JP2020019960A - Composition for formation of release layer - Google Patents

Abstract

To provide a composition for the formation of a release layer for peeling without giving any damage to a resin substrate of a flexible electronic device.SOLUTION: The composition for the formation of a release layer includes a polyamic acid produced by reacting an aromatic diamine with an aromatic tetracarboxylic acid dianhydride and an organic solvent. The aromatic diamine includes an aromatic diamine including an ether bond and/or the aromatic tetracarboxylic acid dianhydride includes an aromatic tetracarboxylic acid dianhydride including an ether bond.SELECTED DRAWING: None

Description

  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 provided on a substrate.

  2. Description of the Related Art In recent years, electronic devices have been required to have functions such as imparting a function of bending and reducing the thickness and weight. For this reason, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy and fragile glass substrate which cannot be bent. In the new generation display, there is a demand for the development of an active full-color TFT display panel using a lightweight flexible plastic substrate. Therefore, various methods for manufacturing an electronic device using a resin film as a substrate have begun to be studied, and for a new generation display, a manufacturing study is being conducted by a process that can use existing TFT equipment.

  Patent Documents 1, 2, and 3 disclose that an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side to accompany crystallization of the amorphous silicon. A method for separating a plastic substrate from a glass substrate with generated hydrogen gas is disclosed. In Patent Document 4, a layer to be peeled (described as “transferred layer” in Patent Document 4) is attached to a plastic film using the techniques disclosed in Patent Documents 1 to 3, thereby completing a liquid crystal display device. A method is disclosed.

  However, the methods disclosed in Patent Documents 1 to 4, particularly the method disclosed in Patent Document 4, require the use of a substrate having high translucency. Irradiation with a relatively large laser beam is required to give sufficient energy to release the contained hydrogen, which causes a problem that the layer to be peeled is damaged. In addition, since laser treatment requires a long time and it is difficult to remove a layer to be separated having a large area, there is also a problem that it is difficult to increase the productivity of device fabrication.

JP-A-10-125929 JP-A-10-125931 International Publication No. 2005/050754 JP-A-10-125930

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

  The present inventors have conducted intensive studies to solve the above-described problems, and as a result, a polyamic acid obtained by reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride, and a composition containing 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 at least one of an ester bond and an ether bond. In the case of containing an anhydride, it is possible to obtain a composition capable of forming a release layer having excellent adhesion to a substrate and appropriate adhesion to a resin substrate used as a flexible electronic device and appropriate release properties. Heading, the present invention has been completed.

３．前記エーテル結合を含む芳香族テトラカルボン酸二無水物が、式（Ｂ３）、（Ｂ４）、（Ｂ８）〜（Ｂ１０）及び（Ｂ１２）〜（Ｂ１４）からなる群から選ばれる少なくとも１種である１又は２の剥離層形成用組成物。

４．前記芳香族テトラカルボン酸二無水物が、更にエステル結合及びエーテル結合のいずれも含まない芳香族テトラカルボン酸二無水物を含む１又は２の剥離層形成用組成物。
５．前記エステル結合及びエーテル結合のいずれも含まない芳香族テトラカルボン酸二無水物が、ベンゼン骨格、ナフチル骨格又はビフェニル骨格を含むものである４の剥離層形成用組成物。
６．前記エステル結合及びエーテル結合のいずれも含まない芳香族テトラカルボン酸二無水物が、式（Ｃ１）〜（Ｃ１２）からなる群から選ばれる少なくとも１種である５の剥離層形成用組成物。

７．前記有機溶媒が、式（Ｓ１）で表されるアミド類、式（Ｓ２）で表されるアミド類及び式（Ｓ３）で表されるアミド類から選ばれる少なくとも１つを含む１又は２の剥離層形成用組成物。

（式中、Ｒ¹及びＲ²は、互いに独立して、炭素数１〜１０のアルキル基を表す。Ｒ³は、水素原子、又は炭素数１〜１０のアルキル基を表す。ｈは、自然数を表す。）
８．１〜７のいずれかの剥離層形成用組成物を用いて形成される剥離層。
９．８の剥離層を用いることを特徴とする、樹脂基板を備えるフレキシブル電子デバイスの製造方法。
１０．８の剥離層を用いることを特徴とする、樹脂基板を備えるタッチパネルセンサーの製造方法。
１１．前記樹脂基板が、ポリイミドからなる基板である９又は１０の製造方法。 That is, the present invention provides the following composition for forming a release layer.
1. Including a polyamic acid obtained by reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride, and an organic solvent,
The peeling-off, wherein the aromatic diamine contains an aromatic diamine containing an ether bond, and / or the aromatic tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride containing an ether bond. Composition for forming a layer.
2. The aromatic diamine containing an 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). 1. A composition for forming a release layer, which is a seed.

3. 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). The composition for forming a release layer according to 1 or 2.

4. The composition for forming a release layer according to 1 or 2, wherein the aromatic tetracarboxylic dianhydride further contains an aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond.
5. 4. 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. 5. 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. 1 or 2 peeling wherein the organic solvent 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 for forming a layer.

(Wherein, 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. H is a natural number. Represents.)
A release layer formed using the composition for forming a release layer according to any one of 8.1 to 7.
9.8. A method for manufacturing a flexible electronic device having a resin substrate, comprising using the release layer of 9.8.
A method for manufacturing a touch panel sensor having a resin substrate, comprising using a release layer of 10.8.
11. The method according to 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, a film having excellent adhesion to a substrate, appropriate adhesion to a resin substrate, and appropriate release properties can be obtained with good reproducibility. By using the composition of the present invention, in the process of manufacturing a flexible electronic device, the resin substrate formed on the base and the resin substrate together with the circuit and the like are not damaged without damaging the circuit and the like provided thereon. Can be separated from the substrate. Therefore, the composition for forming a release layer of the present invention can contribute to simplification of a manufacturing process of a flexible electronic device having a resin substrate, improvement of the yield, and the like.

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

Hereinafter, the present invention will be described in more detail.
The composition for forming a release layer of the present invention comprises a polyamic acid obtained by reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride, and an organic solvent, wherein the aromatic diamine is an ester. An aromatic diamine containing at least one of a 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. . Here, the release layer in the present invention is a layer provided immediately above a glass substrate for a predetermined purpose, and a typical example thereof is a flexible electronic device made of a resin such as polyimide in a substrate in a flexible electronic device manufacturing process. It is provided between the device and the resin substrate to fix the resin substrate during a predetermined process, and after forming an electronic circuit or the like on the resin substrate, the resin substrate is easily separated from the substrate. What is provided in order to be able to do it is mentioned.

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

  Examples of such an aromatic diamine include a diamine 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. Among them, a diamine having a structure in which two or three aromatic rings are connected by an ester bond or an ether bond is preferable from the viewpoint of ensuring the solubility of the polyamic acid in an organic solvent.

  In the present invention, preferred examples of the aromatic diamine containing at least one of an ester bond and an ether bond include the following.

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

  Examples of such an aromatic tetracarboxylic dianhydride include a 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. Specific examples of the aromatic ring include the same as described above. Among them, those having a structure in which three or four aromatic rings are connected by an ester bond or an ether bond are preferable from the viewpoint of securing the solubility of the polyamic acid in an organic solvent.

  In the present invention, preferred examples of the aromatic tetracarboxylic dianhydride containing at least one of an ester bond and an ether bond include the following.

  In the present invention, other diamines can be used together with the aromatic diamine containing at least one of the ester bond and the ether bond described above.

  Such a diamine may be either an aliphatic diamine or an aromatic diamine, but is preferably an aromatic diamine containing neither an ester bond nor an ether bond from the viewpoint of securing the strength and heat resistance of the obtained thin film.

  Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), and 2,4-diamino Toluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 4,6-Trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 5-trifluoromethylbenzene-1 1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5-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′-biphenyldiamine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diamino Diphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenyl Tan, 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'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 3,3'-bis (trifluoromethyl) biphenyl-4,4'-diamine, 3,3 Diamine containing two benzene nuclei such as', 5,5'-tetrafluorobiphenyl-4,4'-diamine, 4,4'-diaminooctafluorobiphenyl; 1,5-diaminoanthracene, 2,6-diaminoanthracene , 1,10-diaminoanthracene, 1,8-diaminophenanthrene, 2,7-diaminophenanthrene, 3,6-diaminophenanthrene, 9,10-diaminophenanthrene, 1,3-bis (3-aminophenyl) benzene, 1,3 -Bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (3-aminophenylsulfide) benzene, 1,3-bis (4-aminophenylsulfide) benzene, 1,4-bis (4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4- Aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3-bis [2- (4-aminophenyl) isopropyl] benzene, And diamines having three benzene nuclei such as 1,4-bis [2- (3-aminophenyl) isopropyl] benzene and 1,4-bis [2- (4-aminophenyl) isopropyl] benzene. It is not limited to. These can be used alone or in combination of two or more.

  In the present invention, together with an aromatic diamine containing at least one of an ester bond and an ether bond, when using other diamines, the amount of the aromatic diamine containing at least one of an ester bond and an ether bond is preferably used in all diamines. Is at least 70 mol%, more preferably at least 80 mol%, still more preferably at least 90 mol%, further preferably at least 95 mol%. By employing such an amount, a film having excellent adhesion to the base, appropriate adhesion to the resin substrate, and appropriate peelability can be obtained with good reproducibility.

  In the present invention, in addition to the above-mentioned aromatic tetracarboxylic dianhydride containing at least one of an ester bond and an ether bond, other tetracarboxylic dianhydrides can be used.

  Such a tetracarboxylic dianhydride may be any of an aliphatic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride, but from the viewpoint of securing the strength and heat resistance of the obtained thin film, an ester bond is preferred. And an aromatic tetracarboxylic dianhydride containing neither ether bond nor ether bond.

  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-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene- 2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, biphenyl -2,2 ', 3,3'-tetracarboxylic dianhydride, biphenyl-2,3,3', 4'-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetra Carboxylic dianhydride, anthracene-1,2,3,4-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-tetracarboxylic dianhydride, phenanthrene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-2,3,9,10-tetracarboxylic dianhydride, phenanthrene -3,4,5,6-tetracarbo Dianhydride, although phenanthrene-3,4,9,10-tetracarboxylic dianhydride, and the like, without limitation. These can be used alone or in combination of two or more.

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

  In the present invention, when another tetracarboxylic dianhydride 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 is used. The amount of the carboxylic dianhydride to be used is preferably at least 70 mol%, more preferably at least 80 mol%, still more preferably at least 90 mol%, and still more preferably at least 95 mol%, of all the tetracarboxylic dianhydrides. It is. By adopting such an amount, a film having sufficient adhesion to the base, appropriate adhesion to the resin substrate, and appropriate peelability can be obtained with good reproducibility.

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

  The organic solvent used in 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-. Pyrrolidone, 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-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3 -Tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone and the like. In addition, you may use an organic solvent individually by 1 type or in combination of 2 or more types.

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

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. h represents a natural number, preferably 1 to 3, 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, and n- Examples include a hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Among them, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable.

  The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C. However, the imidization of the resulting polyamic acid in the solution is prevented to increase the content of polyamic acid units. In order to maintain the amount, the temperature is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.

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

  By the method described above, a reaction solution containing the desired polyamic acid can be obtained.

  The weight average molecular weight of the polyamic acid is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and still more preferably 15,000 to 200,000 from the viewpoint of handling properties. In the present invention, the weight average molecular weight is an average molecular weight obtained by gel permeation chromatography (GPC) analysis in terms of standard polystyrene.

  In the present invention, usually, a solution obtained by filtering the reaction solution and then diluting or concentrating the filtrate can be used as the composition for forming a release layer of the present invention. By doing so, it is possible not only to reduce the incorporation of impurities that may cause the deterioration of the adhesion and the releasability of the obtained release layer, but also to obtain a release layer-forming composition efficiently. Alternatively, the polyamic acid may be isolated from the reaction solution and then dissolved in a solvent again to obtain a composition for forming a release layer. Examples of the solvent in this case include the organic solvents used in the above-described reaction.

  The solvent used for the dilution is not particularly limited, and specific examples thereof include those similar to the specific examples of the reaction solvent in the above reaction. The solvent used for dilution may be used alone or in combination of two or more. Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2, which dissolve polyamic acid well. -Pyrrolidone and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred.

  Further, even if the solvent alone does not dissolve the polyamic acid, it can be mixed with the composition for forming a release layer of the present invention as long as the polyamic acid does not precipitate. Particularly, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy -2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxy Solvents having low surface tension such as propoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate and isoamyl lactate can be mixed appropriately. This is known to improve the uniformity of the coating film when applied to the substrate, and is suitably used in the composition for forming a release layer of the present 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, and the like, but is usually about 1 to 30% by mass, preferably It is about 1 to 20% by mass. With such a concentration, a release layer having a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. The concentration of the polyamic acid is adjusted by adjusting the amounts of the diamine and the tetracarboxylic dianhydride used as the raw materials of the polyamic acid, and after filtering the reaction solution, diluting or concentrating the filtrate. Can be adjusted by adjusting the amount thereof when dissolving in a solvent.

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

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

  By applying the release layer forming composition of the present invention described above to a substrate, and heating the resulting coating film to thermally imidize the polyamic acid, excellent adhesion to the substrate, and moderate to resin substrate It is possible to obtain a release layer composed of a polyimide film having excellent adhesion and appropriate release properties.

  When the release layer of the present invention is formed on a substrate, the release layer may be formed on a partial surface of the substrate or on the entire surface. As a mode of forming the release layer on a part of the surface of the substrate, a release layer is formed only in a predetermined range on the surface of the substrate, and the release layer is formed in a pattern such as a dot pattern, a line and space pattern on the entire surface of the substrate. There is a mode of forming. In the present invention, the term “substrate” refers to a substrate whose surface is coated with the composition for forming a release layer according to the present invention, and which 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, triacetylcellulose, ABS, AS, norbornene-based resin, etc.), metal (silicon wafer, etc.), Examples thereof include wood, paper, and slate, and glass is particularly preferable because a release layer obtained from the composition for forming a release layer according to the present invention has sufficient adhesion to the release layer. The substrate surface may be made of a single material, or may be made of two or more materials. As an aspect in which the substrate surface is composed of two or more materials, a certain area of the substrate surface is composed of a certain material, and the remaining surface is composed of another material. There is a mode in which a material in a pattern such as a line and space pattern is present in another material.

  The application method is not particularly limited, and examples thereof include 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 ink jet method, and a printing method (letterpress, intaglio, lithographic). , Screen printing, etc.).

  The heating temperature for imidization is appropriately determined usually within the range of 50 to 550 ° C, but is preferably 200 ° C or higher, and more preferably 500 ° C or lower. By setting the heating temperature in this manner, the imidization reaction can sufficiently proceed while preventing the obtained film from becoming brittle. The heating time cannot be specified unconditionally because it varies depending on the heating temperature, but is usually 5 minutes to 5 hours. Further, the imidation ratio may be in the range of 50 to 100%.

  As a preferable 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 increased stepwise as it is, and finally at 375 ° C. to 450 ° C. for 30 minutes to 4 hours. There is a heating method. In particular, after heating at 50 to 100 ° C for 5 minutes to 2 hours, it is preferable to heat at more than 100 ° C to 375 ° C for 5 minutes to 2 hours, and finally at more than 375 ° C to 450 ° C for 30 minutes to 4 hours.

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

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

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

Hereinafter, an example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described.
Using the composition for forming a release layer according to the present invention, a release layer is formed on a glass substrate by the method described above. On this release layer, a resin solution for forming a resin substrate is applied, and by heating this coating film, a resin substrate fixed to a glass substrate is formed via the release layer according to the present invention. . At this time, the resin substrate is formed so as to cover the entire release layer and to have an area larger than the area of the release layer. Examples of the resin substrate include a resin substrate made of polyimide as a typical resin substrate of a flexible electronic device, and examples of a resin solution for forming the same include a polyimide solution and a polyamic acid solution. The method for forming the resin substrate may be a conventional method.

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

  On the other hand, in the production of flexible displays, it has been reported that a polymer substrate can be suitably peeled from a glass carrier using a laser lift-off method (LLO method) which has been used in the production of high-brightness LEDs and three-dimensional semiconductor packages. (Japanese Patent Application Laid-Open No. 2013-147599). In the manufacture of a flexible display, a polymer substrate made of polyimide or the like is provided on a glass carrier, and a circuit including electrodes and the like is formed on the substrate, and the substrate is finally peeled off from the glass carrier together with the circuit and the like. There is a need. In this peeling step, the LLO method is adopted, that is, when a light beam having a wavelength of 308 nm is irradiated on the glass carrier from the surface opposite to the surface on which the circuit or the like is formed, the light beam having the wavelength passes through the glass carrier, Only the nearby polymer (polyimide) absorbs this light beam and evaporates (sublimates). As a result, it is reported that peeling of the substrate from the glass carrier can be selectively performed without affecting circuits and the like provided on the substrate, which determine the performance of the display.

  When a desired circuit is formed on the resin substrate fixed to the base via the release layer according to the present invention, and then the LLO method is adopted, only the release layer absorbs the light and evaporates (sublimates). ). That is, the peeling layer is sacrificed (acting as a sacrificial layer), and the peeling of the substrate from the glass carrier can be selectively performed. Since the composition for forming a release layer of the present invention has a feature of sufficiently absorbing a light beam having a specific wavelength (for example, 308 nm) to which the LLO method can be applied, it can be used as a sacrificial layer for the LLO method.

  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 a 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-benzimidazole APAB-E: 4-aminophenyl-4'-aminobenzoate 6FAP: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane TFMB: 2,2'-bis (trifluoromethyl) biphenyl-4,4'-diamineBPDA: 3,3 ', 4,4'-biphenyltetracarboxylic acid Anhydride TAHQ: p-phenylenebis (trimellitic acid monoester anhydride)
PMDA: pyromellitic dianhydride BPTME: p-biphenylene bis (trimellitic acid monoester anhydride)
BPODA: 4,4 '-(biphenyl-4,4'-diylbisoxy) bisphthalic dianhydride CF3-BP-TMA: N, N'-[2,2'-bis (trifluoromethyl) biphenyl-4 , 4'-Diyl] bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbamide)
6FDA: 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride IPBBT: N, N'-isophthalbis (benzoxazoline-2-thione )
NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve

<Measurement of weight average molecular weight and molecular weight distribution>
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were measured using a GPC apparatus manufactured by JASCO Corporation (column: OHpak SB803-HQ and OHpak SB804-HQ manufactured by Showa Denko KK; eluent). : Dimethylformamide / LiBr.H ₂ O (29.6 mM) / H ₃ PO ₄ (29.6 mM) / THF (0.1% by mass); flow rate: 1.0 mL / min; column temperature: 40 ° C .; (Standard polystyrene conversion value) (the same in the following Examples and Comparative Examples).

[1] Synthesis of Polymer A polyamic acid and a polybenzoxazole precursor were synthesized by the following method.
The polymer was not isolated from the obtained polymer-containing reaction solution, and the reaction solution was diluted as described below to prepare a resin substrate-forming composition or a release layer-forming composition.

[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 to 15 ° C, 50.112 g (230 mmol) of PMDA was added thereto, the temperature was raised to 50 ° C under a nitrogen atmosphere, and the reaction was carried out for 48 hours to obtain a polyamic acid S1. 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, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid S2. 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. To the resulting solution, 6.3 g (14 mmol) of 6FDA and 42.8 g (64 mmol) of CF3-BP-TMA were added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid S3. Mw of the 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, and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid S4. 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, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L1. 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. 9.878 g (18 mmol) of BPTME was added to the obtained solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain polyamic acid L2. Mw of the 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. 9.461 g (18 mmol) of BPTME was added to the obtained solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L3. Mw of the polyamic acid L3 was 43,600, and Mw / Mn was 2.6.

[Synthesis Example L4] Synthesis of polyamic acid L4 3.984 g (15 mmol) of DATP was dissolved in 88 g of NMP. 8.016 g (15 mmol) of BPTME was added to the obtained solution and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L4. Mw of the 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. 6.83 g (13 mmol) of BPTME was added to the obtained solution and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L5. Mw of the 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. 6.11 g (11 mmol) of BPTME was added to the obtained solution and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L6. 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. 8.40 g (16 mmol) of BPTME was added to the obtained solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L7. 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, and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L8. 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, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L9. Mw of the 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. 3.900 g (8 mmol) of BPODA was added to the obtained solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L10. Mw of the 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. 3.086 g (6 mmol) of BPODA was added to the obtained solution and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L11. Mw of the 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, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L12. Mw of the 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 resulting solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L13. Mw of the 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, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L14. Mw of the 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, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L15. Mw of the 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, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L16. Mw of the 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 resulting solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain polyamic acid L17. 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. 3.838 g (8 mmol) of TAHQ was added to the obtained solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L18. 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. 3.794 g (8 mmol) of TAHQ was added to the obtained solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L19. Mw of the 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, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L20. 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, and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L21. Mw of the 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. 1.339 g (5 mmol) of BPDA was added to the obtained solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyamic acid L22. Mw of the 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 reacted at 23 ° C. for 3 hours under a nitrogen atmosphere. Thereafter, this solution was poured into 300 g of pure water, and after stirring for 24 hours, the precipitate was filtered. Thereafter, the resultant was dried under reduced pressure to obtain a polybenzoxazole precursor B1. Mw of the polybenzoxazole precursor B1 was 2,1000, and Mw / Mn was 3.9.

[2] Preparation of Composition for Forming Resin Substrate The reaction liquids obtained in Synthesis Examples S1 to S4 were respectively used as compositions W, X, Y and Z for forming a resin substrate as they were.

[3] Preparation of composition for forming release layer [Example 1-1]
BCS was added to the reaction solution obtained in Synthesis Example L1, and diluted with NMP so that the polymer concentration was 5% by mass and the 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 solutions obtained in Synthesis Examples L2 to L22 were used instead of the reaction solutions obtained in Synthesis Example L1. Was.

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

[4] Formation of release layer and its evaluation [Example 2-1]
The composition for forming a release layer obtained in Example 1-1 was applied on a 100 mm × 100 mm glass substrate (the same applies hereinafter) as a glass substrate using a spin coater (condition: about 30 seconds at a rotation speed of 3000 rpm). .
Then, the obtained coating film is 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 is increased to 400 ° C. (10 ° C./min.). ) And further heated at 400 ° C. for 30 minutes to form a release layer having a thickness of about 0.1 μm on the glass substrate. During the temperature rise, the substrate with the film was not taken out of the oven, but was heated in the oven.

[Examples 2-2 to 2-22]
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. A release layer was formed in the same manner as described above.

[Example 2-23]
The composition for forming a release layer obtained in Example 1-12 was applied on a 100 mm × 100 mm glass substrate using a spin coater (condition: about 30 seconds at a rotation speed of 3000 rpm).
Then, the obtained coating film is heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 140 ° C. for 30 minutes using an oven, and the heating temperature is increased to 250 ° C. (2 ° C./minute). ) And further heating at 250 ° C. for 60 minutes to form a release layer having a thickness of about 0.1 μm on the glass substrate. During the temperature rise, the substrate with the film was not taken out of the oven, but was heated in the oven.

[Example 2-24]
The composition for forming a release layer obtained in Example 1-8 was applied onto a 100 mm × 100 mm glass substrate as a glass substrate using a spin coater (condition: about 30 seconds at a rotation speed of 3000 rpm).
Then, the obtained coating film is heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes under a nitrogen atmosphere using an oven, and the heating temperature is raised to 400 ° C. (10 ° C.). ° C / min), and further heated at 400 ° C for 60 minutes, and finally heated at 500 ° C for 10 minutes to form a release layer having a thickness of about 0.1 µm on the glass substrate. During the temperature rise, the substrate with the film was not taken out of the oven, but was heated in 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. Formed.

[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 releasability of the release layer and the glass substrate obtained in Examples 2-1 to 2-25 and the releasability of the release layer (resin thin film) and the resin substrate were confirmed. Note that a resin substrate made of polyimide was used as the resin substrate.
First, the cross-cut of the release layer on the glass substrate with the release layer obtained in Examples 2-1 to 2-25 (1 mm length and width, the same applies hereinafter), and the resin substrate and the resin substrate on the glass substrate with the release layer -100 cuts were made by cross-cutting the release layer. That is, 100 cross sections of 1 mm square were formed by this cross cutting.
Then, an adhesive tape was attached to the 100 muscat portions, the tape was peeled off, and the degree of peeling was evaluated based on the following criteria (5B to 0B, B, A, and AA) (Examples 3-1 to 3-A). 47). In addition, a similar test was performed using the glass substrate with a resin thin film obtained in Comparative Example 2 according to the above method (Comparative Example 3). Table 1 shows the results. The evaluation criteria for the releasability in Table 1 are as follows.

5B: 0% peeling (no peeling)
4B: less than 5% peel 3B: 5 to 15% peel 2B: less than 15 to 35% peel 1B: less than 35 to 65% peel 0B: 65% to less than 80% peel B: 80% to 95% Peeling less than 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.
Using a bar coater (gap: 250 μm), either the resin substrate forming composition W or X was applied on the release layer (resin thin film) on the glass substrate. Then, the obtained coating film is heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 140 ° C. for 30 minutes using an oven, and the heating temperature is increased to 210 ° C. (10 ° C./min.). The same shall apply hereinafter), the heating temperature was raised to 300 ° C. at 210 ° C. for 30 minutes, the heating temperature was raised to 300 ° C. for 30 minutes, the heating temperature was raised to 400 ° C., and the heating was performed at 400 ° C. for 60 minutes. A polyimide substrate having a thickness of about 20 μm was formed. During the heating, the substrate with the film was not taken out of the oven, but was heated in the oven.

The resin substrates of Examples 3-42 to 3-43 were formed by the following method.
Using a bar coater (gap: 50 μm), either the resin substrate forming composition Y or Z was applied on the release layer on the glass substrate. Then, the obtained coating film is heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 140 ° C. for 30 minutes using an oven, and the heating temperature is increased to 250 ° C. (2 ° C./minute). ) And heated at 250 ° C. for 60 minutes to form a polyimide substrate having a thickness of about 0.8 μm on the release layer. During the heating, the substrate with the film was not taken out of the oven, but was heated in the oven.

  As shown in Tables 1 and 2, it was found that the release layers of the examples had excellent adhesion to the glass substrate and also excellent release to the resin substrate. On the other hand, the release layer of the comparative example did not peel off from the resin substrate and the glass substrate and did not function as a release layer.

[6] Evaluation of transmittance [Example 4]
The composition for forming a release layer obtained in Example 2-8 was applied onto a 100 mm × 100 mm glass substrate (the same applies hereinafter) as a glass substrate using a spin coater (condition: about 30 seconds at a rotation speed of 800 rpm). .
Then, the obtained coating film is 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 is increased to 400 ° C. (10 ° C./min.). ) And further heating at 400 ° C. for 30 minutes to form a release layer having a thickness of about 0.4 μm on the glass substrate. During the temperature rise, the substrate with the film was not taken out of the oven, but was heated in the oven. The transmittance of the obtained film was measured using an ultraviolet-visible spectrophotometer (SIMADSU UV-2550, manufactured by Shimadzu Corporation).
The results are shown in FIG. The transmittance of the obtained film was 1% or less with respect to the wavelength of 308 nm, and showed a transmittance usable as a sacrificial layer.

３．前記エーテル結合を含む芳香族ジアミンが、式（Ａ８）、（Ａ９）、（Ａ１１）、（Ａ２６）〜（Ａ３３）及び（Ａ４０）〜（Ａ４２）からなる群から選ばれる少なくとも１種である２の剥離層形成用組成物。
４．前記エーテル結合を含む芳香族テトラカルボン酸二無水物が、式（Ｂ３）、（Ｂ４）、（Ｂ８）〜（Ｂ１０）及び（Ｂ１２）〜（Ｂ１４）からなる群から選ばれる少なくとも１種である１〜３のいずれかの剥離層形成用組成物。

５．前記エーテル結合を含む芳香族テトラカルボン酸二無水物が、式（Ｂ３）、（Ｂ４）及び（Ｂ８）〜（Ｂ１０）からなる群から選ばれる少なくとも１種である４の剥離層形成用組成物。
６．前記芳香族テトラカルボン酸二無水物が、更にエステル結合及びエーテル結合のいずれも含まない芳香族テトラカルボン酸二無水物を含む１〜５のいずれかの剥離層形成用組成物。
７．前記エステル結合及びエーテル結合のいずれも含まない芳香族テトラカルボン酸二無水物が、ベンゼン骨格、ナフチル骨格又はビフェニル骨格を含むものである６の剥離層形成用組成物。
８．前記エステル結合及びエーテル結合のいずれも含まない芳香族テトラカルボン酸二無水物が、式（Ｃ１）〜（Ｃ１２）からなる群から選ばれる少なくとも１種である７の剥離層形成用組成物。

９．前記有機溶媒が、式（Ｓ１）で表されるアミド類、式（Ｓ２）で表されるアミド類及び式（Ｓ３）で表されるアミド類から選ばれる少なくとも１つを含む１〜８のいずれかの剥離層形成用組成物。

（式中、Ｒ¹及びＲ²は、互いに独立して、炭素数１〜１０のアルキル基を表す。Ｒ³は、水素原子、又は炭素数１〜１０のアルキル基を表す。ｈは、自然数を表す。）
１０．１〜９のいずれかの剥離層形成用組成物を用いて形成される剥離層。
１１．１０の剥離層を用いることを特徴とする、樹脂基板を備えるフレキシブル電子デバイスの製造方法。
１２．１０の剥離層を用いることを特徴とする、樹脂基板を備えるタッチパネルセンサーの製造方法。
１３．前記樹脂基板が、ポリイミドからなる基板である１１又は１２の製造方法。 That is, the present invention provides the following composition for forming a release layer.
1. A weight-average molecular weight obtained by reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride contains a polyamic acid of 15,000 to 200,000, and an organic solvent,
The peeling-off, wherein the aromatic diamine contains an aromatic diamine containing an ether bond, and / or the aromatic tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride containing an ether bond. Composition for forming a layer (provided that the polyamic acid is 2,2′-dimethylbenzidine, 1,3-bis (4-aminophenoxy) benzene, pyromellitic dianhydride, 3,3 ′, 4 , 4'-biphenyltetracarboxylic acid dianhydride.)
2. The aromatic diamine containing an 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). 1. A composition for forming a release layer, which is a seed.

3. The aromatic diamine containing an ether bond is at least one selected from the group consisting of formulas (A8), (A9), (A11), (A26) to (A33), and (A40) to (A42). A composition for forming a release layer.
4 . 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). The composition for forming a release layer according to any one of 1 to 3 .

5. 4. The composition for forming a release layer according to 4, wherein the aromatic tetracarboxylic dianhydride containing an ether bond is at least one selected from the group consisting of formulas (B3), (B4) and (B8) to (B10). .
6 . The composition for forming a release layer according to any one of 1 to 5 , wherein the aromatic tetracarboxylic dianhydride further contains an aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond.
7 . 6. The composition for forming a release layer according to 6 , 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.
<8 . 7. The composition for forming a release layer according to 7 , 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).

9 . Any of 1 to 8 wherein the organic solvent 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) Such a composition for forming a release layer.

(Wherein, 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. H is a natural number. Represents.)
10 ． A release layer formed using the composition for forming a release layer according to any one of 1 to 9 .
11 . A method for manufacturing a flexible electronic device having a resin substrate, comprising using 10 release layers.
1 2. A method for manufacturing a touch panel sensor having a resin substrate, comprising using 10 release layers.
1 3. It said resin substrate, 11 or 1 second manufacturing method is a substrate made of polyimide.

<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'-dihydroxy benzidine 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-benzimidazole APAB-E: 4-aminophenyl-4'-aminobenzoate 6FAP: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane TFMB: 2 , 2'-bis (trifluoromethyl) biphenyl-4,4'-diamineBPDA: 3,3 ', 4,4'-biphenyltetracarboxylic acid Anhydride TAHQ: p- phenylene bis (trimellitic acid monoester acid anhydride)
PMDA: pyromellitic dianhydride BPTME: p-biphenylene bis (trimellitic acid monoester anhydride)
BPODA: 4,4 '-(biphenyl-4,4'-diylbisoxy) bisphthalic dianhydride CF3-BP-TMA: N, N'-[2,2'-bis (trifluoromethyl) biphenyl-4 , 4'-Diyl] bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbamide)
6FDA: 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride IPBBT: N, N'-isophthalbis (benzoxazoline-2-thione )
NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve

[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 reacted at 23 ° C. for 3 hours under a nitrogen atmosphere. Thereafter, this solution was poured into 300 g of pure water, and after stirring for 24 hours, the precipitate was filtered. Thereafter, the resultant was dried under reduced pressure to obtain a polybenzoxazole precursor B1. Mw of the polybenzoxazole precursor B1 was 21,000 , and Mw / Mn was 3.9.

Claims (11)

Including a polyamic acid obtained by reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride, and an organic solvent,
The peeling-off, wherein the aromatic diamine contains an aromatic diamine containing an ether bond, and / or the aromatic tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride containing an ether bond. Composition for forming a layer. The aromatic diamine containing an 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). The composition for forming a release layer according to claim 1, which is a seed.

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). The composition for forming a release layer according to claim 1.

  The composition for forming a release layer according to claim 1 or 2, wherein the aromatic tetracarboxylic dianhydride further contains an aromatic tetracarboxylic dianhydride containing neither an ester bond nor an ether bond.   The composition for forming a release layer according to claim 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. The composition for forming a release layer according to claim 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). object.

The organic solvent 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). The composition for forming a release layer according to the above.

(Wherein, 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. H is a natural number. Represents.)   A release layer formed using the composition for forming a release layer according to claim 1.   A method for manufacturing a flexible electronic device comprising a resin substrate, comprising using the release layer according to claim 8.   A method for manufacturing a touch panel sensor including a resin substrate, comprising using the release layer according to claim 8.   The method according to claim 9, wherein the resin substrate is a substrate made of polyimide.

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