KR20190089208A - Manufacturing method of release layer - Google Patents

Abstract

(식 중, X는, 서로 독립하여, 2개의 카르복실산 유도체를 갖는 4가의 방향족 기이고, Y는, 서로 독립하여, 2가의 방향족 기이고, Z¹ 및 Z²는, 서로 독립하여, 1가의 유기기이며, 식 (1A)에서, Y, Z¹ 및 Z² 중 적어도 1개가 알칼리 가용성 기를 갖고, 식 (1B)에서, Y 및 2개의 Z¹ 중 적어도 1개가 알칼리 가용성 기를 갖고, 식 (1C)에서, Y 및 2개의 Z² 중 적어도 1개가 알칼리 가용성 기를 갖고, m은 서로 독립하여 자연수를 나타낸다.)A peeling layer comprising a step of applying a composition for forming a peeling layer containing at least one of polyamic acids represented by the following formulas (1A) to (1C) and an organic solvent on a substrate and baking at a maximum temperature of 450 to 550 캜 Of the present invention.

(Wherein X is a quadrivalent aromatic group having two carboxylic acid derivatives, Y is independently of each other a bivalent aromatic group, and Z ¹ and Z ² are independently of each other 1 (1B) wherein at least one of Y, Z ¹ and Z ² has an alkali-soluble group, and at least one of Y and two Z ^{1 s} in formula (1B) has an alkali-soluble group, 1C), at least one of Y and two Z ² has an alkali-soluble group, and m represents a natural number independently of each other.

Description

Manufacturing method of release layer

The present invention relates to a method for producing a release layer.

In recent years, electronic devices are required to have a function of being bent in addition to the characteristics of being thinned and lightweight. For this reason, it is required to use a lightweight flexible plastic substrate in place of the conventional heavy, fragile and non-bendable glass substrate.

In particular, in the new generation display, development of an active matrix type full color TFT display panel using a lightweight flexible plastic substrate (hereinafter referred to as a resin substrate) is required.

Therefore, various methods for manufacturing an electronic device using a resin film as a substrate are being studied, and in a new-generation display, a process capable of reusing an existing facility for manufacturing a TFT display panel is being studied. 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 on the glass substrate side to crystallize the amorphous silicon, Discloses a method for peeling a plastic substrate from a glass substrate by hydrogen gas.

Also, in Patent Document 4, a method of completing a liquid crystal display by attaching a layer to be peeled (described as "transfer layer" in Patent Document 4) to a plastic film using the technique disclosed in Patent Documents 1 to 3 Lt; / RTI >

However, in the methods disclosed in Patent Documents 1 to 4, in particular, in the method disclosed in Patent Document 4, it is necessary to use a substrate having high light transmittance in order to transmit laser light. In order to pass through a substrate, It is necessary to irradiate laser light having a relatively large energy sufficient to emit the laser light, and there is a problem that the layer to be peeled may be damaged by irradiation with laser light.

In addition, when the layer to be peeled is large in size, it takes a long time to perform the laser processing, so that it is difficult to increase the productivity of device manufacture.

As a means for solving such a problem, Patent Document 5 discloses a technique in which an existing glass substrate is used as a substrate (hereinafter referred to as a glass substrate), and a polymer such as a cyclic olefin copolymer is used on the glass substrate, A heat-resistant resin film such as a polyimide film is formed on the release layer, and an ITO transparent electrode, a TFT, or the like is formed and sealed in a vacuum process on the film, and finally a glass substrate is peeled off and removed Was adopted.

Now, as the TFT, a low-temperature polysilicon TFT whose mobility is twice as fast as the amorphous silicon TFT is used. This low-temperature polysilicon TFT needs to be subjected to dehydrogenation annealing at 400 DEG C or higher after deposition of amorphous silicon and to crystallize silicon by irradiating a pulsed laser (hereinafter referred to as a TFT process), but in the dehydrogenation annealing process Is higher than the glass transition (Tg) of the conventional polymer.

However, it is known that the existing polymer has a high adhesion when heated to a temperature of Tg or higher (see, for example, Patent Document 6), and the adhesion between the release layer and the resin substrate after the heat treatment is improved, It sometimes becomes difficult to peel off from the gas.

Japanese Patent Publication No. 10-125929 Japanese Patent Publication No. 10-125931 International Publication No. 2005/050754 Japanese Patent Publication No. 10-125930 Japanese Patent Application Laid-Open No. 2010-111853 Japanese Patent Laid-Open No. 2008-188792

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

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive investigations to solve the above problems. As a result, they have found that a composition containing an organic solvent and a polyamic acid having an alkali-soluble group in a molecule is used, It is possible to form a peeling layer having good adhesion with a substrate, suitable adhesiveness to a resin substrate used in a flexible electronic device, and suitable peeling property, thereby completing the present invention.

Therefore,

1. A process for producing a peeling layer comprising a step of applying a composition for forming a peeling layer containing at least one of polyamic acids represented by the following formulas (1A) to (1C) and an organic solvent onto a substrate and baking at a maximum temperature of 450 to 550 캜 A method for producing a release layer,

(Wherein X is a quadrivalent aromatic group having two carboxylic acid derivatives, Y is independently of each other a bivalent aromatic group, and Z ¹ and Z ² are independently of each other 1 (1B) wherein at least one of Y, Z ¹ and Z ² has an alkali-soluble group, and at least one of Y and two Z ^{1 s} in formula (1B) has an alkali-soluble group, 1C), at least one of Y and two Z ² has an alkali-soluble group, and m represents a natural number independently of each other.

2. A process for producing a release layer 1 in which the alkali-soluble group is a carboxyl group or a phenolic hydroxyl group,

3. A process for producing a peeling layer of 1 or 2 wherein Y has an aromatic group represented by the following formulas (2) to (5)

R ¹ to R ³ independently represent an alkylene group having 1 to 20 carbon atoms or an alkylene group having 2 to 20 carbon atoms which may be substituted with a halogen atom, An alkynylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 2 to 20 carbon atoms, an ether group, an ester group or an amide group, and?

4. A method for producing a peel layer 3 in which Y includes an aromatic group represented by the following formulas (6) to (9)

(In the formula, & cir & indicates a binding hand.)

5. A production method of any one of the peeling layers 1 to 4 wherein Z ¹ is a monovalent organic group represented by the following formula (10)

(Wherein Z ³ represents a carboxyl group or a hydroxyl group, and O represents a bond).

6. A production method of any one of the peel layers 1 to 5 wherein Z ² is a monovalent organic group represented by the following formula (11)

(Wherein Z ³ represents a carboxyl group or a hydroxyl group, and O represents a bond).

7. The method for producing a peeling layer according to any one of 3 to 6, wherein the Y further comprises an aromatic group having no alkali-soluble group,

8. A process for producing a release layer 7 in which the aromatic group not having an alkali-soluble group is a phenylene group, a biphenylene group or a terphenylene group,

9. A method of manufacturing a flexible electronic device having a resin substrate, characterized by using a release layer formed using any one of the manufacturing methods 1 to 8,

10. A flexible electronic device comprising a step of forming a resin substrate by applying a composition for forming a resin substrate on a release layer formed by using any one of the manufacturing methods 1 to 8, A method of manufacturing a device,

11. A manufacturing method of a flexible electronic device of 9 or 10 wherein the resin substrate is a polyimide resin substrate

.

By employing the production method of the release layer of the present invention, a release layer having good adhesion with a substrate, suitable adhesiveness to a resin substrate, and suitable release properties can be obtained with high reproducibility. Therefore, by carrying out the manufacturing method of the present invention, it is possible to manufacture the flexible electronic device without damaging the resin substrate formed on the substrate, the circuit provided thereon, and the like, It becomes possible to separate from the gas. Therefore, the manufacturing method of the present invention can contribute to simplification of the manufacturing process of the flexible electronic device having the resin substrate and improvement of the yield thereof.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in more detail.

A method for producing a release layer according to the present invention comprises the steps of applying a composition for forming a release layer containing at least one polyamic acid represented by the following formulas (1A) to (1C) and an organic solvent onto a substrate, And firing at 550 캜.

Here, the peeling layer in the present invention is a layer provided directly on a glass substrate for a predetermined purpose. As a typical example thereof, in a manufacturing process of a flexible electronic device, a flexible substrate made of a resin such as polyimide, The resin substrate is provided for fixing the resin substrate between the resin substrate of the device and the resin substrate in a predetermined process so that the resin substrate can be easily peeled off from the substrate after an electronic circuit or the like is formed on the resin substrate. And the like.

X is a tetravalent aromatic group having two carboxylic acid derivatives independently of each other, Y is, independently of each other, a bivalent aromatic group, and Z ¹ and Z ² are each independently a monovalent organic group (1C), at least one of Y, Z ¹ and Z ² has an alkali-soluble group, Y in formula (1B) and at least one of Z ^{1 s} have an alkali- , At least one of Y and two Z ² has an alkali-soluble group.

m are independent from each other and represent a natural number, but an integer of 2 or more is preferable.

X is preferably a tetravalent aromatic ring containing 1 to 5 benzene rings, more preferably a tetravalent benzene ring, a tetravalent naphthalene ring or a tetravalent biphenyl ring, more preferably a tetravalent benzene ring or a tetravalent biphenyl ring Do.

As the divalent aromatic group of Y, an aromatic group containing 1 to 5 benzene rings is preferable, and those represented by the following formulas (2 ') to (5') are more preferable.

In the formulas (2 ') to (5'), R ¹ to R ³ independently represent an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, An alkynylene group of 2 to 20 carbon atoms, an arylene group of 6 to 20 carbon atoms, a heteroarylene group of 2 to 20 carbon atoms, an ether group, an ester group or an amide group, and?

The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a fluorine atom is preferable.

The alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms may be any of linear, branched and cyclic alkylene groups. Examples thereof include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, propylene, Pentamethylene, hexamethylene group and the like.

The alkenylene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms may be any of linear, branched and cyclic, and examples thereof include ethenylene, propenylene, butenylene, pentenylene, hexenylene, Nhenylene, octenylene, noneneylene group and the like.

The alkynylene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms may be any of linear, branched and cyclic, and examples thereof include ethynylene, propynylene, butynylene, pentynylene, hexynylene, heptynylene, Octynylene, nonynylene group and the like.

When Y is a divalent aromatic group having at least one alkali-soluble group, it is preferably an organic group containing a benzene ring substituted with at least one alkali-soluble group. In particular, when the benzene ring substituted with at least one alkali- More preferably an aromatic group represented by any one of the following formulas (2) to (5), more preferably a structure represented by any of the following formulas (6) to (9) The structures represented by the formulas (6), (7) and (9) having a phenolic hydroxyl group at the ortho position are optimal.

(Wherein W represents an alkali-soluble group, preferably a carboxyl group or a phenolic hydroxyl group, and R ¹ to R ³ and O have the same meanings as defined above.)

(In the formula, "? &Quot;

In the polyamic acid used in the present invention, Y may include both a divalent aromatic group having an alkali-soluble group and a divalent aromatic group having no alkali-soluble group.

In this case, the proportion of the divalent aromatic group having an alkali-soluble group in the whole Y may be about 0.1 to 99.9 mol%, preferably 1 to 50 mol%, and more preferably 1 to 10 mol%.

In the above formulas (1A) to (1C), Z ¹ and Z ² are monovalent organic groups, but a monovalent organic group containing a benzene ring is preferable, and a monovalent organic group containing one benzene ring is preferable , Z ¹ bonded to the tetracarboxylic acid terminal side is preferably a monovalent organic group represented by the following formula (10A), and Z ² bonded to the diamine terminal side is preferably a monovalent organic group represented by the following formula (11A) Do.

(In the formula, "? &Quot;

When Z ¹ and Z ² are a divalent aromatic group having an alkali-soluble group, the alkali-soluble group is preferably bonded directly to the aromatic ring, and the number of the alkali-soluble groups is preferably one.

More specifically, Z ¹ bonded to the tetracarboxylic acid terminal side is preferably a monovalent organic group represented by the following formula (10B), and the alkali-soluble group is represented by the following formula (10) in which the alkali- Z ² bonded to the diamine terminal side is preferably a monovalent organic group represented by the following formula (11B), more preferably a monovalent organic group represented by the following formula (11) wherein the alkali-soluble group is present at the ortho position with respect to CO The monovalent organic group to be displayed is more preferable.

Particularly, since the polymer terminal has a hydroxyl group, a difference in skeleton from that of the flexible substrate used in the upper layer can be caused, so that the function of the obtained film as a release layer can be improved.

(Wherein Z ³ represents a carboxyl group or a hydroxyl group, and O represents a bond).

(Wherein Z ³ represents a carboxyl group or a hydroxyl group, and O represents a bond).

The polyamic acid represented by the above formulas (1A) to (1C) can be obtained by reacting a predetermined aromatic tetracarboxylic acid dianhydride component and an aromatic diamine component at a predetermined ratio.

Hereinafter, the aromatic tetracarboxylic dianhydride component and aromatic diamine component used in the synthesis of the polyamic acid used in the production method of the present invention will be described.

The aromatic tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid represented by the above formulas (1A) to (1C) is specifically limited to those having two dicarboxylic acid anhydride moieties in the molecule and having an aromatic ring However, aromatic tetracarboxylic acid dianhydride containing 1 to 5 benzene nuclei is preferable.

Specific examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, naphthalene-1,2,3,4-tetracarboxylic acid dianhydride, Naphthalene-1,2,5,6-tetracarboxylic acid dianhydride, naphthalene-1,2,6,7-tetracarboxylic acid dianhydride, naphthalene-1,2,7,8-tetracarboxylic acid dianhydride , Naphthalene-2,3,5,6-tetracarboxylic acid dianhydride, naphthalene-2,3,6,7-tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride Water, biphenyl-2,2 ', 3,3'-tetracarboxylic dianhydride, biphenyl-2,3,3', 4'-tetracarboxylic dianhydride, biphenyl- 4,4'-tetracarboxylic dianhydride, anthracene-1,2,3,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene- 2,6,7-tetracarboxylic acid dianhydride, anthracene-1,2,7,8-tetracarboxylic acid dianhydride, Anthracene-2,3,6,7-tetracarboxylic acid dianhydride, phenanthrene-1,2,3,4-tetracarboxylic acid dianhydride, phenanthrene-1,2,5,6-tetracarboxylic acid Dianhydride, phenanthrene-1,2,6,7-tetracarboxylic acid dianhydride, phenanthrene-1,2,7,8-tetracarboxylic acid dianhydride, phenanthrene-1,2,9,10- Tetracarboxylic acid dianhydride, phenanthrene-2,3,5,6-tetracarboxylic acid dianhydride, phenanthrene-2,3,6,7-tetracarboxylic acid dianhydride, phenanthrene-2,3, Tetracarboxylic acid dianhydride, phenanthrene-3,4,5,6-tetracarboxylic acid dianhydride, phenanthrene-3,4,9,10-tetracarboxylic acid dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4,4'-diphenyl ether tetracarboxylic acid, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene, Fluoroisov And the like Philippe dendi acid, which are also be used alone or used in combination of two or more.

On the other hand, the diamine component is preferably an aromatic diamine containing 1 to 5 benzene nuclei, more preferably an aromatic diamine substituted with at least one alkali-soluble group, and an aromatic diamine having an aromatic ring having a carboxyl group or a phenolic hydroxyl group, More preferred are aromatic diamines comprising an aromatic group substituted with a phenolic hydroxyl group.

Examples of the aromatic diamine having a phenolic hydroxyl group include 3,3'-diamino-4,4'-dihydroxybiphenyl (4BP), 3,3'-diamino-2,2'-dihydro (2BP), 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2,2- Bis (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane, bis (3-amino-4-hydroxyphenyl) methane (BAPF) 3,3'-diamino-4,4'-dihydroxybenzophenone (AHPK), 3,3'-diamino-4,4'-dihydroxy-phenyl ether (AHPE) Dihydroxy-thiophenyl ether, 2,2'-bis (3-amino-4-hydroxyphenyl) propane (BAPA) Amino-4-hydroxyphenyl) sulfide (BSDA), bis-N, N '- (p- aminobenzoyl) -hexafluoro-2, 2'-bis (4-hydroxyphenyl) propane (BABHBPA), [4- (4-aminophenoxy) ] Sulfone, 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis Amino-4-hydroxyphenyl) thioether, bis (4-amino-3,5-dihydroxyphenyl) thioether, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) (4-amino-3,5-dihydroxyphenyl) sulfone, 4,4'-diamino-3,3'-dihydroxybiphenyl (3BP), 4,4'- 3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4 Benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1,4-bis (4-amino-3-hydroxyphenoxy) benzene, Benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- Bis (4-hydroxyphenoxy) phenyl] sulfone, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane or 1,4- But is not limited to this.

Of the above diamine components, preferably 3,3'-diamino-4,4'-dihydroxybiphenyl (4BP), 3,3'-diamino-2,2'-dihydroxybiphenyl ), Hexafluoropropane (BAHF), 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane (3-amino-4-hydroxyphenyl) methane (BAPF), 3,3'-hydroxyphenoxyphenyl) hexafluoropropane, 2,2- Diamino-4,4'-dihydroxybenzophenone (AHPK), 3,3'-diamino-4,4'-dihydroxy-phenyl ether (AHPE), 3,3'- (3-amino-4-hydroxyphenyl) phenyl (3-amino-4-hydroxyphenyl) propane (BAPA) (3-amino-4-hydroxyphenyl) sulfone (BSDA), bis-N, N '- (p- aminobenzoyl) -hexafluoro-2,2'-bis 4-hydroxyphenyl) propane (BABHBPA), [4- (4-aminophenoxy) phenyl] sulfone, 2,4- , 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) thioether, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) thioether, bis ) Sulfone, 4,4'-diamino-3,3'-dihydroxybiphenyl (3BP), 4,4'-diamino-3,3'-dihydroxy-5,5'- , 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3 Bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, Benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) benzene.

(3-amino-4-hydroxyphenyl) methane (BAPF), 2,2'-bis -Amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 3,3'-diamino-4,4'-dihydroxy-phenyl ether (AHPE), 3,3'- (3-amino-4-hydroxyphenyl) sulfide (BSDA), (3-amino-4-hydroxyphenyl) ) Anilide (AHPA), and bis-N, N '- (p-aminobenzoyl) -hexafluoro-2,2'-bis (4-hydroxyphenyl) propane (BABHBPA).

Examples of the aromatic diamine having a carboxyl group include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino- Amino-3, 5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'- 5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis (4-amino (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, 3,3'-dicarboxy-4 , 4'-diaminodiphenylmethane and the like The can.

As described above, as the diamine component used in the synthesis of the polyamic acid, an aromatic diamine having no alkali-soluble group may also be used.

Specific examples of the aromatic diamine having no alkali-soluble group include p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl- , 4-phenylenediamine, 4,4'-diaminodiphenyl ether (ODA), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diamino Diphenylsulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4-methylene-bis (2- ), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4-methylene- bis (2,6- Methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3,5- , 1,3-bis (3-aminophenoxy) benzene, bis [4- Bis (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2- (3-aminophenoxy) phenyl] propane.

The charging ratio of the diamine component and the tetracarboxylic dianhydride component can not be uniformly determined because it is appropriately determined in consideration of the aimed molecular weight or molecular weight distribution, kind of diamine, kind of tetracarboxylic acid dianhydride, etc., Based on the molar ratio of 1 (molar ratio) to the end of the desired molecular chain, and when the terminal chain is derived from both tetracarboxylic acid-derived molecular chains (formula (1B)), tetracarboxylic acid dianhydride Preferably 1.0 to 2.0 moles, more preferably 1.1 to 2.0 moles, more preferably 1.0 to 3.0 moles of the water component, more preferably 1.0 to 2.0 moles of the tetracarboxylic acid dianhydride component (1) Is preferably 1.00 to 2.5 moles, more preferably 1.01 to 1.5 moles, and further preferably 1.02 to 1.3 moles, relative to the moles of the diamine component.

The organic solvent used in this 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- N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy- N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylpropylamide, 3- sec-butoxy-N, N-dimethylpropylamide, 3-tert-butoxy-N, N-dimethylpropylamide and? -butyrolactone. The organic solvents may be used alone or in combination of two or more.

Particularly, the organic solvent used in the reaction is preferably an amide represented by the formula (S1), an amide represented by the formula (S2) and an amide represented by the formula (S3) in that the diamine and the tetracarboxylic acid dianhydride and the polyamic acid are well dissolved. And amides represented by the following general formula (1).

In the formulas, 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, but is preferably 1 to 3, more preferably 1 or 2.

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, -Hexyl group, n-octyl group, n-nonyl group, and n-decyl group. Among these, 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 of the solvent to be used to the boiling point and is usually about 0 to 100 DEG C. In order to prevent the imidization in the solution of the obtained polyamic acid and to maintain the high content of the polyamic acid unit, , More preferably about 0 to about 60 캜, and still more preferably about 0 to about 50 캜.

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

A polyamic acid obtained by reacting a tetracarboxylic acid dianhydride component and diamine component described above, and, Z ¹ and / or the end cap compound which Z ^2, which does not have a terminal sealing compound or an alkali-soluble having an alkali-soluble group To give the polyamic acid represented by the formulas (1A) to (1C).

More specifically, an aromatic monoamine may suitably be used as a terminal sealing compound which provides Z ¹ to be bonded to the tetracarboxylic acid terminal side.

The aromatic monoamine preferably has an aromatic ring having 6 to 30 carbon atoms, more preferably an aromatic ring having 6 to 15 carbon atoms, further preferably an aromatic ring having 6 to 10 carbon atoms, It is preferable to include one ring.

Specific examples of the aromatic monoamine having no alkali-soluble group include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, , 3-aminobiphenyl, 4-aminobiphenyl, and the like.

Specific examples of the aromatic monoamine having an alkali-soluble group include aromatic monoamines having a phenolic hydroxyl group such as 2-aminophenol, 3-aminophenol and 4-aminophenol; And aromatic monoamines having a carboxyl group such as 2-aminobenzoic acid, 3-aminobenzoic acid and 4-aminobenzoic acid.

Of these, as the end-sealing compound for providing Z ¹ , an aromatic monoamine having an alkali-soluble group is preferable, an aromatic monoamine having a phenolic hydroxyl group is more preferable, and 2-aminophenol is further preferable.

On the other hand, an aromatic carboxylic acid can be suitably used as a terminal sealing compound which provides Z ² bonded to the diamine terminal side.

The aromatic carboxylic acid preferably has an aromatic ring having 6 to 30 carbon atoms, more preferably an aromatic ring having 6 to 15 carbon atoms, further preferably an aromatic ring having 6 to 10 carbon atoms, It is preferable to include one ring.

Specific examples of the aromatic carboxylic acid not having an alkali-soluble group after terminal sealing include aromatic carboxylic acids such as benzoic acid, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid, And aromatic monocarboxylic acids such as 2-phenylbenzoic acid, 3-phenylbenzoic acid and 4-phenylbenzoic acid.

Specific examples of the aromatic carboxylic acid having an alkali-soluble group after terminal sealing include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; And aromatic monocarboxylic acids having a phenolic hydroxyl group such as salicylic acid, 3-hydroxybenzoic acid and 4-hydroxybenzoic acid.

The carboxylic acid may be in the form of an acid halide or an acid anhydride.

Of these, as the end-sealing compound providing Z ² , an aromatic carboxylic acid having an alkali-soluble group after terminal sealing is preferable, and an aromatic dicarboxylic acid is preferable, and phthalic acid is further preferable.

When the polyamic acid represented by the formulas (1A) to (1C) of the present invention uses only a diamine component having no alkali-soluble group as the diamine component (that is, when all Y have no alkali-soluble group), Z ¹ and / or Z ² must have an alkali-soluble group. In this case, either or both of the molecular chain terminals of the synthesized polyamic acid may be sealed with a monoamine or carboxylic acid having the above-mentioned alkali-soluble group.

The amount of the terminal sealing compound to be charged may be 1 mole or more per mole of the polyamic acid, but is preferably 2 moles or more, more preferably 2 to 4 moles, and still more preferably 2 to 3 moles. When an aromatic monoamine is used, the addition amount thereof is preferably 0.1 mol or more, more preferably 0.2 to 4 mol, and still more preferably 0.1 mol or more, per mol of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid May be from 0.2 to 3 moles. The amount of the aromatic carboxylic acid to be added is aimed at preferably 0.1 mol or more, more preferably 0.2 to 4 mol, and still more preferably 0.2 to 3 mol, based on 1 mol of the diamine component used in the synthesis of the polyamic acid .

The organic solvent used in the sealing of the molecular chain terminal of the polyamic acid is not particularly limited as long as it does not adversely affect the reaction, and the same solvent as that exemplified in the above polyamic acid synthesis can be used.

The reaction temperature at the time of sealing the molecular chain terminal of the polyamic acid 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, as in the case of the synthesis of the polyamic acid, From the viewpoint of reliably sealing the molecular chain terminal of the mixed acid, preferably about 0 to 70 캜, more preferably about 0 to 60 캜, even more preferably about 0 to 50 캜. Since the reaction time depends on the reaction temperature and the reactivity of the raw material, it can not be uniformly defined, but is usually about 1 to 100 hours.

The weight average molecular weight of the polyamic acid in which one or both of the molecular chain terminals is thus obtained is usually from about 5,000 to 500,000. From the viewpoint of improving the function of the obtained film as a release layer, the weight average molecular weight is preferably about 6,000 to 200,000, More preferably about 7,000 to 150,000. In the present invention, the weight average molecular weight is a polystyrene reduced value measured by gel permeation chromatography (GPC).

In the present invention, a solution obtained by directly or after diluting or concentrating the reaction solution after end-sealing can be used as a composition for forming a release layer of the present invention. The reaction solution may be filtered if necessary. It is possible not only to reduce the incorporation of impurities which may cause deterioration of the adhesion and peelability of the peeling layer obtained by filtration but also to obtain a composition for forming a peeling layer efficiently. Further, the polyamic acid may be isolated from the reaction solution and then dissolved in a solvent to prepare a composition for forming a release layer. Examples of the solvent in this case include an organic solvent used in the above-mentioned reaction.

The solvent used for the dilution is not particularly limited, and specific examples thereof include the same ones as specific examples of the reaction solvent for the above reaction. The solvent used for dilution may be used alone or in combination of two or more. Among them, polyamic acid is preferable because it dissolves polyamic acid well, and therefore, it is preferable to use N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Ethyl-2-pyrrolidone and? -Butyrolactone are preferable, and N-methyl-2-pyrrolidone is more preferable.

Even if the solvent does not dissolve the polyamic acid, it can be mixed with the composition for forming a release layer of the present invention only if the polyamic acid is not precipitated. Particularly, it is preferable to use ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1- Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- A solvent having a low surface tension such as dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate can be appropriately mixed . By this, it is known that the uniformity of the coating film is improved at the time of application to the substrate, and it is also 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 and the viscosity of the composition, but is usually about 1 to 30 mass%, preferably 1 to 20 mass% Respectively. With such a concentration, a peel layer having a thickness of about 0.05 to 5 mu m can be obtained with good reproducibility. The concentration of the polyamic acid can be adjusted by adjusting the amount of the diamine and the tetracarboxylic dianhydride, which are the raw materials of the polyamic acid, by diluting or concentrating the filtrate after filtering the reaction solution. When the polyamic acid is dissolved in a solvent, The amount can be adjusted by adjusting the amount.

The viscosity of the composition for forming a release layer is suitably set in consideration of the thickness of the release layer to be produced. Particularly when a film having a thickness of about 0.05 to 5 탆 is to be obtained with good reproducibility, To about 10,000 mPa · s, and preferably about 20 to 5,000 mPa · s.

Here, the viscosity can be measured by using a commercially available viscometer for viscosity measurement of liquid, for example, at a temperature of 25 ° C of the composition, with reference to the procedure described in JIS K7117-2. Preferably, a cone-plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably, 1 ° 34 '× R24 is used as a standard cone rotor as a viscometer of the same type, can do. As such a rotational viscometer, for example, TVE-25L manufactured by Toki Sangyo Co., Ltd. can be mentioned.

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

The polyamic acid is thermally imidized by a firing method including a step of applying the composition for forming a peeling layer described above on a substrate and firing at a maximum temperature of 450 to 550 DEG C or more to obtain a good adhesion with a substrate, A peeling layer composed of a polyimide film having suitable adhesiveness and suitable peeling property of the peeling layer can be obtained.

In the present invention, the maximum temperature at the time of firing is not particularly limited as long as it is in the range of 450 to 550 占 폚 and the heat-resistant temperature of the polyimide is in a range of not more than the heat-resistant temperature of polyimide. However, the above-mentioned adhesiveness to the substrate, It is preferable that the temperature is 500 DEG C or higher. The upper limit thereof is usually about 550 ° C, but preferably about 510 ° C. By setting the heating temperature within the above range, it becomes possible to sufficiently progress the imidization reaction while preventing the film from being weakened.

Since the heating time varies depending on the heating temperature, it is usually 1 minute to 5 hours although it can not be uniformly defined. The imidization rate may be in the range of 50 to 100%.

The firing temperature may include a step of firing at a temperature lower than the maximum temperature as long as the firing temperature is within the above range. As a preferred example of the heating method in the present invention, heating at 50 to 150 캜, followed by heating stepwise as it is, and finally heating at 450 to 550 캜 may be mentioned. Particularly, as a more preferable example of the heating furnace, there is a method of heating at 50 to 100 占 폚, heating at a temperature higher than 100 占 폚 to lower than 450 占 폚, and heating at 450 占 폚 or higher. As another preferable example of the heating furnace, the heating furnace is heated at 50 to 150 占 폚, then heated at a temperature higher than 150 占 폚 to 350 占 폚, subsequently heated at a temperature higher than 350 占 폚 to 450 占 폚 and finally heated at 450 to 550 占 폚 There is a technique.

As a preferable example of the heating in consideration of the firing time, there is a method of heating at 50 to 150 占 폚 for 1 minute to 2 hours, heating the temperature stepwise as it is, and finally heating at 400 占 폚 or more for 30 minutes to 4 hours . As a more preferable example of the heating furnace, a method of heating at 50 to 100 ° C for 1 minute to 2 hours, heating at a temperature higher than 100 ° C to 450 ° C for 5 minutes to 2 hours and heating at 450 ° C or higher for 30 minutes to 4 hours . Another example of a more preferable example of the heating furnace is heating at 50 to 150 占 폚 for 1 minute to 2 hours, then heating at a temperature higher than 150 占 폚 to 350 占 폚 for 5 minutes to 2 hours, subsequently heating at a temperature higher than 350 占 폚 to lower than 450 占 폚 for 30 minutes to 4 hours , And finally heating at 450 to 510 DEG C for 30 minutes to 4 hours.

When the release layer of the present invention is formed on a base body, the release layer may be formed on a part of the surface of the substrate or may be formed on the entire surface. Examples of the method of forming the release layer on a part of the surface of the base include a method of forming a release layer only in a predetermined range of the surface of the base, a method of forming a release layer in the form of a dot pattern, a line and space pattern, . Further, in the present invention, the term "base body" refers to a material used for manufacturing a flexible electronic device or the like, to which the composition for forming a release layer of the present invention is applied.

As the substrate (substrate), for example, glass, metal (silicon wafer or the like), slate and the like can be mentioned. Particularly, since the release layer obtained from the composition for forming a release layer according to the present invention has sufficient adhesiveness thereto, Glass is preferred. Further, the base surface may be composed of a single material or may be composed of two or more materials. As a mode in which the surface of the substrate is constituted by two or more materials, it is preferable that the surface of the substrate is composed of a certain material and the remaining surface is composed of other materials, a dot pattern, a line and space pattern And a material in which a material exists in other materials in the pattern shape of the substrate.

The coating method is not particularly limited. For example, a coating method such as cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, , Flat panel, screen printing, etc.).

Examples of a mechanism used for heating include a hot plate, an oven, and the like. The heating atmosphere can be an air hirer, an inert gas hirer, or an atmospheric pressure hier or a decompression hier.

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

The peeling layer described above has excellent adhesion with a substrate, in particular, a glass substrate, suitable adhesion with a resin substrate, and appropriate peeling property. Therefore, in the manufacturing process of a flexible electronic device, the peeling layer of the present invention can prevent the resin substrate of the device from being damaged without causing damage to the resin substrate together with a circuit formed on the resin substrate, It can be suitably used.

Hereinafter, an example of a manufacturing method of a flexible electronic device using the release layer of the present invention will be described.

By using the composition for forming a release layer of the present invention, a release layer is formed on the glass substrate by the above-described method. A solution for forming a resin substrate for forming a resin substrate is coated on the release layer and the resin film is fired to form a resin substrate fixed to the glass substrate through the release layer of the present invention.

The firing temperature of the coated film is suitably set according to the type of the resin and the like. In the present invention, the maximum temperature at the firing is preferably 450 to 550 캜 or more, more preferably 480 캜 or more, Or more, more preferably 500 ° C or higher. By setting the maximum temperature at the time of firing at the time of firing at the time of manufacturing the resin substrate within this range, it is possible to further improve the adhesion between the underlying release layer and the substrate, and the appropriate adhesion and peelability between the release layer and the resin substrate.

Also in this case, as long as the maximum temperature falls within the above-mentioned range, the step may include a step of firing at a temperature lower than the above range.

As a preferable example of the heating temperature at the time of manufacturing the resin substrate, there is a method of heating at 50 to 150 占 폚, raising the heating temperature stepwise as it is, and finally heating at 450 to 550 占 폚. Particularly, as a more preferable example of the heating furnace, there is a method of heating at 50 to 100 占 폚, heating at a temperature higher than 100 占 폚 to lower than 450 占 폚, and heating at 450 占 폚 or higher. Another example of a more preferable example of the heating furnace is a heating furnace at a temperature of from 50 to 100 占 폚, a heating furnace at a temperature higher than 100 占 폚 to 200 占 폚, a temperature higher than 200 占 폚 and lower than 300 占 폚, Heating at a temperature lower than 400 ° C to 450 ° C, and finally heating at 450 ° C to 550 ° C.

As a preferable example of the heating in consideration of the firing time, heating is carried out at 50 to 150 占 폚 for 5 minutes to 2 hours, then the heating temperature is increased stepwise as it is, and finally heated at 450 to 550 占 폚 for 30 minutes to 4 hours . In particular, as a more preferable example of the heating furnace, heating is carried out at 50 to 100 占 폚 for 5 minutes to 2 hours, heating at a temperature higher than 100 占 폚 to 450 占 폚 for 5 minutes to 2 hours, and heating at 450 占 폚 or more for 30 minutes to 4 hours There is a technique. Another example of a more preferable example of the heating furnace is heating at 50 to 100 占 폚 for 5 minutes to 2 hours and heating at a temperature higher than 100 占 폚 to 200 占 폚 for 5 minutes to 2 hours and then at a temperature higher than 200 占 폚 and lower than 300 占 폚 for 30 minutes to 4 For 30 minutes to 4 hours at less than 300 ° C to 400 ° C, for 30 minutes to 4 hours at less than 400 ° C to 450 ° C, and finally at 450 to 550 ° C for 30 minutes to 4 hours.

The resin substrate covers all of the peeling layer and forms a resin substrate with a large area compared with the area of the peeling layer. As the resin substrate, a resin substrate made of polyimide typical of a resin substrate of a flexible electronic device can be mentioned, and as a resin solution for forming it, a polyimide solution or a polyamic acid solution can be mentioned. The method of forming the resin substrate may be according to a conventional method.

Next, a desired circuit is formed on the resin substrate fixed to the substrate through the release layer of the present invention, and thereafter, the resin substrate is cut along, for example, the release layer, To separate the resin substrate from the gas. At this time, a part of the gas may be cut together with the release layer.

Japanese Laid-Open Patent Application No. 2013-147599 discloses a laser lift-off method (LLO method) that has been used in the manufacture of a high-brightness LED or a three-dimensional semiconductor package until now for application to the production of a flexible display. The LLO method is characterized by irradiating a light beam of a specific wavelength, for example, a light beam with a wavelength of 308 nm, from the surface opposite to the surface on which the circuit or the like is formed from the glass substrate side. The irradiated light beam passes through the glass substrate, and only the polymer (polyimide) near the glass substrate absorbs the light beam and evaporates (sublimes). As a result, it becomes possible to selectively peel the resin substrate from the glass substrate without affecting the circuit provided on the resin substrate, which determines the performance of the display.

Since the release layer of the present invention is characterized in that it sufficiently absorbs light of a specific wavelength (for example, 308 nm) at which the LLO method can be applied, it can be used as a sacrifice layer of the LLO method. Therefore, when a desired circuit is formed on a resin substrate fixed on a glass substrate through a release layer formed by using the composition of the present invention, and thereafter the LLO method is performed to irradiate a light beam of 308 nm, It absorbs light and evaporates (sublimes). This makes it possible to selectively peel the resin substrate from the glass substrate by sacrificing the peeling layer (serving as a sacrificial layer).

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[1] Abbreviation for Compound

NMP: N-methylpyrrolidone

BCS: butyl cellosolve

p-PDA: p-phenylenediamine

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

2AP: 2-aminophenol

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

TFMB: 2,2'-bis (trifluoromethyl) benzidine

PMDA: pyromellitic dianhydride

PA: phthalic anhydride

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid-1,2: 3,4-dianhydride

[2] Measurement of weight average molecular weight and molecular weight distribution

(Shodex (registered trademark) columns KF803L and KF805L) manufactured by Nihon Bunko Co., Ltd., dimethylformamide was used as an eluting solvent at a flow rate of 1 ml / min, and the weight average molecular weight (hereinafter abbreviated as Mw) And a column temperature of 50 캜. Mw was a polystyrene conversion value.

[3] Synthesis of polymers

Polyamic acid was synthesized by the following method.

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

Synthesis Example S1 Polyamic acid (Synthesis of S1)

3.176 g (0.02937 mol) of p-PDA was dissolved in 88.2 g of NMP, and 8.624 g (0.02931 mol) of BPDA was added, followed by reaction at 23 占 폚 for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 107,300 and the molecular weight distribution was 4.6.

Synthesis Example L1 Synthesis of Polyamic acid (L1)

1.507 g (0.0139 mol) of p-PDA was dissolved in 43.2 g of NMP, 3.166 g (0.01452 mol) of PMDA was added, and the mixture was allowed to react at 23 deg. C for 2 hours under a nitrogen atmosphere. Thereafter, 0.127 g (0.0012 mol) of 2AP was further added, and the reaction was allowed to proceed at 23 deg. C for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 48,500 and the molecular weight distribution was 2.08.

Synthesis Example L2 Synthesis of polyamic acid (L2)

1.119 g (0.01103 mole) of p-PDA was dissolved in 35.2 g of NMP, and 3.006 g (0.01378 mole) of PMDA was added, followed by reaction at 23 占 폚 for 2 hours under a nitrogen atmosphere. Thereafter, 0.602 g (0.00551 mol) of 2AP was further added, and the reaction was allowed to proceed at 23 deg. C for 24 hours under a nitrogen atmosphere. The polymer thus obtained had Mw of 11,700 and a molecular weight distribution of 1.76.

<Synthesis Example L3> Synthesis of polyamic acid (L3)

0.681 g (0.00629 mole) of p-PDA was dissolved in 35.2 g of NMP, 2.746 g (0.01259 mole) of PMDA was added, and the mixture was reacted at 23 deg. C for 2 hours under a nitrogen atmosphere. Thereafter, 1.373 g (0.012588 mol) of 2AP was further added, and the reaction was allowed to proceed at 23 占 폚 for 24 hours under a nitrogen atmosphere. The polymer obtained had Mw of 8,000 and a molecular weight distribution of 1.57.

Synthesis Example L4 Synthesis of polyamic acid (L4)

1.5206 g (0.01406 mol) of p-PDA and 0.105 g (0.00287 mol) of 6FAP were dissolved in 35.2 g of NMP, and 3.004 g (0.01377 mol) of PMDA was added and the reaction was allowed to proceed at 23 占 폚 for 22 hours under a nitrogen atmosphere. Thereafter, 0.170 g (0.00115 mol) of PA was further added, and the reaction was allowed to proceed at 23 deg. C for 22 hours under a nitrogen atmosphere. The polymer thus obtained had Mw of 22,100 and a molecular weight distribution of 1.93.

<Comparative Synthesis Example B1> Synthesis of polyamic acid (B1)

1.29 g (0.00107 mol) of p-PDA was dissolved in 43.2 g of NMP, 3.509 g (0.00119 mol) of BPDA was added, and the reaction was allowed to proceed at 23 占 폚 for 24 hours under a nitrogen atmosphere. The polymer thus obtained had Mw of 34,000 and a molecular weight distribution of 2.03.

&Lt; Comparative Synthesis Example B2 > Synthesis of polyamic acid (B2)

2.88 g (0.0089 mol) of TFMB was dissolved in 35.2 g of NMP, 1.944 g (0.00991 mol) of CBDA was added, and the reaction was allowed to proceed at 23 deg. C for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 69,200 and the molecular weight distribution was 2.2. The obtained solution was soluble in PGME.

[4] Preparation of composition for resin substrate formation

The reaction liquid obtained in Synthesis Example S1 was directly used as a composition for forming a resin substrate.

[5] Preparation of composition for forming release layer

[Example 1-1]

BCS and NMP were added to the reaction solution obtained in Synthesis Example L1, and the composition was diluted to a polymer concentration of 5 wt% and a BCS of 20 mass% to obtain a composition for forming a release layer.

[Examples 1-2 to 1-4]

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 L4 was used instead of the reaction solution obtained in Synthesis Example L1.

[Comparative Examples 1-1 to 1-2]

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 Comparative Synthesis Examples B1 and B2 was used instead of the reaction solution obtained in Synthesis Example L1.

[6] Fabrication of release layer and resin substrate

[Example 2-1]

The composition for forming a release layer L1 obtained in Example 1-1 was coated on a 100 mm x 100 mm glass substrate (hereinafter the same) as a glass substrate by using a spin coater (condition: about 30 seconds at a revolution of 3,000 rpm).

Then, the coating film thus obtained was heated at 100 DEG C for 2 minutes using a hot plate, and then heated at 300 DEG C for 30 minutes using an oven, heated to 400 DEG C (10 DEG C / min) (10 占 폚 / min) to 500 占 폚 and heated at 500 占 폚 for 10 minutes to form a release layer having a thickness of about 0.1 占 퐉 on the glass substrate to obtain a glass substrate with a release layer. During the heating, the film-attached substrate was heated in an oven without removing it from the oven.

Using a bar coater (gap: 250 mu m), the composition S2 for forming a resin substrate was applied onto the release layer (resin thin film) on the glass substrate obtained above. The coated film thus obtained was heated at 80 DEG C for 30 minutes using a hot plate and then heated to 140 DEG C for 30 minutes using an oven to raise the heating temperature to 210 DEG C The heating temperature was raised to 300 ° C, the heating temperature was raised to 300 ° C for 30 minutes, the heating temperature was raised to 400 ° C, the heating temperature was 400 ° C for 30 minutes, the heating temperature Was heated to 500 DEG C and heated at 500 DEG C for 60 minutes to form a polyimide substrate having a thickness of about 20 mu m on the release layer to obtain a glass substrate having a resin substrate and a release layer. During the heating, the film-adhered substrate was heated in an oven without taking it out of the oven.

[Examples 2-2 to 2-4]

The same procedures as in Example 2-1 were repeated except that the release layer forming compositions L2 to L4 obtained in Examples 1-2 to 1-4 were used in place of the release layer forming composition L1 obtained in Example 1-1, , A peeling layer and a polyimide substrate were produced, and a glass substrate with a peeling layer and a glass substrate with a resin substrate and peeling layer were obtained.

[Comparative Examples 2-1 to 2-2]

Except that the release layer forming compositions B1 and B2 obtained in Comparative Examples 1-1 and 1-2 were used instead of the release layer forming composition L1 obtained in Example 1-1, , A peeling layer and a polyimide substrate were produced, and a glass substrate with a peeling layer and a glass substrate with a resin substrate and peeling layer were obtained.

[7] Evaluation of peelability

With respect to the glass substrate with the release layer obtained in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2, peelability between the release layer and the glass substrate was confirmed by the following method. Further, the following tests were performed on the same glass substrate.

&Lt; Evaluation of peelability of cross-cut test of resin thin film &

The peeling layers on the glass substrate with the peeling layer obtained in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 were cross-cut (longitudinally and laterally at intervals of 1 mm, the same applies hereinafter), and 100 rectangular cuts were performed. That is, by this cross cut, 100 square pieces of 1 mm square were formed.

Then, an adhesive tape was affixed to the 100 rectangular cut portions, the tape was peeled off, and the peelability was evaluated based on the following criteria. The results are shown in Table 1.

<Criteria>

5B: 0% peeling (no peeling)

4B: Less than 5% exfoliation

3B: peeling less than 5 to 15%

2B: peeling less than 15 to 35%

1B: peeling less than 35 to 65%

0B: peeling of less than 65% to less than 80%

B: 80% to less than 95% peeling

A: peeling less than 95% to less than 100%

AA: 100% peeling (all peeling)

<Evaluation of peelability of resin substrate>

The resin substrates of the resin substrates and release-bonded glass substrates obtained in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 were cut into strips of 25 mm width using a cutter. Then, a cellophane tape was attached to the tip of the cut resin substrate, and this was used as a test piece. This test piece was subjected to a peel test so that the peel angle was 90 ° using an Attonic push fly tester, and the peelability was evaluated based on the following criteria. The results are shown in Table 1.

<Criteria>

5B: 0% peeling (no peeling)

4B: Less than 5% exfoliation

3B: peeling less than 5 to 15%

2B: peeling less than 15 to 35%

1B: peeling less than 35 to 65%

0B: peeling of less than 65% to less than 80%

B: 80% to less than 95% peeling

A: peeling less than 95% to less than 100%

AA: 100% peeling (all peeling)

Peeling layer Resin substrate Peelability of resin substrate and release layer Peelability of peeling layer and glass substrate Example 2-1 L1 S1 AA 5B Example 2-2 L2 S1 AA 5B Example 2-3 L3 S1 AA 5B Examples 2-4 L4 S1 AA 5B Comparative Example 2-1 B1 S1 5B 5B Comparative Example 2-2 B2 S1 5B 5B

From the results shown in Table 1, it was found that the peeling layers of Examples 2-1 to 2-4 could peel off only the resin substrate without peeling the peeling layer from the glass substrate, but in Comparative Examples 2-1 and 2-2, It was confirmed that it could not be done.

Claims (11)

A peeling layer comprising a step of applying a composition for forming a peeling layer containing at least one of polyamic acids represented by the following formulas (1A) to (1C) and an organic solvent on a substrate and baking at a maximum temperature of 450 to 550 캜 &Lt; / RTI &gt;

(Wherein X is a quadrivalent aromatic group having two carboxylic acid derivatives, Y is independently of each other a bivalent aromatic group, and Z ¹ and Z ² are independently of each other 1 (1B) wherein at least one of Y, Z ¹ and Z ² has an alkali-soluble group, and at least one of Y and two Z ^{1 s} in formula (1B) has an alkali-soluble group, 1C), at least one of Y and two Z ² has an alkali-soluble group, and m represents a natural number independently of each other. The method according to claim 1,
Wherein the alkali-soluble group is a carboxyl group or a phenolic hydroxyl group. 3. The method according to claim 1 or 2,
Wherein Y is an aromatic group represented by the following formulas (2) to (5).

R ¹ to R ³ independently represent an alkylene group having 1 to 20 carbon atoms or an alkylene group having 2 to 20 carbon atoms which may be substituted with a halogen atom, An alkynylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 2 to 20 carbon atoms, an ether group, an ester group or an amide group, and? The method of claim 3,
And Y is an aromatic group represented by the following formulas (6) to (9).

(In the formula, &quot;?&Quot; 5. The method according to any one of claims 1 to 4,
Wherein the Z ¹ is a monovalent organic group represented by the following formula (10).

(Wherein Z ³ represents a carboxyl group or a hydroxyl group, and O represents a bond). 6. The method according to any one of claims 1 to 5,
And Z ² is a monovalent organic group represented by the following formula (11).

(Wherein Z ³ represents a carboxyl group or a hydroxyl group, and O represents a bond). 7. The method according to any one of claims 3 to 6,
Wherein the Y further comprises an aromatic group having no alkali-soluble group. 8. The method of claim 7,
Wherein the aromatic group not having an alkali-soluble group is a phenylene group, a biphenylene group or a terphenylene group. A manufacturing method of a flexible electronic device comprising a resin substrate characterized by using a release layer formed by the manufacturing method according to any one of claims 1 to 8. A step of forming a resin substrate by applying a composition for forming a resin substrate on the release layer formed by the manufacturing method according to any one of claims 1 to 8 and then firing at a maximum temperature of 450 캜 or higher Of the flexible electronic device. 11. The method according to claim 9 or 10,
Wherein the resin substrate is a polyimide resin substrate.