KR20190038846A - Composition for releasing layer - Google Patents

Abstract

A polyimide resin composition comprising a polyamic acid represented by the following formula (1), a polyamic acid represented by the following formula (2), a polyamic acid represented by the following formula (3) or a polyamide represented by the following formula (4) To provide a composition for forming a release layer. (Wherein X ₁ represents a tetravalent aromatic group having no fluorine atom, X ₂ represents a tetravalent aromatic group having a fluorine atom, X ₃ represents a divalent aromatic group having no fluorine atom, Y ₁ represents a fluorine atom Y ₂ represents a divalent aromatic group having no fluorine atom, and m represents a natural number.)

Description

Composition for releasing layer

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

[0002] In recent years, electronic devices are required to have a function of bending in addition to the characteristics of thinning and lightening. In this respect, it is required to use a lightweight flexible plastic substrate in place of the conventional heavy, fragile and non-bendable glass substrate.

Particularly, it is required to develop an active matrix type full color TFT display panel using a lightweight flexible plastic substrate (hereinafter referred to as a resin substrate) in a new generation display. This new generation display technology is expected to be used in various fields such as flexible display, flexible smart phone, and mirror display.

Therefore, various methods for manufacturing an electronic device using a resin film as a substrate have started to be examined variously, and a process capable of reusing a facility for manufacturing a conventional TFT display panel in a new-generation display is being studied. In addition, in a touch panel type display, a measure for efficiently manufacturing a resin substrate for a transparent electrode of a touch panel used in combination with a display panel has been studied. Generally, the resin substrate used for the touch panel is made of a film substrate such as a polyimide resin substrate or an acrylic resin substrate, a polyethylene terephthalate (PET) resin substrate, a cycloolefin resin substrate or the like having transparency equivalent to that of glass, Has been used.

For example, in Patent Documents 1, 2 and 3, an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, a laser is irradiated from the glass surface side, Discloses a method of peeling a plastic substrate from a glass substrate by hydrogen gas. In Patent Document 4, a method of completing a liquid crystal display device by attaching 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 Lt; / RTI >

However, in the methods disclosed in Patent Documents 1 to 4, in particular, in the method disclosed in Patent Document 4, it is necessary to use a substrate having high light transmittance in order to transmit laser light. It is necessary to pass through a substrate and emit hydrogen contained in amorphous silicon There is a problem in that irradiation with a laser beam having a relatively large energy sufficient to cause the layer to be peeled off may be required and that the layer to be peeled may be damaged by irradiation with laser light.

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

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

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a resin substrate for a flexible electronic device, particularly a resin substrate formed of polyimide resin, acrylic resin, cycloolefin polymer resin or the like, And to provide a composition for forming a release layer.

As a result of intensive investigations to solve the above problems, the present inventors have found that a composition comprising a polyamic acid or a polyamide having a specific structure and an organic solvent has excellent adhesion with a substrate such as a glass substrate and is used as a flexible electronic device A release layer having appropriate adhesiveness to a resin substrate and appropriate releasability is provided, thereby completing the present invention.

That is,

1. A polyamic acid composition comprising a polyamic acid represented by the following formula (1), a polyamic acid represented by the following formula (2), a polyamic acid represented by the following formula (3) or a polyamide represented by the following formula (4) A composition for forming a release layer,

(Wherein X ₁ represents a tetravalent aromatic group having no fluorine atom, X ₂ represents a tetravalent aromatic group having a fluorine atom, X ₃ represents a divalent aromatic group having no fluorine atom, Y ₁ represents a fluorine atom Y ₂ represents a divalent aromatic group having no fluorine atom, and m represents a natural number.)

2. The composition for forming a peel layer 1, wherein Y ₁ is an aromatic group selected from the group consisting of the following formulas (5) to (9)

3. The composition for forming a peel layer, wherein Y ₁ is an aromatic group represented by the following formula (10)

4. The composition for forming a release layer according to any one of 1 to 3, wherein X < ₂ > is an aromatic group represented by the following formula (11) or (12)

5. The composition for forming a release layer according to any one of 1 to 4, wherein X &_lt; 1 > is an aromatic group containing 1 to 5 benzene rings,

6. The composition for forming a release layer according to any one of 1 to 5, wherein X < ₃ > is an aromatic group containing 1 to 5 benzene rings,

7. The composition for forming a release layer according to any one of 1 to 6, wherein Y < ₂ > is an aromatic group containing 1 to 5 benzene rings,

8. The organic solvent as described in any one of 1 to 7, wherein the organic solvent comprises at least one selected from amides represented by the formula (S1), amides represented by the formula (S2) and amides represented by the formula (S3) A composition for forming a release layer,

(Wherein R ¹ and R ² represent, independently of each other, 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, and h denotes a natural number.)

9. A peeling layer formed by using any one of the peeling layer forming compositions 1 to 8,

10. A method of manufacturing a flexible electronic device having a resin substrate,

11. A method of manufacturing a touch panel sensor comprising a resin substrate characterized by using a release layer,

12. The method for producing a resin substrate as described above, wherein the resin substrate is a polyimide resin substrate or a resin substrate having a light transmittance of at least 80%

.

By using the composition for forming a release layer of the present invention, it is possible to obtain a film having good adhesion with a substrate, suitable adhesiveness to a resin substrate, and appropriate releasability with good reproducibility. By using the composition of the present invention, in the process of manufacturing a flexible electronic device, the resin substrate is separated from the substrate together with the circuit and the like without damaging the resin substrate formed on the substrate or the circuit provided thereon Lt; / RTI > Therefore, the composition for forming a release layer of the present invention can contribute to simplification of a manufacturing process of a flexible electronic device having a resin substrate and improvement of the yield thereof.

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

The composition for forming a release layer comprises a polyamic acid represented by the following formula (1), a polyamic acid represented by the following formula (2), a polyamic acid represented by the following formula (3) or a polyamic acid represented by the following formula (4) Polyamide, and an organic solvent.

In the present invention, the release layer is a layer provided directly on a substrate (glass substrate or the like) on which the resin substrate is formed. As a typical example thereof, in the manufacturing process of a flexible electronic device, the resin substrate is sandwiched between the substrate and a resin substrate of a flexible electronic device formed of polyimide resin, acrylic resin, cycloolefin polymer resin or the like in a predetermined process And a release layer provided for fixing the resin substrate to the substrate after the formation of an electronic circuit or the like on the resin substrate.

In the formulas (1) to (4), X ₁ represents a tetravalent aromatic group having no fluorine atom, X ₂ represents a tetravalent aromatic group having a fluorine atom, and X ₃ represents a divalent aromatic group having no fluorine atom Y ₁ is a bivalent aromatic group having a fluorine atom, Y ₂ is a bivalent aromatic group having no fluorine atom, and m is a natural number.

X ₁ is preferably an aromatic group having no fluorine atom and containing 1 to 5 benzene rings. X ₁ may contain either or both of an ester bond and an ether bond.

Y ₁ is preferably an aromatic group having a fluorine atom and 1 to 5 benzene rings, more preferably an aromatic group selected from the group consisting of the following formulas (5) to (9) Is more preferable, and an aromatic group represented by the following formula (10) is further preferable.

X ₂ is preferably an aromatic group having a fluorine atom and further containing 1 to 5 benzene rings, and more preferably an aromatic group represented by the following formula (11) or (12).

Y ₂ is preferably an aromatic group having no fluorine atom and containing 1 to 5 benzene rings, more preferably an aromatic group containing 1 to 3 carbon atoms. Y ₂ may include either or both of an ester bond and an ether bond.

X ₃ is preferably an aromatic group having no fluorine atom and containing 1 to 5 benzene rings, more preferably an aromatic group containing 1 to 2 benzene rings, and more preferably a biphenyl group.

The m may be a natural number, preferably a natural number of 100 or less, more preferably a natural number of 2 to 100.

[Polyamic acid 1]

The polyamic acid represented by the above formula (1) is obtained by reacting an aromatic tetracarboxylic acid dianhydride having no fluorine atom with an aromatic diamine having a fluorine atom. Hereinafter, the aromatic tetracarboxylic dianhydrides and aromatic diamines usable for the synthesis of the polyamic acid represented by the formula (1) will be described in detail.

In the present invention, the aromatic tetracarboxylic acid dianhydride is not particularly limited as long as it does not have a fluorine atom and has two dicarboxylic acid anhydride moieties in the molecule, but an aromatic tetracarboxylic acid dianhydride having 1 to 5 benzene rings .

Specific examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic acid dianhydride, naphthalene-1,2,5 , 6-tetracarboxylic acid dianhydride, naphthalene-1,2,6,7-tetracarboxylic acid dianhydride, naphthalene-1,2,7,8-tetracarboxylic acid dianhydride, naphthalene-2,3,5,6-tetracarboxylic acid Dianhydride, naphthalene-2,3,6,7-tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, biphenyl-2,2 ', 3,3'-tetracarboxylic acid dianhydride , Biphenyl-2,3,3 ', 4'-tetracarboxylic dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, anthracene-1,2,3,4-tetracarboxylic acid dianhydride Water, anthracene-1,2,5,6-tetracarboxylic acid dianhydride, anthracene-1,2,6,7-tetracarboxylic acid dianhydride, anthracene-1,2,7,8-tetracarboxylic acid dianhydride, anthracene- , 3,6,7-tetracarboxylic acid Anhydride, phenanthrene-1,2,3,4-tetracarboxylic acid dianhydride, phenanthrene-1,2,5,6-tetracarboxylic acid dianhydride, phenanthrene-1,2,6,7-tetracarboxylic acid dianhydride, Phenanthrene-1,2,7,8-tetracarboxylic acid dianhydride, phenanthrene-1,2,9,10-tetracarboxylic acid dianhydride, phenanthrene-2,3,5,6-tetracarboxylic acid dianhydride, phenanthrene -2,3,6,7-tetracarboxylic acid dianhydride, phenanthrene-2,3,9,10-tetracarboxylic acid dianhydride, phenanthrene-3,4,5,6-tetracarboxylic acid dianhydride, phenanthrene-3 , 4,9,10-tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydrides represented by the following formulas (B1) to (B12), and the like. These may be used singly or in combination of two or more kinds.

On the other hand, the aromatic diamine is not particularly limited as long as it has a fluorine atom and two amino groups directly linked to the aromatic ring in the molecule, but an aromatic diamine containing 1 to 5 benzene rings is preferable. Further, it is more preferable to have a fluoroalkyl group or a perfluoroalkyl group, and a perfluoroalkyl group is more preferable. Examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, and an i-heptafluoropropyl group.

Specific examples of the aromatic diamine include 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 2-trifluoromethylbenzene- , 3,5-bis (trifluoromethyl) benzene-1,2-diamine, 2,2'-bis (trifluoromethyl) -4,4'- diaminobiphenyl, 2,2-bis 3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoro (Trifluormethyl) biphenyl-4,4'-diamine, 3,3 ', 5,5'-tetrafluorobiphenyl-4,4'-diamine , 4,4'-diaminooctafluorobiphenyl, aromatic diamines represented by the following formulas (A1) to (A5), and the like, but are not limited thereto. These may be used singly or in combination of two or more kinds.

[Polyamic acid 2]

The polyamic acid represented by the formula (2) is obtained by reacting an aromatic tetracarboxylic acid dianhydride having a fluorine atom with an aromatic diamine having no fluorine atom. Hereinafter, the aromatic tetracarboxylic acid dianhydride and the aromatic diamine usable for the synthesis of the polyamic acid represented by the formula (2) will be described in detail.

The aromatic tetracarboxylic acid dianhydride is not particularly limited as long as it has a fluorine atom and also has two dicarboxylic acid anhydride sites in the molecule. Further, it is more preferable to have a fluoroalkyl group or a perfluoroalkyl group, and a perfluoroalkyl group is more preferable. Examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, and an i-heptafluoropropyl group.

Specific examples of the aromatic tetracarboxylic acid dianhydride include 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, N, N' - [2,2'-bis (trifluoromethyl) biphenyl- -Diiyl] bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboamide), 3,6-difluoropyromellitic dianhydride, 3,6-bis 3-fluoropyrimellitic acid dianhydride, 3-trifluoromethyl pyromellitic acid dianhydride, 3-fluoro-3-methylimidazolium dianhydride, 3- 9-phenyl-9- (trifluoromethyl) xanthene tetracarboxylic acid dianhydride, 3,3 ', 4'-bis (trifluoromethyl) xanthene tetracarboxylic dianhydride, , 5,5 ', 6,6'-hexafluorooxy-4,4'-diphthalic acid dianhydride and the like. These may be used singly or in combination of two or more kinds.

On the other hand, the aromatic diamine is not particularly limited as long as it has no fluorine atom and has two amino groups directly linked to the aromatic ring in the molecule, but an aromatic diamine containing 1 to 5 benzene rings is preferable.

Specific examples of the aromatic diamine include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2- Dimethyl-m-phenylenediamine, 2,5-dimethyl-p-toluenesulfonic acid, 2,5-dimethylaniline, 2,6- Phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl- Diamines including one benzene ring such as phenylene diamine, m-xylylenediamine, p-xylylenediamine, and the like; 1,2-naphthalene diamine, 1,3-naphthalene diamine, 1,4-naphthalene diamine, 1,5-naphthalene diamine, 1,6-naphthalene diamine, Naphthalene diamine, 2,6-naphthalene diamine, 4,4'-biphenyldiamine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane , 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, '-Diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4 (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 3'-diaminodiphenylmethane, , 3'-diaminodiphenylsulfoxide, 3,4'-diaminodiphenylsulfoxide, and 4,4'-diaminodiphenylsulfoxide. A diamine containing 2; 1,5-diaminoanthracene, 1,5-diaminoanthracene, 1,5-diaminoanthracene, 2,6-diaminoanthracene, 1,5-diaminoanthracene, 1,5- (3-aminophenyl) benzene, 1, 3-bis (3-aminophenyl) benzene, Benzene, 1,3-bis (4-aminophenylsulfide) benzene, 1,4-bis (4-aminophenyl) Benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) Bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- ] Benzene, and aromatic diamines represented by the following formulas (A6) to (A44), and the like, but not limited thereto It is. These may be used singly or in combination of two or more kinds.

[Polyamic acid 3]

The polyamic acid represented by the formula (3) is obtained by reacting an aromatic tetracarboxylic acid dianhydride having a fluorine atom with an aromatic diamine having a fluorine atom.

As the aromatic tetracarboxylic acid dianhydride, an aromatic tetracarboxylic acid dianhydride having a fluorine atom similar to that usable for the synthesis of the polyamic acid represented by the formula (2) can be used.

As the aromatic diamine, an aromatic diamine having a fluorine atom similar to that usable for the synthesis of the polyamic acid represented by the formula (1) can be used.

[Polyamide]

The polyamide represented by the formula (4) is obtained by reacting an aromatic dicarboxylic acid having no fluorine atom or a derivative thereof with an aromatic diamine having a fluorine atom. Hereinafter, the aromatic dicarboxylic acid or its derivative and aromatic diamine which can be used for the synthesis of the polyamide represented by the formula (4) will be described in detail.

In the present invention, the aromatic dicarboxylic acid or derivative thereof is not particularly limited as long as it does not have a fluorine atom and has two carboxyl groups or a derivative thereof in the molecule. However, it is preferable that the aromatic dicarboxylic acid or its derivative has 1 to 5, And two aromatic dicarboxylic acids or derivatives thereof are preferable.

Specific examples of the aromatic dicarboxylic acid or a derivative thereof include aromatic dicarboxylic acids such as o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, Naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4 Anthracene dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 2-anthracene dicarboxylic acid, 2-anthracene dicarboxylic acid, , 2'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4'-terphenyl dicarboxylic acid, 4,4'- Carboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxyl Acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ethanedicarboxylic acid, 4,4'-bibenzyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, '-Tolandicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 4,4'-dithiobenzoic acid, p-phenylene diacetic acid, 3,3'- 4,4 '- [4, 4' - (4,4 '- (methylene di-p-phenylene)] dicopropionic acid, 4,4'-dibromophenylacetic acid, - (oxydi-p-phenylene)] dicopropionic acid, 4,4 '- [4,4' - (oxydi-p-phenylene)] dibutyrate, (isopropylidene di- Dioxane) dicarboxylic acids such as butyric acid and bis (p-carboxyphenyl) dimethylsilane;

Terephthalic acid dichloride, tetrachloroterephthalic acid dichloride, terephthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, 3-chloroisophthalic acid dichloride, 3-methoxyisophthalic acid dichloride, 2,5-dichloroterephthalic acid dichloride, 4-naphthalene dicarboxylic acid dichloride, 2,6-naphthalene dicarboxylic acid dichloride, 3,3'-biphenyldicarboxylic acid dichloride, 4,4'-biphenyldicarboxylic acid dichloride, 2,2'- Carboxylic acid dichloride, 3,4'-biphenyldicarboxylic acid dichloride, and the like. These may be used singly or in combination of two or more kinds. In addition, the various dicarboxylic acids may be a water-free structure.

As the aromatic diamine, an aromatic diamine having a fluorine atom similar to that usable for the synthesis of the polyamic acid represented by the formula (1) can be used.

When the polyamic acid represented by the formula (1) and the polyamic acid represented by the formula (2) are synthesized, the ratio of the mole number of the total tetracarboxylic dianhydride component to the total number of moles of the diamine component is the tetracarboxylic acid component / diamine Component = 0.8 to 1.2. The ratio of the number of moles of the total dicarboxylic acid component to the total number of moles of the diamine component in synthesizing the polyamide represented by the formula (4) is preferably 0.8 to 1.2 in terms of the dicarboxylic acid component / diamine component.

The polyamic acid represented by the formula (1), the polyamic acid represented by the formula (2) and the polyamic acid represented by the formula (3) contained in the composition for forming a peel layer according to the present invention, by reacting the aromatic diamine described above with the aromatic tetracarboxylic dianhydride, ) Can be obtained. Further, by reacting the above aromatic diamine with an aromatic dicarboxylic acid, the polyamide represented by the formula (4) contained in the composition for forming a release layer according to the present invention can be obtained.

[Organic solvents]

The organic solvent used in such a reaction is not particularly limited so long as it does not adversely affect the reaction, and specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, Pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N- dimethylformamide, 3-methoxy- Isopropoxy-N, N-dimethyl propylamide, 3-propoxy-N, N-dimethyl propylamide, Methylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3-tert-butoxy-N, N-dimethylpropylamide, and γ-butyrolactone. The organic solvents may be used alone or in combination of two or more.

Particularly, the organic solvent to be used in the reaction is an amide represented by the formula (S1), a compound represented by the formula (S2) in that the diamine, the tetracarboxylic acid dianhydride, the dicarboxylic acid, the polyamic acid and the polyamide described above are dissolved well. Amides and amides represented by the formula (S3) are preferable.

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

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, -Hexyl group, n-octyl group, n-nonyl group, and n-decyl group. Of these, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable.

The reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point, and is usually about 0 to 100 ° C. For example, imidization in a solution of the obtained polyamic acid is inhibited and a high content of polyamic acid units is maintained The temperature is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, even more preferably about 0 to 50 ° C.

Further, in the production of the polyamide, a polymerization catalyst may be used to increase the polymerization efficiency. Examples of the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphoric acid or a salt thereof, and pyridine. The addition amount of the polymerization catalyst is usually preferably not more than 2 mol% based on the total monomers constituting the polyamide.

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

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

The weight average molecular weight of the polyamic acid or polyamide is preferably 5,000 to 1,000,000, more preferably 6,000 to 500,000, and still more preferably 7,000 to 200,000 from the viewpoint of handling. In the present invention, the weight average molecular weight is an average molecular weight obtained by standard gel electrophoresis chromatography (GPC) analysis in terms of polystyrene standards.

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

The solvent used for the dilution is not particularly limited, and specific examples thereof are the same as specific examples of the reaction solvent for the above reaction. The solvent used for dilution may be used alone or in combination of two or more. Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl- Imidazololidinone, N-ethyl-2-pyrrolidone and? -Butyrolactone are preferable, and N-methyl-2-pyrrolidone is more preferable.

Insofar as the polyamic acid or the polyamide can not be solely precipitated, it can be mixed with the release layer forming composition of the present invention even if it is a solvent that does not dissolve the polyamic acid or polyamide. Particularly preferred are ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol Propyl alcohol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like can be used. Can suitably be mixed with a solvent having a low surface tension. As a result, it is known that the coating film uniformity is improved during coating onto a substrate, and it is suitably used also in the composition for forming a release layer of the present invention.

The concentration of the polyamic acid or polyamide in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced and the viscosity of the composition and is usually about 1 to 30 mass% About 1 to 20% by mass. With such a concentration, a peel layer having a thickness of about 0.05 to 5 mu m can be obtained with good reproducibility. The concentration of the polyamic acid or polyamide may be adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride or dicarboxylic acid as the raw material of these, or by diluting or concentrating the filtrate after the reaction solution is filtered, When the polyamide is dissolved in a solvent, it can be adjusted by adjusting its amount.

The viscosity of the composition for forming a release layer is suitably set in view of the thickness of the release layer to be produced. Particularly when it is intended to obtain a film having a thickness of about 0.05 to 5 탆 with good reproducibility, mPa 占 퐏, and preferably about 20 to 5,000 mPa 占 퐏. Here, the viscosities can be measured using a commercially available viscometer for viscosity measurement of liquid, for example, at a temperature of 25 ° C of the composition, with reference to the procedure described in JIS K7117-2. Preferably, a cone-plate type (cone plate type) rotational viscometer is used as the viscometer, preferably 1 ° 34 '× R24 is used as a standard cone rotor as a viscometer of the same type, . An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.

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

By applying the peeling layer forming composition of the present invention described above to a substrate and heating the obtained coating film, it is possible to obtain a peeling layer having good adhesion with a substrate, suitable adhesiveness to a resin substrate, and appropriate releasability.

When the release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the surface of the substrate or on the entire surface. Examples of the method of forming the release layer on a part of the surface of the base include a method of forming a release layer only in a predetermined range of the surface of the substrate, a method of forming a release layer in a pattern of a dot pattern, a line and space pattern, . Further, in the present invention, the base means that the base is coated with the composition for forming a release layer according to the present invention on the surface thereof, and used for manufacturing a flexible electronic device or the like.

Examples of the base material include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS and norbornene resins) ), Wood, paper, and slate. In particular, the release layer obtained from the composition for forming a release layer according to the present invention is preferably free from the viewpoint of having sufficient adhesion to the release layer. The surface of the substrate may be composed of a single material or may be composed of two or more materials. As a mode in which the surface of the base is composed of two or more materials, any of the surfaces of the base is composed of any material, and the remaining surface is composed of other materials; a pattern such as a dot pattern, a line and space pattern, And a material in which a material is present in other materials.

The coating method is not particularly limited, and examples thereof include a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an ink jet printing method, Flat plate, screen printing, etc.).

The heating temperature for imidization is appropriately determined within a range of usually 50 to 550 ° C, preferably 200 ° C or more, and more preferably 500 ° C or less. By performing the heating temperature in this way, it becomes possible to sufficiently progress the imidization reaction while preventing the obtained film from being weakened. Since the heating time differs depending on the heating temperature, it can not be defined collectively, but is usually 5 minutes to 5 hours. The imidization ratio may be in the range of 50 to 100%.

As a preferred example of the heating method of the present invention, heating is carried out at 50 to 100 ° C for 5 minutes to 2 hours, followed by heating stepwise as it is, and finally heating at 375 ° C to 450 ° C for 30 minutes to 4 hours . Particularly, it is preferable to heat at 50 to 100 ° C for 5 minutes to 2 hours, then to heat at more than 100 ° C to 375 ° C for 5 minutes to 2 hours, and finally to heat at 375 ° C to 450 ° C for 30 minutes to 4 hours.

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

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

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

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

Using the composition for forming a release layer according to the present invention, a release layer is formed on a glass substrate by the above-described method. A resin solution for forming a resin substrate is applied on the release layer and the resin film is fixed to the glass substrate via the release layer according to the present invention by heating the coating film. At this time, the entirety of the release layer is covered, and the resin substrate is formed with a large area as compared with the area of the release layer. Examples of the resin substrate include a polyimide resin, a resin substrate made of an acrylic resin and a cycloolefin polymer resin, which are typical resin substrates for a flexible electronic device, and resin solutions for forming the resin substrate include polyimide solutions, polyamic acid solutions, Solutions and cycloolefin polymer solutions. The method of forming the resin substrate may be according to a conventional method. As the resin substrate having high transparency, a resin substrate formed of acrylic resin or cycloolefin polymer resin can be exemplified. In particular, it is preferable that the light transmittance at a wavelength of 400 nm is 80% or more.

Then, a desired circuit is formed on the resin substrate fixed on the base body with the release layer according to the present invention interposed therebetween. Thereafter, the resin substrate is cut along the peeling layer, for example, To separate the resin substrate from the gas. At this time, a part of the base may be cut together with the release layer.

On the other hand, it has been reported that the polymer substrate can be suitably peeled off from the glass carrier by using the laser lift-off method (LLO method), which has been used in the production of a high-brightness LED or a three- (JP-A-2013-147599). In the manufacture of a flexible display, a polymer substrate made of polyimide or the like is provided on a glass carrier, a circuit including electrodes and the like is formed on the substrate, and finally the substrate is peeled off from the glass carrier together with this circuit . When the LLO method is employed in this peeling step, that is, when a glass carrier is irradiated with a light beam having a wavelength of 308 nm from the surface opposite to the surface on which the circuit or the like is formed, the light beam of the wavelength is transmitted through the glass carrier, Only the polymer (polyimide resin) absorbs this light and evaporates (sublimes). As a result, it has been reported that the peeling of the substrate from the glass carrier can be selectively performed without affecting the circuit mounted on the substrate or the like, which determines the performance of the display.

When a desired circuit is formed on the resin substrate fixed on the substrate via the release layer according to the present invention and then the LLO method is employed, only this release layer absorbs the light and evaporates (sublimes). That is, this peeling layer is sacrificed (serving as a sacrificial layer), and the peeling of the substrate from the glass carrier can be selectively performed. The composition for forming a release layer of the present invention is characterized in that it sufficiently absorbs light of a specific wavelength (for example, 308 nm) at which the LLO method can be applied, so that it can be used as a sacrifice layer of the LLO method.

(Example)

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

[1] Abbreviation for Compound

p-PDA: p-phenylenediamine

DDE; 4,4'-oxydianiline

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

BPTP: bis (4-aminophenoxy) terephthalate

HFBAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane

Bis-F: 2,2-bis (4-aminophenyl) hexafluoropropane

BTFDPE: 4,4-oxybis [(3-trifluoromethyl) benzenamine]

6FAPB: 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl

FDA: 9,9-bis (4-aminophenyl) fluorene

TPDA: 4,4 " -diamino-p-terphenyl

a-ODPA: 3,4'-oxydiphthalic anhydride

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

DPDOC: biphenyl-4,4'-dicarboxylic acid chloride

PMDA: pyromellitic dianhydride

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

BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride

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

BPTME: p-biphenylene bis (trimellitic acid monoester acid anhydride)

MMA: methyl methacrylate

MAA: methacrylic acid

HEMA: 2-hydroxyethyl methacrylate

AIBN: azobisisobutyronitrile

CHMI: cyclohexylmaleimide

Epolide GT-401: epoxidated vitaetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) ε-caprolactone,

NMP: N-methyl-2-pyrrolidone

PGMEA: propylene glycol monomethyl ether acetate

BCS:

[2] Method of measuring weight average molecular weight and molecular weight distribution

The measurement of the weight average molecular weight of the polymer (hereinafter referred to as Mw) and the molecular weight distribution were performed using a GPC apparatus (column: KD801 and KD805, column: Shimadzu; dimethylformamide / LiBr.H ₂ O (29.6 mM) / H ₃ PO ₄ (29.6 mM) / THF (0.1 mass%), flow rate: 1.0 mL / min; column temperature: 40 ° C; Mw: standard polystyrene conversion value).

[3] Synthesis of polymers

Various polymers used in Examples and Comparative Examples were synthesized by the following methods.

Further, the polymer-containing reaction solution was diluted with the reaction solution as described later without isolating the polymer to prepare a composition for forming a resin substrate or a composition for forming a release layer.

Synthesis Example S1 Synthesis of acrylic polymer (S1)

(0.0503 mol) of MAA and 2.46 g (0.0150 mol) of AIBN were dissolved in 46.9 g of PGMEA, and a solution of 60 to 100 g Deg.] C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 40% by mass). The obtained acrylic polymer had Mn of 3,800 and Mw of 7,300.

Synthesis Example S2 Synthesis of polyamic acid (S2)

20.3 g (188 mmol) of p-PDA and 12.2 g (46.9 mmol) of TPDA were dissolved in 617 g of NMP. After cooling to 15 캜, 50.1 g (230 mmol) of PMDA was added and the mixture was reacted at 50 캜 for 48 hours under a nitrogen atmosphere. The polymer obtained had Mw of 82,100 and a molecular weight distribution of 2.7.

Synthesis Example S3 Synthesis of polyamic acid (S3)

3.22 g (29.8 mmol) of p-PDA was dissolved in 88.2 g of NMP. To the obtained solution, 8.58 g (29.2 mmol) of BPDA was added and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere 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 Polyamic acid (L1)

1.74 g (8.70 mmol) of DDE was dissolved in 14.0 g of NMP. 1.17 g (1.74 mmol) of CF3-BP-TMA and 3.09 g (6.96 mmol) of 6FDA were added to the obtained solution, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The polymer obtained had Mw of 19,600 and a molecular weight distribution of 2.1.

Synthesis Example L2 Synthesis of polyamic acid (L2)

2.82 g (5.43 mmol) of HFBAPP was dissolved in 10.5 g of NMP. 1.69 g (5.43 mmol) of a-ODPA was added to the obtained solution, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 33,800 and a molecular weight distribution of 2.0.

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

1.62 g (3.12 mmol) of HFBAPP was dissolved in 7.0 g of NMP. To the obtained solution, 1.38 g (3.12 mmol) of 6FDA was added and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 56,600 and a molecular weight distribution of 1.8.

Synthesis Example L4 Synthesis of polyamic acid (L4)

1.92 g (5.70 mmol) of BTFDPE was dissolved in 35.6 g of NMP. 2.99 g (5.59 mmol) of BPTME was added to the obtained solution, and the reaction was allowed to proceed at 23 占 폚 in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 38,300 and a molecular weight distribution of 2.3.

Synthesis Example L5 Synthesis of polyamic acid (L5)

1.67 g (4.80 mmol) of BPTP was dissolved in 35.8 g of NMP. 3.21 g (4.78 mmol) of CF3-BP-TMA was added to the obtained solution, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 7,300 and a molecular weight distribution of 1.9.

Synthesis Example L6 Synthesis of polyamic acid (L6)

1.70 g (3.3 mmol) of HFBAPP was dissolved in 17.6 g of NMP. 0.70 g (3.2 mmol) of PMDA was added to the obtained solution, and the reaction was allowed to proceed at 23 占 폚 in a nitrogen atmosphere for 24 hours. The Mw of the obtained polymer was 48,300 and the molecular weight distribution was 2.6.

Synthesis Example L7 Synthesis of polyamic acid (L7)

1.46 g (4.4 mmol) of Bis-F was dissolved in 17.6 g of NMP. 0.93 g (4.3 mmol) of PMDA was added to the obtained solution, and the reaction was allowed to proceed at 23 占 폚 in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 16,000 and a molecular weight distribution of 1.6.

Synthesis Example L8 Synthesis of polyamic acid (L8)

2.86 g (8.9 mmol) of TFMB was dissolved in 35.2 g of NMP. 1.95 g (8.9 mmol) of PMDA was added to the obtained solution, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 70,300 and a molecular weight distribution of 1.7.

Synthesis Example L9 Synthesis of polyamic acid (L9)

1.18 g (3.7 mmol) of TFMB and 0.93 g (8.6 mmol) of p-PDA were dissolved in 35.2 g of NMP. 2.69 g (12.3 mmol) of PMDA was added to the obtained solution, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 60,700 and a molecular weight distribution of 3.3.

Synthesis Example L10 Polyamic acid (L10)

2.16 g (5.04 mmol) of 6FAPB was dissolved in 35.2 g of NMP. 2.64 g (4.94 mmol) of BPTME was added to the obtained solution, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 87,700 and a molecular weight distribution of 3.3.

Synthesis Example P1 Synthesis of polyamide (P1)

2.34 g (4.51 mmol) of HFBAPP was dissolved in 26.4 g of NMP, and 0.90 g (11.28 mmol) of pyridine was added. 1.26 g (4.51 mmol) of DPDOC was added to the obtained solution, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. Thereafter, the obtained solution was poured into 500 mL of pure water. The resulting precipitate was filtered and dried under reduced pressure at 70 ° C for 24 hours to obtain the desired polyamide P1. The Mw of the obtained polymer was 88,200 and the molecular weight distribution was 1.8.

&Lt; Comparative Synthesis Example > Synthesis of HL1 polyamic acid (HL1)

1.56 g (4.47 mmol) of FDA was dissolved in 7.0 g of NMP. 1.44 g (4.47 mmol) of BTDA was added to the obtained solution, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 67,300 and a molecular weight distribution of 2.0.

&Lt; Comparative Synthesis Example > Synthesis of HL2 polyamic acid (HL2)

0.98 g (9.02 mmol) of p-PDA was dissolved in 36.0 g of NMP. 3.03 g (9.39 mmol) of BTDA was added to the obtained solution, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The polymer thus obtained had Mw of 67,600 and a molecular weight distribution of 1.8.

[4] Preparation of composition for resin substrate formation

A composition for forming a resin substrate was prepared by the following method.

&Lt; Preparation Example 1 Composition F1 for resin substrate formation >

0.61 g of GT-401 and 5.06 g of PGMEA were added to 10 g of the reaction solution obtained in Synthesis Example S1 and stirred at 23 占 폚 for 24 hours to prepare a resin composition F1 for forming a substrate.

&Lt; Preparation Example 2 Composition F2 for resin substrate formation >

The reaction solution obtained in Synthesis Example S2 was directly used as the resin composition for forming a substrate F2.

&Lt; Preparation Example 3 Composition for resin substrate formation F3 >

The reaction solution obtained in Synthesis Example S3 was directly used as the resin composition for forming a substrate F3.

&Lt; Preparation Example 4 Composition F4 for resin substrate formation >

10 g of Zeonoa (registered trademark) 1020R (cycloolefin polymer resin, manufactured by Nippon Zeon Co., Ltd.) and 3 g of GT-401 were added to a branch flask containing 100 g of carbon tetrachloride. This solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare a composition F4 for resin substrate formation.

&Lt; Preparation Example 5 Composition F5 for resin substrate formation >

10 g of Zeonor (registered trademark) 1060R (cycloolefin polymer resin, manufactured by Nippon Zeon Co., Ltd.) was added to a flask containing 100 g of carbon tetrachloride. This solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare a resin composition for forming a substrate F5.

[5] Preparation of composition for forming release layer

[Example 1-1]

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

[Examples 1-2 to 1-10]

The compositions L2 to L10 for forming a release layer were obtained in the same manner as in Example 1-1 except that the reaction solutions obtained in Synthesis Examples L2 to L10 were used instead of the reaction solutions obtained in Synthesis Example L1.

[Example 1-11]

BCS and NMP were added to and dissolved in 0.5 g of the polyamide obtained in Synthesis Example P1 to dilute the polymer to a concentration of 5% by mass and a BCS of 20% by mass to obtain a release layer composition P1.

[Comparative Example 1-1]

BCS and NMP were added to the reaction solution obtained in Comparative Synthesis Example HL1 and diluted to a polymer concentration of 5% by mass and a BCS of 20% by mass to obtain a release layer composition HL1.

[Comparative Example 1-2]

BCS and NMP were added to the reaction solution obtained in Comparative Synthesis Example HL2 and diluted to a polymer concentration of 5 mass% and a BCS of 20 mass% to obtain a release layer composition HL2.

[6] Fabrication of release layer and resin substrate

[Example 2-1]

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

Then, the obtained coating film was heated at 80 DEG C for 10 minutes using a hot plate, and then heated at 300 DEG C for 30 minutes using an oven. The heating temperature was increased to 400 DEG C (10 DEG C / min) For 30 minutes to form a release layer having a thickness of about 0.1 mu m on the glass substrate to obtain a glass substrate with a release layer. While the temperature was raised, the glass substrate was not taken out of the oven but heated in an oven.

The resin composition F1 for forming a substrate was applied on a release layer (resin thin film) on a glass substrate using a spin coater (condition: about 10 seconds at a revolution of 500 rpm). The obtained coating film was heated at 80 캜 for 10 minutes using a hot plate and then heated at 230 캜 for 30 minutes using a hot plate to form a resin substrate having a thickness of about 5 탆 on the peeling layer, A glass substrate with a peel layer was obtained. Thereafter, the light transmittance was measured using an ultraviolet visible spectrophotometer (UV-2600, Shimadzu Corporation), and as a result, the resin substrate exhibited a transmittance of 80% or more at 400 nm.

[Examples 2-2 to 2-5]

Except that the release layer forming compositions L2 to L5 obtained in Examples 1-2 to 1-5 were used in place of the release layer forming composition L1 obtained in Example 1-1, And a resin substrate were formed, and a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer were produced.

[Example 2-6]

A release layer was formed in the same manner as in Example 2-1 by using the release layer forming composition L6 obtained in Example 1-6 instead of the release layer formation composition L1 obtained in Example 1-1, An attached glass substrate was obtained.

Subsequently, using a bar coater (gap: 250 mu m), the composition F2 for forming a resin substrate was coated on the release layer (resin thin film) on the glass substrate obtained above. Then, the obtained coating film was heated at 80 DEG C for 30 minutes using a hot plate, then heated at 140 DEG C for 30 minutes using an oven, heated to 210 DEG C (10 DEG C / The heating temperature was raised to 300 DEG C for 30 minutes at 300 DEG C for 30 minutes and the heating temperature was increased to 400 DEG C and heated at 400 DEG C for 60 minutes to form a resin substrate having a thickness of about 20 mu m on the peeling layer, A glass substrate having a substrate and a release layer was obtained. While the temperature was raised, the glass substrate was not taken out of the oven but heated in an oven.

[Example 2-7]

A release layer was formed in the same manner as in Example 2-1 by using the release layer forming composition L7 obtained in Example 1-7 instead of the release layer formation composition L1 obtained in Example 1-1, An attached glass substrate was obtained.

Subsequently, using a bar coater (gap: 250 mu m), the composition F3 for forming a resin substrate was coated on the release layer (resin thin film) on the glass substrate obtained above. Then, 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, heated to 210 ° C (2 ° C / The heating temperature was raised to 300 DEG C for 30 minutes at 300 DEG C for 30 minutes and the heating temperature was increased to 400 DEG C and heated at 400 DEG C for 60 minutes to form a resin substrate having a thickness of about 20 mu m on the peeling layer, A glass substrate having a substrate and a release layer was obtained. While the temperature was raised, the glass substrate was not taken out of the oven but heated in an oven.

[Example 2-8]

A release layer and a resin substrate were formed in the same manner as in Example 2-6 except that the release layer forming composition L8 obtained in Example 1-8 was used in place of the release layer formation composition L1 obtained in Example 1-1 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were produced.

[Example 2-9]

A release layer and a resin substrate were formed in the same manner as in Example 2-7 except that the release layer forming composition L8 obtained in Example 1-8 was used in place of the release layer formation composition L1 obtained in Example 1-1 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were produced.

[Example 2-10]

A release layer and a resin substrate were formed in the same manner as in Example 2-7 except that the release layer forming composition L9 obtained in Example 1-9 was used in place of the release layer formation composition L1 obtained in Example 1-1 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were produced.

[Example 2-11]

A release layer and a resin substrate were formed in the same manner as in Example 2-6 except that the release layer forming composition L10 obtained in Example 1-10 was used in place of the release layer formation composition L1 obtained in Example 1-1 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were produced.

[Example 2-12]

A release layer and a resin substrate were formed in the same manner as in Example 2-7 except that the release layer forming composition L10 obtained in Example 1-10 was used in place of the release layer formation composition L1 obtained in Example 1-1 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were produced.

[Example 2-13]

Using a spin coater (condition: about 30 seconds at 3,000 rpm of revolution), the composition P1 for peeling layer formation obtained in Example 1-11 was applied on a 100 mm x 100 mm glass substrate as a glass substrate.

The obtained coating film was heated at 80 DEG C for 10 minutes using a hot plate and then heated at 300 DEG C for 30 minutes using an oven to form a release layer having a thickness of about 0.1 mu m on the glass substrate, A glass substrate was obtained.

Subsequently, a resin substrate was formed in the same manner as in Example 2-1 to obtain a glass substrate having a resin substrate and a release layer.

[Examples 2-14]

Using the composition for forming a release layer L8 obtained in Example 1-8, a release layer was formed in the same manner as in Example 2-1 to obtain a glass substrate with a release layer.

Subsequently, the composition F4 for forming a resin substrate was coated on the release layer (resin thin film) on the glass substrate using a spin coater (condition: about 15 seconds at a revolution of 200 rpm). The obtained coating film was heated at 80 캜 for 2 minutes using a hot plate and then heated at 230 캜 for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 탆 on the peeling layer, Thereby obtaining a layered glass substrate. Thereafter, the light transmittance was measured using an ultraviolet visible spectrophotometer (UV-2600, Shimadzu Corporation), and as a result, the resin substrate exhibited a transmittance of 80% or more at 400 nm.

[Example 2-15]

A release layer and a resin substrate were prepared in the same manner as in Example 2-14 except that the release layer forming composition L9 obtained in Example 1-9 was used in place of the release layer formation composition L8 obtained in Example 1-8 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were obtained.

[Examples 2-16]

Using the composition for forming a release layer L8 obtained in Example 1-8, a release layer was formed in the same manner as in Example 2-1 to obtain a glass substrate with a release layer.

Subsequently, the composition F5 for forming a resin substrate was coated on the release layer (resin thin film) on the glass substrate using a spin coater (condition: about 15 seconds at a revolution of 200 rpm). The obtained coating film was heated at 80 캜 for 2 minutes using a hot plate and then heated at 230 캜 for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 탆 on the peeling layer, Thereby obtaining a layered glass substrate. Thereafter, the light transmittance was measured using an ultraviolet visible spectrophotometer (UV-2600, Shimadzu Corporation), and as a result, the resin substrate exhibited a transmittance of 80% or more at 400 nm.

[Example 2-17]

A release layer and a resin substrate were prepared in the same manner as in Example 2-16 except that the release layer forming composition L9 obtained in Example 1-9 was used in place of the release layer formation composition L8 obtained in Example 1-8 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were obtained.

[Comparative Example 2-1]

A release layer and a resin substrate were formed in the same manner as in Example 2-1 except that the release layer forming composition HL1 obtained in Comparative Example 1-1 was used in place of the release layer formation composition L1 obtained in Example 1-1 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were obtained.

[Comparative Example 2-2]

A release layer and a resin substrate were formed in the same manner as in Example 2-7 except that the release layer forming composition HL1 obtained in Comparative Example 1-1 was used in place of the release layer formation composition L1 obtained in Example 1-1 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were obtained.

[Comparative Example 2-3]

A release layer and a resin substrate were formed in the same manner as in Example 2-1 except that the release layer forming composition HL2 obtained in Comparative Example 1-2 was used in place of the release layer formation composition L1 obtained in Example 1-1 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were obtained.

[7] Evaluation of peelability

The peelability of the release layer and the glass substrate with respect to the glass substrate with the release layer obtained in Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2-3 was measured with respect to the glass substrate with resin substrate and release layer The peeling property between the release layer and the resin substrate was confirmed by the following method.

&Lt; Evaluation of peeling property of a resin thin film in a cross-

The peeling layer on the glass substrate with the peeling layer obtained in Examples 2-1 to 2-17 and the comparative examples 2-1 to 2-3 and the peeling layer and the resin substrate on the glass substrate with resin substrate / 25 mm apart at intervals of 2 mm, the same applies hereinafter). In other words, 25 checkerboards of 2 mm in each side were formed by the cross skirt.

Then, an adhesive tape was attached to the 25th checkerboard cut portion and the tape was peeled off to evaluate the degree of peeling based on the following criteria (5B to 0B, B, A, AA).

Of the peeled substrates, peelability evaluation tests were conducted using the resin substrates and release layer-attached glass substrates produced in Examples 2-14 to 2-17. In the test method, a resin substrate of a glass substrate with a release layer and a release layer was formed into a rectangular shape with a width of 25 mm x 50 mm by inserting a slit through a cutter knife to the backside of the resin substrate. Cellotape (registered trademark, Nichiban CT-24) was affixed on the prepared strip, and the surface of the substrate was polished at 90 占 폚, that is, perpendicular to the surface of the substrate, using an Autograph AG-500N (manufactured by Shimadzu Corporation) And the peel force was measured. The peel force was 100% peel (all peel), and the peel force was less than 0.1 N / 25 mm.

Table 1 shows the above results.

<Criteria>

5B: 0% peeling (no peeling)

4B: Less than 5% exfoliation

3B: peeling less than 5 ~ 15%

2B: peeling less than 15 ~ 35%

1B: peeling less than 35 to 65%

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

B: 80% to less than 95% exfoliation

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

AA: 100% peeling (all peeling)

AAA: 100% peel, peel force less than 0.1N / 25mm

Type of release layer Type of resin substrate Peelability of peeling layer and glass substrate Peelability of peeling layer and resin substrate Example 2-1 L1 F1 5B AA Example 2-2 L2 F1 5B AA Example 2-3 L3 F1 5B AA Examples 2-4 L4 F1 5B AA Example 2-5 L5 F1 5B AA Examples 2-6 L6 F2 5B AA Examples 2-7 L7 F3 5B AA Examples 2-8 L8 F2 5B AA Examples 2-9 L8 F3 5B AA Examples 2-10 L9 F3 5B AA Examples 2-11 L10 F2 5B AA Examples 2-12 L10 F3 5B AA Examples 2-13 P1 F1 5B AA Examples 2-14 L8 F4 5B AAA Examples 2-15 L9 F4 5B AAA Examples 2-16 L8 F5 5B AAA Examples 2-17 L9 F5 5B AAA Comparative Example 2-1 HL1 F1 5B 5B Comparative Example 2-2 HL1 F3 5B 5B Comparative Example 2-3 HL2 F1 5B 5B

As shown in Table 1, it was confirmed that the peeling layers of Examples 2-1 to 2-17 had excellent adhesion to the glass substrate and easily peeled off from the resin film. On the other hand, it was confirmed that the peeling layers of Comparative Examples 2-1 to 2-3 were excellent in adhesion to a glass substrate, but were inferior in peelability to a resin substrate.

Claims (12)

A polyimide resin composition comprising a polyamic acid represented by the following formula (1), a polyamic acid represented by the following formula (2), a polyamic acid represented by the following formula (3) or a polyamide represented by the following formula (4) By weight based on the total weight of the composition.

(Wherein X ₁ represents a tetravalent aromatic group having no fluorine atom, X ₂ represents a tetravalent aromatic group having a fluorine atom, X ₃ represents a divalent aromatic group having no fluorine atom, Y ₁ represents a fluorine atom Y ₂ represents a divalent aromatic group having no fluorine atom, and m represents a natural number.) The composition for forming a release layer according to claim 1, wherein Y ₁ is an aromatic group selected from the group consisting of the following formulas (5) to (9).

The composition for forming a release layer according to claim 2, wherein the Y ₁ is an aromatic group represented by the following formula (10).

The composition for forming a release layer according to any one of claims 1 to 3, wherein X ₂ is an aromatic group represented by the following formula (11) or (12).

The composition for forming a release layer according to any one of claims 1 to 4, wherein X ₁ is an aromatic group containing 1 to 5 benzene rings. The composition for forming a release layer according to any one of claims 1 to 5, wherein X ₃ is an aromatic group containing 1 to 5 benzene rings. The composition for forming a release layer according to any one of claims 1 to 6, wherein the Y ₂ is an aromatic group containing 1 to 5 benzene rings. The method according to any one of claims 1 to 7, wherein the organic solvent is selected from amides represented by the formula (S1), amides represented by the formula (S2) and amides represented by the formula (S3) At least one kind of a release layer.

(Wherein R ¹ and R ² represent, independently of each other, 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, and h denotes a natural number.) A release layer formed by using the composition for forming a release layer according to any one of claims 1 to 8. A manufacturing method of a flexible electronic device comprising a resin substrate characterized by using the release layer according to claim 9. A manufacturing method of a touch panel sensor comprising a resin substrate characterized by using the peeling layer according to claim 9. The method according to claim 10 or 11, wherein the resin substrate is a polyimide resin substrate or a resin substrate having a light transmittance of 400 nm or more at 80% or more.