TW201817775A - Composition for forming release layer, and release layer - Google Patents

Abstract

Provided is a composition for forming a release layer, the composition including polyamic acid represented by formula (1) and an organic solvent. (In the formula, X represents an aromatic group represented by formula (2a) or (2b), Y represents a divalent aromatic group having a fluorine atom, Z each independently represent an aromatic group represented by formula (3a) or (4a) when X is represented by formula (2a) or each independently represent an aromatic group represented by formula (3b) or (4b) when X is represented by formula (2b), and m represents a natural number.).

Description

Composition for release layer formation and release layer

[0001] The present invention relates to a composition for forming a release layer and a release layer.

[0002] In recent years, in addition to characteristics such as thickness reduction and weight reduction, electronic devices are also required to provide functions such as bendability. Therefore, it is required to use a lightweight flexible plastic substrate instead of a conventional glass substrate that is heavy, fragile and cannot be bent. In particular, the new generation of display systems requires the development of active-array full-color TFT display panels that use lightweight, flexible plastic substrates (hereinafter referred to as resin substrates). The technology of this new generation display is expected to be applied to various fields such as flexible displays, flexible smartphones, and mirror displays. [0003] Here, various reviews of manufacturing methods of electronic devices using resin films as substrates have begun, and a review of manufacturing processes that can apply existing TFT display panel manufacturing equipment to new-generation displays. Moreover, in the touch panel type display, the resin substrate for transparent electrodes of the touch panel used in combination with a display panel, etc., have reviewed the measures for efficiently manufacturing the resin substrate. In general, the resin substrate used for a touch panel is the same as a TFT display panel or the like. A polyimide resin substrate, an acrylic resin substrate, or poly (phenylene terephthalate) having the same degree of transparency as glass is used. Film substrates such as ethylene formate (PET) resin substrates and cycloolefin resin substrates. [0004] As a method for manufacturing a flexible display, a direct method is known (Non-Patent Document 1). As a direct method, there are the following methods: a method of attaching a resin substrate prepared in advance to a glass substrate through an adhesive layer, and directly forming a pixel circuit including an TFT and an organic EL on the substrate; and fabricating on a glass substrate A resin substrate on which a pixel circuit including a TFT and an organic EL are directly formed. [0005] Then, in this direct method, the resin substrate on which a pixel circuit or the like is formed on a glass substrate is peeled by various methods described later, and is provided for the manufacture of an electronic device for the purpose of a display panel or the like. [0006] For example, Patent Documents 1, 2, and 3 disclose a method of forming an amorphous silicon thin film layer on a glass substrate, forming a plastic substrate on the thin film layer, and then irradiating a laser from the glass substrate side to make Amorphous silicon is crystallized, and the plastic substrate is peeled from the glass substrate by the hydrogen gas generated by the crystallization. [0007] In addition, Patent Document 4 discloses a method of attaching a peeled layer (described as a “transferred layer” in Patent Document 4) to a plastic film using the techniques disclosed in Patent Documents 1 to 3. Liquid crystal display device. [0008] However, the methods disclosed in Patent Documents 1 to 4, especially the method disclosed in Patent Document 4, have the following problems: in order to transmit laser light, a substrate having a high light transmittance must be used; To pass through the substrate and further release the hydrogen contained in the amorphous silicon, it must be irradiated with laser light of sufficient and relatively large energy; there may be cases where the peeled layer is damaged due to the irradiation of laser light. Furthermore, when the peeled layer has a large area, laser processing takes a long time, so it is difficult to improve the productivity of device manufacturing. [0009] In order to solve such a problem, Patent Document 5 uses the following manufacturing steps: a current glass substrate is used as a substrate (hereinafter referred to as a glass substrate), and a glass substrate such as a cyclic olefin copolymer is used. The polymer is used to form a release layer. A heat-resistant resin film (resin substrate) such as a polyimide film is formed on the release layer. Then, an ITO transparent electrode or a TFT is formed on the film by a vacuum process, and the glass is finally sealed. The substrate is peeled and removed. [0010] On the other hand, the new-generation display is required to increase the area of the substrate because it corresponds to a demand for a large screen or an increase in productivity. In order to uniformly apply the resin composition to a large-area coating surface, a slit coating method using a slit coater or the like is generally suitable. The slit coating method is a coating method using a slit nozzle, and it is not necessary to rotate the substrate like the conventional spin coating method. Therefore, from the viewpoints of reduction of the amount of resin composition and safety of steps, Language is widely used. However, such a slit coating method is expected to increase the speed of the coating step from the viewpoint of improving productivity. In order to increase the speed of the slit coating method, it is necessary to suppress the occurrence of streaky irregularity and the like during coating. Therefore, it is necessary to reduce the viscosity of the solution, which is one of the most important parameters. [0011] For example, Patent Documents 6 and 7 disclose the use of a composition made of a so-called low viscosity solvent such as propylene glycol monomethyl ether acetate or propylene glycol monomethyl ether as a suitable coating method for the slit coating method. Photoresist composition. However, the resin (or the precursor) such as polyimide resin generally used in the composition for forming the release layer cannot be dissolved in these low-viscosity solvents, so it is difficult to form the release layer by a slit coating method. . Therefore, as long as the resin (or the precursor) used in the composition for forming a release layer can be dissolved in the above-mentioned low-viscosity solvent, not only the applicability when using the conventional spin coating method can be improved, but also It is a composition for forming a release layer suitable for a slit coating method. [Prior Art Document] [Patent Document] [0012] [Patent Document 1] Japanese Patent Application Laid-Open No. 10-125929 [Patent Literature 2] Japanese Patent Application Laid-Open No. 10-125931 [Patent Literature 3] International Publication No. 2005/050754 [Patent Document 4] Japanese Patent Laid-Open No. 10-125930 [Patent Document 5] Japanese Patent Laid-Open No. 2010-111853 [Patent Document 6] International Publication No. 2011/030744 [Patent Document 7] Japanese Patent Laid-Open No. 2008-70480 Bulletin [Non-Patent Documents] [0013] [Non-Patent Documents 1] NHK Technical Research R & D / No.145 / 2014.5

[Problems to be Solved by the Invention] The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a composition for forming a release layer, which is also soluble in a so-called low viscosity solvent such as propylene glycol monomethyl ether. It can also be easily applied to the slit coating method, and can be used to provide resin substrates (especially polyimide resins, acrylic resins, and cycloolefin polymer resins) that do not damage the flexible electronic devices formed on them. The formed thin film substrate) is peeled. [Means for Solving the Problems] As a result of intensive research in order to solve the above-mentioned problems, the inventors found that a polyamic acid having a specific structure can be easily dissolved in a low-viscosity solvent, and also found that the polyamino acid is contained The composition with an organic solvent can impart a release layer, which has excellent adhesion to a substrate such as a glass substrate, and a resin substrate (especially light transmission at a wavelength of 400 nm) used in flexible electronic devices. A resin substrate having a rate of 80% or more) has moderate adhesion and moderate peelability, and thus completed the present invention. [0016] Accordingly, the present invention is to provide a composition for forming a release layer and a release layer described below. [1]. A composition for forming a release layer, comprising a polyamic acid represented by the following formula (1) and an organic solvent, (In the formula, X represents an aromatic group represented by the following formula (2a) or (2b), Y represents a divalent aromatic group having a fluorine atom, and when X is an aromatic group represented by formula (2a) When X is an aromatic group represented by the following formula (3a) or (4a), Z is independently of each other, and when X is an aromatic group represented by the formula (2b), Z is independently of the following formula (3b) ) Or an aromatic group represented by (4b), where m is a natural number) . [2]. The composition for forming a release layer according to the above [1], wherein Y is an aromatic group represented by the following formula (5), . [3]. The composition for forming a release layer according to the above [2], wherein Y is an aromatic group represented by the following formula (6), . [4]. The composition for forming a release layer according to any one of the above [1] to [3], wherein in the X, the aromatic group represented by the formula (2a) is the following formula (7a) or In the aromatic group represented by (8a), the Z is independently an aromatic group represented by the following formula (9a) or (10a). . [5]. The composition for forming a release layer according to any one of [1] to [3] above, wherein in X, the aromatic group represented by the formula (2b) is the following formula (7b) or The aromatic group represented by (8b), the above-mentioned Z is independently an aromatic group represented by the following formula (9b) or (10b), . [6]. The composition for forming a release layer according to any one of the above [1] to [5], wherein the organic solvent is an organic solvent selected from the group having a structure represented by the following formulae (S1) to (S7) At least 1 kind of solvent, . (In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number 1 to 10 fluorene groups, b and n are natural numbers). [7]. The composition for forming a release layer according to the above [6], wherein the organic solvent is propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate. [8]. A release layer formed by using the composition for forming a release layer according to any one of the above [1] to [7]. [9]. A method for producing a resin substrate, which uses the release layer described in [8] above. [10]. The manufacturing method according to the above [9], wherein the resin substrate is a polyimide resin substrate or a resin substrate having a light transmittance at a wavelength of 400 nm of 80% or more. [Effects of the Invention] [0017] By using the composition for forming a release layer of the present invention, a release layer having good reproducibility is obtained, which has excellent adhesion to a substrate and moderate adhesion to a resin substrate. Adhesiveness and moderate peelability. In particular, the polyamidic acid used in the present invention has excellent solubility in low-viscosity solvents, so it can be easily prepared by using a low-viscosity solvent, and can also be applied to a slit coating system composition, uniformly. It becomes easy to apply to a large-area coated surface. Furthermore, in the manufacturing process of the flexible electronic device, the resin substrate formed on the base body or the circuit or the like provided on the resin substrate will not be damaged, and the resin substrate and the circuit and the like can be simultaneously made. Separation is performed from this substrate. Therefore, the composition for forming a release layer according to the present invention can contribute to speeding up the manufacturing process of a flexible electronic device including a resin substrate, improving the yield, and the like.

[Best Mode for Carrying Out the Invention] The present invention will be described in more detail below. The composition for forming a release layer according to the present invention includes a polyamic acid represented by the following formula (1) and an organic solvent. [0019] In the present invention, the so-called release layer is a layer provided directly above a substrate (such as a glass substrate) on which a resin substrate is to be formed. As a typical example, for example, in the manufacturing process of a flexible electronic device, a resin substrate of a flexible electronic device formed with the substrate and a polyimide resin, an acrylic resin, or the like is used to make the resin The substrate is fixedly provided in a predetermined process, and after an electronic circuit or the like is formed on the resin substrate, a release layer is provided so that the resin substrate can be easily peeled from the substrate. [0020] [0021] In the formula (1), X is an aromatic group represented by the following formula (2a) or (2b), and Y is a divalent aromatic group having a fluorine atom. When X is a formula (2a), Z is independently an aromatic group represented by the following formula (3a) or (4a); if X is formula (2b), it is independently an aromatic group represented by the following formula (3b) or (4b) Family base, m is a natural number. [0022] In the X, the aromatic group represented by the formula (2a) is preferably an aromatic group represented by the following formula (7a) or (8a), and the aromatic group represented by the formula (2b) It is preferably an aromatic group represented by the following formula (7b) or (8b). [0023] [0024] In the above Z, the aromatic group represented by the formula (3a) or (4a) is preferably an aromatic group represented by the following formula (9a) or (10a), and the formula (3b) Or, the aromatic group represented by (4b) is preferably an aromatic group represented by the following formula (9b) or (10b). [0025] [0026] The Y is preferably an aromatic group having a fluorine atom and containing 1 to 5 benzene rings, and more preferably an aromatic group selected from the following formula (5), selected from the following The aromatic group of the formula (6) is more preferred. [0027] [0028] [0029] The above-mentioned m may be a natural number, and a natural number of 100 or less is preferable, and a natural number of 2 to 100 is more preferable. [0030] The polyamidic acid represented by the above formula (1) is obtained by reacting a specified tetracarboxylic dianhydride component with a diamine component. As the tetracarboxylic dianhydride component, pyromellitic dianhydride or biphenyltetracarboxylic dianhydride is used. The diamine component may be any of an alicyclic chain, an alicyclic ring, an aromatic ring, and an aromatic alicyclic ring as long as it has a fluorine atom. However, in the present invention, in particular, the solubility in a low-viscosity solvent is improved. From the viewpoint of improving the function of the release layer of the obtained film, the pyromellitic dianhydride or biphenyltetracarboxylic dianhydride is reacted with a diamine component containing the aromatic diamine to The obtained polyamic acid is more preferred, and the fully aromatic polyamino acid obtained by reacting the above-mentioned tetracarboxylic dianhydride with an aromatic diamine is even more preferred. Hereinafter, a pyromellitic dianhydride component, a biphenyltetracarboxylic dianhydride, and a diamine component which can be used for synthesizing the polyamidic acid having the structure represented by the formula (1) will be described in detail. [0031] The pyromellitic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has a benzene ring. Specific examples thereof include pyromelite dianhydride and benzene-1,2,3,4-tetracarboxylic dianhydride. In the present invention, pyromelite dianhydride is preferred. These systems can be used alone or in combination of two or more. [0032] The biphenyltetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has biphenyl. Specific examples thereof include 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4 , 4'-biphenyltetracarboxylic dianhydride, etc. In the present invention, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferred. These systems can be used alone or in combination of two or more. [0033] On the other hand, the aromatic diamine is not particularly limited as long as it is two amine groups having a fluorine atom and having a direct bond with an aromatic ring in the molecule. The aromatic diamine is one to five benzene rings. In particular, 1 to 2 and more preferably two aromatic diamines are included. A fluoroalkyl group or a perfluoroalkyl group is more preferable, and a perfluoroalkyl group is more preferable. Examples of the perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl, and i-heptafluoropropyl. [0034] Specific examples of the aromatic diamine include 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, and 2,2 ' -Bis (trifluoromethyl) -4,4'-diaminobiphenyl and 3,3'-bis (trifluoromethyl) biphenyl-4,4'-diamine, etc., but it is not limited to Of these. In the present invention, even among these, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl can be suitably used. These systems can be used alone or in combination of two or more. [0035] Since the feed ratio of the diamine component and the tetracarboxylic dianhydride component is determined appropriately by taking into consideration the target molecular weight or molecular weight distribution, the type of the diamine or the tetracarboxylic dianhydride, and so on, it cannot be specified in general, However, in order to obtain the polyamic acid of the formula (1), it is preferable to increase the molar number of the tetracarboxylic dianhydride component to the molar number of the diamine component. As a specific mole ratio, with respect to 1 mole of the diamine component, 1.05 to 2.5 moles of the tetracarboxylic dianhydride component is preferable, 1.07 to 1.5 moles is more preferable, and 1.1 to 1.3 moles is preferable. Further preferred. [0036] By reacting the tetracarboxylic dianhydride component and the diamine component described above, the polyamic acid contained in the release layer forming composition of the present invention can be obtained. [0037] The organic solvent used in the synthesis of polyamidic acid is not particularly limited as long as it does not adversely affect the reaction, and specific examples thereof include m-cresol, 2-pyrrolidone, and N -Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Formamidine, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-propoxy-N, N-dimethyl Propylpropylamine, 3-isopropoxy-N, N-dimethylpropylamine, 3-butoxy-N, N-dimethylpropylamine, 3-sec-butoxy-N, N-dimethylpropanamide, 3-tert-butoxy-N, N-dimethylpropanamide, γ-butyrolactone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like. The organic solvent may be used alone or in combination of two or more. [0038] The reaction temperature when synthesizing polyamidic acid may be appropriately set within a range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ° C, but in order to prevent the obtained polyamidoamine From the viewpoint of the imidation of the acid in the solution to maintain the high content of the polyamidic acid unit, it is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and more preferably 0 to 50 ° C about. Since the reaction time depends on the reaction temperature or the reactivity of the raw materials, it cannot be specified in general, but it is usually about 1 to 100 hours. [0039] The weight average molecular weight of the polyamic acid obtained in such a manner is usually about 5,000 to 500,000, but from the viewpoint of improving the function of the release layer of the obtained film, it is preferably 10,000 to About 200,000, and preferably about 10,000 to 150,000. In the present invention, the weight average molecular weight is a polystyrene conversion value obtained by measurement by gel permeation chromatography (GPC). [0040] Specific examples of the polyamidic acid that can be suitably used in the present invention include those represented by the following formulae, but they are not limited thereto. [0041] (In the formula, m1 and m2 represent the number of repeating units, and the total of m1 and m2 is the same as the above-mentioned m.) [0042] (In the formula, m1 and m2 represent the number of repeating units, and the total of m1 and m2 is the same as the above-mentioned m.) [0043] The composition system for forming a release layer of the present invention contains an organic solvent. As the organic solvent, the same as the specific examples of the reaction solvent of the above reaction can be used. Since the polyamidic acid of the present invention is sufficiently dissolved and a composition having a high uniformity is easily prepared, it is selected from the group consisting of amines, alcohols Organic solvents of the group consisting of amines, esters, ethers and ketones are preferred, and it is particularly preferred that they contain at least one of the structures represented by the following formulae (S1) to (S7). [0044] [0045] In the above formula, R ¹ ~ R ⁸ They are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. R ⁹ And R ¹⁰ Each of them is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or a fluorenyl group having 1 to 5 carbon atoms, preferably 1 to 5 carbon atoms. The b system indicates that the natural number is preferably a natural number of 1 to 5, and a natural number of 1 to 3 is more preferable. The n-series means that natural numbers of 1 to 5 are preferable, and natural numbers of 1 to 3 are more preferable. [0046] Specific examples of the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples include methyl, ethyl, n-propyl, isopropyl, Cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3- Methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl -N-propyl, cyclopentyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl- n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl -N-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n- Butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1- Ethyl-2-methyl-n-propyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the like. [0047] Specific examples of the fluorenyl group having 1 to 10 carbon atoms include methyl fluorenyl, ethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, isobutyl fluorenyl, pentyl fluorenyl, isopentyl fluorenyl, hexamethylene, and isohexan Fluorenyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl and benzyl. [0048] Specific examples of the organic solvent represented by the formulae (S1) to (S7) include the following. Formula (S1): 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-propoxy-N, N-di Methamphetamine, 3-isopropoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 3-sec-butoxy-N , N-dimethylpropanilamine, 3-tert-butoxy-N, N-dimethylpropanilamine Formula (S2): 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone formula (S3): N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropanamide, N, N-dimethylbutyramine (S4): γ-butyrolactone (S5): cyclopentanone, cyclohexanone, cycloheptanone (S6): methyl lactate, ethyl lactate, lactic acid n- Propyl ester, n-butyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, propyl 2-hydroxyisobutyrate, butyl 2-hydroxyisobutyrate (S7): ethyl cellosolve, butyl cellosolve, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol Propylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate [0049] In the present invention, even among these, N- 2-Pyrrolidone, butyl cellosolve, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferred, Propylene glycol monomethyl ether is more preferred. These organic solvents may be used alone or in combination of two or more. [0050] Especially when the propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are used as the above-mentioned organic solvent (that is, a low viscosity solvent), it is possible to obtain and also be suitable for slit coating. A composition for forming a low-viscosity release layer. When the composition for forming a release layer of the present invention is used for slit coating, the proportion of the low-viscosity solvent in the entire solvent is preferably 60% by mass or more, and 70% by mass or more. To be more preferable, 80% by mass or more is the most preferable. [0051] Even if it is a solvent that cannot dissolve polyamic acid when used alone, as long as the polyamic acid does not precipitate, it can be used for the preparation of a composition. In particular, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, Solvents with low surface tension such as dipropylene glycol and 2- (2-ethoxypropoxy) propanol. Accordingly, it is known that the uniformity of a coating film can be improved when applied to a substrate, and can be suitably used in the present invention. [0052] The composition for forming a release layer of the present invention can be prepared by a usual method. As a preferred example of the preparation method, the reaction solution containing the target polyamic acid obtained by the method described above is filtered, and the concentration of the obtained filtrate is specified using the organic solvent described above. Concentration. By adopting such a method, it is possible not only to reduce the mixing of impurities that can cause deterioration of the adhesiveness, peelability, etc. of the release layer manufactured from the obtained composition, but also to effectively obtain the release layer formation.组合 物。 Composition. [0053] The concentration of the polyamic acid in the release layer forming composition 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., and is generally about 1 to 30% by mass. It is preferably about 1 to 20% by mass. By setting such a concentration, a peelable layer having a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. The concentration of the polyamic acid can be adjusted by using the amount of the diamine component, the tetracarboxylic dianhydride component, and the aromatic monoamine as raw materials of the polyamino acid, or when the isolated polyamic acid is dissolved in a solvent The amount is adjusted. [0054] 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 in particular, when a film having a thickness of about 0.05 to 5 μm with good reproducibility is targeted. In this case, the temperature is usually about 10 to 10,000 mPa · s at 25 ° C, preferably about 20 to 5,000 mPa · s. When the composition for forming a release layer of the present invention is used in the case of a slit coating method, its viscosity is preferably about 2 to 100 mPa · s, and from the viewpoint of productivity, 2 to 25 mPa · s Left and right are better. [0055] Here, the viscosity can be measured by using a commercially available viscometer for measuring the viscosity of a liquid, referring to, for example, a program described in JIS K7117-2, and using a temperature of the composition at 25 ° C. It is preferable to use a cone-and-plate rotary viscometer as the viscosity meter, and it is preferable to use the same type of viscosity meter, using 1 ° 34 '× R24 as the standard cone rotor, and The measurement was performed under the condition that the temperature of the composition was 25 ° C. An example of such a rotary viscosity meter is TVE-25L manufactured by Toki Sangyo Co., Ltd. [0056] In addition, in addition to the polyamic acid and the organic solvent, the composition for forming a release layer of the present invention may contain a cross-linking agent and the like in order to improve the film strength, for example. [0057] By applying the composition for forming a release layer of the present invention described above to a substrate, and heating the resulting coating film, the polyamic acid is thermally imidized to obtain an adhesive having excellent adhesion to the substrate. A release layer made of a polyimide film, which has a good adhesion to the resin substrate and a moderate peeling property. [0058] When such a release layer of the present invention is formed on a substrate, the release 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 is a form in which the peeling layer is formed only within a specified range of the surface of the substrate. The entire surface of the substrate is formed as a dot pattern, Line and space patterns and the like. In the present invention, the term “base system” refers to a person who can apply the composition for forming a release layer of the present invention on the surface thereof, and means that it can be used by a manufacturer of a flexible electronic device or the like. [0059] Examples of the substrate (substrate) include glass, plastic (polycarbonate, polymethacrylic ester, polystyrene, polyester, polyolefin, epoxy, melamine, triethyl cellulose, ABS, AS, norbornene-based resin), metal (silicon wafer, etc.), wood, paper, slate, etc. In the present invention, in particular, since the release layer has sufficient adhesion, a glass substrate can be suitably used. The surface of the substrate may be composed of a single material or two or more materials. As a state in which the surface of the substrate is composed of 2 or more materials, a certain range of the surface of the substrate is composed of a certain material, and the remaining range is composed of other materials on the entire surface of the substrate. Some materials exist in other materials in the form of dot patterns, line and space patterns, and the like. [0060] The method for applying the composition for forming a release layer of the present invention to a substrate is not particularly limited, and examples thereof include a casting coating method, a spin coating method, a slit coating method, a doctor blade coating method, and a dip coating. Cloth method, roll coating method, rod coating method, die coating method, inkjet method, printing method (relief, gravure, lithography, screen printing, etc.) and the like. [0061] The heating temperature for the imidization is generally determined within a range of 50 to 550 ° C, and preferably over 150 ° C to 510 ° C. By setting the heating temperature in this manner, the obtained film can be prevented from being weakened, and at the same time, the amidine imidization reaction can be sufficiently performed. The heating time varies depending on the heating temperature, so it cannot be specified in general, but it is usually 5 minutes to 5 hours. The fluorene imidization rate may be within a range of 50 to 100%. [0062] As a preferred example of the heating state in the present invention, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, the heating temperature can be directly increased stepwise, and the final heating temperature can be higher than 150 ° C. to 510 Heating at ℃ for 30 minutes to 4 hours. In particular, after heating at 50 to 150 ° C for 5 minutes to 2 hours, heating at more than 150 ° C to 350 ° C for 5 minutes to 2 hours and finally heating at more than 350 ° C to 450 ° C for 30 minutes to 4 hours . [0063] The appliance used for heating may be, for example, a hot plate or an oven. The heating environment can be under air or under inert gas, and it can also be under normal pressure or under reduced pressure. [0064] 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. However, the desired thickness can be achieved by adjusting the thickness of the coating film before heating. [0065] The peeling layer described above has excellent adhesion to a substrate (especially a glass substrate), and moderate adhesion to a resin substrate and moderate peelability. Therefore, the release layer of the present invention can be applied to a flexible electronic device without removing the resin substrate of the device from the substrate at the same time as the circuit formed on the resin substrate without damaging the resin substrate of the device. Perform peeling. [0066] Hereinafter, an example of a method for 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 a glass substrate according to the method described above. A resin solution for forming a resin substrate is applied on the release layer, and the coating film is heated to form a resin substrate that is fixed to a glass substrate through the release layer of the present invention. At this time, in order to cover the entire release layer, the substrate is formed with an area larger than the area of the release layer. Examples of the resin substrate include a polyimide resin, an acrylic resin, and a cycloolefin polymer resin, which are representative of a resin substrate for a flexible electronic device, as a resin solution for forming the substrate. Examples thereof include polyimide solutions, polyamidic acid solutions, acrylic polymer solutions, and cycloolefin polymer solutions. The method for forming the resin substrate may be in accordance with a commonly used method. In addition, as the highly transparent resin substrate, a resin substrate formed of an acrylic resin or a cycloolefin polymer resin can be exemplified, and a light transmittance with a wavelength of 400 nm of 80% or more is preferable. [0067] Next, a desired circuit is formed on the resin substrate fixed to the base with the release layer of the present invention interposed therebetween, and then, for example, the resin substrate is cut along the release layer, and the resin substrate is removed from the circuit together with the circuit. The release layer is peeled to separate the resin substrate from the substrate. At this time, a part of the substrate may be cut together with the release layer. [0068] It is reported in Japanese Patent Application Laid-Open No. 2013-147599 that a laser lift-off method (LLO method) widely used in the manufacture of high-brightness LEDs, three-dimensional semiconductor packages, and the like has been applied to the manufacture of flexible displays. The above-mentioned LLO method is characterized by irradiating light of a specific wavelength, for example, light of a wavelength of 308 nm from the glass substrate side from the side opposite to the surface on which a circuit or the like is formed. The irradiated light can penetrate the glass substrate, and only the polymer (polyimide resin) near the glass substrate absorbs this light and evaporates (sublimates). As a result, the resin substrate can be selectively peeled from the glass substrate without affecting the circuit or the like provided on the resin substrate, which determines the performance of the display. [0069] Since the composition for forming a release layer according to the present invention has a characteristic that it can sufficiently absorb light of a specific wavelength (for example, 308 nm) to which the above-mentioned LLO method can be applied, it can be used as a coating layer for the LLO method. Therefore, when a desired circuit is formed on a resin substrate fixed to a glass substrate via a release layer formed by using the composition of the present invention, and then, when the LLO method is used to irradiate light at 308 nm, only the release layer is used. It absorbs this light and evaporates (sublimates). According to this, the above-mentioned peeling layer will serve as a substrate (playing a role as a substrate), and the resin substrate can be selectively peeled from the glass substrate. [Examples] [0070] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. [1] Abbreviation of compound p-PDA: p-phenylenediamine TPDA: 4,4 "-diamino-p-terphenyl TFMB: 2,2'-bis (trifluoromethyl) benzidine BPDA: 3, 3 ', 4,4'-biphenyltetracarboxylic dianhydride PMDA: pyromelite dianhydride DMCBDA: 1,3-dimethylcyclobutyric dianhydride CBDA: cyclobutyric dianhydride MMA: methyl methacrylate Esters MAA: HEMA methacrylate: 2-hydroxyethyl methacrylate AIBN: azobisisobutyronitrile CHMI: cyclohexylmaleimide EPOLEAD GT-401: butane tetracarboxylic acid, tetrakis (3,4- (Epoxycyclohexylmethyl), modified ε-caprolactone, CELOXIDE 2021P manufactured by DAICEL (stock): 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate VESTAGON B 1530 made by DAICEL (stock): NMP: N-methyl-2-pyrrolidone made by Evonik Japan (stock): BCS: butyl cellosolve PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate [2] Method for measuring weight average molecular weight and molecular weight distribution The weight average molecular weight (hereinafter referred to as Mw) of polymer and the measurement of molecular weight distribution are measured using a GPC device (column: KD801 manufactured by Shodex) and KD805; eluent: dimethylformamide / LiBr · H ₂ O (29.6mM) / 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 conversion value). [3] Synthesis of polymer Various polymers used in the examples and comparative examples were synthesized according to the following methods. The polymer is not isolated from the obtained polymer-containing reaction solution, but a composition for resin substrate formation or a release layer formation can be prepared by diluting the reaction solution as described later. [0073] <Synthesis of Synthesis Example S1 Polyamidic Acid (S1)> p-PDA3.218g (30m mol) was dissolved in NMP88.2g. To the obtained solution was added 8.581 g (29 m mol) of BPDA, and the mixture was allowed to react at 23 ° C. for 24 hours under a nitrogen environment. The obtained polymer had a Mw of 107,300 and a molecular weight distribution of 4.6. [0074] <Synthesis of Synthesis Example S2 Polyamidic Acid (S2)> p-PDA20.261g (0.1875 mol) and TPDA12.206g (0.0469 mol) were dissolved in NMP617.4g, and PMDA50 was added after cooling to 15 ° C. .112 g (0.2298 mol) was reacted at 50 ° C for 48 hours under a nitrogen environment. The obtained polymer had an Mw of 82,100 and a molecular weight distribution of 2.7. [Synthesis of Synthesis Example S3 Acrylic Polymer (S3)> MMA7.20g (0.0719 mol), HEMA7.20g (0.0553 mol), CHMI10.8g (0.0603 mol), MAA4.32g (0.0502 mol), AIBN2 .46 g (0.0150 mol) was dissolved in 46.9 g of PGMEA and reacted at 60 to 100 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration: 40% by mass). Mn of the obtained acrylic polymer was 3,800 and Mw was 7,300. [0076] <Synthesis of Synthesis Example L1 Polyamic Acid (L1)> 2.73 g (8.53 m mol) of TFMB was dissolved in 38.5 g of NMP. 2.06g (9.47m mol) of PMDA was added to the obtained solution, and it was made to react at 23 degreeC for 24 hours in nitrogen environment. The obtained polymer had a Mw of 17,100 and a molecular weight distribution of 1.7. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, no precipitation was particularly observed. [0077] <Synthesis of Synthesis Example L2 Polyamidic Acid (L2)> 2.73 g (8.53 m mol) of TFMB was dissolved in 40 g of PGME. To the obtained solution, 2.06 g (9.47 m mol) of PMDA was added, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen environment. The obtained polymer had a Mw of 20,100 and a molecular weight distribution of 1.8. [0078] <Synthesis of Synthesis Example L3 Polyamidic Acid (L3)> 23.7 g (74.2 m mol) of TFMB was dissolved in 352 g of NMP. 24.2 g (82.5 m mol) of BPDA was added to the obtained solution, and the mixture was allowed to react at 23 ° C. for 24 hours under a nitrogen environment. The obtained polymer had a Mw of 16,500 and a molecular weight distribution of 1.7. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, no precipitation was particularly observed. [0079] <Synthesis of Synthesis Example L4 Polyamic Acid (L4)> TFMB 9.89 g (30.9 m mol) was dissolved in PGME 380 g. 10.0 g (34.3 m mol) of BPDA was added to the obtained solution, and it was made to react at 50 degreeC for 72 hours in nitrogen environment. The obtained polymer had a Mw of 14,700 and a molecular weight distribution of 1.7. [0080] <Synthesis of Comparative Synthesis Example HL1 Polyamic Acid (HL1)> p-PDA3.90g (3.60m mol) was dissolved in 35.2g of NMP. DMCBDA9.27g (4.00m mol) was added to the obtained solution, and it was made to react at 23 degreeC for 24 hours in nitrogen environment. The obtained polymer had a Mw of 45,000 and a molecular weight distribution of 3.9. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, polyamic acid was precipitated. [0081] <Synthesis of Comparative Synthesis Example HL2 Polyamidic Acid (HL2)> 2.86 g (8.91 m mol) of TFMB was dissolved in 35.2 g of NMP. 1.94 g (9.91 m mol) of CBDA was added to the obtained solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen environment. The obtained polymer had a Mw of 69,200 and a molecular weight distribution of 2.2. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, no precipitation was particularly observed. [0081] [4] Preparation of Composition for Forming Resin Substrate The composition for forming the resin substrate was prepared according to the following method. [0083] <Preparation Example 1 Composition for Resin Substrate Formation F1> The reaction solution obtained in Synthesis Example S1 was used as it is as the composition F1 for resin substrate formation. [0083] <Preparation Example 2 Composition F2 for Resin Substrate Formation> The reaction solution obtained in Synthesis Example S2 was directly used as the composition F2 for resin substrate formation. [0085] <Preparation Example 3 Composition for Resin Substrate Formation F3> To 10 g of the reaction solution obtained in Synthesis Example S3, 0.60 g of EPOLEADGT-401 and 11.8 g of PGMEA were added and stirred at 23 ° C. for 24 hours to prepare a resin substrate formation. Composition F3. [Preparation Example 4 Composition F4 for Resin Substrate Formation] To 10 g of the reaction solution obtained in Synthesis Example S3, 0.80 g of CELOXIDE 2021P and 11.8 g of PGMEA were added, and the composition for resin substrate formation was stirred at 23 ° C. for 24 hours.物 F4. [0085] <Preparation Example 5 Composition F5 for resin substrate formation> To 10 g of the reaction solution obtained in Synthesis Example S3, 0.60 g of VESTAGON B 1530 and 11.8 g of PGMEA were added and stirred at 23 ° C. for 24 hours to prepare a resin substrate for formation. Composition F5. [Preparation Example 6 Composition F6 for Resin Substrate Formation] To an eggplant-shaped flask in which 100 g of carbon tetrachloride was put, Zeonor (registered trademark) 1020R (Cycloolefin polymer resin manufactured by Zeon Corporation) was added. 10g and GT-401 3g. This solution was stirred and dissolved in a nitrogen environment for 24 hours to prepare a composition F6 for resin substrate formation. [Preparation Example 7 Composition F7 for Resin Substrate Formation] To an eggplant-shaped flask containing 100 g of carbon tetrachloride, Zeonor (registered trademark) 1060R (Cycloolefin polymer resin manufactured by Zeon Corporation) was added. 10g. This solution was stirred and dissolved in a nitrogen environment for 24 hours to prepare a resin substrate forming composition F7. [5] Preparation of composition for forming peeling layer [Example 1-1] To the reaction solution obtained in Synthesis Example L1, BCS and NMP were added so that the polymer concentration became 5 mass% and BCS became 20 The composition was diluted by mass% to obtain a composition for forming a release layer. [Example 1-2] The reaction solution obtained in Synthesis Example L2 was directly used as a composition for forming a release layer. [Example 1-3] To the reaction solution obtained in Synthesis Example L3, BCS and NMP were added to dilute the polymer so that the polymer concentration became 5% by mass and BCS became 20% by mass, thereby obtaining peeling. Composition for layer formation. [Example 1-4] The reaction solution obtained in Synthesis Example L4 was directly used as a composition for forming a release layer. [Comparative Example 1-1] To the reaction solution obtained in Comparative Synthesis Example HL1, BCS and NMP were added so that the concentration of the polymer was 5 mass% and the BCS was 20 mass%, and diluted to obtain Composition for release layer formation. [Comparative Example 1-2] To the reaction solution obtained in Comparative Synthesis Example HL2, BCS and NMP were added so that the polymer concentration became 5% by mass and BCS was diluted by 20% by mass to obtain Composition for release layer formation. [6] Production of Release Layer and Resin Substrate [Example 2-1] Using a spin coater (condition: about 30 seconds at a number of rotations of 3,000 rpm), the release layer obtained in Example 1-1 was used. The forming composition L1 was applied on a 100 mm × 100 mm glass substrate (the same applies hereinafter) as a glass substrate. Then, the obtained coating film was heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes using an oven, and the heating temperature was raised to 400 ° C. (10 ° C./minute, and further heated at 400 ° C. for 30 minutes). After a minute, a peeling layer having a thickness of about 0.1 μm was formed on the glass substrate to obtain a glass substrate with a peeling layer. However, the substrate with the film was not taken out of the oven between heating, but was heated in the oven. [0097] Using a bar coater (gap: 250 μm), the composition F1 for resin substrate formation was applied on the release layer (resin film) on the glass substrate obtained above. Then, a heating plate was used at 80 ° C. The obtained coating film was heated for 30 minutes, and then heated at 140 ° C. for 30 minutes using an oven, and the heating temperature was raised to 210 ° C. (2 ° C./minute, the same below), and then heated at 210 ° C. for 30 minutes, and the heating temperature was The temperature was raised to 300 ° C, followed by heating at 300 ° C for 30 minutes, and the heating temperature was increased to 400 ° C, followed by heating at 400 ° C for 60 minutes. A resin substrate having a thickness of about 20 μm was formed on the release layer to obtain a resin substrate with peeling. Glass substrate Between heating, the substrate with the film is not taken out from the oven, but is heated in the oven. [Example 2-2] Instead of using the composition F2 for resin substrate formation, Example 2-1 was used. Except for the resin substrate forming composition F1, a peeling layer and a resin substrate were produced in the same manner as in Example 2-1, and a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer were obtained. [Example 2-3] The composition L2 obtained in Example 1-2 was used in place of the composition L1 for release layer obtained in Example 1-2, except that the composition L1 obtained in Example 1-1 was used. -1 was used to prepare a release layer and a resin substrate to obtain a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer. [0100] [Example 2-4] Composition for forming a release layer As the composition, the release layer-forming composition L2 obtained in Example 1-2 was used, and as the resin substrate-forming composition, the resin substrate-forming composition F2 used in Example 2-2 was used. 2-1 the same method to make the release layer Resin substrate to obtain a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer. [Example 2-5] As a composition for forming a release layer, Example 1-1 was used. The composition L1 for forming a release layer was formed using the composition F4 for forming a resin substrate as a composition for forming a resin substrate, and a release layer and a resin substrate were produced in the same manner as in Example 2-1 to obtain peeling. [0102] [Example 2-6] As the composition for forming a release layer, the composition for forming a release layer L1 obtained in Example 1-1 was used. As the resin substrate forming composition system, a resin substrate forming composition F5 was used, and a release layer and a resin substrate were produced in the same manner as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a release layer were obtained. Resin substrate • Glass substrate with release layer. [Example 2-7] As the composition for forming a release layer, the composition for forming a release layer L2 obtained in Example 1-2 was used, and as the composition for forming a resin substrate, a composition for forming a resin substrate was used. F5, and a peeling layer and a resin substrate were produced in the same manner as in Example 2-1, and a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer were obtained. [Example 2-8] The release layer-forming composition L1 obtained in Example 1-1 was used to form a release layer in the same manner as in Example 2-1 to obtain a release layer-attached Glass base board. Immediately thereafter, the composition F6 for resin substrate formation was applied on the release layer (resin film) on the glass substrate using a spin coater (condition: about 15 seconds at 200 rpm). The obtained coating film was heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer to obtain a resin substrate with a release layer. Glass base board. Then, as a result of measuring the light transmittance using an ultraviolet visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation), the resin substrate showed a transmittance of 80% or more at 400 nm. [Example 2-9] Except that the composition for forming a release layer L2 obtained in Example 1-2 was used instead of the composition for forming a release layer L1 obtained in Example 1-1, the same procedure as in Example was used. 2-8 The same method was used to produce a release layer and a resin substrate, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained. [Example 2-10] Using the composition for forming a release layer L1 obtained in Example 1-1, a release layer was formed in the same manner as in Example 2-1 to obtain a glass with a release layer. Substrate. Immediately thereafter, the composition F7 for resin substrate formation was applied on the release layer (resin film) on the glass substrate using a spin coater (condition: about 15 seconds at 200 rpm). The obtained coating film was heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer to obtain a resin substrate with a release layer. Glass base board. Then, as a result of measuring the light transmittance using an ultraviolet visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation), the resin substrate showed a transmittance of 80% or more at 400 nm. [Example 2-11] Except that the composition for forming a release layer L2 obtained in Example 1-2 was used instead of the composition for forming a release layer L1 obtained in Example 1-1, the same procedure as in Example was used. 2-10 The same method was used to produce a release layer and a resin substrate, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained. [Comparative Examples 2-1 to 2-4] Instead of using the composition for forming a release layer obtained in Comparative Examples 1-1 to 1-2, the composition for forming a release layer obtained in Example 1-1 was used. Other than that, a peeling layer and a resin substrate were produced by the same method as the above-mentioned example, and a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer were obtained. The combination of the release layer and the resin substrate is as shown in Table 1. [Example 2-12] Using a spin coater (condition: about 30 seconds at a number of rotations of 3,000 rpm), the composition L3 for forming a release layer obtained in Example 1-3 was applied to glass. 100mm × 100mm glass substrate (the same applies hereinafter) on the substrate. Then, the obtained coating film was heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes using an oven, and the heating temperature was raised to 400 ° C. (10 ° C./minute, and further heated at 400 ° C. for 30 minutes). After a minute, a peeling layer having a thickness of about 0.1 μm was formed on the glass substrate to obtain a glass substrate with a peeling layer. However, the substrate with the film was not taken out of the oven between heating, but was heated in the oven. [0110] Using a spin coater (condition: about 10 seconds at 800 rpm), the composition F3 for resin substrate formation was applied on the release layer (resin film) on the glass substrate obtained as described above. Then, The obtained coating film was heated at 80 ° C. for 30 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using an oven to form an acrylic substrate having a thickness of about 3 μm on the release layer. The temperature was not taken out from the oven The substrate with the film is heated in an oven. [0111] [Example 2-13] A composition F4 for resin substrate formation was used instead of the composition F3 for resin substrate formation used in Examples 2-12. To match with Example 2-1 2 The same method was used to produce a release layer and a resin substrate to obtain a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer. [0112] [Example 2-14] A composition for forming a resin substrate was used. The object F5 was used in place of the resin substrate forming composition F3 used in Example 2-12, and a release layer and a resin substrate were produced in the same manner as in Example 2-12 to obtain a glass substrate with a release layer and Glass substrate with resin substrate and release layer [0113] [Example 2-15] Instead of using the release layer formation composition L4 obtained in Example 1-4, the release layer formation obtained in Example 1-3 was used. Except for the composition L3, a release layer and a resin substrate were produced in the same manner as in Example 2-12, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained. [0114] [Implementation Example 2-16] The composition for forming a release layer was formed using the composition for forming a release layer L4 obtained in Example 1-4, and the composition for forming a resin substrate was formed using the resin substrate used in Example 2-14. With Composition F 5. In the same manner as in Example 2-12, a peeling layer and a resin substrate were prepared to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer. [0115] [Example 2- 17] Using the composition for forming a release layer L3 obtained in Example 1-3, a release layer was formed in the same manner as in Example 2-12 to obtain a glass substrate with a release layer. Immediately thereafter, spin coating was used. A cloth spreader (condition: about 15 seconds at a number of rotations of 200 rpm) applied the composition F6 for resin substrate formation on the release layer (resin film) on the glass substrate. The obtained coating film was heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer to obtain a resin substrate with a release layer. Glass base board. Then, as a result of measuring the light transmittance using an ultraviolet visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation), the resin substrate showed a transmittance of 80% or more at 400 nm. [Example 2-18] Except that the composition for forming a release layer L4 obtained in Example 1-4 was used instead of the composition for forming a release layer L3 obtained in Example 1-3, the same procedure as in Example was used. 2-17 The same method was used to produce a release layer and a resin substrate, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained. [Example 2-19] Using the composition for forming a release layer L3 obtained in Example 1-3, a release layer was formed in the same manner as in Example 2-12 to obtain a glass with a release layer. Substrate. Immediately thereafter, the composition F7 for resin substrate formation was applied on the release layer (resin film) on the glass substrate using a spin coater (condition: about 15 seconds at 200 rpm). The obtained coating film was heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer to obtain a resin substrate with a release layer. Glass base board. Then, as a result of measuring the light transmittance using an ultraviolet visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation), the resin substrate showed a transmittance of 80% or more at 400 nm. [Example 2-20] Except that the composition for forming a release layer L4 obtained in Example 1-4 was used instead of the composition for forming a release layer L3 obtained in Example 1-3, the same procedure as in Example was used. 2-19 The same method was used to produce a release layer and a resin substrate, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained. [Comparative Example 2-5] Except that the composition HL1 for forming a release layer obtained in Comparative Example 1-1 was used in place of the composition L3 for forming a release layer obtained in Example 1-3, it was the same as the example. 2-12 The same method was used to produce a release layer and a resin substrate, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained. The combination of the release layer and the resin substrate is shown in Table 2. [Comparative Example 2-6] As the composition for forming a release layer, the composition HL2 for forming a release layer obtained in Comparative Example 1-2 was used, and as the composition for forming a resin substrate, the composition of Example 2-13 was used. The resin substrate forming composition F4 was used to prepare a release layer and a resin substrate in the same manner as in Example 2-12, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained. [7] Evaluation of the solvent resistance of the release layer NMP and PGME were added dropwise to the obtained Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6 using a pipette at 0.1 ml. On a release layer of a glass substrate with a release layer. After 1 minute, the release layer was washed with pure water, and the state of the release layer in which the solvent portion was dropped was visually observed to evaluate the solvent resistance of the release layer. The determination criteria are as follows. The results are shown in Tables 1 and 2. <Criterion> ○: No traces of liquid droplets were found, and no dissolution was observed. (Triangle | delta): Although the trace of a droplet was found, the residual film was found. ×: Dissolved. When the release layer is not dissolved in the dropped solvent, it means that when the resin substrate is formed on the release layer, the organic solvent contained in the resin substrate forming composition is not dissolved, and the resin substrate is not damaged from the glass substrate The meaning of peeling. [8] Evaluation of Peelability The glass substrate with a resin substrate and a release layer obtained in the above Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6 was subjected to the following method To confirm the peelability between the peeling layer and the glass substrate. The following tests were performed on the same glass substrate. [0123] <Evaluation of Peelability of Release Layer and Glass Substrate> The release layers on the glass substrate with a release layer obtained in Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6 were cross-cut. (1 mm interval in vertical and horizontal directions, the same applies hereinafter), and block cutting of 100 grids was performed. That is, by this cross cutting, 100 1 mm square grids were formed. Then, the adhesive tape was affixed to the cut portion of the 100 grid, and the tape was removed to evaluate the degree of peeling based on the following criteria (5B ~ 0B, B, A, AA). Furthermore, the peeling force evaluation test was performed using the glass substrate with a resin substrate and a peeling layer produced in Examples 2-5 to 2-20 among all the peeled substrates. The test method uses a blade to cut into the back surface of the resin substrate in a penetrating manner to make the resin substrate of the glass substrate with the resin substrate and the release layer into a rectangle having a width of 25 mm × 50 mm to form a strip. Furthermore, after attaching a Nichiban CT-24 tape to the produced strip, an Autograph AG-500N (manufactured by Shimadzu Corporation) was used to peel the substrate at 90 degrees, that is, in a vertical direction. The peeling force was measured, and 100% peeling (all peeling) was performed, and the peeling force was less than 0.1N / 25mm, and it was set to AAA. The above results are shown in Tables 1 and 2. <Judgment criteria> 5B: 0% peeling (no peeling) 4B: Less than 5% peeling 3B: 5 to less than 15% peeling 2B: 15 to less than 35% peeling 1B: 35 to less than 65% Peel 0B: 65% to less than 80% peel B: 80% to less than 95% peel A: 95% to less than 100% peel AA: 100% peel (all peel) AAA: 100% peel and peel The force is less than 0.1N / 25mm. [0124] <Evaluation of Peelability of Peeling Layer and Resin Substrate> For the resin substrate with resin obtained in Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6 • The glass substrate of the release layer was evaluated for peelability according to the same procedure as the peelability evaluation described above. The results are shown in Tables 1 and 2. [0125] [0126] [0127] As shown in Tables 1 and 2, it was confirmed that the peeling layers of Examples 2-1 to 2-20 were excellent in adhesion to the glass substrate and were easily peeled from the resin film. It was also confirmed from the results of the solubility test that it was not dissolved in the organic solvent contained in the composition for forming a resin substrate. On the other hand, it was confirmed that although the peeling layers of Comparative Examples 2-1 to 2-6 had excellent adhesion to the glass substrate, they had poor peelability from the resin substrate.

Claims (10)

A composition for forming a release layer, comprising a polyamic acid represented by the following formula (1) and an organic solvent, (In the formula, X represents an aromatic group represented by the following formula (2a) or (2b), Y represents a divalent aromatic group having a fluorine atom, and when X is an aromatic group represented by formula (2a) When X is an aromatic group represented by the following formula (3a) or (4a), Z is independently of each other, and when X is an aromatic group represented by the formula (2b), Z is independently of the following formula (3b) ) Or an aromatic group represented by (4b), where m is a natural number) . The composition for forming a release layer according to claim 1, wherein Y is an aromatic group represented by the following formula (5), . The composition for forming a release layer according to claim 2, wherein Y is an aromatic group represented by the following formula (6), . The composition for forming a release layer according to any one of claims 1 to 3, wherein in X, the aromatic group represented by the formula (2a) is an aromatic group represented by the following formula (7a) or (8a) Group group, the above-mentioned Z is independently an aromatic group represented by the following formula (9a) or (10a), . The composition for forming a release layer according to any one of claims 1 to 3, wherein in the X, the aromatic group represented by the formula (2b) is an aromatic group represented by the following formula (7b) or (8b) Group group, the above-mentioned Z series are independently an aromatic group represented by the following formula (9b) or (10b), . The composition for forming a release layer according to any one of claims 1 to 5, wherein the organic solvent is at least one selected from organic solvents having a structure represented by the following formulae (S1) to (S7), (In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number 1 to 10 fluorene groups, b and n are natural numbers). The composition for forming a release layer according to claim 6, wherein the organic solvent is propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate. A release layer is formed using the composition for forming a release layer according to any one of claims 1 to 7. A method for manufacturing a resin substrate, which uses the release layer of claim 8. The manufacturing method according to claim 9, wherein the resin substrate is a polyimide resin substrate or a resin substrate having a light transmittance at a wavelength of 400 nm of 80% or more.