TWI817931B - laminated body - Google Patents

Abstract

The present invention provides a composition for forming a peeling layer for a transparent resin substrate, which is a polyamide containing a reactant of a diamine component and a tetracarboxylic dianhydride component, and an organic solvent. The diamine component contains an ester bond. and/or an aromatic diamine having an ether bond, and at least one of an aromatic diamine having no ester bond and an ether bond, and the tetracarboxylic dianhydride component contains an aromatic tetracarboxylic acid having an ester bond and/or an ether bond. At least one of the acid dianhydride and the aromatic tetracarboxylic dianhydride that does not have an ester bond and an ether bond, and at least one of the diamine component and the tetracarboxylic dianhydride component that has an ester bond and/or an ether bond. Element.

Description

laminated body

The present invention relates to a composition for forming a peeling layer, specifically a composition for forming a peeling layer for forming a peeling layer provided on a substrate.

In recent years, electronic devices are required to have features such as thinness and weight reduction, as well as functions such as flexibility. Therefore, there is a requirement to use lightweight flexible plastic substrates to replace the previous heavy, fragile and unbendable glass substrates.

In particular, in line with the requirements of the new generation of display systems, we have developed active array full-color TFT display panels using lightweight, flexible plastic substrates (hereinafter referred to as resin substrates). This new-generation display technology is expected to be applied to various fields such as flexible displays, flexible smartphones, and mirror displays.

Here, various reviews have begun on manufacturing methods of electronic devices using resin films as substrates, and processes are being reviewed to apply existing TFT display panel manufacturing equipment to new-generation displays. In addition, in the case of touch panel displays, resin substrates for transparent electrodes of the touch panel used in combination with the display panel have been Examine strategies for efficiently manufacturing the resin substrate. Generally speaking, the resin substrate used for touch panels, like TFT display panels, etc., is a polyimide resin substrate, an acrylic resin substrate, or a polyterephthalate resin substrate that has the same level of transparency as glass. Film substrates such as ethylene formate (PET) resin substrate and cycloolefin resin substrate.

For example, Patent Documents 1, 2, and 3 disclose a method in which an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and a laser is irradiated from the glass surface side. The hydrogen gas produced by the crystallization of amorphous silicon peels the plastic substrate away from the glass substrate. Furthermore, Patent Document 4 discloses a method of attaching a peeled layer (described as "transferred layer" in Patent Document 4) to a plastic film using the technology disclosed in Patent Documents 1 to 3 to complete a liquid crystal display device. .

However, the methods disclosed in Patent Documents 1 to 4, especially the method disclosed in Patent Document 4, have the following problems: in order for laser light to pass through, a highly translucent substrate must be used; In order to further release the hydrogen contained in the amorphous silicon, the substrate must be irradiated with sufficient and relatively high-energy laser light; the irradiation of laser light may cause damage to the peeled layer.

Furthermore, when the layer to be peeled has a large area, laser processing takes a long time, so it is difficult to improve the productivity of device manufacturing.

[Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-125929 [Patent Document 2] Japanese Patent Application Laid-Open No. 10-125931 [Patent Document 3] International Publication No. 2005/050754 [Patent Document 4] Japanese Patent Application Laid-Open No. 10 - Gazette No. 125930

[Problems to be solved by the invention] [0007] The present invention was invented in view of the above-mentioned circumstances, and its object is to provide a composition for forming a peeling layer for a transparent resin substrate, which can be provided without damage, especially by using acrylic resin, cyclic olefin A peeling layer that peels off a transparent resin substrate of a flexible electronic device made of polymer resin or the like. [Means for Solving the Problems] [0008] As a result of in-depth research in order to solve the above-mentioned problems, the inventors found that a composition including a polyamic acid, a reactant of a diamine component and a tetracarboxylic dianhydride component, and an organic solvent , if the above-mentioned diamine component contains at least one of an aromatic diamine having an ester bond and/or an ether bond, and an aromatic diamine having no ester bond or an ether bond, the above-mentioned tetracarboxylic dianhydride component contains At least one of aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond and an aromatic tetracarboxylic dianhydride not having an ester bond and an ether bond, and including the above-mentioned aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond. In the case of at least one of the aromatic diamine and the above-mentioned aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond, it is possible to form a product that has excellent adhesion to the substrate and can be used as a The present invention was completed because a transparent resin substrate of a flexible electronic device is a composition of a peeling layer having moderate adhesion and moderate peelability. [0009] That is, the present invention provides the following invention. 1. A composition for forming a peeling layer for a transparent resin substrate, which is a polyamide containing a reaction product of a diamine component and a tetracarboxylic dianhydride component, and an organic solvent, characterized in that: the diamine component contains At least one of an aromatic diamine having an ester bond and/or an ether bond, and an aromatic diamine that does not have an ester bond or an ether bond; the above-mentioned tetracarboxylic dianhydride component includes an aromatic diamine having an ester bond and/or an ether bond. At least one of aromatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride that does not have an ester bond or an ether bond; and at least one of the above-mentioned diamine component and the tetracarboxylic dianhydride component contains an ester bond. and/or components of ether bonds. 2. The composition for forming a peeling layer for a transparent resin substrate according to the above 1, wherein the aromatic diamine having an ester bond and/or an ether bond is selected from at least one of the group consisting of formulas (A1) to (A39). 1 species, 3. The composition for forming a release layer for a transparent resin substrate according to the above 1 or 2, wherein the aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond is selected from the group consisting of formulas (B1) to (B16). At least 1 species of the group, 4. The composition for forming a release layer for a transparent resin substrate according to any one of 1 to 3 above, wherein the aromatic diamine having no ester bond or ether bond is an aromatic diamine containing 1 to 5 benzene rings. . 5. The composition for forming a peeling layer for a transparent resin substrate according to the above 4, wherein the aromatic diamine type p-phenylenediamine does not have an ester bond or an ether bond. 6. The composition for forming a release layer for a transparent resin substrate according to any one of 1 to 5 above, wherein the aromatic tetracarboxylic dianhydride system having no ester bond or ether bond contains 1 to 5 benzene rings. of aromatics. 7. The composition for forming a peeling layer for a transparent resin substrate according to any one of 1 to 6 above, wherein the organic solvent contains at least 1 amide selected from the group consisting of amide represented by formulas (S1) to (S3). kind, . (In the formula, R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and h represents a natural number). 8. A peeling layer formed using the composition for forming a peeling layer for a transparent resin substrate according to any one of 1 to 7 above. 9. A method of manufacturing a flexible electronic device having a transparent resin substrate, characterized by using the release layer of 8 above. [Effects of the Invention] [0010] By using the composition for forming a release layer for a transparent resin substrate of the present invention, it is possible to reproducibly obtain a composition having excellent adhesion to a substrate and having moderate adhesion to a transparent resin substrate. A film with good adhesion and moderate peelability. By using the composition of the present invention, the resin substrate formed on the base body or the circuits provided thereon will not be damaged during the manufacturing process of the flexible electronic device, and the resin substrate can be combined with The circuit is detached from the base body simultaneously. Therefore, the composition for forming a peeling layer of the present invention can contribute to the simplification of the manufacturing process of a flexible electronic device including a resin substrate, the improvement of the productivity, and the like.

[Best Mode for Carrying Out the Invention] [0011] The present invention will be described in more detail below. The peeling layer forming composition for a transparent resin substrate of the present invention is a polyamide containing a reaction product of a diamine component and a tetracarboxylic dianhydride component, and an organic solvent. The diamine component contains an ester bond and /or at least one of an aromatic diamine having an ether bond and an aromatic diamine having no ester bond or an ether bond, and the above-mentioned tetracarboxylic dianhydride component contains an aromatic tetracarboxylic acid having an ester bond and/or an ether bond. At least one of acid dianhydride and aromatic tetracarboxylic dianhydride without ester bond and ether bond, and including the above-mentioned aromatic diamine with ester bond and/or ether bond, and the above-mentioned aromatic diamine with ester bond and/or At least one of the aromatic tetracarboxylic dianhydrides with ether bonds. [0012] In the present invention, the so-called peeling layer is a layer provided directly above the base (glass base, etc.) that will form the resin substrate. As a typical example of this, in the manufacturing process of the flexible electronic device, the resin substrate of the flexible electronic device formed between the above-mentioned base and a transparent resin such as acrylic resin, polycarbonate, cycloolefin polymer, etc. The release layer is provided to fix the resin substrate in a specified process, and to enable the resin substrate to be easily peeled off from the base after electronic circuits and the like are formed on the resin substrate. [Diamine Component] In the present invention, the above-mentioned diamine component may be either an aliphatic diamine or an aromatic diamine, but from the perspective of ensuring the strength and heat resistance of the resulting film , preferably containing aromatic diamines. In the present invention, the diamine component includes at least one of an aromatic diamine having an ester bond and/or an ether bond, and an aromatic diamine having no ester bond or ether bond. [0014] The above-mentioned aromatic diamine having an ester bond and/or an ether bond contains one of an ester bond and an ether bond in the molecule, or contains both of them. Examples of such aromatic diamines include diamines having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are connected with an ester bond or an ether bond. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like. Among them, from the viewpoint of ensuring the solubility of polyamide acid in organic solvents, a diamine having a structure in which two or three aromatic rings are connected by an ester bond or an ether bond is preferred. In the present invention, preferred specific examples of the aromatic diamine having an ester bond and/or an ether bond include those shown below. [0016] [0017] [0018] [0019] [0020] [0021] In the present invention, the above-mentioned aromatic diamines without ester bonds and ether bonds are preferably those containing 1 to 5 benzene rings, and those containing benzene skeleton, naphthalene skeleton or biphenyl skeleton are preferably good. Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene Benzene (o-phenylenediamine), 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3, Diamines containing one benzene ring such as 5,6-tetramethyl-p-phenylenediamine, m-xylenediamine, p-xylenediamine; 1,2-naphthylenediamine, 1,3- Naphthalene diamine, 1,4-naphthalene diamine, 1,5-naphthalene diamine, 1,6-naphthalene diamine, 1,7-naphthalene diamine, 1,8-naphthalene diamine, 2,3-naphthalene diamine Amine, 2,6-naphthalenediamine, 4,4'-biphenyldiamine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy- 4,4'-Diaminodiphenylmethane, 3,3',5,5'-Tetramethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diaminobenzyl Benzidine, 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-aminobenzene) base) propane, 3,3'-diaminodiphenyl styrene, 3,4'-diaminodiphenyl styrene, 4,4'-diaminodiphenyl styrene, etc. including 2 Diamines of benzene ring; 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-Aminophenylene sulfide) benzene, 1,4-bis (4-aminophenylene sulfide) benzene, 1,3-bis (3-aminophenyl sulfonate) benzene, 1,3-bis ( 4-Aminophenylsulfonate)benzene, 1,4-bis(4-aminophenylsulfonate)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, etc. contain 3 benzene rings diamines, etc., but are not limited to these. In the present invention, p-phenylenediamine is particularly suitably used among these. Moreover, these systems may be used individually by 1 type, and may be used in combination of 2 or more types. [Tetracarboxylic dianhydride component] In the present invention, the above-mentioned tetracarboxylic dianhydride component system may include any one of aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride, but it is sufficient to ensure that From the viewpoint of the strength and heat resistance of the resulting film, it is preferable to contain aromatic tetracarboxylic dianhydride. In the present invention, the tetracarboxylic dianhydride component is at least one of an aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond and an aromatic tetracarboxylic dianhydride having no ester bond or an ether bond. One. The above-mentioned aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond contains one of an ester bond and an ether bond in the molecule, or contains both of them. Examples of such aromatic tetracarboxylic dianhydride include tetracarboxylic dianhydride having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are connected with an ester bond or an ether bond. Specific examples of the aromatic ring include those mentioned above. Among them, from the viewpoint of ensuring the solubility of polyamide acid in organic solvents, those having a structure in which three or four aromatic rings are connected by ester bonds or ether bonds are preferred. In the present invention, preferred specific examples of the aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond include those represented below. [0027] Such tetracarboxylic dianhydride can be any of aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride, but from the perspective of ensuring the strength and heat resistance of the obtained film , aromatic tetracarboxylic dianhydride without ester bonds and ether bonds is preferred. In the present invention, the above-mentioned aromatic tetracarboxylic dianhydride having no ester bond or ether bond is preferably one that contains 1 to 5 benzene rings, and one that contains a benzene skeleton, a naphthalene skeleton or a biphenyl skeleton is another. Better. Specific examples thereof include pyromelite dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, Naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene- 2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, biphenyl- 2,2',3,3'-tetracarboxylic dianhydride, biphenyl-2,3,3',4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'- Tetracarboxylic dianhydride, anthracene-1,2,3,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2,6,7-tetracarboxylic dianhydride Acid dianhydride, anthracene-1,2,7,8-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,3,4-tetracarboxylic dianhydride Anhydride, 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, phenanthrene-2,3,5,6-tetracarboxylic dianhydride, phenanthrene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene- 2,3,9,10-tetracarboxylic dianhydride, phenanthrene-3,4,5,6-tetracarboxylic dianhydride, phenanthrene-3,4,9,10-tetracarboxylic dianhydride, etc., but are not Limited to these. These systems may be used individually by 1 type, or in combination of 2 or more types. In particular, as the aromatic tetracarboxylic dianhydride that does not have an ester bond or an ether bond, from the viewpoint of ensuring heat resistance, at least one selected from the group consisting of formulas (C1) to (C12) More preferably, at least one selected from the group consisting of formula (C1) and formula (C9) is preferred. [0031] In the present invention, the usage amount of the above-mentioned aromatic diamine with ester bond and/or ether bond, if the above-mentioned tetracarboxylic dianhydride component does not include the aromatic tetracarboxylic acid with ester bond and/or ether bond In the case of dianhydride, the total diamine component is preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, and more preferably 95 mol% or more. Optimum is 100 mol%. By employing such a usage amount, a film having excellent adhesion to the base, moderate adhesion to the resin substrate, and moderate peelability can be obtained with good reproducibility. In the present invention, the usage amount of the above-mentioned aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond, if the above-mentioned diamine component does not include an aromatic diamine having an ester bond and/or an ether bond, In this case, in all the tetracarboxylic dianhydride components, it is preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, and more preferably 95 mol% or more, Optimum is 100 mol%. By employing such a usage amount, a film having sufficient adhesion to the base, moderate adhesion to the resin substrate, and moderate peelability can be obtained with good reproducibility. Also, if any one of the aromatic diamine having an ester bond and/or an ether bond and the aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond is included, the total usage amount is The total amount of the diamine component and the tetracarboxylic dianhydride component is preferably 35 mol% or more, more preferably 40 mol% or more, more preferably 45 mol% or more, and still more preferably 50 mol%. More than % of ears. In this case, the ratio of the molar number of the aromatic diamine having an ester bond and/or an ether bond to the molar number of an aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond is: Any. The ratio of the molar number of all tetracarboxylic dianhydride components and the molar number of all diamine components when synthesizing the polyamic acid of the present invention is tetracarboxylic acid component/diamine component=0.8~1.2. Better. By reacting the diamine component and the tetracarboxylic dianhydride component described above, the polyamic acid contained in the release layer forming composition for a transparent resin substrate related to the present invention can be obtained. [Organic solvent] 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 and 2-pyrrolidine. Ketone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-propoxy-N,N -Dimethylpropylamide, 3-isopropoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-dimethylpropylamide, 3-sec-butoxy -N,N-dimethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, γ-butyrolactone, etc. Alternatively, the organic solvent system may be used alone or in combination of two or more types. In particular, the organic solvent used in the reaction is selected from the group consisting of amide represented by formula (S1) and amide represented by formula (S2) because it fully dissolves diamine, tetracarboxylic dianhydride and polyamide. At least one kind of amide represented by amide and formula (S3) is preferred. [0039] In the formula, R ¹ and R ² represent an alkyl group having 1 to 10 carbon atoms independently of each other. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. h represents a natural number, but is preferably 1 to 3, and more preferably 1 or 2. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. Among these, an alkyl group having 1 to 3 carbon atoms is preferred, and an alkyl group having 1 or 2 carbon atoms is further preferred. The reaction temperature can be appropriately set within the range from the melting point to the boiling point of the solvent used, usually about 0 to 100° C., but in order to prevent the resulting polyamide acid from dissolving the imine in the solution In order to maintain a high content of polyamide units, the temperature is preferably about 0 to 70°C, more preferably about 0 to 60°C, and further preferably about 0 to 50°C. [0043] Since the reaction time depends on the reaction temperature or the reactivity of the raw material, it cannot be specified uniformly, but it is usually about 1 to 100 hours. [0044] According to the method described above, a reaction solution containing the target polyamide can be obtained. [0045] The weight average molecular weight of the above-mentioned polyamide acid is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and further preferably 15,000 to 200,000 from the viewpoint of operability. However, in the present invention, the weight average molecular weight is the average molecular weight obtained by gel permeation chromatography (GPC) analysis and conversion to standard polystyrene. [0046] In the present invention, usually after filtering the reaction solution, the filtrate, or the solution obtained after diluting or concentrating, can be used as the peeling layer forming composition of the present invention. In this way, not only can the mixing of impurities that cause deterioration in the adhesion, peelability, etc. of the obtained peeling layer be reduced, but also the composition for forming a peeling layer can be obtained efficiently. In addition, after the polyamide is isolated from the reaction solution, it can be dissolved in a solvent again to obtain a composition for forming a peeling layer. Examples of the solvent in this case include the organic solvent used in the aforementioned reaction. [0047] The solvent used for dilution is not particularly limited, and specific examples thereof include the same specific examples as the reaction solvent for the above reaction. The solvent used for dilution may be used individually or in combination of 2 or more types. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethylformamide are used because polyamide acid is fully dissolved. Methyl-2-imidazolinone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone is even more preferred. [0048] In addition, even a solvent that cannot dissolve polyamic acid when used alone can be mixed with the composition for forming a peeling layer of the present invention as long as the polyamic acid does not precipitate. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 1-methoxy-2-propanol can be mixed appropriately. Alcohol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1 -Monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, lactic acid Solvents with low surface tension such as ethyl ester, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. Based on this, it is known that the uniformity of the coating film can be improved when coating on a substrate, and it can also be suitably used in the composition for forming a release layer of the present invention. [0049] The concentration of the polyamide in the peeling layer forming composition of the present invention is appropriately set with reference to the thickness of the peeling layer to be produced, the viscosity of the composition, etc., and is usually about 1 to 30 mass%, which is relatively high. Preferably, it is about 1 to 20% by mass. By setting such a concentration, a peeling layer with a thickness of approximately 0.05 to 5 μm can be obtained with good reproducibility. Furthermore, the concentration of polyamide can be adjusted by adjusting the usage amounts of diamine and tetracarboxylic dianhydride as the raw materials of polyamide. After filtering the above reaction solution, the filtrate can be diluted or concentrated, or the separated polyamide can be mixed with The amount is adjusted when the amino acid is dissolved in the solvent, etc. [0050] In addition, the viscosity of the composition for forming a peeling layer is appropriately set with reference to the thickness of the peeling layer to be produced, etc. Especially when the target is to obtain a film with a thickness of about 0.05 to 5 μm with good reproducibility, usually It is about 10~10,000mPa·s at 25℃, preferably about 20~5,000mPa·s. Here, the viscosity can be measured using a commercially available viscometer for measuring liquid viscosity, referring to the procedure described in JIS K7117-2, for example, and using the temperature of the composition at 25°C. It is preferable to use a cone-and-plate rotational viscometer as the viscometer, and it is preferable to use the same type of viscometer and use 1°34'×R24 as the standard conical rotor, and The temperature of the composition is measured at 25°C. As such a rotational viscometer. An example of the system is TVE-25L manufactured by Toki Industrial Co., Ltd. [0051] Furthermore, the peeling layer forming composition related to the present invention, in addition to polyamide and organic solvent, may also contain components such as a cross-linking agent in order to improve the film strength. By applying the peeling layer-forming composition of the present invention described above to a substrate and heating the obtained coating film to thermally imidize the polyamide acid, a polyimide film can be obtained. In the formed release layer, the polyimide film has excellent adhesion to the substrate, and has moderate adhesion and moderate peelability to the transparent resin substrate. [0053] When the release layer of the present invention is formed on a base, the release layer may be formed on a part of the surface of the base or may be formed on the entire surface. As a method of forming the peeling layer on a part of the surface of the substrate, there are methods of forming the peeling layer only in a specified range of the surface of the substrate, forming the peeling layer in a dot pattern on the entire surface of the substrate, Patterns of graphic shapes such as line and space graphics, etc. Incidentally, in the present invention, the term "substrate" refers to one whose surface can be coated with the peeling layer-forming composition related to the present invention, which means that the substrate can be used by manufacturers of flexible electronic devices and the like. Examples of the substrate (substrate) include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene-based resin, etc.), metals (silicon wafers, etc.), wood, paper, slate, etc. In particular, the release layer obtained by the composition for forming a release layer related to the present invention has sufficient properties for these. Due to its tightness, glass is preferred. Furthermore, the surface of the substrate may be composed of a single material or two or more materials. The base surface is made of two or more materials. A certain range of the base surface is made of a certain material, and the rest of the base surface is made of another material. The entire base surface is A state in which a certain material exists in other materials in the form of a dot pattern, a line and space pattern, etc. The method of coating is not particularly limited, and examples thereof include cast coating, spin coating, blade coating, dip coating, roll coating, rod coating, die coating, Inkjet method, printing method (relief, gravure, offset, screen printing, etc.), etc. [0056] The heating temperature used for imidization is usually determined appropriately in the range of 50 to 550°C, and is preferably above 200°C, and preferably below 500°C. By setting the heating temperature in this way, the obtained film can be prevented from being brittle and the imidization reaction can be sufficiently performed. The heating time varies depending on the heating temperature, so it cannot be specified uniformly, but it is usually 5 minutes to 5 hours. In addition, the imidization rate only needs to be in the range of 50 to 100%. As a preferred example of the heating mode in the present invention, it can be cited that after heating at 50 to 100°C for 5 minutes to 2 hours, the heating temperature is directly increased in stages, and finally the heating temperature exceeds 375°C to 450°C. Method of heating at ℃ for 30 minutes to 4 hours. In particular, it is better to heat at 50 to 100°C for 5 minutes to 2 hours, then to heat over 100°C to 375°C for 5 minutes to 2 hours, and finally to heat over 375°C to 450°C for 30 minutes to 4 hours. . [0058] Examples of equipment used for heating include a heating plate, an oven, and the like. The heating environment may be under air or under inert gas, and it may be under normal pressure or under reduced pressure. The thickness of the peeling layer is usually about 0.01 to 50 μm. From the viewpoint of productivity, it is preferably about 0.05 to 20 μm, and more preferably about 0.05 to 5 μm. The thickness of the coating film before heating is adjusted to achieve the desired thickness. desired thickness. [0060] The release layer system described above has excellent adhesion to the substrate (especially the glass substrate) and moderate adhesion to the resin substrate and moderate peelability. Therefore, the release layer system related to the present invention can be used in the manufacturing process of a flexible electronic device to simultaneously remove the resin substrate and the circuit formed on the resin substrate without causing damage to the resin substrate of the device. The matrix is peeled off. [0061] Hereinafter, an example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described. The composition for forming a peeling layer related to the present invention is used, and a peeling layer is formed on the glass substrate according to the aforementioned method. An acrylic polymer solution, a polycarbonate, or a cyclic olefin polymer solution used to form a transparent resin substrate of a flexible electronic device is coated on the peeling layer, and the coating film is heated to form a transparent resin substrate through which the present invention is connected. A transparent resin substrate that is fixed to a glass substrate by peeling off the layer. At this time, in order to cover the entire peeling layer, a transparent resin substrate is formed with an area larger than the area of the peeling layer. The formation method of the resin substrate may be based on common methods. Examples of the highly transparent resin substrate include those made of acrylic resin, polycarbonate, or cycloolefin polymer resin. In particular, those having a light transmittance of 80% or more at a wavelength of 400 nm are preferred. [0062] Next, a desired circuit is formed on the resin substrate fixed to the base body via the release layer related to the present invention, and then, for example, the resin substrate is cut along the release layer, and the resin substrate together with the circuit is The resin substrate is separated from the base by peeling from the peeling layer. At this time, a part of the base body may be cut together with the peeling layer. [0063] On the other hand, in the manufacture of flexible displays, a laser lift-off method (LLO method) that has been widely used in the manufacture of high-brightness LEDs or three-dimensional semiconductor packages has been reported, which can polymerize from a glass carrier. The object substrate is preferably peeled off (Japanese Patent Application Publication No. 2013-147599). In the manufacture of flexible displays, a polymer substrate made of polyimide, etc. is placed on a glass carrier. Next, a circuit including electrodes, etc. is formed on the substrate. Finally, it must be integrated with the circuit, etc. Peel the substrate from the glass carrier. The LLO method is used in this peeling step, that is, when light with a wavelength of 308 nm is irradiated on the glass carrier from the surface opposite to the surface on which the circuit, etc. is formed, the light of this wavelength penetrates the glass carrier and only aggregates near the glass carrier The material (polyimide resin) absorbs this light and evaporates (sublimes). As a result, it is reported that the substrate can be selectively peeled off from the glass carrier without affecting circuits and the like provided on the substrate that determine the performance of the display. On the resin substrate that is fixed to the base through the release layer related to the present invention, a desired circuit is formed, and then, when the LLO method is used, only the release layer absorbs the light and evaporates (sublimes) . That is, the peeling layer becomes a sacrificial layer (functions as a sacrificial layer), and the substrate can be selectively peeled off from the glass carrier. The composition for forming a peeling layer of the present invention has the characteristic that it can fully absorb light of a specific wavelength (for example, 308 nm) so that the LLO method can be applied. Therefore, it can be used as a sacrificial layer for the LLO method. [Examples] [0065] Hereinafter, the present invention will be further 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 DDE; 4,4'-oxodiphenylamine BPTP: bis (4-aminophenoxy) terephthalate APAB-E : 4-Aminophenyl-4'-aminobenzoate FDA: 9,9-bis(4-aminophenyl)a-ODPA: 3,4'-Oxobisphthalic anhydride TAHQ: p-phenylene-bis(trimellitic acid monoester acid anhydride) (p-phenylene-bis(trimellitic acid monoester acid anhydride)) PMDA: pyromelite dianhydride BPTME: p-phenylene-bis(trimellitic acid monoester anhydride) p-biphenylene-bis(trimellitic acid monoester acid anhydride) BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride MMA: methyl methacrylate MAA : Methacrylic acid HEMA: 2-Hydroxyethyl methacrylate AIBN: Azobisisobutyronitrile CHMI: Cyclohexylmaleimide EPOLEAD GT-401: Epoxidized butane tetracarboxylic acid 4-(3-cyclohexyl Methyl) modified ε-caprolactone, manufactured by DAICEL Co., Ltd. NMP: N-methyl-2-pyrrolidinone PGMEA: Propylene glycol monomethyl ether acetate BCS: Butyl cellosolve [0067] [2] Weight average Measuring method of molecular weight and molecular weight distribution The weight average molecular weight (hereinafter referred to as Mw) and molecular weight distribution of the polymer were measured using a GPC device manufactured by JASCO Corporation (column: KD801 and KD 805 manufactured by Shodex; eluent: dimethyl Methamide/LiBr·H ₂ O (29.6mM)/H ₃ PO ₄ (29.6mM)/THF (0.1 mass%); flow rate: 1.0mL/min; column temperature: 40℃; Mw: standard polystyrene Ethylene conversion value). [3] Synthesis of polymers Various polymers used in the examples and comparative examples were synthesized according to the following methods. Furthermore, the polymer is not isolated from the obtained polymer-containing reaction liquid, and the resin substrate forming composition or the peeling layer forming composition can be prepared by diluting the reaction liquid as described below. <Synthesis Example S1 Synthesis of Acrylic Polymer (S1)> MMA 7.20g (7.19mmol), HEMA 7.20g (5.53mmol), CHMI 10.8g (6.03mmol), MAA 4.32g (5.02mmol), AIBN 2.46 g (1.50 mmol) was dissolved in 46.9 g of PGMEA, and the solution was reacted at 60 to 100° C. for 20 hours to obtain an acrylic polymer solution (solid concentration 40 mass %). The obtained acrylic polymer had an Mw of 7,300 and a molecular weight distribution of 1.9. <Synthesis Example L1 Synthesis of Polyamic Acid (L1)> 5.24 g (15.05 mmol) of BPTP was dissolved in 88.0 g of NMP. TAHQ 6.76g (14.75mmol) was added to the obtained solution, and the reaction was carried out at 23°C for 24 hours in a nitrogen environment. The obtained polymer had an Mw of 85,900 and a molecular weight distribution of 3.0. <Synthesis Example L2 Synthesis of Polyamic Acid (L2)> APAB-E 4.04g (17.71mmol) was dissolved in NMP 88.0g. TAHQ 7.96g (17.37mmol) was added to the obtained solution, and the reaction was carried out at 23°C for 24 hours in a nitrogen environment. The obtained polymer had an Mw of 33,100 and a molecular weight distribution of 1.8. <Synthesis Example L3 Synthesis of Polyamic Acid (L3)> APAB-E 3.64g (15.96mmol) was dissolved in NMP 88.0g. 8.36g (15.64mmol) of BPTME was added to the obtained solution, and the reaction was carried out at 23°C for 24 hours in a nitrogen environment. The obtained polymer had an Mw of 41,600 and a molecular weight distribution of 3.5. <Synthesis Example L4 Synthesis of Polyamic Acid (L4)> 0.96 g (2.75 mmol) of BPTP was dissolved in 17.6 g of NMP. 1.44g (2.70mmol) of BPTME was added to the obtained solution, and the reaction was carried out at 23°C for 24 hours in a nitrogen environment. The obtained polymer had an Mw of 112,800 and a molecular weight distribution of 3.6. <Synthesis Example L5 Synthesis of Polyamic Acid (L5)> Dissolve 1.77g (8.82mmol) of DDE in 10.5g of NMP. 2.74g (8.82mmol) of a-ODPA was added to the obtained solution, and the reaction was carried out at 23°C for 24 hours in a nitrogen environment. The obtained polymer had an Mw of 46,400 and a molecular weight distribution of 2.2. <Synthesis Example L6 Synthesis of Polyamic Acid (L6)> 0.93 g (8.61 mmol) of p-PDA was dissolved in 35.2 g of NMP. TAHQ 3.87g (8.44mmol) was added to the obtained solution, and the reaction was carried out at 23°C for 24 hours in a nitrogen environment. The obtained polymer had an Mw of 45,000 and a molecular weight distribution of 2.7. <Synthesis Example L7 Synthesis of Polyamic Acid (L7)> DDE 17.41g (86.96mmol) was dissolved in NMP 264.0g. 18.59g (85.22mmol) of PMDA was added to the obtained solution, and the reaction was carried out at 23°C for 24 hours in a nitrogen environment. The obtained polymer had an Mw of 52,800 and a molecular weight distribution of 2.4. <Comparative synthesis example HL1: Synthesis of polyamide (HL1)> 1.56 g (4.47 mmol) of FDA was dissolved in 7.0 g of NMP. 1.44g (4.47mmol) of BTDA was added to the obtained solution, and the reaction was carried out at 23°C for 24 hours in a nitrogen environment. The obtained polymer had an Mw of 67,300 and a molecular weight distribution of 2.0. <Synthesis of Comparative Synthesis Example HL2 Polyamide (HL2)> 0.98 g (9.02 mmol) of p-PDA was dissolved in 36.0 g of NMP. BTDA 3.03g (9.39mmol) was added to the obtained solution, and the reaction was carried out at 23°C for 24 hours in a nitrogen environment. The obtained polymer had an Mw of 67,600 and a molecular weight distribution of 1.8. [4] Preparation of the resin substrate forming composition The resin substrate forming composition was prepared according to the following method. <Preparation Example 1 Resin Substrate Forming Composition F1> Add 0.61 g of GT-401 and 5.06 g of PGMEA to 10 g of the reaction liquid obtained in Synthesis Example S1, and stir at 23° C. for 24 hours to prepare a resin substrate forming composition. Object F1. <Preparation Example 2 Resin Substrate Forming Composition F2> In an eggplant-shaped flask containing 100 g of carbon tetrachloride, Zeonor (registered trademark) 1020R (manufactured by Japan Zeon Co., Ltd., cycloolefin polymer resin) was added 10g and GT-401 3g. The solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare a resin substrate forming composition F2. <Preparation Example 3 Resin Substrate Forming Composition F3> In an eggplant-shaped flask containing 100 g of carbon tetrachloride, Zeonor (registered trademark) 1060R (manufactured by Japan Zeon Co., Ltd., cycloolefin polymer resin) was added 10g. The solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare resin substrate forming composition F3. [5] Preparation of composition for forming peeling layer [Example 1-1] To the reaction liquid obtained in Synthesis Example L1, BCS and NMP were added so that the polymer concentration became 5% by mass and BCS became 20 The composition was diluted by mass % to obtain the composition L1 for forming a peeling layer. [Examples 1-2 to 1-7] In the same manner as in Example 1-1, except that the reaction liquid obtained in Synthesis Examples L2 to L7 was used instead of the reaction liquid obtained in Synthesis Example L1, Thus, peeling layer forming compositions L2 to L7 were obtained. [Comparative Example 1-1] To the reaction liquid obtained in Comparative Synthesis Example HL1, BCS and NMP were added, and the polymer concentration was diluted so that the polymer concentration became 5% by mass and the BCS became 20% by mass, to obtain Composition HL1 for peeling layer formation. [Comparative Example 1-2] To the reaction liquid obtained in Comparative Synthesis Example HL2, BCS and NMP were added, and the polymer concentration was diluted so that the polymer concentration became 5% by mass and the BCS became 20% by mass, to obtain Composition HL2 for peeling layer formation. [6] Preparation of peeling layer and resin substrate [Example 2-1] Using a spin coater (condition: rotating at 3,000 rpm for about 30 seconds), the peeling layer obtained in Example 1-1 was The composition L1 for formation was applied on a 100 mm×100 mm glass substrate (the same below) as a glass base. 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/min, and further heated at 400°C for 30 minutes). Minutes, a peeling layer with a thickness of about 0.1 μm is formed on the glass substrate, and a glass substrate with a peeling layer is obtained. During the heating period, the glass substrate is not taken out from the oven, but is heated in the oven. [0088] Use The composition F1 for forming a resin substrate is coated on the peeling layer (resin film) on the glass substrate obtained above using a spin coater (condition: rotating at 500 rpm for about 10 seconds). Then, a hot plate is used The obtained coating film was heated at 80°C for 10 minutes, and then heated at 230°C for 30 minutes using a hot plate to form a resin substrate with a thickness of about 5 μm on the release layer, thereby obtaining a glass substrate with a resin substrate and release layer. After that, the light transmittance was measured using an ultraviolet visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation). The resin substrate showed a transmittance of more than 80% at 400 nm. [0089] [Example] 2-2~2-7] In addition to using the peeling layer forming compositions L2~L7 obtained in Examples 1-2~1-7 instead of the peeling layer forming composition L1 obtained in Example 1-1, The peeling layer and the resin substrate were formed in the same manner as in Example 2-1 to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and peeling layer. [0090] [Example 2-8] Use The peeling layer forming composition L6 obtained in Example 1-6 was used to form a peeling layer in the same manner as in Example 2-1 to obtain a glass substrate with a peeling layer. Immediately thereafter, a spin coater ( Conditions: Apply the composition F2 for forming a resin substrate on the release layer (resin film) on the above-mentioned glass substrate at a rotation speed of 200 rpm for about 15 seconds). Use a hot plate to heat the obtained coating film at 80°C. 2 minutes, and then heated at 230°C for 30 minutes using a hot plate to form a resin substrate with a thickness of about 3 μm on the peeling layer, thereby obtaining a glass substrate with a resin substrate and peeling layer. After that, a UV-visible spectrophotometer (Shimadzu) was used to As a result of measuring the light transmittance using UV-2600 manufactured by Seisakusho Co., Ltd., the resin substrate showed a transmittance of more than 80% at 400 nm. [0091] [Example 2-9] In addition to using Example 1- 7 was obtained by producing a peeling layer and a resin substrate in the same manner as in Example 2-8, except that the composition L7 for forming a peeling layer was substituted for the composition L6 for forming a peeling layer obtained in Example 1-6. A glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer. [0092] [Example 2-10] The composition L6 for forming a peeling layer obtained in Examples 1-6 was used to compare with Example 1-6. 2-1 Use the same method to form a peeling layer to obtain a glass substrate with a peeling layer. Immediately thereafter, the composition F3 for forming a resin substrate was coated on the release layer (resin film) on the above-mentioned glass substrate using a spin coater (condition: rotation speed: 200 rpm for about 15 seconds). 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 with a thickness of about 3 μm on the peeling layer, thereby obtaining a resin substrate and peeling layer. Glass base board. After that, the light transmittance was measured using an ultraviolet visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation). The resin substrate showed a transmittance of more than 80% at 400 nm. [Example 2-11] The same procedure as in Example 1-7 was used except that the composition L7 for forming a release layer obtained in Example 1-7 was used instead of the composition L6 for forming a release layer obtained in Example 1-6. 2-10 Use the same method to prepare a peeling layer and a resin substrate to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and peeling layer. [Comparative Examples 2-1, 2-2] Except for using the peeling layer forming compositions HL1 and HL2 obtained in Comparative Examples 1-1 and 1-2 instead of the peeling layer forming compositions obtained in Example 1-1. Except for composition L1, a release layer and a resin substrate were formed in the same manner as in the above-mentioned Examples, thereby obtaining a glass substrate with a release layer and a glass substrate with a resin substrate and release layer. [7] Evaluation of peelability The following method was used to confirm peeling of the glass substrates with peeling layers obtained in the above-mentioned Examples 2-1 to 2-11 and Comparative Examples 2-1 and 2-2. The peelability between the layer and the glass substrate, and for the glass substrate with a resin substrate and peeling layer, confirm the peelability between the peeling layer and the resin substrate. <Evaluation of the peelability of the peeling layer and the glass substrate> The peeling layer on the glass substrate with the peeling layer obtained in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-2, and The peeling layer and the resin substrate on the glass substrate with the resin substrate and peeling layer are cut cross-cut (2mm vertical and horizontal intervals, the same below), and cut into 25-square blocks. That is, by this cross cutting, 25 square meshes of 2 mm square are formed. Then, adhere the adhesive tape to the 25-square cut section and peel off the tape to evaluate the degree of peeling based on the following standards (5B~0B, B, A, AA). Furthermore, among all the peeled substrates, a peeling force evaluation test was performed using the glass substrates with resin substrates and peeling layers produced in Examples 2-8 to 2-11. The test method is to use a blade to cut through the back of the resin substrate to make the resin substrate with the resin substrate and the glass substrate with the peeling layer into a rectangular shape of 25mm x 50mm wide to make a long strip. Furthermore, after affixing Cellophane tape (NichibanCT-24) to the prepared strip, Autograph AG-500N (manufactured by Shimadzu Corporation) was used to peel it off at 90 degrees to the surface of the substrate, that is, in the vertical direction. The peeling force is measured, and those with 100% peeling (complete peeling) and a peeling force of less than 0.1N/25mm are regarded as AAA. The above results are shown in Table 1. <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% peeling Peeling 0B: 65% to less than 80% peeling B: 80% to less than 95% peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling) AAA: 100% peeling and peeling The force is less than 0.1N/25mm [0097] <Evaluation of the peelability of the peeling layer and the resin substrate> Regarding the attached resin substrates obtained in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-2. The peelability of the glass substrate of the peelable layer is evaluated according to the same procedure as the peelability evaluation described above. The results are shown in Table 1. [0098] [0099] As shown in Table 1, it was confirmed that the peeling layer system of Examples 2-1 to 2-11 had excellent adhesion to the glass substrate and was easily peeled off from the transparent resin substrate. On the other hand, it was confirmed that the peeling layers of Comparative Examples 2-1 to 2-2 had excellent adhesion to the glass substrate but poor peelability to the resin substrate.

Claims (8)

A laminated body characterized by: a base body, a peeling layer and a transparent resin substrate are laminated in this order, the peeling layer is formed from a composition for forming a peeling layer for a transparent resin substrate, and the composition for forming a peeling layer for a transparent resin substrate is provided A polyamide containing a reaction product of a diamine component and a tetracarboxylic dianhydride component, and an organic solvent. The diamine component is an aromatic diamine containing an ester bond and/or an ether bond, and an aromatic diamine that does not have an ester bond and At least one of the aromatic diamines with ether bonds; the above-mentioned tetracarboxylic dianhydride component includes aromatic tetracarboxylic dianhydrides with ester bonds and/or ether bonds, and aromatic tetracarboxylic dianhydrides without ester bonds and ether bonds. At least one of the carboxylic dianhydride; and at least one of the diamine component and the tetracarboxylic dianhydride component contains a component having an ester bond and/or an ether bond, and the transparent resin substrate is selected from the group consisting of acrylic resin, Resin substrate for polycarbonate and cycloolefin polymer resins. The laminated body of claim 1, wherein the aromatic diamine having an ester bond and/or an ether bond is at least one selected from the group consisting of formulas (A1) to (A39),

The laminate of claim 1 or 2, wherein the aromatic tetracarboxylic dianhydride having an ester bond and/or an ether bond is at least one selected from the group consisting of formulas (B1) to (B16),

The laminated body of claim 1 or 2, wherein the aromatic diamine having no ester bond or ether bond is an aromatic containing 1 to 5 benzene rings. The laminate according to claim 4, wherein the aromatic diamine having no ester bond or ether bond is p-phenylenediamine. The laminated body of claim 1 or 2, wherein the aromatic tetracarboxylic dianhydride having no ester bond or ether bond is an aromatic containing 1 to 5 benzene rings. The laminated body of claim 1 or 2, wherein the above-mentioned organic solvent contains at least one selected from the group consisting of amides represented by formulas (S1) to (S3),

(In the formula, R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and h is 1 to 3). A method of manufacturing a flexible electronic device having a transparent resin substrate, characterized by using the laminate according to any one of claims 1 to 7.