes to 5 hours. In the dispersion treatment, heat treatment may be performed as necessary. The solvent used for dilution is not particularly limited, and specific examples thereof include the same examples as the specific examples of the reaction solvent for the above reaction. The solvent used for dilution may be used singly or in combination of two or more.

  The concentration of the polyamic 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., but is usually about 1 to 30% by mass, preferably It is about 1-20 mass%. By setting it as such a density | concentration, the peeling layer about 0.05-5 micrometers thick can be obtained with reproducibility. The concentration of the polyamic acid should be adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride used as the raw material for the polyamic acid, adjusting the amount when the isolated polyamic acid is dissolved in the solvent, etc. Can do.

  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, but a film having a thickness of about 0.05 to 5 μm is particularly reproducible. When it is intended to obtain, it is usually about 10 to 10,000 mPa · s, preferably about 20 to 5,000 mPa · s at 25 ° C. Here, the viscosity can be measured using a commercially available liquid viscosity measurement viscometer, for example, with reference to the procedure described in JIS K7117-2, at a temperature of the composition of 25 ° C. . Preferably, a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably the composition temperature is 25 ° C. using 1 ° 34 ′ × R24 as a standard cone rotor. It can be measured under the condition of ° C. An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.

  In addition, the composition for peeling layer formation of this invention may contain the crosslinking agent etc. in order to improve film | membrane intensity | strength other than a polyamic acid and an organic solvent, for example.

  The above-described release layer forming composition of the present invention is applied to a substrate, and the resulting coating film is heated to thermally imidize the polyamic acid. A release layer made of a polyimide film having adhesion and moderate peelability can be obtained.

  When such a release layer of the present invention is formed on a substrate, the release layer may be formed on a partial surface of the substrate, or may be formed on the entire surface. As an aspect of forming a release layer on a part of the surface of the substrate, an embodiment in which the release layer is formed only within a predetermined range of the substrate surface, a release layer is formed in a pattern such as a dot pattern or a line and space pattern on the entire surface of the substrate. There are forms to be formed. In addition, in this invention, a base | substrate means what is used for manufacture of a flexible electronic device etc. by which the composition for peeling layer formation of this invention is applied to the surface.

  Examples of the substrate (substrate) include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.), Although wood, paper, slate, etc. are mentioned, since the peeling layer of this invention has sufficient adhesiveness with respect to it, glass is preferable. In addition, the base | substrate surface may be comprised with the single material and may be comprised with two or more materials. As an aspect in which the substrate surface is composed of two or more materials, a certain range of the substrate surface is composed of a certain material, and the other surface is composed of other materials. A dot pattern is formed on the entire surface of the substrate. There is a mode in which a material in a pattern such as a line and space pattern is present in other materials.

  The coating method is not particularly limited, but for example, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate) , Intaglio, lithographic, screen printing, etc.).

  The heating temperature for imidization is usually appropriately determined within the range of 50 to 550 ° C, but is preferably more than 150 ° C to 510 ° C. By setting the heating temperature in this way, it is possible to sufficiently advance the imidization reaction while preventing the obtained film from being weakened. The heating time varies depending on the heating temperature and cannot be defined unconditionally, but is usually 5 minutes to 5 hours. Moreover, the imidation ratio should just be the range of 50 to 100%.

  As a preferable example of the heating mode in the present invention, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, the heating temperature is gradually increased as it is, and finally from 150 ° C. to 510 ° C. for 30 minutes to 4 hours. The method of heating is mentioned. In particular, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, above 150 ° C. to 350 ° C. for 5 minutes to 2 hours, then above 350 ° C. to 450 ° C. for 30 minutes to 4 hours, and finally above 450 ° C. to 510 ° C. It is preferable to heat at 30 ° C. for 30 minutes to 4 hours.

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

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

  The release layer described above has excellent adhesion to a substrate, particularly a glass substrate, moderate adhesion to a resin substrate, and moderate release. Therefore, the release layer according to the present invention, in the manufacturing process of the flexible electronic device, without damaging the resin substrate of the device, the resin substrate together with the circuit and the like formed on the resin substrate from the substrate. It can be suitably used for peeling.

Hereinafter, an example of the manufacturing method of the flexible electronic device using the peeling layer of this invention is demonstrated.
Using the composition for forming a release layer of the present invention, a release layer is formed on a glass substrate by the method described above. A resin solution for forming a resin substrate is applied on the release layer, and this 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 is formed with a larger area than the area of the release layer so as to cover the entire release layer. Examples of the resin substrate include a resin substrate made of polyimide, which is a typical resin substrate for flexible electronic devices, and examples of the resin solution for forming the resin substrate include a polyimide solution and a polyamic acid solution. The method for forming the resin substrate may follow a conventional method.

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

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this 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 Co., Ltd.)
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 and OHpak SB804-HQ manufactured by Showa Denko KK); : Dimethylformamide / LiBr.H ₂ O (29.6 mM) / H ₃ PO ₄ (29.6 mM) / THF (0.1% by mass); flow rate: 1.0 mL / min; column temperature: 40 ° C .; Mw: (Standard polystyrene equivalent value) was used (same in the following examples and comparative examples).

[2] Preparation Example of Resin Substrate Composition <Preparation Example 1-1 Synthesis of Polyamic Acid>
20.3 g (188 mmol) of p-PDA and 12.2 g (47 mmol) of DATP were dissolved in 617.4 g of NMP. The obtained solution was cooled to 15 ° C., PMDA 50.1 g (230 mmol) was added thereto, and the temperature was raised to 50 ° C. in a nitrogen atmosphere to react for 48 hours. Mw of the obtained polymer was 82,100, and molecular weight distribution was 2.7. In addition, the polyamic acid was not isolated from the obtained reaction liquid, but the reaction liquid was directly used as a resin substrate forming composition.

[3] Preparation of filler dispersion <Preparation 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. Then, while stirring the obtained mixture, an ultrasonic generator (UIP1000hd (manufactured by Transducer), the same shall apply hereinafter) Sonication was performed for 10 minutes to obtain a filler dispersion.

<Preparation 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.
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 500 minutes with an ultrasonic generator while stirring the mixture, to disperse the filler. A liquid was obtained.

<Preparation Example 2-3>
3.59 g (15.9 mmol) of ABO 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. 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 obtained mixture was stirred for 10 minutes with an ultrasonic generator while stirring the mixture, to disperse the filler. A liquid was obtained.

<Preparation Example 2-4>
3.59 g (15.9 mmol) of ABO was dissolved in 63 g of NMP. PMDA 3.40 g (15.6 mmol) was added to the resulting solution, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. Then, 0.07 g of GRA was added to the obtained solution, and the mixture was further stirred for 30 minutes at room temperature. Then, the resulting mixture was stirred for 500 minutes with an ultrasonic generator while stirring the mixture, and the filler dispersion was performed. A liquid was obtained.

[4] Preparation of release layer forming composition <Preparation Example 3-1>
10 g of the filler dispersion obtained in Preparation Example 2-1 and NMP were mixed to obtain a peelable composition having a solid content concentration of 5% by mass. In addition, solid content here means what combined polyamic acid and a filler.

<Preparation Examples 3-2 to 3-4>
Instead of the dispersion obtained in Preparation Example 2-1, the solid content was obtained in the same manner as in Example 3-1, except that the dispersion obtained in Preparation Examples 2-2 to 2-4 was used. A composition for forming a release layer having a concentration of 5% by mass was obtained.

[5] Formation of Release Layer <Example 1-1>
Using a spin coater (conditions: rotation speed 3000 rpm × 30 seconds), the peeling composition obtained in Preparation Example 3-1 was applied onto a 100 mm × 100 mm non-alkali glass substrate, and the resulting coating film was applied. The mixture was heated at 80 ° C. for 10 minutes using a hot plate.
The obtained film was placed in a vacuum gas replacement furnace (KDF-900GL (manufactured by Denken Hydental Co., Ltd.)), and the inside of the furnace was depressurized at room temperature for 60 minutes, followed by nitrogen replacement.
Thereafter, the temperature was raised from room temperature to 300 ° C., and heated sequentially at 300 ° C. for 30 minutes, 400 ° C. for 60 minutes, and 500 ° C. for 10 minutes to produce a release layer having a thickness of about 0.1 μm on the glass substrate.
In addition, the temperature increase rate of room temperature-300 degreeC, 300-400 degreeC, 400-500 degreeC was 10 degreeC / min.

<Examples 1-2 to 1-4>
A release layer was formed in the same manner as in Example 1-1 except that the release layer forming composition obtained in Preparation Example 3-1 was used.

[6] Evaluation of Release Layer For the prepared release layer, the function as the release layer was evaluated by the following method.
<Evaluation of adhesion between glass substrate and release layer>
The release layer formed on the glass substrate was cross-cut (1 mm in length and width, the same applies hereinafter) and 100 muscuts. That is, 100 crosses of 1 mm square were formed by this cross cut.
And the adhesive tape was affixed on this 100 muscat part, the tape was peeled off, and the grade of peeling was evaluated based on the following references | standards (5B-0B, B, A, AA).
5B: 0% peeling (no peeling)
4B: Less than 5% peeling 3B: Less than 5-15% peeling 2B: 15-35% peeling 1B: 35-65% peeling 0B: 65-80% peeling B: 80-95% peeling Peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling)

<Evaluation of adhesion between release layer and resin substrate>
Using the 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. Thereafter, the obtained coating film was heated at 80 ° C. for 30 minutes using a hot plate.
The obtained film was placed in a vacuum gas replacement furnace (KDF-900GL (manufactured by Denken Hydental Co., Ltd.)), and the inside of the furnace was depressurized at room temperature for 60 minutes, followed by nitrogen replacement.
Thereafter, the temperature was raised from room temperature to 300 ° C., and heated successively at 300 ° C. for 30 minutes, 400 ° C. for 30 minutes, and 500 ° C. for 60 minutes to form a resin substrate having a thickness of about 10 μm on the glass substrate.
In addition, the temperature increase rate of room temperature-300 degreeC, 300-400 degreeC, 400-500 degreeC was 10 degreeC / min. Similarly, a resin substrate was produced on the release layer obtained in Examples 1-2 to 1-4.
Then, by performing a cross-cut of the resin substrate / peeling layer (cutting 1 mm in length and width, the same applies hereinafter), 100 mass cuts are performed, and adhesive tape is applied to the 100 mass cut portions, and the tape is peeled off. Based on (5B to 0B, B, A, AA), the degree of peeling was evaluated.

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

Claims (8)

  A composition for forming a release layer comprising a polyamic 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 release layer-forming composition according to claim 2, wherein the aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei.   The composition for forming a release layer according to claim 2 or 3, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 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.   The peeling layer formed using the composition for peeling layer formation of any one of Claims 1-5.   A method for producing a flexible electronic device comprising a resin substrate, wherein the release layer according to claim 6 is used.   The manufacturing method according to claim 7, wherein the resin substrate is a substrate made of polyimide.