KR20220091609A - Composition for forming release layer - Google Patents

Abstract

A polyamic acid obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride, and an organic solvent, wherein the aromatic diamine contains an aromatic diamine containing at least one of an ester bond and an ether bond, and/or the aromatic Provided is a composition for forming a release layer in which tetracarboxylic dianhydride contains at least one of an ester bond and an ether bond.

Description

Composition for forming a release layer

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

In recent years, performance, such as provision of a bending function, and thickness reduction and weight reduction, is calculated|required by an electronic device. In this regard, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, brittle, and unbendable glass substrate. In addition, in the new generation display, the development of an active full-color TFT display panel using a lightweight flexible plastic substrate is required. Then, the manufacturing method of the electronic device which used the resin film as a board|substrate is beginning to be examined in various ways, and in a new-generation display, manufacturing examination is advancing by the process which can divert existing TFT equipment.

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

However, in the method disclosed in Patent Documents 1 to 4, particularly the method disclosed in Patent Document 4, it is essential to use a substrate with high light transmittance, and in order to give sufficient energy to pass through the substrate and release hydrogen contained in amorphous silicon. , a relatively large laser beam irradiation is required, and there is a problem that the layer to be peeled is damaged. Moreover, since it requires a long time for laser processing and it is difficult to peel the to-be-released layer which has a large area, there also exists a problem that it is difficult to improve the productivity of device manufacture.

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

This invention was made in view of the said situation, and an object of this invention is to provide the composition for peeling layer formation which can peel without damaging the resin substrate of a flexible electronic device.

The present inventors, as a result of repeated intensive studies in order to solve the above problems, in a composition comprising a polyamic acid obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride, and an organic solvent, wherein the aromatic diamine is an ester bond and When it contains an aromatic diamine containing at least one of an ether bond, and/or the aromatic tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride containing at least one of an ester bond and an ether bond, It discovered that the composition which can form the peeling layer which has the outstanding adhesiveness and moderate adhesiveness with the resin substrate used as a flexible electronic device, and moderate peelability is obtained, and completed this invention.

That is, the present invention is

1. A polyamic acid obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride, and an organic solvent,

The aromatic diamine contains an aromatic diamine containing at least one of an ester bond and an ether bond, and/or the aromatic tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride containing at least one of an ester bond and an ether bond. A composition for forming a release layer, characterized in that

2. The composition for forming a release layer according to 1, wherein the aromatic diamine containing at least one of an ester bond and an ether bond is at least one selected from the group consisting of formulas (A1) to (A42);

3. The composition for forming a release layer according to 1 or 2, wherein the aromatic tetracarboxylic dianhydride containing at least one of an ester bond and an ether bond is at least one selected from the group consisting of formulas (B1) to (B14);

4. The composition for forming a release layer according to any one of 1 to 3, wherein the aromatic tetracarboxylic dianhydride further contains an aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond;

5. The composition for forming a release layer according to 4, wherein the aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond contains a benzene skeleton, a naphthyl skeleton or a biphenyl skeleton;

6. The composition for forming a release layer according to 5, wherein the aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond is at least one selected from the group consisting of formulas (C1) to (C12);

7. Any one of 1 to 6 wherein the organic solvent contains at least one selected from amides represented by formula (S1), amides represented by formula (S2), and amides represented by formula (S3) composition for forming a release layer of

(Wherein, R ¹ and R ² each 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. h represents a natural number.)

8. A release layer formed using the composition for forming a release layer according to any one of 1 to 7;

9. A method for manufacturing a flexible electronic device comprising a resin substrate, comprising the use of the release layer of 8;

10. A method of manufacturing a touch panel sensor having a resin substrate, characterized in that using the release layer of 8;

11. It provides the manufacturing method of 9 or 10, wherein the resin substrate is a substrate made of polyimide.

By using the composition for forming a release layer of the present invention, it is possible to obtain a film having excellent adhesion to a substrate, and moderate adhesion to a resin substrate and appropriate peelability, with good reproducibility. In the manufacturing process of a flexible electronic device by using the composition of the present invention, without damaging the resin substrate formed on the substrate or the circuit installed thereon, separating the resin substrate together with the circuit and the like from the substrate it becomes possible Therefore, the composition for forming a release layer of the present invention can contribute to the simplification of the manufacturing process of the flexible electronic device provided with the resin substrate, the improvement of the yield, etc.

1 is a graph showing the transmittance measured in Example 4.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in more detail.

The composition for forming a release layer of the present invention comprises a polyamic acid obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride, and an organic solvent, wherein the aromatic diamine contains at least one of an ester bond and an ether bond. Min and/or the aromatic tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride containing at least one of an ester bond and an ether bond. Here, the release layer in the present invention is a layer provided directly on the glass substrate for a predetermined purpose, and a typical example thereof is a flexible electronic device composed of a substrate and a resin such as polyimide in the manufacturing process of the flexible electronic device. It is provided between the resin substrate and the resin substrate to fix the resin substrate in a predetermined process, and is provided so that the resin substrate can be easily peeled from the substrate after an electronic circuit or the like is formed on the resin substrate. can be heard

The aromatic diamine containing at least one of an ester bond and an ether bond contains either an ester bond or an ether bond in the molecule, or contains both of these.

Examples of such aromatic diamine include diamines having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are connected by an ester bond or an ether bond. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Especially, from a viewpoint of ensuring the solubility to the organic solvent of a polyamic acid, the diamine which has a structure in which 2 or 3 aromatic rings were connected by ester bond or ether bond is preferable.

In this invention, what is shown below is mentioned as a preferable specific example of the aromatic diamine containing at least one of an ester bond and an ether bond.

The aromatic tetracarboxylic dianhydride containing at least one of an ester bond and an ether bond contains either an ester bond or an ether bond in its molecule, or contains both of these.

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 by an ester bond or an ether bond. As a specific example of the said aromatic ring, the thing similar to the above is mentioned. Especially, from a viewpoint of ensuring the solubility to the organic solvent of a polyamic acid, it is preferable to have a structure in which 3 or 4 aromatic rings were connected by the ester bond or an ether bond.

In this invention, what is shown below is mentioned as a preferable specific example of the aromatic tetracarboxylic dianhydride containing at least one of an ester bond and an ether bond.

In this invention, with the aromatic diamine containing at least one of the above-mentioned ester bond and an ether bond, other diamines can be used.

The diamine may be either an aliphatic diamine or an aromatic diamine, but an aromatic diamine containing neither an ester bond nor an ether bond is preferable from the viewpoint of ensuring the strength and heat resistance of the resulting thin film.

Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine) , 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylene Diamine, 2,6-dimethyl-p-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylene Diamine, m-xylylenediamine, p-xylylenediamine, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5 -diamine containing one benzene nucleus, such as -bis(trifluoromethyl)benzene-1,2-diamine; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine, 1,7-naphthalenediamine, 1, 8-naphthalenediamine, 2,3-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-biphenyl diamine, 2,2'-bis(trifluoromethyl)-4,4'- Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2, 2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3 -Aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane , 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylsulfoxide, 3,4'-diamino Diphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 3,3'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 3,3',5,5'- diamines containing two benzene nuclei, such as tetrafluorobiphenyl-4,4'-diamine and 4,4'-diaminooctafluorobiphenyl; 1,5-diaminoanthracene, 2,6-diaminoanthracene, 9,10-diaminoanthracene, 1,8-diaminophenanthrene, 2,7-diaminophenanthrene, 3,6-diaminophenanthrene , 9,10-diaminophenanthrene, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1 ,4-bis(4-aminophenyl)benzene, 1,3-bis(3-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenyl) Sulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)benzene, 1,3- Bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl ] Although the diamine containing three benzene nuclei, such as benzene, etc. are mentioned, It is not limited to these. These can also be used individually by 1 type or in combination of 2 or more type.

In the present invention, when a diamine other than that is used together with an aromatic diamine containing at least one of an ester bond and an ether bond, the amount of the aromatic diamine containing at least one of an ester bond and an ether bond is used in the total diamine. It is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol% or more. By employing such an amount, it is possible to obtain a film having excellent adhesion to the substrate and suitable adhesion to the resin substrate and suitable peelability with good reproducibility.

In this invention, together with the aromatic tetracarboxylic dianhydride containing at least one of the above-mentioned ester bond and an ether bond, tetracarboxylic dianhydride other than that can be used.

The tetracarboxylic dianhydride may be either an aliphatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride. An aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond, from the viewpoint of ensuring the strength and heat resistance of the resulting thin film. This is preferable.

Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, and naphthalene-1,2,5,6-tetra. Carboxylic acid dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene-2,3,5,6-tetracarboxylic dianhydride, naphthalene -2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, biphenyl-2,2',3,3'-tetracarboxylic dianhydride, biphenyl- 2,3,3',4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, anthracene-1,2,3,4-tetracarboxylic dianhydride, anthracene- 1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2,6,7-tetracarboxylic dianhydride, anthracene-1,2,7,8-tetracarboxylic dianhydride, anthracene-2,3,6 ,7-tetracarboxylic dianhydride, phenanthrene-1,2,3,4-tetracarboxylic dianhydride, phenanthrene-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-tetra Carboxylic acid dianhydride, phenanthrene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-2,3,9,10-tetracarboxylic dianhydride, phenanthrene-3,4,5,6-tetracarboxylic dianhydride Although water, phenanthrene-3,4,9,10-tetracarboxylic dianhydride, etc. are mentioned, It is not limited to these. These can also be used individually by 1 type or in combination of 2 or more type.

In particular, as the aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond, from the viewpoint of ensuring heat resistance, at least one selected from the group consisting of formulas (C1) to (C12) is preferable, and the formula (C1 ) and at least one selected from the group consisting of formula (C9) is more preferable.

In the present invention, when a tetracarboxylic dianhydride other than that is used together with an aromatic tetracarboxylic dianhydride containing at least one of an ester bond and an ether bond, an aromatic tetracarboxylic acid containing at least one of an ester bond and an ether bond The amount of the dianhydride used is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol% or more in the total tetracarboxylic dianhydride. By employing such an amount, it is possible to obtain a film having sufficient adhesion to the substrate, adequate adhesion to the resin substrate, and adequate releasability, with good reproducibility.

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

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

In particular, since the organic solvent used for the reaction dissolves diamine and tetracarboxylic dianhydride and polyamic acid well, the amides represented by the formula (S1), the amides represented by the (S2), and the amides represented by the formula (S3) At least one selected from amides is preferable.

In the formula, R ¹ and R ² each 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. Although h represents a natural number, Preferably it is 1-3, More preferably, it is 1 or 2.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned. Among these, a C1-C3 alkyl group is preferable, and a C1-C2 alkyl group is more preferable.

The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C. In order to prevent imidization in the solution of the resulting polyamic acid and maintain a high content of the polyamic acid unit, it is preferable Preferably it is about 0-70 degreeC, More preferably, it is about 0-60 degreeC, More preferably, it is about 0-50 degreeC.

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

By the method demonstrated above, the reaction solution containing the target polyamic acid can be obtained.

5,000-1,000,000 are preferable, as for the weight average molecular weight of the said polyamic acid, 10,000-500,000 are more preferable, and 15,000-200,000 are still more preferable from a handleability viewpoint. In addition, in the present invention, the weight average molecular weight is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (GPC) analysis.

In the present invention, after filtering the reaction solution, the filtrate as it is or a solution obtained by diluting or concentrating can be used as the composition for forming a release layer of the present invention. By doing in this way, not only can mixing of impurities which may cause deterioration of adhesiveness, peelability, etc. of the peeling layer obtained by doing this be reduced, but the composition for peeling layer formation can be obtained efficiently. Moreover, after isolating a polyamic acid from the said reaction solution, it is good also as a composition for peeling layer formation by melt|dissolving in a solvent again. As a solvent in this case, the organic solvent etc. used for the reaction mentioned above are mentioned.

The solvent used for dilution is not specifically limited, The thing similar to the specific example of the reaction solvent of the said reaction is mentioned as the specific example. The solvent used for dilution may be used individually by 1 type or in combination of 2 or more type. Among them, since it dissolves polyamic acid well, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone Dinone, N-ethyl-2-pyrrolidone and γ-butyrolactone are preferable, and N-methyl-2-pyrrolidone is more preferable.

Moreover, even if it is a solvent which does not melt|dissolve a polyamic acid independently, if it is a range in which a polyamic acid does not precipitate, it can mix with the composition for peeling layer formation of this invention. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1- Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol -1-Monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. A solvent having a low surface tension of Thereby, it is known that the uniformity of a coating film improves at the time of application|coating to a board|substrate, and it uses also suitably also with the composition for peeling layer formation of this invention.

The concentration of the polyamic acid in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, etc., but is usually about 1 to 30 mass%, preferably 1 to 20 mass % is about By setting it as such a density|concentration, the peeling layer with a thickness of about 0.05-5 micrometers can be obtained with good reproducibility. In addition, the concentration of the polyamic acid is adjusted when the amount of diamine and tetracarboxylic dianhydride, which are raw materials of the polyamic acid, is adjusted, the filtrate is diluted or concentrated after filtering the reaction solution, or the isolated polyamic acid is dissolved in a solvent. It can be adjusted by adjusting the amount, etc.

In addition, although the viscosity of the composition for forming a release layer is appropriately set in consideration of the thickness of the release layer to be produced, in particular, when the purpose of obtaining a film having a thickness of about 0.05 to 5 µm with good reproducibility is usually 10 to at 25°C. It is about 10,000 mPa*s, Preferably it is about 20-5,000 mPa*s. Here, the viscosity can be measured using a commercially available viscometer for measuring the viscosity of a liquid, for example, referring to the procedure described in JIS K7117-2, under the condition of a temperature of 25°C of the composition. Preferably, a cone plate type (cone plate type) rotational viscometer is used as the viscometer, and 1°34'×R24 is used as a standard cone rotor in a viscometer of the same type, and the composition temperature is 25°C. can As such a rotational viscometer, TVE-25L manufactured by Toki Sangyo Co., Ltd. is mentioned, for example.

In addition to the polyamic acid and the organic solvent, the composition for forming a release layer according to the present invention may contain components such as a crosslinking agent in order to improve film strength, for example.

A polyimide having excellent adhesion to the substrate and suitable adhesion to the resin substrate and suitable peelability by applying the release layer-forming composition of the present invention described above to a substrate, heating the obtained coating film to thermally imidize the polyamic acid. A release layer made of a film can be obtained.

When the 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 on the entire surface. As an aspect of forming the release layer on a part of the surface of the substrate, the release layer is formed only in a predetermined range on the surface of the substrate, and the release layer is formed on the entire surface of the substrate in a pattern shape such as a dot pattern, a line and space pattern, etc. There is this. In addition, in the present invention, the substrate means that the composition for forming a release layer according to the present invention is applied to the surface thereof, and is used for manufacturing a flexible electronic device or the like.

As the substrate (substrate), for example, glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene-based resin, etc.), metal (silicone) wafer, etc.), wood, paper, slate, etc. are mentioned, In particular, the release layer obtained from the composition for forming a release layer according to the present invention has sufficient adhesiveness to it, and glass is preferable. In addition, the base|substrate surface may be comprised from a single material, and may be comprised from two or more materials. As an aspect in which the surface of the base body is composed of two or more materials, an aspect in which a certain range of the base surface is composed of a certain material and the remaining surface is composed of other materials, a dot pattern, a line and space pattern, etc. There are aspects such as a pattern in which a certain material is present among other materials in the shape of a pattern.

The coating method is not particularly limited, but for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, a printing method (iron plate, intaglio , flat plate, screen printing, etc.) and the like.

The heating temperature for imidization is usually appropriately determined within the range of 50 to 550°C, but is preferably 200°C or higher, and preferably 500°C or lower. By setting the heating temperature in this way, it becomes possible to sufficiently advance the imidization reaction while preventing the resulting film from becoming brittle. Since the heating time varies depending on the heating temperature, it cannot be defined uniformly, but is usually 5 minutes to 5 hours. In addition, the imidation ratio should just be in the range of 50 to 100%.

As a preferred example of the heating mode in the present invention, after heating at 50 to 100° C. for 5 minutes to 2 hours, the heating temperature is raised stepwise as it is, and finally heating to over 375° C. to 450° C. for 30 minutes to 4 hours. can be heard In particular, after heating at 50 to 100° C. for 5 minutes to 2 hours, heating is preferably performed at over 100° C. to 375° C. for 5 minutes to 2 hours, and finally at over 375° C. to 450° C. for 30 minutes to 4 hours.

As a mechanism used for heating, a hot plate, an oven, etc. are mentioned, for example. The heating atmosphere may be air or inert gas, and may be under normal pressure or under reduced pressure.

The thickness of the release layer is usually about 0.01 to 50 µm, from the viewpoint of productivity, preferably about 0.05 to 20 µm, more preferably about 0.05 to 5 µm, and the desired thickness is achieved by adjusting the thickness of the coating film before heating. .

The release layer described above has excellent adhesion to the substrate, particularly glass, and moderate adhesion to the resin substrate and moderate peelability. Therefore, in the manufacturing process of a flexible electronic device, the release layer according to the present invention does not damage the resin substrate of the device, and the resin substrate, together with the circuit formed on the resin substrate, is released from the base. can be used appropriately for

Hereinafter, an example of the manufacturing method of the flexible electronic device using the peeling layer of this invention is demonstrated.

Using the composition for forming a release layer according to the present invention, a release layer is formed on the glass substrate by the method described above. On this release layer, a resin solution for forming a resin substrate is applied, and the coating film is heated to form a resin substrate fixed to a glass substrate through the release layer according to the present invention. At this time, the resin substrate is formed with an area larger than the area of the release layer so as to cover all of the release layer. As said resin substrate, the resin substrate etc. which consist of a polyimide typical as a resin substrate of a flexible electronic device are mentioned, As a resin solution for forming it, a polyimide solution and a polyamic acid solution are mentioned. What is necessary is just to follow a conventional method for the formation method of the said resin substrate.

Next, a desired circuit is formed on the resin substrate fixed to the base through the release layer according to the present invention, and then, for example, the resin substrate is cut along the release layer, and the resin substrate is peeled off together with the circuit. It peels from a layer, and isolate|separates a resin substrate and a base|substrate. At this time, you may cut off a part of base|substrate together with a peeling layer.

On the other hand, in the manufacture of flexible displays, it is possible to appropriately peel a polymer substrate from a glass carrier using the laser lift-off method (LLO method), which has been used in the manufacture of high-brightness LEDs and three-dimensional semiconductor packages, etc. It has been reported (Japanese Patent Laid-Open No. 2013-147599). In the manufacture of a flexible display, it is necessary to install a polymer substrate made of polyimide or the like on a glass carrier, then to form a circuit including electrodes and the like on the substrate, and finally to peel the substrate together with the circuit from the glass carrier. there is In this peeling step, the LLO method is employed, that is, when a light beam having a wavelength of 308 nm is irradiated to a glass carrier from the surface opposite to the surface on which a circuit or the like is formed, the light beam of the wavelength is transmitted through the glass carrier, Only the polymer (polyimide) absorbs this light and evaporates (sublimes) it. As a result, it is reported that the peeling of the substrate from the glass carrier is selectively feasible without affecting the circuitry installed on the substrate, etc., which determines the performance of the display.

A desired circuit is formed on the resin substrate fixed to the base through the release layer according to the present invention, and then, if the LLO method is employed, only the release layer absorbs this light and evaporates (sublimes). That is, this release layer becomes sacrificial (acting as a sacrificial layer), making it possible to selectively perform peeling of the substrate from the glass carrier. Since the composition for forming a release layer of the present invention has the characteristic of sufficiently absorbing light of a specific wavelength (eg, 308 nm) to which the LLO method can be applied, it can be used as a sacrificial layer for the LLO method.

Example

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Comparative Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, the abbreviation of the compound used in the following example, and the measuring method of a number average molecular weight and weight average molecular weight are as follows.

<Abbreviation of compound>

p-PDA: p-phenylenediamine

m-PDA: m-phenylenediamine

DATP: 4,4'''-diamino-p-terphenyl

DBA: 3,5-diaminobenzoic acid

HAB: 3,3'-dihydroxybenzidine

DDE: 4,4'-oxydianiline

BAPB: 4,4'-bis(4-aminophenoxy)biphenyl

FAPB: 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl

APAB: 5-amino-2-(4-aminophenyl)-1H-benzoimidazole

APAB-E: 4-Aminophenyl-4'-aminobenzoate

6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

TFMB: 2,2'-bis(trifluoromethyl)biphenyl-4,4'-diamine

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

TAHQ: p-phenylenebis (trimellitic acid monoester anhydride)

PMDA: pyromellitic dianhydride

BPTME: p-biphenylenebis (trimellitic acid monoester anhydride)

BPODA: 4,4'-(biphenyl-4,4'-biylbisoxy)bisphthalic dianhydride

CF3-BP-TMA: N,N'-[2,2'-bis(trifluoromethyl)biphenyl-4,4'-diyl]bis(1,3-dioxo-1,3-dihydro isobenzofuran-5-carbamide)

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

IPBBT: N,N'-isophthalbis(benzooxazoline-2-thion)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

<Measurement of weight average molecular weight and molecular weight distribution>

The measurement of the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polymer was performed using a Nippon Bunko Co., Ltd. GPC apparatus (Column: Showa Denko Co., Ltd. OHpak SB803-HQ and OHpak SB804-HQ; Eluent: Die Methylformamide/LiBr·H ₂ O (29.6 mM)/H ₃ PO ₄ (29.6 mM)/THF (0.1 mass %); Flow rate: 1.0 mL/min; Column temperature: 40° C.; Mw: Standard polystyrene conversion value) was used (in the following Examples and Comparative Examples, the same).

[1] Synthesis of polymers

A polyamic acid and a polybenzoxazole precursor were synthesize|combined with the following method.

In addition, a composition for forming a resin substrate or a composition for forming a release layer was prepared by diluting the reaction solution as described later without isolating the polymer from the obtained polymer-containing reaction solution.

[Synthesis Example S1] Synthesis of polyamic acid S1

20.261 g (187 mmol) of p-PDA and 12.206 g (47 mmol) of DATP were dissolved in 617.4 g of NMP. The obtained solution was cooled at 15 degreeC, PMDA 50.112g (230 mmol) was added there, it heated up to 50 degreeC in nitrogen atmosphere, it was made to react for 48 hours, and polyamic acid S1 was obtained. Mw of polyamic acid S1 was 82,100, and Mw/Mn was 2.7.

[Synthesis Example S2] Synthesis of polyamic acid S2

3.218 g (30 mmol) of p-PDA was dissolved in 88.2 g of NMP. 8.581 g (29 mmol) of BPDA was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid S2 was obtained. Mw of polyamic acid S2 was 107,300, and Mw/Mn was 4.6.

[Synthesis Example S3] Synthesis of polyamic acid S3

17.8 g (56 mmol) of TFMB, 0.4 g (1 mmol) of BAPB and 2.5 g (23 mmol) of p-PDA were dissolved in 430 g of NMP. 6FDA 6.3g (14mmol) and CF3-BP-TMA 42.8g (64mmol) were added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid S3 was obtained. Mw of polyamic acid S3 was 38,700, and Mw/Mn was 2.1.

[Synthesis Example S4] Synthesis of polyamic acid S4

30.6 g (153 mmol) of DDE was dissolved in 440 g of NMP. 29.4 g (150 mmol) of CBDA was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid S4 was obtained. Mw of polyamic acid S4 was 29,800, and Mw/Mn was 2.2.

[Synthesis Example L1] Synthesis of polyamic acid L1

2.054 g (19 mmol) of p-PDA was dissolved in 88 g of NMP. 9.946 g (19 mmol) of BPTME was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L1 was obtained. Mw of polyamic acid L1 was 57,500, and Mw/Mn was 3.0.

[Synthesis Example L2] Synthesis of polyamic acid L2

1.836 g (17 mmol) of p-PDA and 0.287 g (1.9 mmol) of DBA were dissolved in 88 g of NMP. BPTME 9.878 g (18 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L2 was obtained. Mw of polyamic acid L2 was 65,100, and Mw/Mn was 3.0.

[Synthesis Example L3] Synthesis of polyamic acid L3

1.367 g (13 mmol) of p-PDA and 1.172 g (5.4 mmol) of HAB were dissolved in 88 g of NMP. BPTME 9.461 g (18 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L3 was obtained. Mw of polyamic acid L3 was 43,600 and Mw/Mn 2.6.

[Synthesis Example L4] Synthesis of polyamic acid L4

3.984 g (15 mmol) of DATP was dissolved in 88 g of NMP. BPTME 8.016g (15 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L4 was obtained. Mw of polyamic acid L4 was 42,600, and Mw/Mn was 3.9.

[Synthesis Example L5] Synthesis of polyamic acid L5

5.17 g (14 mmol) of BAPB was dissolved in 88 g of NMP. BPTME 6.83 g (13 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L5 was obtained. Mw of polyamic acid L5 was 52,100, and Mw/Mn was 2.7.

[Synthesis Example L6] Synthesis of polyamic acid L6

5.89 g (12 mmol) of FAPB was dissolved in 88 g of NMP. BPTME 6.11 g (11 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L6 was obtained. Mw of polyamic acid L6 was 87,700, and Mw/Mn was 3.3.

[Synthesis Example L7] Synthesis of polyamic acid L7

3.60 g (16 mmol) of APAB was dissolved in 88 g of NMP. BPTME 8.40 g (16 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L7 was obtained. Mw of polyamic acid L7 was 58,300, and Mw/Mn was 2.8.

[Synthesis Example L8] Synthesis of polyamic acid L8

2.322 g (12 mmol) of DDE was dissolved in 35.2 g of NMP. 2.478 g (11 mmol) of PMDA was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L8 was obtained. Mw of polyamic acid L8 was 22,600, and Mw/Mn was 2.1.

[Synthesis Example L9] Synthesis of polyamic acid L9

1.762 g (7 mmol) of DATP was dissolved in 35.2 g of NMP. 3.038 g (7 mmol) of TAHQ was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L9 was obtained. Mw of polyamic acid L9 was 61,300, and Mw/Mn was 3.3.

[Synthesis Example L10] Synthesis of polyamic acid L10

0.899 g (8 mmol) of p-PDA was dissolved in 35.2 g of NMP. BPODA 3.900 g (8 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L10 was obtained. Mw of polyamic acid L10 was 17,300, and Mw/Mn was 2.4.

[Synthesis Example L11] Synthesis of polyamic acid L11

1.713 g (7 mmol) of DATP was dissolved in 35.2 g of NMP. BPODA 3.086g (6 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L11 was obtained. Mw of polyamic acid L11 was 27,000, and Mw/Mn was 2.4.

[Synthesis Example L12] Synthesis of polyamic acid L12

0.931 g (9 mmol) of p-PDA was dissolved in 35.2 g of NMP. 3.868 g (8 mmol) of TAHQ was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L12 was obtained. Mw of polyamic acid L12 was 45,000, and Mw/Mn was 2.7.

[Synthesis Example L13] Synthesis of polyamic acid L13

0.839 g (8 mmol) of p-PDA and 0.093 g (1 mmol) of m-PDA were dissolved in 35.2 g of NMP. 3.868 g (8 mmol) of TAHQ was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L13 was obtained. Mw of polyamic acid L13 was 39,100, and Mw/Mn was 2.6.

[Synthesis Example L14] Synthesis of polyamic acid L14

0.652 g (6 mmol) of p-PDA and 0.280 g (3 mmol) of m-PDA were dissolved in 35.2 g of NMP. 3.868 g (8 mmol) of TAHQ was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L14 was obtained. Mw of polyamic acid L14 was 42,700, and Mw/Mn was 2.6.

[Synthesis Example L15] Synthesis of polyamic acid L15

0.931 g (9 mmol) of m-PDA was dissolved in 35.2 g of NMP. 3.868 g (8 mmol) of TAHQ was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L15 was obtained. Mw of polyamic acid L15 was 36,100, and Mw/Mn was 2.5.

[Synthesis Example L16] Synthesis of polyamic acid L16

0.816 g (8 mmol) of p-PDA and 0.218 g (1 mmol) of DATP were dissolved in 35.2 g of NMP. 3.765 g (8 mmol) of TAHQ was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L16 was obtained. Mw of polyamic acid L16 was 43,800, and Mw/Mn was 2.5.

[Synthesis Example L17] Synthesis of polyamic acid L17

0.603 g (6 mmol) of p-PDA and 0.622 g (2 mmol) of DATP were dissolved in 35.2 g of NMP. 3.575 g (8 mmol) of TAHQ was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L17 was obtained. Mw of polyamic acid L17 was 46,000, and Mw/Mn was 2.6.

[Synthesis Example L18] Synthesis of polyamic acid L18

0.832 g (8 mmol) of p-PDA and 0.130 g (1 mmol) of DBA were dissolved in 35.2 g of NMP. TAHQ 3.838g (8 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L18 was obtained. Mw of polyamic acid L18 was 57,000, and Mw/Mn was 3.0.

[Synthesis Example L19] Synthesis of polyamic acid L19

0.822 g (8 mmol) of p-PDA and 0.183 g (1 mmol) of HAB were dissolved in 35.2 g of NMP. TAHQ 3.794g (8 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L19 was obtained. Mw of polyamic acid L19 was 54,200, and Mw/Mn was 2.7.

[Synthesis Example L20] Synthesis of polyamic acid L20

0.616 g (6 mmol) of p-PDA and 0.528 g (2 mmol) of HAB were dissolved in 35.2 g of NMP. 3.655 g (8 mmol) of TAHQ was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L20 was obtained. Mw of polyamic acid L20 was 55,900, and Mw/Mn was 2.6.

[Synthesis Example L21] Synthesis of polyamic acid L21

1.239 g (5 mmol) of APAB-E was dissolved in 17.6 g of NMP. 1.160 g (5 mmol) of PMDA was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L21 was obtained. Mw of polyamic acid L21 was 20,900, and Mw/Mn was 2.1.

[Synthesis Example L22] Synthesis of polyamic acid L22

1.060 g (5 mmol) of APAB-E was dissolved in 17.6 g of NMP. BPDA 1.339 g (5 mmol) was added to the obtained solution, it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours, and polyamic acid L22 was obtained. Mw of polyamic acid L22 was 26,600, and Mw/Mn was 2.3.

[Comparative Synthesis Example 1] Synthesis of polybenzoxazole precursor B1

5.49 g (0.015 mol) of 6FAP was dissolved in 27 g of NMP. 6.48 g (0.015 mol) of IPBBT was added to the obtained solution, and it was made to react at 23 degreeC in nitrogen atmosphere for 3 hours. Then, this solution was thrown into 300 g of pure water, and the precipitate was filtered after stirring for 24 hours. Then, it dried under reduced pressure and obtained polybenzoxazole precursor B1. Mw of polybenzoxazole precursor B1 was 2,1000, and Mw/Mn was 3.9.

[2] Preparation of a composition for forming a resin substrate

The reaction liquids obtained in Synthesis Examples S1 to S4 were used as compositions W, X, Y and Z for resin substrate formation as they were, respectively.

[3] Preparation of a composition for forming a release layer

[Example 1-1]

BCS was added to the reaction solution obtained in Synthesis Example L1, and the mixture was diluted with NMP so that the polymer concentration was 5% by mass and BCS was 20% by mass to obtain a composition for forming a release layer.

[Examples 1-2 to 1-22]

A composition for forming a release layer was obtained in the same manner as in Example 1-1 except that the reaction solution obtained in Synthesis Examples L2 to L22 was used instead of the reaction solution obtained in Synthesis Example L1.

[Comparative Example 1]

The reaction solution obtained in Comparative Synthesis Example 1 was diluted with NMP so that the polymer concentration was 5% by mass to obtain a composition.

[4] Formation of release layer and evaluation thereof

[Example 2-1]

Using a spin coater (condition: rotation speed of about 30 seconds at 3000 rpm), the composition for forming a release layer obtained in Example 1-1 was applied as a glass substrate onto a 100 mm×100 mm glass substrate (the same hereinafter).

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), 400 It was further heated at 占폚 for 30 minutes to form a release layer having a thickness of about 0.1 占퐉 on the glass substrate. In addition, during the temperature increase, the film-attached substrate was heated in the oven without taking it out of the oven.

[Examples 2-2-2 to 2-22]

The release layer was prepared in the same manner as in Example 2-1 except that the composition for forming a release layer obtained in Examples 1-2 to 1-22 was used instead of the composition for forming a release layer obtained in Example 1-1. formed

[Example 2-23]

Using a spin coater (condition: about 30 seconds at 3000 rpm of rotation), the composition for forming a release layer obtained in Examples 1-12 was applied onto a 100 mm×100 mm glass substrate.

Then, the obtained coating film was heated at 80° C. for 10 minutes using a hot plate, then heated to 140° C. for 30 minutes using an oven, and the heating temperature was raised to 250° C. (2° C./min), 250 It further heated at ℃ for 60 minutes to form a release layer with a thickness of about 0.1 μm on the glass substrate. In addition, during the temperature increase, the film-attached substrate was heated in the oven without taking it out of the oven.

[Example 2-24]

Using a spin coater (condition: rotation speed of about 30 seconds at 3000 rpm), the composition for forming a release layer obtained in Example 1-8 was applied onto a 100 mm x 100 mm glass substrate 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 in a nitrogen atmosphere, and the heating temperature was raised to 400° C. (10° C./min). , further heated at 400° C. for 60 minutes, and finally heated at 500° C. for 10 minutes to form a release layer with a thickness of about 0.1 μm on the glass substrate. In addition, during the temperature increase, the film-attached substrate was heated in the oven without taking it out of the oven.

[Example 2-25]

A resin thin film was formed in the same manner as in Example 2-24 except that the composition obtained in Example 1-12 was used instead of the composition for forming a release layer obtained in Example 1-8.

[Comparative Example 2]

A resin thin film was formed in the same manner as in Example 2-1 except that the composition obtained in Comparative Example 1 was used instead of the composition for forming a release layer obtained in Example 1-1.

[5] Evaluation of peelability

[Examples 3-1 to 3-47, Comparative Example 3]

The peelability of the peeling layer and the glass substrate obtained in Examples 2-1 to 2-25, and the peelability of the said peeling layer (resin thin film) and a resin substrate were confirmed. In addition, as a resin substrate, the resin substrate which consists of polyimide was used.

First, a cross cut of the release layer on a glass substrate with a release layer obtained in Examples 2-1 to 2-25 (1 mm in length and width, the same hereinafter) and a cross between a resin substrate and a release layer on a glass substrate with a release layer and a resin substrate By performing the cut, 100 grid cells were cut. That is, 100 grid cells of 1 mm square were formed by this cross cut.

And the adhesive tape was affixed on this 100-mass cut part, the tape was peeled, and the degree of peeling was evaluated based on the following criteria (5B-0B, B, A, AA) (Examples 3-1 - 3) -47). Moreover, according to the said method, the same test was done using the glass substrate with a resin thin film obtained in the comparative example 2 (comparative example 3). A result is shown in Table 1. In addition, the evaluation criteria of peelability in Table 1 are as follows.

5B: 0% peeling (no peeling)

4B: less than 5% peeling

3B: 5-15% peeling

2B: peeling less than 15-35%

1B: less than 35-65% 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)

The resin substrates of Examples 3-1 to 3-41, 3-44 to 3-47 and Comparative Example 3 were formed by the following method.

Either the composition W or X for resin substrate formation was apply|coated on the peeling layer (resin thin film) on a glass substrate using the bar coater (gap: 250 micrometers). Then, the obtained coating film was heated at 80 ° C. for 10 minutes using a hot plate, and then heated to 140 ° C. for 30 minutes using an oven, and the heating temperature was raised to 210 ° C. (10 ° C./min, hereinafter the same) , 210 °C for 30 minutes, heating temperature up to 300 °C, 300 °C for 30 minutes, heating temperature up to 400 °C, heating at 400 °C for 60 minutes, polyimide substrate with a thickness of about 20 µm on the release layer has formed During the temperature increase, the film-attached substrate was heated in the oven without taking it out of the oven.

The resin substrates of Examples 3-42 to 3-43 were formed by the following method.

Either the composition Y or Z for resin substrate formation was apply|coated on the peeling layer on a glass substrate using the bar coater (gap: 50 micrometers). Then, the obtained coating film was heated at 80° C. for 10 minutes using a hot plate, and then heated to 140° C. for 30 minutes using an oven, and the heating temperature was raised to 250° C. (2° C./min), 250 It was heated at 占폚 for 60 minutes to form a polyimide substrate having a thickness of about 0.8 占퐉 on the release layer. During the temperature increase, the film-attached substrate was heated in the oven without taking it out of the oven.

As shown in Tables 1 and 2, it turned out that the peeling layer of an Example was excellent in adhesiveness with a glass substrate, and was excellent in peelability with a resin substrate. On the other hand, the peeling layer of the comparative example did not peel from a resin substrate and a glass substrate, but did not function as a peeling layer.

[6] Evaluation of transmittance

[Example 4]

Using a spin coater (condition: rotation speed of 800 rpm for about 30 seconds), the composition for forming a release layer obtained in Example 2-8 was applied as a glass substrate onto a 100 mm×100 mm glass substrate (the same as below).

Then, the obtained coating film was heated at 80° C. for 10 minutes using a hot plate, then heated at 300° C. for 30 minutes using an oven, the heating temperature was raised to 400° C. (10° C./min), and 400° C. By further heating with a furnace for 30 minutes, a peeling layer with a thickness of about 0.4 µm was formed on the glass substrate. In addition, during the temperature increase, the film-attached substrate was heated in the oven without taking it out of the oven. Transmittance was measured for the obtained film using the ultraviolet-visible spectrophotometer (SIMADSU UV-2550 model number manufactured by Shimadzu Corporation).

The results are shown in FIG. 1 . The transmittance of the obtained film was 1% or less with respect to a wavelength of 308 nm, indicating transmittance usable as a sacrificial layer.

Claims (11)

A polyamic acid obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride, and an organic solvent,
The composition for forming a release layer, characterized in that the aromatic diamine comprises an aromatic diamine having an ether linkage, and/or the aromatic tetracarboxylic dianhydride comprises an aromatic tetracarboxylic acid dianhydride comprising an ether linkage. The method of claim 1,
The aromatic diamine containing the ether bond is at least one selected from the group consisting of formulas (A1) to (A3), (A7) to (A12), (A25) to (A33), and (A40) to (A42). A composition for forming a release layer, characterized in that.

The method of claim 1,
Exfoliation characterized in that the aromatic tetracarboxylic dianhydride containing an ether bond is at least one selected from the group consisting of formulas (B3), (B4), (B8) to (B10) and (B12) to (B14). A composition for forming a layer.

The method of claim 1,
The composition for forming a release layer, wherein the aromatic tetracarboxylic dianhydride further comprises an aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond. 5. The method of claim 4,
The composition for forming a release layer, characterized in that the aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond contains a benzene skeleton, a naphthyl skeleton, or a biphenyl skeleton. 6. The method of claim 5,
The composition for forming a release layer, wherein the aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond is at least one selected from the group consisting of formulas (C1) to (C12).

The method of claim 1,
The organic solvent for forming a release layer, characterized in that it contains at least one selected from the amides represented by the formula (S1), the amides represented by the formula (S2), and the amides represented by the formula (S3) composition.

(Wherein, R ¹ and R ² each 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. h represents a natural number.) A release layer formed using the composition for forming a release layer according to claim 1 . The manufacturing method of the flexible electronic device provided with the resin substrate characterized by using the peeling layer of Claim 8. The manufacturing method of the touch panel sensor provided with the resin substrate characterized by using the peeling layer of Claim 8. 11. The method according to claim 9 or 10,
The manufacturing method characterized in that the said resin substrate is a board|substrate which consists of polyimide.

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