KR20160142331A - Composition for forming releasing layer - Google Patents

Abstract

According to the present invention, the adhesiveness to the glass substrate on which the release layer is formed is maintained and separation at the interface with the glass substrate does not occur, while the layer or layer group formed above the release layer is easily peeled off from the release layer There is provided a composition for forming the release layer. The present invention provides a composition for forming a release layer comprising a polyamic acid having a monomer unit represented by formula (1) in an amount of 50 mol% or more and a weight average molecular weight of 10,000 or more and an organic solvent. In the formula (1), X ¹ represents a tetravalent organic group, and Y ¹ represents a divalent group represented by the following formula (P).

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for forming a release layer,

The present invention relates to a composition for forming a release layer formed directly on a glass substrate.

BACKGROUND ART [0002] In recent years, electronic devices are required to be provided with a function of bending, performance such as reduction in thickness and weight. From this, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, fragile and non-bendable glass substrate. In addition, in the new generation display, development of an active full-color TFT display panel using a lightweight flexible plastic substrate is required.

Therefore, various methods for manufacturing an electronic device using a resin film as a substrate have been started to be examined. In the new-generation display, the manufacturing process of a conventional TFT device by a process capable of being converted is underway.

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, irradiating a laser from the glass surface side, A method for peeling a plastic substrate from a glass substrate by hydrogen gas is disclosed.

In Patent Document 4, a liquid crystal display device is completed by adhering a layer to be peeled (referred to as "transfer layer" in Patent Document 4) to a plastic film using the technique disclosed in Patent Documents 1 to 3 The method comprising:

However, the method disclosed in Patent Documents 1 to 4, particularly the method disclosed in Patent Document 4, requires the use of a substrate having high light transmittance and requires sufficient energy to pass through the substrate and release hydrogen contained in the amorphous silicon There is a problem that irradiation with a relatively large laser beam is required and damage to the layer to be peeled is caused. Further, it takes a long time to perform the laser processing, and it is difficult to peel off the layer to be peeled having a large area, so that it is also difficult to increase the productivity of device manufacturing.

Japanese Unexamined Patent Application Publication No. 10-125929. Japanese Patent Application Laid-Open No. 10-125931. WO2005 / 050754 pamphlet. Japanese Patent Application Laid-Open No. 10-125930.

Therefore, an object of the present invention is to solve the above problems.

Specifically, it is an object of the present invention to provide a composition for forming a peeling layer for peeling without damaging a substrate applied to a flexible electronic device.

It is another object of the present invention to provide a method for manufacturing a semiconductor device in which adhesion to a glass substrate on which a peeling layer is formed is maintained in addition to or in addition to the above object and peeling does not occur at the interface with the glass substrate, Which is capable of easily peeling off a layer or group of layers formed from the release layer.

The present inventor has found out the following invention at this time. That is, the present inventors have found that when a release layer is formed using a composition comprising a polyamic acid having a specific weight average molecular weight of not less than a predetermined value and a monomer unit of a specific structure in an amount of not less than 50 mol% It has been found out that it has a suitable characteristic that can be peeled off without damaging the substrate applied to an electronic device or the like. This layer maintains adhesiveness with the glass substrate on which the release layer is formed and does not easily peel off from the interface with the glass substrate while it is formed on the layer or layer group formed above the release layer opposite to the glass substrate It was possible to peel off easily from the release layer. The present invention is based on this finding.

≪ 1 > A composition for forming a release layer, comprising a polyamic acid containing 50 mol% or more of monomer units represented by the following formula (1) and having a weight average molecular weight of 10,000 or more and an organic solvent.

[Chemical Formula 1]

Wherein X ¹ represents a tetravalent organic group and Y ¹ represents a divalent group represented by the following formula (P):

(2)

(Wherein R represents F, Cl, an alkyl group having 1 to 3 carbon atoms or a phenyl group, m represents an integer of 0 to 4, and r represents an integer of 1 to 4).

<2> The compound according to <1>, wherein Y ¹ is a bivalent group represented by any one of the following formulas (P1) to (P3).

(3)

(Wherein,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents F, Cl, an alkyl group having 1 to 3 carbon atoms or a phenyl group,

m1, m2, m3, m4, m5 and m6 may be the same or different and represent an integer of 0 to 4).

&Lt; 3 &gt;&lt; 2 &gt; The Y &lt; ¹ &gt; preferably includes at least a divalent group represented by formula (P1).

&Lt; 4 &gt; In any one of &lt; 1 &gt; to &lt; 3 &gt;, it is preferable that the polyamic acid further includes a monomer unit represented by the following formula (2).

[Chemical Formula 4]

[Wherein,

X ¹ is as defined in <1>, Y ² is a group represented by the following formula (P4)

[Chemical Formula 5]

(Wherein,

R ⁷ and R ⁸ may be the same or different and each represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group,

R 'represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group,

l represents an integer of 0 to 4, and

m is as defined in <1> above).

<5> In any one of <1> to <4>, X ¹ is preferably a tetravalent aromatic group.

<6> In the above-mentioned <5>, it is preferable that the tetravalent aromatic group has at least one kind selected from a benzene skeleton, a naphthalene skeleton and a biphenyl skeleton.

<7> The organic electroluminescent device according to any one of <1> to <6>, wherein the organic solvent is a solvent represented by the following formula (A) or (B)

[Chemical Formula 6]

(Wherein R ^a and R ^b may be the same or different, represent an alkyl group having 1 to 4 carbon atoms, and h represents a natural number).

<8> The polyamic acid according to any one of <1> to <7>, wherein the content of the monomer unit represented by the formula (1) in the polyamic acid is 60 mol% or more.

<9> In any one of the above items <1> to <8>, the composition for forming a release layer according to the present invention may be one for forming a release layer formed directly on a glass substrate.

<10> A release layer produced by using the composition for forming a release layer according to any one of <1> to <9> as a release layer formed between a flexible substrate and a base substrate to be applied to a flexible electronic device.

<11> A substrate structure applied to a flexible electronic device,

A base substrate,

A peeling layer formed by the composition for forming a peeling layer according to any one of &lt; 1 &gt; to &lt; 9 &gt;, as a peeling layer for covering the base gas in one or two or more regions;

A base substrate, a flexible substrate covering the release layer,

/ RTI &gt;

Wherein the adhesion between the flexible substrate and the release layer is greater than the adhesion between the release layer and the base substrate.

<12> In <11>, it is preferable that the base substrate includes glass.

<13> A method for producing a release layer, which comprises using a composition for forming a release layer according to any one of <1> to <9>. In one preferred embodiment, the method for producing a release layer includes a step of applying the resin composition for forming a release layer to a substrate and heating.

[14] A method of manufacturing a substrate structure applied to a flexible electronic device,

A step of preparing a base substrate,

A process for producing a release layer covering the base gas in one or two or more regions by using the composition for forming a release layer according to any one of <1> to <9>

And a step of forming a flexible substrate on the base substrate and the release layer,

Wherein the adhesion between the flexible substrate and the release layer is greater than the adhesion between the release layer and the base substrate.

The above problems can be solved by the present invention.

Specifically, the present invention can provide a composition for forming a release layer for peeling without damaging the substrate applied to the flexible electronic device.

Further, according to the present invention, in addition to the above effect, or in addition to the above effect, adhesion with the glass substrate on which the release layer is formed is maintained so that separation at the interface with the glass substrate does not occur, Which is capable of easily peeling off a layer or a group of layers from the peeling layer.

Hereinafter, the present invention will be described in detail.

Composition for releasing layer

As described above, the composition for forming a release layer of the present invention is a polyamic acid containing at least 50 mol% of a monomer unit represented by the formula (1), and a polyamic acid having a weight average molecular weight of 10,000 or more, will be.

(7)

As described above, in the formula (1), X ¹ represents a tetravalent organic group, and Y ¹ represents a divalent group represented by the following formula (P).

[Chemical Formula 8]

In formula (P), R represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, preferably F or Cl. Similarly, in the above formula (P), m represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0. In the above formula (P), r represents an integer of 1 to 3.

Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl and i-propyl, and the alkyl group having 1 to 3 carbon atoms is preferably methyl, more preferably methyl.

The weight average molecular weight of the polyamic acid having a monomer unit represented by the formula (1) used in the present invention should be 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more . On the other hand, the upper limit of the weight average molecular weight of the polyamic acid used in the present invention is usually 2,000,000 or less, but considering that the viscosity of the resin composition is prevented from becoming excessively high, or the resin thin film having high flexibility is obtained with good reproducibility , Preferably 1,000,000 or less, and more preferably 200,000 or less.

The polyamic acid used in the present invention has a monomer unit represented by the formula (1) in an amount of 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more , More preferably 90 mol% or more. By using the polyamic acid having such a monomer unit content, a resin thin film having properties suitable for the release film can be obtained with good reproducibility.

According to a preferred embodiment of the present invention, the polyamic acid contained in the composition for forming a release layer of the present invention is a polymer comprising only a monomer unit represented by formula (1), that is, a monomer unit represented by formula (1) . At this time, the monomer unit in such a polyamic acid may be a specific one or two or more types as long as it is represented by the formula (1). In the latter case, the number of monomer units of the formula (1) contained in the polyamic acid is preferably 2 to 4, and more preferably 2 to 3.

In the present invention, the group represented by the formula (P) preferably includes a divalent group represented by any one of the formulas (P1) to (P3), more preferably a divalent group represented by the formula (P1) Group, more preferably a bivalent group represented by formula (P3).

[Chemical Formula 9]

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different from each other and may be the same or different from each other in the formula (P1), the formula (P2) and the formula (P3) An alkyl group having 1 to 3 carbon atoms, or a phenyl group, preferably F or Cl.

In these formulas, m1, m2, m3, m4, m5 and m6 may be the same or different, represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1 , And particularly preferably 0.

The polyamic acid used in the present invention may contain other monomer units in addition to the monomer units represented by the formula (1). The content of such other monomer units should be less than 50 mol%, preferably less than 40 mol%, more preferably less than 30 mol%, even more preferably less than 20 mol%, further preferably less than 10 mol% desirable.

Examples of such another monomer unit include a monomer unit of the formula (2).

[Chemical formula 10]

In the formula (2), X ¹ represents a tetravalent organic group, and Y ² represents a group represented by the above formula (P4).

(11)

In the formula (P4), R ⁷ and R ⁸ may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. R ⁷ preferably represents F or Cl. R ⁸ preferably represents F or Cl.

R 'represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

Further, 1 and m may be the same or different and represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0.

Examples of such other monomer units include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 5 Methyl-1,3-phenylenediamine, 2- (trifluoromethyl) -1,4-phenylenediamine, 2- (trifluoromethyl) -1 , 3-phenylenediamine and 4- (trifluoromethyl) -1,3-phenylenediamine, benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, (Trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, 2,3'-bis (trifluoromethyl) benzidine, 4,4'-diphenyl ether , 4,4'-diaminobenzanilide, 5-amino-2- (3-aminophenyl) -1H-benzoimidazole, 9,9- A diamine such as bis (4-aminophenyl) fluorene and a diamine such as pyromellitic anhydride (PMDA), 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 4,4'- There may be mentioned the anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid structure derived from a dianhydride, such as the anhydride or the like.

In the formulas (1) and (2), as described above, X ¹ is a tetravalent organic group, preferably a tetravalent aromatic group.

The tetravalent aromatic group that X &lt; ^{1 &gt;} can take can be prepared by using the following aromatic tetracarboxylic acid dianhydride in the production of the polyamic acid to be used in the present invention.

Namely, it is possible to use pyromellitic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3 ', 4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride , 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3, 3 ', 4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) Diphenyl propane dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride, p-phenylenedi phthalic acid dianhydride, 2,2-bis ((3,4-dicarboxyphenyl) -hexafluoropropane 2 (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9,9'-bis [4- Water, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracar 4,4'-tetracarboxylic acid dianhydride, metaterephenyl-3,3 ', 4,4' -tetracarboxylic dianhydride, 4,4'-tetramethyldicarboxylic acid dianhydride, -Tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylether tetracarboxylic acid dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3 - tetramethyldisiloxane dianhydride, 1- (2,3-dicarboxyphenyl) -3- (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 3,3 ', 4,4'-hydroquinone dibenzoate tetracarboxylic acid dianhydride, 2,2'-bis (4-hydroxyphenyl) propane dibenzoate-3,3', 4,4'-tetracarboxyl And the like.

Preferably, the aromatic tetracarboxylic acid dianhydride is selected from the following group of compounds.

[Chemical Formula 12]

(Wherein R ₃ is a divalent organic group having at least one aromatic ring, preferably a group having a phenyl, biphenyl, or naphthalene skeleton).

Therefore, according to a preferred embodiment of the present invention, the tetravalent aromatic group that X ¹ can take is any of benzene skeleton, naphthalene skeleton, biphenyl skeleton and terphenyl skeleton, more preferably benzene skeleton, naphthalene skeleton, A biphenyl skeleton, and more preferably a benzene skeleton or a biphenyl skeleton.

According to a preferred embodiment of the present invention, the polyamic acid used in the present invention is a mixture of 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) (formula (4)) as an acid dianhydride, As the diamine, p-phenylenediamine (pPDA) (formula (5)) and 4,4'-diamino-p-terphenyl (DATP) (formula (6)), or pyromellitic acid dianhydride (PMDA) (formula (7)) and pPDA (formula (5)) as a diamine.

[Chemical Formula 13]

In the above reaction, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), p-phenylenediamine (pPDA) and 4,4'-diamino- DAMP) or pyromellitic dianhydride (PMDA) and pPDA (molar ratio) can be appropriately set in consideration of the molecular weight of the desired polyamic acid and the ratio of the monomer units, , And the acid anhydride component can usually be set to about 0.7 to 1.3, preferably about 0.8 to 1.2.

On the other hand, the diamine of tuipbi of pPDA and DATP, in the case when the amount of substance (m ²⁾ of a DATP to 1, the amount of substance (m ¹⁾ of pPDA, can typically about 1.7 ~ 20, but, preferably 2.1 ~ 20 , More preferably 2.2 to 20, still more preferably 2.3 to 19, still more preferably 2.3 to 18. That is, m ¹ and m ² are usually in the range of m ¹ / m ² = 1.7 to 20, preferably 2.1 to 20, more preferably 2.2 to 20, still more preferably 2.3 to 19, And preferably 2.3 to 18.

The above reaction is carried out in an organic solvent. That is, the composition for forming a release layer according to the present invention includes such an organic solvent. The organic solvent usable herein may be any solvent as long as it does not adversely affect the reaction.

Specific examples include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, Butoxy-N, N-dimethylpropylamide, 3-tert-butoxy-N, N-dimethylacetamide, , N-dimethylpropylamide, and? -Butyrolactone. These may be used alone or in combination of two or more.

According to a preferred embodiment of the present invention, the organic solvent is a solvent represented by the formula (A) or (B).

[Chemical Formula 14]

In the formulas (A) and (B), R ^a and R ^b may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms. Here, h represents a natural number, preferably 1 to 3.

The reaction temperature is 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. In order to prevent imidization of the obtained polyamic acid and maintain a high content of the polyamic acid unit, , More preferably about 0 to about 60 ° C, and even more preferably about 0 to about 50 ° C.

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

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

In the present invention, usually, the reaction solution is filtered, and the filtrate is directly used, or diluted or concentrated to be used as a composition for forming a release layer. By doing so, it is possible not only to reduce the incorporation of impurities which may cause deterioration of the heat resistance, flexibility or linear expansion coefficient characteristics of the obtained resin thin film, but also to obtain a composition efficiently.

The solvent used for diluting or concentrating is not particularly limited and, for example, the same solvents as the specific examples of the reaction solvent for the above reaction may be used, and they may be used alone or in combination of two or more.

Among these, in consideration of obtaining a resin thin film having high flatness with good reproducibility, examples of the solvent to be used include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- , 3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone and? -Butyrolactone are preferable.

The concentration of the polyamic acid with respect to the total mass of the composition for forming a release layer is appropriately set in consideration of the thickness of the thin film (release layer) to be produced, the viscosity of the composition, and the like, but is usually about 0.5 to 30 mass% 25% by mass.

The viscosity of the composition for forming a release layer is appropriately set in consideration of the thickness of the thin film to be produced. In particular, when a resin thin film having a thickness of about 0.05 to 5 탆 is to be obtained with good reproducibility, Is about 10 to 10,000 mPa · s, preferably about 20 to 1,000 mPa · s, and more preferably about 20 to 200 mPa · s.

Here, the viscosity of the composition for forming a release layer can be measured by using a commercially available viscometer for viscosity measurement, for example, with reference to the procedure described in JIS K7117-2, Can be measured. Preferably, a conical flat plate (cone plate type) rotational viscometer is used as the viscometer, preferably 1 ° 34 '× R24 is used as a standard cone rotor as a viscometer of the same type, At a temperature of 25 占 폚. As such a rotational viscometer, for example, TVE-25H manufactured by TOKI INDUSTRIAL CO., LTD. Can be mentioned.

In addition, the composition of the present invention may have various components in addition to the polyamic acid and the organic solvent. For example, a crosslinking agent (hereinafter also referred to as a crosslinking compound), but the present invention is not limited thereto.

Examples of the crosslinkable compound include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative, glycoluril or the like having a hydrogen atom of the amino group having a methylol group, an alkoxymethyl group, But are not limited to these.

Specific examples of the crosslinkable compound are shown below, but the invention is not limited thereto.

Examples of compounds containing two or more epoxy groups include EPOLED GT-401, EPOLED GT-403, EPOLED GT-301, EPOLED GT-302, CELLOXIDE 2021 and CELLOXIDE 3000 Epicote 1001, Epicote 1002, Epicote 1003, Epicote 1004, Epicote 1007, Epicote 1009, Epicote 1010, Epicote 828 (above, manufactured by Japan Epoxy Co., Bisphenol F type epoxy compounds such as Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd.), Epicote 152, Epi-epoxy resin (Manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series), EPPN201, and EPPN202 (manufactured by Nippon Yakusho Chemical Co., Ltd.) (Manufactured by Mitsubishi Chemical Corporation, Japan Epoxy Resin Co., Ltd. (trade name, manufactured by Mitsubishi Chemical Corporation), ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON- naphthalene type epoxy compounds such as V8000-C7 (manufactured by DIC Co., Ltd.), Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (manufactured by BASF), Epiclon 200, Epiclon 400 (manufactured by DIC Corporation), Epikote 871, Alicyclic epoxy compounds such as Coat 872 (manufactured by Japan Epoxy Resin Co., Ltd. (currently, jER (registered trademark) series manufactured by Mitsubishi Chemical Corporation), ED-5661 and ED-5662 (manufactured by Celanese Coatings Co., Ltd.); Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX Such as Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314 and Denacol EX-312 (manufactured by Nagase ChemteX Corporation) And polyglycidyl ether compounds.

Examples of the melamine derivative, benzoguanamine derivative or glycoluril wherein the hydrogen atom of the amino group has a methylol group, an alkoxymethyl group or both thereof are MX-750 in which methoxymethyl groups are substituted on average 3.7 per one triazine ring, MW-30 (manufactured by Sanwa Chemical Co., Ltd.) having an average of 5.8 methoxymethyl groups per ring of a triazine ring, Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel 771 , Methoxymethylated melamines such as Cymel 325, Cymel 327, Cymel 703, Cymel 712, and the like, such as Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254, Butoxymethylated melamines such as Cymel 506 and Cymel 508, methoxymethylated isobutoxymethylated melamines containing carboxyl groups such as Cymel 1141, methoxymethylated ethoxymethylated melamines such as Cymel 1123, Guanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80, Methylmercury glycoluril such as Cymel 1172 (available from Mitsui Cytec Industries, Inc., Mitsui Cytec Industries, Ltd.), and the like.

By applying the composition for forming a release layer of the present invention described above to a substrate and heating it, a thin film (release layer) composed of polyimide having high heat resistance, suitable flexibility, and appropriate linear expansion coefficient can be obtained.

As the base substrate (substrate), for example, glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS, AS, norbornene- (Silicon wafer or the like), wood, paper, slate, and the like.

The coating method is not particularly limited, and examples of the coating method include a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, , Concave plate, flat plate, screen printing, etc.).

As a method of imidizing the polyamic acid contained in the composition for forming a release layer of the present invention, thermal imidization in which the composition coated on the substrate is heated as it is, and catalyst imidization in which a catalyst is added to the composition to heat the composition .

In the catalyst imidization of polyamic acid, a catalyst thin film (release layer) is obtained by adding a catalyst to the composition for forming a release layer of the present invention and stirring to adjust the catalyst-added composition, and then applying and heating to the substrate. The amount of the catalyst is 0.1 to 30 moles, preferably 1 to 20 moles, of the amide group. Acetic anhydride or the like may be added as a dehydrating agent to the catalyst-added composition, and the amount thereof is 1 to 50 molar equivalents, preferably 3 to 30 molar equivalents, of the amide acid group.

As the imidation catalyst, it is preferable to use a tertiary amine. As the tertiary amine, pyridine, substituted pyridines, imidazole, substituted imidazoles, picoline, quinoline, isoquinoline and the like are preferable.

The heating temperature at the time of thermal imidization and catalyst imidization is preferably 450 ° C or lower. If the temperature is higher than 450 ° C, the obtained thin resin film is decomposed and a thin resin film suitable for the intended use may not be obtained.

Considering the heat resistance and the coefficient of linear expansion coefficient of the obtained resin thin film, the applied composition is heated at 50 to 100 DEG C for 5 minutes to 2 hours, and then the heating temperature is increased stepwise as it is, For 30 minutes to 4 hours.

Particularly, the applied composition is heated at a temperature of 50 to 100 ° C for 5 minutes to 2 hours, then heated at a temperature of more than 100 ° C to 200 ° C for 5 minutes to 2 hours, then at 200 ° C to 375 ° C for 5 minutes to 2 hours, Finally, it is preferable to heat at 375 DEG C to 450 DEG C for 30 minutes to 4 hours.

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

The thickness of the resin thin film is usually about 0.01 to 10 mu m, preferably about 0.05 to 5 mu m, when the resin thin film is used as a peeling layer, and the resin thin film having a desired thickness is formed by adjusting the thickness of the coating film before heating.

The thin film described above is optimal for use as a release layer for peeling off without damaging the substrate applied to the flexible electronic device.

With the composition of the present invention, a release layer formed between a flexible substrate applied to a flexible electronic device and a base substrate can be formed. As the base substrate, it is preferable to include glass or silicon wafer, and more preferably glass.

For example, the composition of the present invention can be applied to a glass substrate by a conventionally known technique, and the resulting coating film can be heated to a predetermined temperature to form a release layer.

Further, the supporting body layer can be formed on the peeling layer. The buffer layer may be a single layer or a plurality of layers. In order to manufacture various devices, it is realistic to have a plurality of layers.

The layer immediately above the peeling layer in the supporting layer is dependent on the peeling layer to be used, but it is preferable to use one having good peelability from the peeling layer, in other words, having poor adhesion to the peeling layer to be used.

As another aspect of the present invention, there is provided a method for producing an Fe-Li body.

That way,

a) applying a composition of the present invention onto a glass substrate, and then forming a release layer;

b) forming, on the release layer, an elastic body; and

c) peeling off the elastic body at the interface between the release layer and the elastic body;

By weight, thereby obtaining an elastic body.

In the step b), the &quot; supporting body &quot; may be a single layer or a plurality of layers. The layer immediately above the release layer in the &quot; backing layer &quot; depends on the release layer to be used, but the release layer has a good releasability with respect to the release layer, in other words, good.

According to another preferred embodiment of the present invention, there is provided a substrate structure applied to a flexible electronic device,

A base substrate,

A peeling layer formed by the composition for forming a peeling layer according to the present invention as a peeling layer covering the base substrate in one or two or more regions,

A base substrate, a flexible substrate covering the release layer,

/ RTI &gt;

Wherein the adhesion between the flexible substrate and the release layer is greater than the adhesion between the release layer and the base substrate. Here, the magnitude of the adhesion force can be confirmed by, for example, a crosscut test shown in the embodiment of the present invention.

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

Example

The abbreviations used in this embodiment are listed and described below.

<Solvent>

NMP: N-methylpyrrolidone.

<Amines>

p-PDA: p-phenylenediamine.

APAB: 2- (3-aminophenyl) -5-aminobenzimidazole.

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

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

<Acid anhydride>

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

BA-TME: 4,4-biphenylene bis (trimellitic acid monoester acid anhydride).

PMDA: pyromellitic dianhydride.

<Aldehyde>

IPHA: isophthalaldehyde.

[Measurement of number-average molecular weight and weight-average molecular weight]

(Shodex (registered trademark) columns KF803L and KF805L) manufactured by Nippon Shokubai Co., Ltd., dimethylformamide was used as an eluting solvent at a flow rate of 1 ml (hereinafter, referred to as &quot; / Min, and a column temperature of 50 캜. Mw was a polystyrene conversion value.

<Synthesis Example>

&Lt; Synthesis Example 1 &gt; Synthesis of polyimide precursor P1 &

BPDA (98) // p-PDA (90) / DATP (10)

2.38 g (0.009 mol) of DATP and 2.05 g (0.009 mol) of APAB were dissolved in 425 g of NMP, followed by addition of 52.8 g (0.179 mol) of BPDA, followed by addition of 17.8 g (0.164 mol) of p- g, and the mixture was allowed to react at 23 deg. C for 24 hours in a nitrogen atmosphere. The Mw of the obtained polyimide precursor P1 was 63000, and the molecular weight distribution was 9.9.

&Lt; Synthesis Example 2 &gt; Synthesis of polyimide precursor P2 &gt;

BPDA (98) / DATP (100)

30.8 g (0.118 mol) of DATP was dissolved in 425 g of NMP, and 34.1 g (0.116 mol) of BPDA was added at the same time. Then, 10 g of NMP was added again and reacted at 23 DEG C for 24 hours under a nitrogen atmosphere. The polyimide precursor P2 thus obtained had Mw of 70700 and a molecular weight distribution of 9.7.

&Lt; Synthesis Example 3 &gt; Synthesis of polyimide precursor P3 &

PMDA 98 / p-PDA 80 / DATP 20

20.261 g (0.1875 mole) of p-PDA and 12.206 g (0.0469 mole) of TPDA were dissolved in 617.4 g of NMP and 50.112 g (0.2298 mole) of PMDA was added after cooling to 15 占 폚. Lt; / RTI &gt; The polyimide precursor P3 had Mw of 82,100 and a molecular weight distribution of 2.7.

&Lt; Synthesis Example 4 &gt; Synthesis of polyimide precursor P4 &

BP-TME (98) // p-PDA (95) / APAB (5)

9.66 g (0.089 mol) of p-PDA and 1.05 g (0.005 mol) of APAB were dissolved in 440 g of NMP, and 49.2 g (0.092 mol) of BP-TME was added and reacted at room temperature for 24 hours under nitrogen atmosphere. The polyimide precursor P4 had Mw of 57000 and a molecular weight distribution of 9.3.

&Lt; Synthesis Example 5 &gt; Synthesis of polyimide precursor P5 &gt;

BPDA (98) // p-PDA (100)

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 polyimide precursor P5 had Mw of 107,300 and a molecular weight distribution of 4.6.

Synthesis Example 6 Synthesis of polybenzoxazole precursor (P6)

IHPA (98) // 6FAP (100)

3.18 g (0.059 mol) of 6FAP was dissolved in 70 g of NMP, 7.92 g (0.060 mol) of IPHA was added, and the reaction was allowed to proceed 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.

&Lt; Synthesis Example 7: Synthesis of polyimide precursor P7 &gt;

PMDA (98) // p-PDA (100)

10.078 g (93 mmol) of p-PDA was dissolved in 220.0 g of NMP. To the obtained solution, 19.922 g (91 mmol) of PMDA 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 55,900 and a molecular weight distribution of 3.1.

&Lt; Preparation of release layer substrate &gt;

P1 to P7 obtained in Synthesis Examples 1 to 7 were diluted to 4 wt% with NMP and applied on a 100 mm x 100 mm glass substrate (OA-10G non-alkali glass) or a silicon wafer using a spin coater, Curing conditions A to C were baked in an oven to prepare a release layer.

Curing condition A : Holding at 120 ° C for 30 minutes → Heating → 300 ° C for 60 minutes → Heating → 400 ° C for 60 minutes. The rate of temperature increase was 10 DEG C / min.

Curing condition B : Holding at 120 占 폚 for 30 minutes? Elevating temperature? 180 占 폚 for 20 minutes? Elevating temperature? 240 占 폚 for 20 minutes? Elevating temperature? Holding at 300 占 폚 for 20 minutes? Elevating temperature? Holding at 400 占 폚 for 20 minutes? Keep at 60 for 60 minutes. The rate of temperature increase was 10 DEG C / min.

Cure condition C : maintained at 80 占 폚 for 10 minutes? Elevated temperature? Maintained at 300 占 폚 for 30 minutes? Elevated temperature? Maintained at 400 占 폚 for 30 minutes. The rate of temperature increase was 10 DEG C / min.

The film thickness of the obtained coating film was measured using a contact type film thickness measuring instrument (Dektak 3ST, manufactured by ULVAC Co., Ltd.).

Table 1 shows the precursors P1 to P7 used, the coated substrate, the curing conditions, and the film thickness of the release layer produced.

&Lt; Crosscut test I &gt;

The adhesion of the substrate (glass or silicon wafer) / peeling layer was confirmed in the cross-cut test I for the substrates provided with the peeling layers in Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1. [

Crosscut test I was carried out as follows.

(1) On a film, 100 squares of 1 mm in length and width were prepared.

(2) Thereafter, the square was pasted with an adhesive tape (Cellotape (registered trademark)) and a peeling step was carried out.

(3) After the peeling step, the square remaining on the substrate was counted.

&Lt; Index of results of crosscut test I &gt;

As a result of the crosscut test, the degree of peeling is shown by the following index.

5B: Not peeled off.

4B: Less than 5% exfoliation.

3B: peeling of 5 to 15%.

2B: peeling of 15 to 35%.

1B: Peeling of 35 to 65%.

0B: 65% to 80% exfoliation.

B: 80% to 95% exfoliation.

A: Peeling from 95% to less than 100%.

AA: 100% peeling.

Separately from the above cross-cut test I, the characteristics of the components constituting the peeling layer of the substrates provided with the peeling layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, that is, (1) (2) the refractive index at a wavelength of 1000 nm, (3) the birefringence at a wavelength of 1000 nm, and (4) the surface energy. The measurement conditions of each characteristic are shown below.

&Lt; (1) Temperature indicating 1% weight reduction in weight change upon heating &gt;

Using a TD-DTA2000ST manufactured by Bruker Co., Ltd., thermogravimetric (TG) measurement was performed under a nitrogen atmosphere, and the temperature at which the weight decreased by 1% was determined.

&Lt; (2) Refractive index at 1000 nm and (3) Birefringence &gt;

Refractive index and birefringence were measured using a high-speed spectroscopic Ellipsometer M-2000 (manufactured by JAE Ullam Japan Co., Ltd.). Further, the refractive index was set to an in-plane refractive index of 1000 nm, and the birefringence was determined as the difference between the in-plane refractive index and the out-of-plane refractive index.

<(4) Surface energy>

The surface energy of each member was measured using an automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). The solvent used in the measurement was water and methylene iodide, and was calculated from the contact angle of these solvents.

&Lt; Formation of an Filler and its peeling test (Crosscut test II) &gt;

[0072] The support was formed on the substrates of the examples 1 to 5 and the comparative examples 1 to 3 with the release layer, and the degree of peeling was confirmed by the crosscut test II.

<< Fabrication of an Fe-Li Li Layer >>

On the release layer of the substrate provided with the release layer, a polyimide layer was formed as an underlayer.

Specifically, the precursors P5 and P1 obtained in the above Synthesis Example 5 or Synthesis Example 1 were laminated on the release layer of the substrate provided with the release layer in Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1 Bar coater. Then, it was maintained in an oven at 120 ° C for 30 minutes → elevated temperature → 180 ° C for 20 minutes → elevated temperature → 240 ° C for 20 minutes → elevated temperature → maintained at 300 ° C for 20 minutes → elevated temperature → maintained at 400 ° C for 20 minutes, Curing was carried out at 450 占 폚 for 60 minutes (the rate was 10 占 폚 / minute even at any temperature rise) to obtain an Fe-Li alloy layer having a thickness of 15 占 퐉 made of polyimide.

<< Crosscut Test II >>

With respect to the substrate provided with the above-described supporting substrate and the peeling layer, the adhesion between the supporting substrate and the peeling layer was confirmed by the crosscut test II.

Cross-cut test II was performed in the same manner as in the cross-cut test I.

(2) a refractive index at a wavelength of 1000 nm (shown in Table 2), (2) a refractive index at a wavelength of 1000 nm (2) "), (3) the difference between the refractive index and the birefringence of the (2) (indicated by" (3) "in Table 2), (4) Quot; (4) &quot;, where the unit is dyne / cm), the polyimide precursor used in the filler metal layer, and the results of the crosscut tests I and II.

*: The birefringence of Comparative Example 2 could not be measured.

**: The crosscut test II of Comparative Example 1 and Comparative Example 3 could not be measured because the adhesiveness between the peel layer and the substrate was low.

Table 2 shows the following. Since the release layer of Examples 1 to 5 has a result of Test I of 5B, there is no case where the release layer is peeled off from the substrate. On the other hand, since the result of Test II is AA, only the support- . In short, it can be seen that the release layer formed from the composition for a release layer of the present invention gives the desired release result.

On the other hand, in Comparative Example 1 and Comparative Example 3, since the result of Test I is AA, it can be seen that the peeling layer is peeled from the substrate. In other words, it can be seen that Comparative Example 1 and Comparative Example 3 can not obtain a desired peeling result. In Comparative Example 2, since the test I and the test II together were 5B, the peeling layer and the substrate were not peeled off at the interface between the peeling layer and the substrate, and the desired peeling result could not be obtained Able to know.

Claims (14)

A composition for forming a release layer comprising a polyamic acid containing 50 mole% or more of monomer units represented by the following formula (1) and having a weight average molecular weight of 10,000 or more, and an organic solvent.
[Chemical Formula 1]

Wherein X ¹ represents a tetravalent organic group, and Y ¹ represents a divalent group represented by the following formula (P):
(2)

(Wherein R represents F, Cl, an alkyl group having 1 to 3 carbon atoms or a phenyl group, m represents an integer of 0 to 4, and r represents an integer of 1 to 4). The method according to claim 1,
Wherein the Y ¹ is a divalent group represented by any one of the following formulas (P1) to (P3).
(3)

(Wherein,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms or a phenyl group,
m1, m2, m3, m4, m5 and m6 may be the same or different and represent an integer of 0 to 4). 3. The method of claim 2,
Wherein the Y ¹ comprises at least a divalent group represented by the formula (P1). 4. The method according to any one of claims 1 to 3,
Wherein the polyamic acid further comprises a monomer unit represented by the following formula (2).
[Chemical Formula 4]

[Wherein,
X ¹ is as defined in claim 1, and Y ² represents a group represented by the following formula (P4):
[Chemical Formula 5]

(Wherein,
R ⁷ and R ⁸ may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group,
R 'represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group,
l represents an integer of 0 to 4, and
m is as defined in claim 1; 5. The method according to any one of claims 1 to 4,
Wherein X &lt; ^{1 &gt;} is a tetravalent aromatic group. 6. The method of claim 5,
Wherein the tetravalent aromatic group has at least one selected from a benzene skeleton, a naphthalene skeleton and a biphenyl skeleton. 7. The method according to any one of claims 1 to 6,
Wherein the organic solvent is a solvent represented by the following formula (A) or (B).
[Chemical Formula 6]

(Wherein R ^a and R ^b may be the same or different, represent an alkyl group having 1 to 4 carbon atoms, and h represents a natural number). 8. The method according to any one of claims 1 to 7,
Wherein the content of the monomer unit represented by the formula (1) in the polyamic acid is 60 mol% or more. 9. The method according to any one of claims 1 to 8,
To form a release layer immediately above the glass substrate. As a release layer formed between a flexible substrate to be applied to a flexible electronic device and a base substrate,
A release layer produced by using the composition for forming a release layer according to any one of claims 1 to 9. A substrate structure applied to a flexible electronic device,
A base substrate,
A release layer formed by the composition for forming a release layer according to any one of claims 1 to 9 as a release layer for covering the base gas in one or more areas,
A base substrate; and a flexible substrate that covers the release layer,
Wherein the adhesion between the flexible substrate and the release layer is greater than the adhesion between the release layer and the base substrate. 12. The method of claim 11,
Wherein the base substrate comprises glass. A method for producing a release layer characterized by using the composition for forming a release layer according to any one of claims 1 to 9. A method of manufacturing a substrate structure applied to a flexible electronic device,
A step of preparing a base substrate,
A step of producing a release layer covering the base gas in one or two or more areas by using the composition for forming a release layer according to any one of claims 1 to 9,
And a step of forming a flexible substrate on the base substrate and the release layer,
Wherein the adhesion between the flexible substrate and the release layer is greater than the adhesion between the release layer and the base substrate.