TWI755459B - Manufacturing method of peeling layer - Google Patents

Abstract

(式中，X相互獨立為具有2個羧酸衍生物之4價的芳香族基，Y相互獨立為2價的芳香族基，Z¹ 及Z² 相互獨立為1價的有機基，式(1A)中，Y、Z¹ 及Z² 之至少1個具有鹼可溶性基，式(1B)中，Y及2個Z¹ 之至少1個具有鹼可溶性基，式(1C)中，Y及2個Z² 之至少1個具有鹼可溶性基，m相互獨立表示自然數)。The present invention provides a method for producing a release layer, comprising the steps of: coating a release layer-forming composition comprising at least one of the polyamides represented by the following formulae (1A) to (1C) and an organic solvent The step of laying on the substrate and firing at the highest temperature of 450~550℃,

(in the formula, X is independently a tetravalent aromatic group having two carboxylic acid derivatives, Y is independently a bivalent aromatic group, Z ¹ and Z ² are independently a monovalent organic group, the formula ( In 1A), at least one of Y, Z ¹ and Z ² has an alkali-soluble group, in formula (1B), at least one of Y and two Z ¹ has an alkali-soluble group, in formula (1C), Y and 2 At least one of Z ² has an alkali-soluble group, and m independently represents a natural number).

Description

Manufacturing method of peeling layer

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

In recent years, in addition to the characteristics of thinning and weight reduction, electronic devices are also required to have a bendable function. Therefore, it is required to use a lightweight flexible plastic substrate to replace the conventional glass substrate that is heavy, fragile, and cannot be bent. In particular, new-generation displays require the development of active-array full-color TFT display panels using lightweight flexible plastic substrates (hereinafter referred to as resin substrates).

Therefore, various manufacturing methods of electronic devices using resin films as substrates have been reviewed, and new-generation displays can be converted to existing TFT display panel manufacturing equipment. Patent Documents 1, 2 and 3 disclose a method of forming an amorphous silicon thin film layer on a glass substrate, forming a plastic substrate on the thin film layer, and irradiating a laser from the glass substrate side to crystallize the amorphous silicon crystallization, and the plastic substrate is peeled off from the glass substrate by the hydrogen gas generated along with the crystallization.

In addition, Patent Document 4 discloses a method of attaching a peelable layer (referred to as "transferred layer" in Patent Document 4) to a plastic film using the techniques disclosed in Patent Documents 1 to 3 to complete a liquid crystal display device.

However, the methods disclosed in Patent Documents 1 to 4, especially the method disclosed in Patent Document 4, have the following problems: in order to transmit the laser light, a substrate with high light transmittance must be used; To further release the hydrogen contained in the amorphous silicon, it is necessary to irradiate the laser light with sufficient and large energy; sometimes, the peeled layer is damaged due to the irradiation of the laser light. Furthermore, when the layer to be peeled has a large area, it takes a long time for laser processing, so it is difficult to improve the productivity of device fabrication.

As a means to solve this problem, Patent Document 5 adopts the following production steps, that is, using an existing glass substrate as a substrate (hereinafter referred to as a glass substrate), and using a polymer such as a cyclic olefin copolymer on the glass substrate, Forming a peeling layer, after forming a heat-resistant resin film such as a polyimide film on the peeling layer, forming an ITO transparent electrode or TFT on the film for packaging, and finally peeling off and removing the glass substrate.

However, nowadays, TFTs use low-temperature polysilicon TFTs whose mobility is twice as fast as that of amorphous silicon TFTs. This low-temperature polysilicon TFT requires dehydrogenation annealing (Dehydrogenation annealing) above 400°C after amorphous silicon evaporation, and irradiating pulsed laser to crystallize the silicon (hereinafter referred to as TFT steps), but the above dehydrogenation annealing The temperature of the step is equal to or higher than the glass transition (hereinafter referred to as Tg) of the existing polymer. However, when the existing polymer is heated to a temperature higher than Tg, it is known that the adhesion is improved (for example, refer to Patent Document 6). After the heat treatment, the adhesion between the peeling layer and the resin substrate is improved, and the resin substrate is removed from the matrix. Peeling becomes difficult. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 10-125929 [Patent Document 2] Japanese Patent Laid-Open No. 10-125931 [Patent Document 3] International Publication No. 2005/050754 [Patent Document 4] Japanese Patent Laid-Open No. 10-125930 Gazette [Patent Document 5] Japanese Patent Application Laid-Open No. 2010-111853 [Patent Document 6] Japanese Patent Application Laid-Open No. 2008-188792

[The problem to be solved by the invention]

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a method for producing a peeling layer that can be peeled off without damaging the resin substrate of a flexible electronic device. [means to solve the problem]

As a result of careful examination in order to solve the above-mentioned problems, the inventors of the present invention found that by using a composition comprising a polyamic acid having an alkali-soluble group in the molecule and an organic solvent, the firing temperature at the time of forming the peeling layer is set to a specific value. At the highest temperature or higher, a peeling layer having excellent adhesion to the substrate and moderate adhesion and moderate releasability to the resin substrate for flexible electronic devices can be formed, thereby completing the present invention.

(式中，X相互獨立為具有2個羧酸衍生物之4價的芳香族基，Y相互獨立為2價的芳香族基，Z¹ 及Z² 相互獨立為1價的有機基，式(1A)中，Y、Z¹ 及Z² 之至少1個具有鹼可溶性基，式(1B)中，Y及2個Z¹ 之至少1個具有鹼可溶性基，式(1C)中，Y及2個Z² 之至少1個具有鹼可溶性基，m相互獨立表示自然數)。 　　2.如1之剝離層之製造方法，其中上述鹼可溶性基為羧基或酚性羥基。 　　3.如1或2之剝離層之製造方法，其中上述Y包含以下述式(2)~(5)表示之芳香族基，

(式中，W相互獨立表示羧基或羥基，R¹ ~R³ 相互獨立表示可經鹵素原子取代之碳數1~20之伸烷基、碳數2~20之伸烯基、碳數2~20之伸炔基、碳數6~20之伸芳基或碳數2~20之雜伸芳基、醚基、酯基或醯胺基，○表示鍵結鍵)。 　　4.如3之剝離層之製造方法，其中上述Y包含以下述式(6)~(9)表示之芳香族基，

(式中，○表示鍵結鍵)。 　　5.如1~4中任一項之剝離層之製造方法，其中上述Z¹ 為以下述式(10)表示之1價有機基，

(式中，Z³ 表示羧基或羥基，○表示鍵結鍵)。 　　6.如1~5中任一項之剝離層之製造方法，其中上述Z² 為以下述式(11)表示之1價有機基，

(式中，Z³ 表示羧基或羥基，○表示鍵結鍵)。 　　7.如3~6中任一項之剝離層之製造方法，其中上述Y進一步包含不具有鹼可溶性基之芳香族基。 　　8.如7之剝離層之製造方法，其中上述不具有鹼可溶性基之芳香族基為伸苯基、伸聯苯基或聯三伸苯(terphenylene)基。 　　9.一種具備樹脂基板之可撓性電子裝置之製造方法，其係使用如1~8中任一項之製造方法所形成的剝離層。 　　10.一種可撓性電子裝置之製造方法，其特性係包含以下步驟： 　　在使用如1~8中任一項之製造方法所形成的剝離層上，塗佈樹脂基板形成用組成物後，以最高溫度450℃以上燒成，形成樹脂基板的步驟。 　　11.如9或10之可撓性電子裝置之製造方法，其中前述樹脂基板為聚醯亞胺樹脂基板。 [發明效果]Therefore, the present invention provides: 1. A method for producing a release layer, comprising the steps of: a release layer comprising at least one of the polyamic acids represented by the following formulae (1A) to (1C) and an organic solvent The forming composition is coated on the substrate and fired at a maximum temperature of 450~550°C,

(in the formula, X is independently a tetravalent aromatic group having two carboxylic acid derivatives, Y is independently a bivalent aromatic group, Z ¹ and Z ² are independently a monovalent organic group, the formula ( In 1A), at least one of Y, Z ¹ and Z ² has an alkali-soluble group, in formula (1B), at least one of Y and two Z ¹ has an alkali-soluble group, in formula (1C), Y and 2 At least one of Z ² has an alkali-soluble group, and m independently represents a natural number). 2. The method for producing a peeling layer according to 1, wherein the alkali-soluble group is a carboxyl group or a phenolic hydroxyl group. 3. The manufacturing method of the peeling layer according to 1 or 2, wherein the above Y comprises an aromatic group represented by the following formulae (2) to (5),

(In the formula, W independently represents a carboxyl group or a hydroxyl group, and R ¹ to R ³ independently represent an alkylene group with 1 to 20 carbon atoms, an alkenyl group with a carbon number of 2 to 20, and an alkylene group with 2 to 20 carbon atoms that can be substituted by halogen atoms. 20 alkynylene group, carbon number 6-20 aryl group or carbon 2-20 heteroaryl group, ether group, ester group or amide group, ○ represents a bond). 4. The manufacturing method of the peeling layer according to 3, wherein the above Y comprises an aromatic group represented by the following formulae (6) to (9),

(In the formula, ○ represents a bonding bond). 5. The manufacturing method of the peeling layer according to any one of 1 to 4, wherein the above Z ¹ is a monovalent organic group represented by the following formula (10),

(In the formula, Z ³ represents a carboxyl group or a hydroxyl group, and ○ represents a bond). 6. The manufacturing method of the peeling layer according to any one of 1 to 5, wherein the above Z ² is a monovalent organic group represented by the following formula (11),

(In the formula, Z ³ represents a carboxyl group or a hydroxyl group, and ○ represents a bond). 7. The manufacturing method of the peeling layer in any one of 3-6 whose said Y further contains the aromatic group which does not have an alkali-soluble group. 8. The method for producing a peeling layer according to 7, wherein the aromatic group having no alkali-soluble group is a phenylene group, a biphenylene group, or a terphenylene group. 9. The manufacturing method of the flexible electronic device provided with a resin substrate using the peeling layer formed by the manufacturing method in any one of 1-8. 10. A method for manufacturing a flexible electronic device, comprising the steps of: coating a composition for forming a resin substrate on the release layer formed by the manufacturing method according to any one of 1 to 8, and then applying A step of firing at a maximum temperature of 450°C or higher to form a resin substrate. 11. The manufacturing method of a flexible electronic device according to 9 or 10, wherein the resin substrate is a polyimide resin substrate. [Inventive effect]

By employing the method for producing a peeling layer of the present invention, a peeling layer having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate releasability can be obtained with good reproducibility. Therefore, by implementing the manufacturing method of the present invention, in the manufacturing process of the flexible electronic device, the resin substrate formed on the base body or the circuit provided thereon will not be damaged, and the circuit and the like can be The resin substrate is separated from the base. Therefore, the manufacturing method of the present invention can provide simplification of the manufacturing process of the flexible electronic device provided with the resin substrate, or improve the yield thereof. [Form of implementing the invention]

The present invention is described in more detail below. The method for producing a release layer of the present invention is characterized by comprising the following steps: Applying a release layer-forming composition comprising at least one of the polyamides represented by the following formulae (1A) to (1C) and an organic solvent On the substrate, the step of firing at the highest temperature of 450~550℃. Here, the peeling layer in the present invention refers to a layer disposed just above the glass substrate for a specific purpose, and a typical example can be listed in the manufacturing process of flexible electronic devices, in the above-mentioned substrate, and the layer made of polyimide Between the resin substrates of the flexible electronic device formed of such resin, in order to fix the resin substrate in a specific process, and after the electronic circuit is formed on the resin substrate, in order to make the resin substrate easy to use. The provided release layer is peeled off from the base.

In the above formulas, X is independently a tetravalent aromatic group having two carboxylic acid derivatives, Y is independently a bivalent aromatic group, Z ¹ and Z ² are independently a monovalent organic group, and the formula In (1A), at least one of Y, Z ¹ and Z ² has an alkali-soluble group, in formula (1B), at least one of Y and two Z ¹ has an alkali-soluble group, in formula (1C), Y and At least one of the two Z ² has an alkali-soluble group. m independently represents a natural number, but an integer of 2 or more is preferred.

The above-mentioned X series is preferably a 4-valent aromatic ring containing 1 to 5 benzene rings, more preferably a 4-valent benzene ring, a 4-valent naphthalene ring, a 4-valent biphenyl ring, and more preferably a 4-valent benzene ring, 4-valent biphenyl ring.

The divalent aromatic group of Y is preferably an aromatic group containing 1 to 5 benzene rings, and more preferably represented by the following formulae (2') to (5').

In the above formulas (2') to (5'), R ¹ to R ³ independently represent alkylene groups with 1 to 20 carbon atoms, alkenylene groups with 2 to 20 carbon atoms, and 2 ~20 alkynylene group, carbon number 6~20 aryl group or carbon 2~20 heteroaryl group, ether group, ester group or amide group, ○ represents a bond.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Carbon number 1-20, preferably carbon number 1-10 alkylene, can be any of straight chain, branched, cyclic, for example, methylene, methylidene, dimethylidene base, ethyl extension, trimethylene, propylene, butyl, pentyl, hexyl, etc. Carbon number 2-20, preferably carbon number 2-10 alkenylene group, can be any of straight chain, branched, cyclic, for example, vinylidene, propenylene, butenyl, pentylene can be exemplified Alkenyl, hexenyl, heptenyl, octenyl, nonenyl, etc. 2-20 carbon atoms, preferably an alkynylene group having 2-10 carbon atoms, which can be linear, branched or cyclic, such as ethynylene, propynylene, butyne base, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and the like.

Furthermore, when Y is a divalent aromatic group having at least one alkali-soluble group, it is preferable to include an organic group containing a benzene ring substituted with at least one alkali-soluble group, especially two or more groups that are substituted by at least one alkali-soluble group. The organic group of the benzene ring substituted by the alkali-soluble group is more preferably, and more preferably an aromatic group represented by the following formulas (2) to (5), especially more preferably the following formulas (6) to (9) The structures represented by the formulae (6), (7) and (9) having a phenolic hydroxyl group at the ortho position with respect to the adjacent bonding bonds are the best.

(式中，W表示鹼可溶性基，較佳為羧基或酚性羥基，R¹ ~R³ 及○表示與上述相同意義)。

(In the formula, W represents an alkali-soluble group, preferably a carboxyl group or a phenolic hydroxyl group, and R ¹ to R ³ and ○ represent the same meanings as described above).

(式中，○表示鍵結鍵)。

(In the formula, ○ represents a bonding bond).

In the polyamic acid used in the present invention, Y may contain both of a divalent aromatic group having an alkali-soluble group and a divalent aromatic group not having an alkali-soluble group. At this time, the ratio of the divalent aromatic group having an alkali-soluble group in all Y may be about 0.1 to 99.9 mol %, preferably 1 to 50 mol %, more preferably 1 to 10 mol % .

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

(式中，○表示鍵結鍵)。

(In the formula, ○ represents a bonding bond).

Moreover, when Z ¹ and Z ² are divalent aromatic groups having an alkali-soluble group, it is preferable that the alkali-soluble group is directly bonded to the aromatic ring, and it is preferable that the number of alkali-soluble groups is one. More specifically, Z ¹ bonded to the terminal side of the tetracarboxylic acid is preferably a monovalent organic group represented by the following formula (10B), and an alkali-soluble group is preferably present in the following formula (10) in the ortho position with respect to NH. The monovalent organic group represented is more preferably, the Z ² bonded to the terminal side of the diamine is preferably the monovalent organic group represented by the following formula (11B), and the alkali-soluble group exists in the ortho position relative to CO with the following formula The monovalent organic group represented by (11) is more preferable. In particular, the polymer terminal has a hydroxyl group and can be different from the skeleton of the flexible substrate used for the upper layer, so that the function as a release layer of the obtained film can be improved.

(式中，Z³ 表示羧基或羥基，○表示鍵結鍵)。

(In the formula, Z ³ represents a carboxyl group or a hydroxyl group, and ○ represents a bond).

(式中，Z³ 表示羧基或羥基，○表示鍵結鍵)。

(In the formula, Z ³ represents a carboxyl group or a hydroxyl group, and ○ represents a bond).

The polyamides represented by the above formulae (1A) to (1C) can be obtained by reacting a specific aromatic tetracarboxylic dianhydride component and an aromatic diamine component at a specific ratio. The aromatic tetracarboxylic dianhydride component and the aromatic diamine component for synthesizing the polyamic acid used in the production method of the present invention will be described below.

The aromatic tetracarboxylic dianhydride used for the synthesis of the polyamic acid represented by the above formulas (1A) to (1C) is not particularly limited as long as it has two dicarboxylic acid anhydride moieties in the molecule and has an aromatic ring , but an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei is preferred.

Specific examples of the above-mentioned aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, and naphthalene-1,2,3,4-tetracarboxylic acid dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride , naphthalene-2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, Phenyl-2,2',3,3'-tetracarboxylic dianhydride, Biphenyl-2,3,3',4'-tetracarboxylic dianhydride, Biphenyl-3,3',4, 4'-tetracarboxylic dianhydride, anthracene-1,2,3,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2,6,7 -tetracarboxylic dianhydride, anthracene-1,2,7,8-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,3,4-tetra Carboxylic acid dianhydride, phenanthrene-1,2,5,6-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic acid Dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, phenanthrene-2,3,5,6-tetracarboxylic dianhydride, phenanthrene-2,3,6,7-tetracarboxylic dianhydride , phenanthrene-2,3,9,10-tetracarboxylic dianhydride, phenanthrene-3,4,5,6-tetracarboxylic dianhydride, phenanthrene-3,4,9,10-tetracarboxylic dianhydride, 3 ,3',4,4'-benzophenone tetracarboxylic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, 3,3',4,4'-diphenyl tetracarboxylic acid acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropylidene, 4, 4'-hexafluoroisopropylidene diphthalic acid etc. may be used individually or in combination of 2 or more types.

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 more preferably a carboxyl group or a phenolic hydroxyl group The aromatic diamine of the aromatic ring is more preferably an aromatic diamine containing an aromatic group substituted with a phenolic hydroxyl group.

Examples of aromatic diamines having a phenolic hydroxyl group include 3,3'-diamino-4,4'-dihydroxybiphenyl (4BP), 3,3'-diamino-2,2'-diphenyl Hydroxybiphenyl (2BP), 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 2,2-bis(4-amino-3,5-dihydroxybenzene) base) hexafluoropropane, 2,2-bis[4-(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), 3 ,3'-Diamino-4,4'-dihydroxy-phenylthio ether, 2,2'-bis(3-amino-4-hydroxyphenyl)propane (BAPA), (3-amino- 4-Hydroxy) phenyl (3-amino 4-hydroxy) aniline (anilide) (AHPA), bis (3-amino-4-hydroxy phenyl) bismuth (BSDA), bis-N,N'-(p -Aminobenzyl)-hexafluoro-2,2'-bis(4-hydroxyphenyl)propane (BABHBPA), [4-(4-aminophenoxy)phenyl]thiane, 2,4 -Diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3- Amino-4-hydroxyphenyl) sulfide, bis(4-amino-3,5-dihydroxyphenyl) sulfide, bis(3-amino-4-hydroxyphenyl) ether, bis(4- Amino-3,5-dihydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, bis(3-amino-3,5-dihydroxyphenyl)methane -amino-4-hydroxyphenyl) bis(4-amino-3,5-dihydroxyphenyl) bis(4-amino-3,5-dihydroxyphenyl), 4,4'-diamino-3,3'-dihydroxybiphenyl ( 3BP), 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5, 5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino- 4-Hydroxyphenoxy)phenyl] bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane, or, 1,4-bis(4-aminophenoxy) Benzene, but not limited to these.

Among the above-mentioned diamine components, 3,3'-diamino-4,4'-dihydroxybiphenyl (4BP), 3,3'-diamino-2,2'-dihydroxybiphenyl Benzene (2BP), 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 2,2-bis(4-amino-3,5-dihydroxyphenyl) Hexafluoropropane, 2,2-bis[4-(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-phenylene ether (AHPE), 3,3 '-Diamino-4,4'-dihydroxy-phenylthio ether, 2,2'-bis(3-amino-4-hydroxyphenyl)propane (BAPA), (3-amino-4- Hydroxy)phenyl(3-amino-4-hydroxy)aniline (AHPA), bis(3-amino-4-hydroxyphenyl) bismuth (BSDA), bis-N,N'-(p-aminobenzyl) Acryloyl)-hexafluoro-2,2'-bis(4-hydroxyphenyl)propane (BABHBPA), [4-(4-aminophenoxy)phenyl]thiane, 2,4-diaminophenol , 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl) sulfide, bis( 4-Amino-3,5-dihydroxyphenyl) sulfide, bis(3-amino-4-hydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl) methane -Amino-4-hydroxyphenyl) bismuth, 4,4'-diamino-3,3'-dihydroxybiphenyl (3BP), 4,4'-diamino-3,3'-diamino Hydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3- Amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3-hydroxyphenoxy) Benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]benzene, bis[4-(3 -amino-4-hydroxyphenoxy)phenyl]propane, or, 1,4-bis(4-aminophenoxy)benzene.

Particularly preferred ones include bis(3-amino-4-hydroxyphenyl)methane (BAPF), 2,2'-bis(3-amino-4-hydroxyphenyl)propane (BAPA), 2,2 '-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 3,3'-diamino-4,4'-dihydroxy-phenyl ether (AHPE), 3,3'- Diamino-4,4'-dihydroxybenzophenone (AHPK), bis(3-amino-4-hydroxyphenyl) bismuth (BSDA), (3-amino-4-hydroxy)phenyl ( 3-Amino-4-hydroxy)aniline (AHPA), bis-N,N'-(p-aminobenzyl)-hexafluoro-2,2'-bis(4-hydroxyphenyl)propane ( BABHBPA), etc.

The aromatic diamine having a carboxyl group includes 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1, 3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl) ether, bis(4-amino-3,5- Dicarboxyphenyl) ether, bis(4-amino-3-carboxyphenyl) bis(4-amino-3,5-dicarboxyphenyl) bis(4-amino-3,5-dicarboxyphenyl) bismuth, 4,4'-diamino-3 ,3'-Dicarboxybiphenyl, 4,4'-Diamino-3,3'-Dicarboxy-5,5'-Dimethylbiphenyl, 4,4'-Diamino-3,3' -Dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxy) phenoxy) benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, etc.

Moreover, as mentioned above, the aromatic diamine which does not have an alkali-soluble group can also be used for the diamine component used for the synthesis|combination of the said polyamic acid. Specific examples of the aromatic diamine not having an alkali-soluble group include p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3, 5,6-Tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenyl ether (ODA), 3,4'-diaminodiphenyl ether, 3,3'-diamine diphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diphenylmethane Amino diphenylmethane, 4,4-methylidene-bis(2-methylaniline), 4,4'-methylidene-bis(2,6-dimethylaniline), 4,4-methylaniline Methyl-bis(2,6-diethylaniline), 4,4'-methylidene-bis(2-isopropyl-6-methylaniline), 4,4'-methylidene-bis( 2,6-Diisopropylaniline), 4,4'-Diaminodiphenylene, 3,3'-Diaminodiphenylene, Benzidine, o-Tolidine, m-Dimethyl Aniline, 3,3',5,5'-tetramethylbenzidine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]benzene, bis[4-(3-aminophenoxy)phenyl] bismuth, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane.

The input ratio of the diamine component and the tetracarboxylic dianhydride component is appropriately determined in consideration of the intended molecular weight or molecular weight distribution, the type of diamine or the type of tetracarboxylic dianhydride, etc., so it cannot be specified in general, as long as it is 1:1 ( Molar ratio) can be used as a ratio according to a desired molecular chain terminal, and when it is used as both ends of a molecular chain derived from tetracarboxylic acid (formula (1B)), with respect to 1 mole of diamine component, tetracarboxylic acid The dianhydride component is preferably 1.05 to 3.0 mol, more preferably 1.07 to 2.5 mol, still more preferably 1.1 to 2.0 mol, and when used as both ends of the molecular chain derived from diamine (formula (1C)), relative to The content of tetracarboxylic dianhydride is 1 mol, and the content of diamine is preferably 1.00-2.5 mol, more preferably 1.01-1.5 mol, and still more preferably 1.02-1.3 mol.

The organic solvent for such a reaction is not particularly limited as long as it does not adversely affect the reaction, and specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropyl amide, 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, etc. In addition, the organic solvent may be used alone or in combination of two or more.

In particular, the organic solvent for the reaction is preferably selected from the group consisting of amides represented by formula (S1), amides represented by (S2) and At least one of the amides represented by the formula (S3).

In the formula, R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. h represents a natural number, preferably 1 to 3, more preferably 1 or 2.

The alkyl group having 1 to 10 carbon atoms includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like. 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 can be appropriately set within the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100°C. When the content of the unit is high, it 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 depends on the reaction temperature and the reactivity of the raw material, and therefore cannot be uniformly defined, but is usually about 1 to 100 hours.

A polyamic acid obtained by reacting the above-described tetracarboxylic dianhydride component and diamine component, and then with ^a terminal blocking ^compound having an alkali-soluble group or without Z1 and/or Z2. The polyamides represented by the formulae (1A) to (1C) can be obtained by reacting the capping compounds of the alkali-soluble groups. More specifically, an aromatic monoamine can be suitably used to provide a capping compound which is bonded to Z ¹ on the terminal side of the tetracarboxylic acid. Aromatic monoamines are preferably those having an aromatic ring with a carbon number of 6 to 30, more preferably those having an aromatic ring with a carbon number of 6 to 15, and more preferably those having an aromatic ring with a carbon number of 6 to 10, as described above , those containing 1 benzene ring are preferred.

Specific examples of the aromatic monoamine not having an alkali-soluble group include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 9- Phenanthrene, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, etc. 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; 2-aminobenzoic acid , 3-aminobenzoic acid, 4-aminobenzoic acid and other aromatic monoamines with carboxyl groups, etc. Among these, the capping compound that provides Z ¹ is preferably an aromatic monoamine having an alkali-soluble group, more preferably an aromatic monoamine having a phenolic hydroxyl group, and still more preferably 2-aminophenol.

In addition, an aromatic carboxylic acid can be suitably used as a capping compound that provides Z ² bonded to the diamine terminal side. The aromatic carboxylic acid is preferably one having an aromatic ring with a carbon number of 6 to 30, preferably one with an aromatic ring with a carbon number of 6 to 15, and more preferably one with an aromatic ring with a carbon number of 6 to 10, as described above, Those containing one benzene ring are preferred.

Specific examples of the aromatic carboxylic acid having no alkali-soluble group after capping include benzoic acid, 1-naphthalene carboxylic acid, 2-naphthalene carboxylic acid, 1-anthracene carboxylic acid, 2-anthracene carboxylic acid, and 9-anthracene carboxylic acid Aromatic monocarboxylic acids such as carboxylic acid, 2-phenylbenzoic acid, 3-phenylbenzoic acid, and 4-phenylbenzoic acid. Specific examples of the aromatic carboxylic acid having an alkali-soluble group after capping include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; salicylic acid, 3-hydroxybenzoic acid, etc. , Aromatic monocarboxylic acids with phenolic hydroxyl groups such as 4-hydroxybenzoic acid, etc. Moreover, the said carboxylic acid may be in the form of an acid halide or an acid anhydride. Among these, the capping compound that provides Z ² is preferably an aromatic carboxylic acid having an alkali-soluble group after capping, preferably an aromatic dicarboxylic acid, and more preferably phthalic acid.

The polyamic acid represented by the formulae (1A) to (1C) of the present invention, when only the diamine component which does not have an alkali-soluble group is used as the diamine component (that is, when all Y does not have an alkali-soluble group) , Z ¹ and/or Z ² must have an alkali-soluble group, in this case, either or both of the ends of the molecular chain of the synthesized polyamic acid are terminated with the above-mentioned monoamine or carboxylic acid with an alkali-soluble group That's it.

The input amount of the end-capping compound is relative to 1 mol of the above-mentioned polyamide acid, as long as it is more than 1 mol, preferably more than 2 mol, more preferably 2-4 mol, and more preferably 2-3 mol. Moore. In addition, when an aromatic monoamine is used, the addition amount is preferably 0.1 mol or more, more preferably 0.2 to 4 mol, relative to 1 mol of the tetracarboxylic dianhydride used in the synthesis of the above-mentioned polyamide acid. More preferably, 0.2 to 3 mol may be used as a reference. In addition, the amount of the aromatic carboxylic acid added is preferably 0.1 mol or more, more preferably 0.2 to 4 mol, and still more preferably 0.2 mol relative to 1 mol of the diamine component used in the synthesis of the polyamide acid. ~3 moles can be used as a benchmark.

The organic solvent used for blocking the ends of the molecular chain of the polyamic acid is not particularly limited as long as it does not adversely affect the reaction, and the same solvents as those exemplified for the synthesis of the polyamic acid can be used. The reaction temperature for blocking the end of the molecular chain of the polyamic acid is the same as that for the synthesis of the polyamic acid, as long as it is appropriately set within the range from the melting point to the boiling point of the solvent to be used, usually about 0 to 100°C, However, from the viewpoint of surely blocking the ends of the molecular chain of the synthesized polyamide, 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 depends on the reaction temperature and the reactivity of the raw material, and therefore cannot be uniformly specified, but is usually about 1 to 100 hours.

The weight-average molecular weight of the polyamic acid in which either or both of the molecular chain ends thus obtained is blocked is usually about 5,000 to 500,000, but from the viewpoint of improving the function of the obtained film as a release layer, it is preferably About 6,000~200,000, more preferably about 7,000~150,000. In addition, in the present invention, the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

In the present invention, the reaction solution after capping is usually used as it is, or a solution obtained by diluting or concentrating it as the composition for forming a peeling layer of the present invention. In addition, the above-mentioned reaction solution may be filtered if necessary. Filtration can not only reduce the contamination of impurities which may cause deterioration of the adhesion, peelability, etc. of the obtained peeling layer, but also can efficiently obtain a composition for forming a peeling layer. Moreover, it can also be used as a composition for forming a peeling layer by redissolving in a solvent after the ionomeric acid in the above-mentioned reaction solution. The solvent at this time includes the organic solvent used for the above-mentioned reaction, and the like.

The solvent for dilution is not particularly limited, and specific examples thereof are the same as the specific examples of the reaction solvent in the aforementioned reaction. The solvent for dilution may be used alone or in combination of two or more. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethylformamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, Methyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ-butyrolactone, more preferably N-methyl-2-pyrrolidone.

Moreover, even if the solvent which does not dissolve polyamic acid alone is in the range in which polyamic acid does not precipitate, it can be mixed with the composition for forming a peeling layer of the present invention. In particular, it can be appropriately mixed with ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2- Propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol- 1-Monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate , n-propyl lactate, n-butyl lactate, isoamyl lactate and other solvents with low surface tension. As a result, it is known to improve the uniformity of the coating film when it is applied to a substrate, and it is also applicable to the composition for forming a peeling layer of the present invention.

The concentration of the polyamic acid in the composition for forming a peeling layer of the present invention is appropriately set in consideration of the thickness of the peeling layer to be produced, the viscosity of the composition, and the like, but is usually about 1 to 30% by mass, preferably 1 ~20% by mass. By setting it as such a density|concentration, the peeling layer of the thickness of about 0.05-5 micrometers can be obtained with good reproducibility. The concentration of polyamic acid can be adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride used as the raw material of polyamic acid. After filtering the above reaction solution, the filtrate is diluted or concentrated, and the isolated polymer is separated. When the amide acid is dissolved in the solvent, it is adjusted by adjusting the amount thereof.

In addition, the viscosity of the composition for forming a peeling layer is appropriately set in consideration of the thickness of the peeling layer to be produced, etc., but especially in order to obtain a film with a thickness of about 0.05 to 5 μm with good reproducibility, it is usually 10 at 25°C. About ~10,000mPa･s, preferably about 20~5,000mPa･s.

Here, the viscosity is measured using a viscometer for measuring the viscosity of a commercially available liquid, for example, referring to the procedure described in JIS K7117-2, and it can be measured at a temperature of the composition of 25°C. The viscometer is preferably a conical plate type (cone plate type) rotational viscometer, preferably a viscometer of the same type, the standard conical rotor is 1°34'×R24, and the temperature of the composition is 25°C. Measurement. As such a rotational viscometer, TVE-25L manufactured by Toki Sangyo Co., Ltd. is exemplified, for example.

Moreover, the composition for peeling layer formation of this invention may contain components, such as a crosslinking agent, in addition to a polyamic acid and an organic solvent, for example, in order to improve film strength.

Thermal imidization of polyamic acid by a firing method including a step of applying the above-described composition for forming a peeling layer on a substrate, followed by firing at a maximum temperature of 450 to 550°C or higher , a release layer made of a polyimide film can be obtained which has excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate releasability. In the present invention, the maximum temperature at the time of firing is 450 to 550°C, and it is not particularly limited when it is within the range of the heat-resistant temperature of polyimide, but it is considered to improve the adhesion to the above-mentioned substrate or In the case of moderate adhesion and peelability of the resin substrate, 500° C. or higher is preferable. In addition, the upper limit is usually about 550°C, but preferably about 510°C. By making the heating temperature into the above-mentioned range, the weakening of the obtained film can be prevented, and the imidization reaction can be sufficiently advanced. The heating time varies depending on the heating temperature and cannot be specified in general, but it is usually 1 minute to 5 hours. In addition, the imidization rate may be in the range of 50 to 100%.

Moreover, when the maximum temperature at the time of the above-mentioned firing is within the above-mentioned range, the step of firing at a temperature lower than this temperature may be included. A preferred example of the heating aspect in the present invention includes a method of heating at 50-150°C, increasing the heating temperature stepwise in this state, and finally heating at 450-550°C. In particular, a more preferable example of the heating aspect includes heating at 50°C to 100°C, then heating at more than 100°C to less than 450°C, and further heating at 450°C or higher. In addition, another more preferable example of the heating state includes heating at 50-150°C, then heating at over 150°C-350°C, then heating at over 350°C-less than 450°C, and finally heating at 450-550°C method.

In addition, a preferred example of the heating state in consideration of the firing time includes heating at 50 to 150° C. for 1 minute to 2 hours, increasing the heating temperature stepwise in this state, and finally heating at 400° C. or more for 30 minutes to 30 minutes. 4 hour method. In particular, a more preferable example of the heating mode includes heating at 50 to 100°C for 1 minute to 2 hours, heating at over 100°C to less than 450°C for 5 minutes to 2 hours, and heating at 450°C or higher for 30 minutes to 4 hours. hour method. In addition, another more preferable example of the heating state may include heating at 50-150°C for 1 minute to 2 hours, then heating at more than 150°C to 350°C for 5 minutes to 2 hours, and then heating at more than 350°C to less than 450°C. The method of heating at ℃ for 30 minutes to 4 hours, and finally heating at 450 to 510℃ for 30 minutes to 4 hours.

Moreover, when the peeling layer of the present invention is formed on the substrate, the peeling layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface. In the form of forming a peeling layer on a part of the surface of the substrate, for example, there are forms in which the peeling layer is formed only in a specific range in the surface of the substrate, dot pattern, line width/space pattern on the entire surface of the substrate, etc. The pattern shape forms the form of the peeling layer, etc. Moreover, in this invention, a base system means the thing which the composition for peeling layer formation of this invention is apply|coated to the surface, and can be used for the manufacture of a flexible electronic device etc..

The substrate (substrate) includes, for example, glass, metal (silicon wafer, etc.), slate, etc. In particular, since the peeling layer obtained from the peeling layer forming composition of the present invention has sufficient adhesion to the substrate, Glass is preferred. In addition, the surface of the base body may be composed of a single material, or may be composed of two or more kinds of materials. A state in which the surface of the substrate is composed of two or more kinds of materials. For example, in the surface of the substrate, a certain area is composed of a certain material, and the rest of the surface is composed of other materials. A state in which a material exists in other materials in a pattern such as a dot pattern, a line width/spacing pattern, or the like.

The coating method is not particularly limited, and examples thereof include cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, ink jet coating, and printing. Method (relief, gravure, lithography, screen printing, etc.) and so on.

As a heating apparatus, a hotplate, an oven, etc. are mentioned, for example. The heating environment can be under air, also under inert gas, under normal pressure or under reduced pressure.

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

The peeling layer described above has excellent adhesion to a substrate, particularly a glass substrate, and moderate adhesion and moderate releasability to a resin substrate. Therefore, the peeling layer of the present invention will not damage the resin substrate of the device during the manufacturing process of the flexible electronic device, and can be applied to peel the resin substrate from the substrate together with the circuits formed on the resin substrate. .

An example of the manufacturing method of the flexible electronic device using the peeling layer of this invention is demonstrated below. Using the composition for forming a peeling layer of the present invention, a peeling layer is formed on a glass substrate by the above method. A resin substrate-forming solution for forming a resin substrate is coated on the peeling layer, and the coating film is fired to form a resin substrate fixed to a glass substrate via the peeling layer of the present invention. The firing temperature of the coating film is appropriately set according to the type of resin, etc. In the present invention, the maximum temperature at the time of firing is preferably 450 to 550° C. or higher, more preferably 480° C. or higher, and more preferably 490° C. ℃ or higher, more preferably 500°C or higher. By setting the maximum temperature at the time of firing at the time of resin substrate production into this range, the adhesion between the peeling layer of the bottom layer and the base, or the appropriate adhesion and peeling between the peeling layer and the resin substrate can be further improved. At this time, when the maximum temperature is within the above range, a step of firing at a temperature lower than this temperature may be included.

A preferable example of the heating form at the time of resin substrate production includes heating at 50 to 150° C., then increasing the heating temperature stepwise in this state, and finally heating at 450 to 550° C. In particular, a more preferable example of the heating aspect includes heating at 50°C to 100°C, then heating at more than 100°C to less than 450°C, and further heating at 450°C or higher. In addition, another more preferable example of the heating state includes heating at 50 to 100°C, then heating at over 100°C to 200°C, then heating at over 200°C to less than 300°C, and heating at 300°C to less than 400°C Heating is a method of heating at 400°C to less than 450°C, and finally heating at 450°C to 550°C.

In addition, a preferable example of the heating state in consideration of the firing time includes heating at 50 to 150°C for 5 minutes to 2 hours, then increasing the heating temperature stepwise in this state, and finally heating at 450 to 550°C for 30 minutes. ~4 hours of manipulation. In particular, a more preferable example of the heating mode includes heating at 50 to 100°C for 5 minutes to 2 hours, heating at more than 100°C to less than 450°C for 5 minutes to 2 hours, and heating at 450°C or higher for 30 minutes to 4 hours method. In addition, another more preferable example of the heating state includes heating at 50 to 100°C for 5 minutes to 2 hours, then heating at over 100°C to 200°C for 5 minutes to 2 hours, and then at over 200°C to less than 300°C. ℃ heating for 30 minutes~4 hours, heating at 300~400℃ for 30 minutes~4 hours, heating at 400~450℃ for 30 minutes~4 hours, and finally heating at 450~550℃ for 30 minutes~4 hours method.

The resin substrate is entirely covered with the peeling layer, and the resin substrate is formed in a larger area than the area of the peeling layer. The resin substrate includes a resin substrate made of polyimide, which is represented by a resin substrate of a flexible electronic device, and the resin solution for forming the resin substrate includes a polyimide solution or a polyamide acid solution. . The method for forming the resin substrate may be based on a conventional method.

Next, through the peeling layer of the present invention, it is fixed on the resin substrate of the base body to form a desired circuit, and then, for example, the resin substrate is cut along the peeling layer, and the resin substrate is peeled off the peeling layer together with the circuit. Resin substrate and matrix. At this time, a part of the base body may also be cut together with the release layer.

Furthermore, Japanese Patent Laid-Open No. 2013-147599 discloses that a laser lift-off method (LLO method) conventionally used in the manufacture of high-brightness LEDs, three-dimensional semiconductor packages, and the like is used in the manufacture of flexible displays. The above-mentioned LLO method is characterized by irradiating light of a specific wavelength, for example, light having a wavelength of 308 nm, from the side of the glass substrate opposite to the surface on which the circuit and the like are formed. The irradiated light penetrates the glass substrate, and only the polymer (polyimide) near the glass substrate absorbs the light and then evaporates (sublimates). This result determines the performance of the display, and does not affect the circuit etc. provided on the resin substrate, and the resin substrate can be selectively peeled off from the glass substrate.

The peeling layer of the present invention has the characteristic of fully absorbing light of a specific wavelength (eg, 308 nm) that can be used in the LLO method, so it can also be used as a sacrificial layer in the LLO method. Therefore, when the peeling layer formed by using the composition of the present invention is fixed on the resin substrate of the glass base to form a desired circuit, and then the LLO method is performed, when irradiated with light of 308 nm, only the peeling layer absorbs the light and Evaporation (sublimation). Thereby, the said peeling layer becomes an animal (functions as an animal layer), and a resin substrate can be selectively peeled from a glass substrate.

[Example]

The following examples are given to describe the present invention in more detail, but the present invention is not limited to these examples.

[1] Abbreviation of 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 dianhydride TFMB: 2,2'-bis(trifluoromethyl)benzidine PMDA: pyromellitic dianhydride PA: ortho Phthalic anhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-dianhydrate

[2] Measurement of Weight-Average Molecular Weight and Molecular Weight Distribution The weight-average molecular weight (hereinafter referred to as Mw) and molecular weight distribution of the polymer were obtained by using a GPC device (Shodex (registered trademark) column KF803L and KF805L) manufactured by Nippon Shoko Co., Ltd. The solvent was dimethylformamide, the flow rate was 1 mL/min, and the column temperature was measured at 50°C. In addition, Mw is a polystyrene conversion value.

[3] Synthesis of polymer Polyamic acid was synthesized according to the following method. In addition, from the obtained polymer-containing reaction solution, the polymer was not isolated, but a resin substrate-forming composition or a release layer-forming composition was prepared by diluting the reaction solution as described later.

<Synthesis example S1 polyamide (S1 synthesis)> 3.176 g (0.02937 mol) of p-PDA was dissolved in 88.2 g of NMP, 8.624 g (0.02931 mol) of BPDA was added, and the mixture was added under a nitrogen atmosphere for 23 The reaction was allowed to proceed at °C for 24 hours. The Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.

<Synthesis example L1: Synthesis of polyamide 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 added under a nitrogen atmosphere for 23 hours. The reaction was allowed to proceed at °C for 24 hours. Then, 0.127 g (0.0012 mol) of 2AP was further added, and the reaction was allowed to proceed at 23° 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 polyamide (L2)> 1.119 g (0.01103 mol) of p-PDA was dissolved in 35.2 g of NMP, 3.006 g (0.01378 mol) of PMDA was added, and the mixture was added under nitrogen atmosphere for 23 The reaction was allowed to proceed at °C for 2 hours. Then, 0.602 g (0.00551 mol) of 2AP was further added, and the reaction was allowed to proceed at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 11,700, and the molecular weight distribution was 1.76.

<Synthesis example L3: Synthesis of polyamide (L3)> 0.681 g (0.00629 mol) of p-PDA was dissolved in 35.2 g of NMP, 2.746 g (0.01259 mol) of PMDA was added, and the mixture was added under nitrogen atmosphere for 23 The reaction was allowed to proceed at °C for 2 hours. Then, 1.373 g (0.012588 mol) of 2AP was further added, and the reaction was allowed to proceed at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 8,000, and the molecular weight distribution was 1.57.

<Synthesis example L4: Synthesis of polyamide (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. Then, it was made to react at 23 degreeC under nitrogen atmosphere for 22 hours. Then, after adding PA 0.170g (0.00115 mol), it was made to react at 23 degreeC under nitrogen atmosphere for 22 hours. The Mw of the obtained polymer was 22,100, and the molecular weight distribution was 1.93.

<Comparative Synthesis Example B1: Synthesis of Polyamide (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 mixture was added to The reaction was allowed to proceed at 23°C for 24 hours. The Mw of the obtained polymer was 34,000, and the molecular weight distribution was 2.03.

<Comparative Synthesis Example B2: Synthesis of Polyamide (B2)> 2.86 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 temperature was kept at 23°C under nitrogen atmosphere. Allow the reaction for 24 hours. The Mw of the obtained polymer was 69,200, and the molecular weight distribution was 2.2. The resulting solution was soluble in PGME.

[4] Preparation of the composition for forming a resin substrate The reaction solutions obtained in Synthesis Example S1 were used as they were as a composition for forming a resin substrate.

[5] Preparation of the composition for forming a peeling layer [Example 1-1] BCS and NMP were added to the reaction solution obtained in Synthesis Example L1, and the mixture was diluted so that the polymer concentration was 5 wt % and BCS was 20 mass % to obtain peeling A composition for forming a layer.

[Examples 1-2 to 1-4] In the same manner as in Example 1-1, except that the reaction solutions obtained in Synthesis Examples L2 to L4 were used in place of the reaction solutions obtained in Synthesis Example L1, respectively, a composition for forming a peeling layer was obtained .

[Comparative Examples 1-1 to 1-2] A composition for forming a peeling layer was obtained in the same manner as in Example 1-1, except that the reaction solutions obtained in Comparative Synthesis Examples B1 and B2 were used instead of the reaction solution obtained in Synthesis Example L1, respectively. thing.

[6] Preparation of peeling layer and resin substrate [Example 2-1] The composition L1 for forming a peeling layer obtained in Example 1-1 was prepared by using a spin coater (conditions: 3,000 rpm, about 30 seconds of rotation), It was coated on a 100 mm×100 mm glass substrate (the same below) as a glass substrate. Then, the obtained coating film was heated at 100°C for 2 minutes using a hot plate, then heated at 300°C for 30 minutes using an oven, the heating temperature was raised (10°C/min) to 400°C, and then heated at 400°C After 30 minutes, the temperature was raised (10°C/min) to 500°C, and heated at 500°C for 10 minutes to form a peeling layer with a thickness of about 0.1 μm on the glass substrate to obtain a glass substrate with a peeling layer. In addition, during the heating period, the film-coated substrate was not taken out from the oven, and was heated in the oven.

Using an applicator bar (gap: 250 μm), the composition S2 for forming a resin substrate was applied on the release layer (resin film) on the glass substrate obtained above. The obtained coating film was heated at 80°C for 30 minutes using a hot plate, then heated at 140°C for 30 minutes using an oven to form a nitrogen atmosphere, and the heating temperature was raised (2°C/min, the same below) to 210°C , heated at 210°C for 30 minutes, then heated to 300°C, heated at 300°C for 30 minutes, heated to 400°C, heated at 400°C for 30 minutes, heated to 500°C, Heating at 500°C for 60 minutes, a polyimide substrate with a thickness of about 20 μm was formed on the peeling layer, and a resin substrate and a glass substrate with peeling layer were obtained. In addition, during the heating period, the film-coated substrate was not taken out from the oven, and was heated in the oven.

[Examples 2-2 to 2-4] Except that the compositions L2 to L4 for forming a peeling layer obtained in Examples 1-2 to 1-4 were used in place of the composition L1 for forming a peeling layer obtained in Example 1-1, respectively In the same manner as in Example 2-1, a peeling layer and a polyimide substrate were produced to obtain a glass substrate with peeling layer, a resin substrate and a composition for forming a peeling layer for glass substrate with peeling layer.

[Comparative Examples 2-1 to 2-2] Except using the compositions B1 and B2 for forming a peeling layer obtained in Comparative Examples 1-1 to 1-2, respectively, in place of the composition L1 for forming a peeling layer obtained in Example 1-1 In the same manner as in Example 2-1, a peeling layer and a polyimide substrate were produced to obtain a glass substrate with peeling layer, a resin substrate and a composition for forming a peeling layer for glass substrate with peeling layer.

[7] Evaluation of peeling properties For the glass substrates with peeling layers obtained in the above-mentioned Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2, the peeling properties of the peeling layers and the glass substrates were confirmed by the following method. In addition, the following test was performed with the same glass substrate.

<Cross-cut test peelability evaluation of resin film> Cross-cut (1 mm vertical and horizontal intervals, the same applies hereinafter), and 100 square cuts were performed. That is, 100 squares of 1 mm square are formed by this cross cutting. Then, an adhesive tape was attached to this 100-square-cut portion, the tape was peeled off, and the peelability was evaluated according to the following criteria. The results are shown in Table 1. <Criteria> 5B: 0% peeling (no peeling) 4B: less than 5% peeling 3B: 5~15% peeling 2B: 15~35% peeling 1B: 35~65% peeling Peel 0B: 65% to less than 80% peel B: 80% to less than 95% peel A: 95% to less than 100% peel AA: 100% peel (all peels)

<Evaluation of peelability of resin substrates> The resin substrates obtained in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 and the resin substrates of the glass substrates with peeling layers were cut into 25 mm using a dicing knife. A wide short booklet. Then, a cellophane tape was pasted on the front end of the diced resin substrate, and this was used as a test piece. This test piece was subjected to a peel test using a push-pull tester manufactured by Attonic, and the peeling angle was set to 90°, and the peelability was evaluated according to the following criteria. The results are shown in Table 1. <Criteria> 5B: 0% peeling (no peeling) 4B: less than 5% peeling 3B: 5~15% peeling 2B: 15~35% peeling 1B: 35~65% peeling Peel 0B: 65% to less than 80% peel B: 80% to less than 95% peel A: 95% to less than 100% peel AA: 100% peel (all peels)

From the results in Table 1, it was confirmed that the peeling layers of Examples 2-1 to 2-4 were not peeled from the glass substrate, but only the resin substrate could be peeled off, but the resin substrate could not be peeled off in Comparative Examples 2-1 and 2-2.

Claims (10)

A method for producing a peeling layer, comprising the steps of: applying a peeling layer-forming composition comprising at least one of the polyamic acids represented by the following formulas (1A) to (1B) and an organic solvent on a substrate , the step of firing at the highest temperature of 450~550℃,

(in the formula, X is independently a tetravalent aromatic group having two carboxylic acid derivatives, Y is independently a bivalent aromatic group, Z ¹ and Z ² are independently a monovalent organic group, the formula ( In 1A), at least one of Y, Z ¹ and Z ² has an alkali-soluble group, in formula (1B), at least one of Y and two Z ¹ has an alkali-soluble group, and the formula m independently represents a natural number) wherein The above-mentioned Z ¹ is a monovalent organic group represented by the following formula (10),

(In the formula, Z ³ represents a carboxyl group or a hydroxyl group, and ○ represents a bond). The method for producing a release layer according to claim 1, wherein the alkali-soluble group is a carboxyl group or a phenolic hydroxyl group. The method for producing a peeling layer according to claim 1, wherein Y contains an aromatic group represented by the following formulae (2) to (5),

(In the formula, W independently represents a carboxyl group or a hydroxyl group, and R ¹ to R ³ independently represent an alkylene group with 1 to 20 carbon atoms, an alkenyl group with a carbon number of 2 to 20, and an alkylene group with 2 to 20 carbon atoms that can be substituted by halogen atoms. 20 alkynylene group, carbon number 6-20 aryl group or carbon 2-20 heteroaryl group, ether group, ester group or amide group, ○ represents a bond). The method for producing a peeling layer according to claim 3, wherein Y contains an aromatic group represented by the following formulae (6) to (9),

(In the formula, ○ represents a bonding bond). The method for producing a peeling layer according to any one of claims 1 to 4, wherein Z ² is a monovalent organic group represented by the following formula (11),

(In the formula, Z ³ represents a carboxyl group or a hydroxyl group, and ○ represents a bond). The manufacturing method of the peeling layer of Claim 3 or 4 whose said Y further contains the aromatic group which does not have an alkali-soluble group. The method for producing a peeling layer according to claim 6, wherein the aromatic group having no alkali-soluble group is a phenylene group, a biphenylene group, or a bitriphenylene group. A manufacturing method of a flexible electronic device provided with a resin substrate using the peeling layer formed by the manufacturing method of any one of claims 1 to 7. A manufacturing method of a flexible electronic device, which is characterized by comprising the following steps: after applying a composition for forming a resin substrate on a peeling layer formed by the manufacturing method according to any one of claims 1 to 7, The step of forming a resin substrate by firing at a maximum temperature of 450°C or higher. The manufacturing method of a flexible electronic device according to claim 8 or 9, wherein the resin substrate is a polyimide resin substrate.