KR20190035757A - Composition for forming a release layer for a transparent resin substrate - Google Patents

Abstract

A composition for forming a release layer comprising a polyamic acid as a reaction product of a diamine component and a tetracarboxylic acid dianhydride component and an organic solvent, wherein the diamine component comprises an aromatic diamine having an ester bond and / or an ether bond, At least one of an aromatic tetracarboxylic dianhydride having at least one of an aromatic diamine having no ester bond and / or an ether bond and a tetracarboxylic dianhydride component having an ester bond and / or an ether bond, and an aromatic tetracarboxylic dianhydride having no ester bond and an ether bond And at least one of the diamine component and the tetracarboxylic acid dianhydride component has a component having an ester bond and / or an ether bond. The present invention also provides a composition for forming a release layer for a transparent resin substrate.

Description

Composition for forming a release layer for a transparent resin substrate

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

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a transparent resin substrate of a flexible electronic device formed using an acrylic resin, a cycloolefin polymer resin or the like, And to provide a composition for forming a peel layer for use.

As a result of intensive studies to solve the above problems, the present inventors have found that, in a composition comprising a polyamic acid and an organic solvent, which are reactants of a diamine component and a tetracarboxylic acid dianhydride component, Or an aromatic tetracarboxylic dianhydride having at least one of an aromatic diamine having an ether bond and an aromatic diamine having no ester bond and an ether bond and the tetracarboxylic dianhydride component having an ester bond and / or an ether bond, and An aromatic tetracarboxylic dianhydride having at least one of an ester bond and an ether bond and an aromatic tetracarboxylic dianhydride having at least one of the ester bond and / or the ether bond, and an aromatic tetracarboxylic dianhydride having the ester bond and / At least one side When also on, taking out that a composition capable of forming a proper adhesion between the release layer with an appropriate peeling property of the transparent resin substrate is used as excellent adhesion, and flexible electronic device of the gas obtained, and completed the present invention.

That is,

1. A composition for forming a release layer for a transparent resin substrate comprising a polyamic acid as a reaction product of a diamine component and a tetracarboxylic dianhydride component and an organic solvent,

Wherein the diamine component comprises at least one of an aromatic diamine having an ester bond and / or an ether bond, and an aromatic diamine having no ester bond and no ether bond, wherein the tetracarboxylic dianhydride component has an ester bond and / And at least one of an aromatic tetracarboxylic acid dianhydride having no ester bond and an ether bond,

Wherein at least one of the diamine component and the tetracarboxylic acid dianhydride component comprises a component having an ester bond and / or an ether bond, and a composition for forming a release layer for a transparent resin substrate,

2. A composition for forming a release layer for a transparent resin substrate, wherein the aromatic diamine having the ester bond and / or the ether bond is at least one selected from the group consisting of formulas (A1) to (A39)

3. The composition for forming a peel layer for a transparent resin substrate according to claim 1, wherein the aromatic tetracarboxylic acid dianhydride having an ester bond and / or an ether bond is at least one selected from the group consisting of formulas (B1) to (B16)

4. The composition for forming a release layer for a transparent resin substrate according to any one of claims 1 to 3, wherein the aromatic diamine having no ester bond and ether bond has 1 to 5 benzene rings,

5. A composition for forming a release layer for a transparent resin substrate, wherein the aromatic diamine having no ester bond and ether bond is p-phenylenediamine,

6. The composition for forming a release layer for a transparent resin substrate according to any one of 1 to 5, wherein the aromatic tetracarboxylic acid dianhydride having no ester bond and ether bond is aromatic containing 1 to 5 benzene rings,

7. The composition for forming a release layer for a transparent resin substrate according to any one of 1 to 6, wherein the organic solvent comprises at least one selected from amides represented by formulas (S1) to (S3)

(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.)

8. A release layer formed by using the composition for forming a release layer for a transparent resin substrate of any one of 1 to 7,

9. A manufacturing method of a flexible electronic device comprising a transparent resin substrate, characterized by using a release layer of 8

.

By using the composition for forming a release layer for a transparent resin substrate of the present invention, it is possible to obtain a film having good adhesion with a substrate, suitable adhesiveness to a transparent resin substrate, and appropriate peelability 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 for a transparent resin substrate of the present invention comprises a polyamic acid which is a reaction product of a diamine component and a tetracarboxylic acid dianhydride component, and an organic solvent, wherein the diamine component has an ester bond and / An aromatic tetracarboxylic dianhydride having at least one of an aromatic diamine and an aromatic diamine having no ester bond and an ether bond and the tetracarboxylic dianhydride component having an ester bond and / or an ether bond, and an ester bond and an ether bond And an aromatic tetracarboxylic acid dianhydride having at least one of an aromatic tetracarboxylic dianhydride having no ester bond and / or an ether bond and having at least one of an aromatic diamine having the ester bond and / or an ether bond and an aromatic tetracarboxylic dianhydride having the ester bond and / will be.

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 a 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 a transparent resin such as an acrylic resin, a polycarbonate, or a cycloolefin polymer, And a release layer provided so as to allow the resin substrate to be easily peeled from the substrate after forming an electronic circuit or the like on the resin substrate.

[Diamine component]

In the present invention, the diamine component may include an aliphatic diamine or an aromatic diamine. From the viewpoint of ensuring the strength and heat resistance of the resulting thin film, it is preferable to include an aromatic diamine. In the present invention, the diamine component includes at least one of an aromatic diamine having an ester bond and / or an ether bond, and an aromatic diamine having no ester bond and an ether bond.

The aromatic diamine having an ester bond and / or an ether bond includes one or both of an ester bond and an ether bond in the molecule thereof. Examples of such aromatic diamines include diamines having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are linked by an ester bond or an ether bond. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among them, a diamine having a structure in which two or three aromatic rings are linked by an ester bond or an ether bond is preferable from the viewpoint of securing the solubility of polyamic acid in an organic solvent.

In the present invention, preferred specific examples of the aromatic diamine having an ester bond and / or an ether bond include those shown below.

In the present invention, the aromatic diamine having no ester bond or ether bond preferably contains 1 to 5 benzene rings, more preferably a benzene skeleton, a naphthyl skeleton, or a biphenyl skeleton.

Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2- , 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl- Diamine, 2,6-dimethyl-p-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl- A diamine containing one benzene ring such as 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 the like, but the present invention is not limited thereto. Among them, p-phenylenediamine can be suitably used in the present invention. These may be used singly or in combination of two or more kinds.

[Component of tetracarboxylic acid dianhydride]

In the present invention, the tetracarboxylic dianhydride component may contain any of aliphatic tetracarboxylic acid dianhydride and aromatic tetracarboxylic dianhydride. From the viewpoint of ensuring the strength and heat resistance of the obtained thin film, those containing aromatic tetracarboxylic dianhydride desirable. In the present invention, the tetracarboxylic dianhydride component includes at least one of an aromatic tetracarboxylic dianhydride having an ester bond and / or an ether bond, and an aromatic tetracarboxylic dianhydride having no ester bond and an ether bond.

The aromatic tetracarboxylic acid dianhydride having an ester bond and / or an ether bond includes one or both of an ester bond and an ether bond in the molecule thereof. Examples of such aromatic tetracarboxylic acid dianhydrides include tetracarboxylic dianhydrides having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are linked by an ester bond or an ether bond. Specific examples of the aromatic ring include the same ones as described above. Among them, from the viewpoint of ensuring the solubility of polyamic acid in an organic solvent, it is preferable that three or four aromatic rings have a structure in which they are linked by an ester bond or an ether bond.

In the present invention, preferred specific examples of the aromatic tetracarboxylic acid dianhydride having an ester bond and / or an ether bond include those shown below.

Such tetracarboxylic acid dianhydride may be any of an aliphatic tetracarboxylic acid dianhydride and an aromatic tetracarboxylic dianhydride. From the viewpoint of securing the strength and heat resistance of the obtained thin film, an aromatic tetracarboxylic acid dianhydride having no ester linkage or ether linkage is preferable Do. In the present invention, the aromatic tetracarboxylic acid dianhydride having no ester bond or ether bond preferably contains 1 to 5 benzene rings, more preferably a benzene skeleton, a naphthyl skeleton or a biphenyl skeleton .

Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, naphthalene-1,2,3,4-tetracarboxylic acid dianhydride, naphthalene-1,2,5,6-tetra Carboxylic 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 dianhydride, anthracene-1,2,3,4-tetracarboxylic acid dianhydride, 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-2,3,6 , 7-tetracarboxylic acid dianhydride, phenanthrene-1,2,3,4-tetra Phenanthrene-1,2,2,6-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, But are not limited to these. These may be used alone or in combination of two or more.

In particular, as the aromatic tetracarboxylic acid dianhydride having no ester bond or ether bond, at least one species selected from the group consisting of the formulas (C1) to (C12) is preferable from the viewpoint of securing the heat resistance, C9). ≪ / RTI >

In the present invention, the amount of the aromatic diamine having the ester bond and / or the ether bond is preferably such that when the tetracarboxylic dianhydride component does not contain an aromatic tetracarboxylic dianhydride having an ester bond and / or an ether bond, Is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably 100 mol%. By employing such a usage amount, 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.

In the present invention, the amount of the aromatic tetracarboxylic dianhydride having the ester bond and / or the ether bond is preferably such that when the diamine component does not contain an aromatic diamine having an ester bond and / or an ether bond, the total tetracarboxylic acid dianhydride Is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably 100 mol%. By employing such a used amount, it is possible to obtain a film having satisfactory adhesion with a substrate, proper adhesiveness to a resin substrate, and appropriate peelability with good reproducibility.

When the aromatic diamine having an ester bond and / or an ether bond and the aromatic tetracarboxylic acid dianhydride having an ester bond and / or an ether bond are both included, the total amount of the diamine component and the tetracarboxylic acid dianhydride component , Preferably at least 35 mol%, more preferably at least 40 mol%, even more preferably at least 45 mol%, and even more preferably at least 50 mol%. Also in this case, the ratio of the number of moles of the aromatic diamine having an ester bond and / or the ether bond to the number of moles of the aromatic tetracarboxylic acid dianhydride having an ester bond and / or an ether bond is arbitrary.

It is preferable that the tetra carboxylic acid component / diamine component ratio is 0.8 to 1.2 in the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component in synthesizing the polyamic acid of the present invention.

By reacting the diamine component and the tetracarboxylic dianhydride component described above, the polyamic acid contained in the composition for forming a release layer for a transparent resin substrate 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 used in the reaction is preferably an amide represented by the formula (S1), an amide represented by the formula (S2) and a compound represented by the formula (S3) in that the diamine and the tetracarboxylic acid dianhydride and the polyamic acid are well dissolved. Is preferably at least one selected from amides.

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 is 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. In order to prevent imidization in the solution of the obtained polyamic acid and to maintain a high content of the polyamic acid unit, Is about 0 to 70 ° C, more preferably about 0 to 60 ° C, even more preferably about 0 to 50 ° C.

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 can be obtained.

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

In the present invention, usually, a solution obtained by filtering the reaction solution and then directly or diluting or concentrating the filtrate can be used as a 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. Alternatively, the polyamic acid may be isolated from the reaction solution and then dissolved in a solvent to prepare a composition for forming a release layer. Examples of the solvent in this case include an organic solvent used in the above-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-2-imide N-ethyl-2-pyrrolidone and? -Butyrolactone are preferable, and N-methyl-2-pyrrolidone is more preferable.

Further, even if the solvent does not dissolve the polyamic acid, it can be mixed with the composition for forming a release layer of the present invention as far as the polyamic acid is not precipitated. 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. By this, it is known that the coating film uniformity is improved at the time of application to the 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 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% by mass, preferably 1 to 20% %. With such a concentration, a peel layer having a thickness of about 0.05 to 5 mu m can be obtained with good reproducibility. The concentration of the polyamic acid can be adjusted by adjusting the amount of diamine and tetracarboxylic acid dianhydride which are the raw materials of the polyamic acid or by diluting or concentrating the filtrate after filtering the reaction solution or by dissolving the isolated polyamic acid in a solvent The amount can be adjusted or adjusted.

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.

In addition to the polyamic acid and the organic solvent, 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.

By applying the peeling layer forming composition of the present invention described above to a substrate and heating the obtained coating film to thermally imidize the polyamic acid, a polyimide film having excellent adhesion with the substrate, suitable adhesiveness to the transparent resin substrate, Can be obtained.

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. An acrylic polymer solution, a polycarbonate, and a cycloolefin polymer solution for forming a transparent resin substrate of a flexible electronic device are applied on the release layer and the coating film is heated to form a release layer according to the present invention, Thereby forming a fixed transparent resin substrate. At this time, the entirety of the release layer is covered, and a transparent resin substrate is formed with a large area as compared with the area of the release layer. 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 an acrylic resin, polycarbonate, 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 examples, but the present invention is not limited to these examples.

[1] Abbreviation for Compound

p-PDA: p-phenylenediamine

DDE; 4,4'-oxydianiline

BPTP: bis (4-aminophenoxy) terephthalate

APAB-E: 4-aminophenyl-4'-aminobenzoate

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

a-ODPA: 3,4'-oxydiphthalic anhydride

TAHQ: p-phenylenebis (trimellitic acid monoester acid anhydride)

PMDA: pyromellitic dianhydride

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

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

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)

A solution of 7.20 g (7.19 mmol) of MMA, 7.20 g (5.53 mmol) of HEMA, 10.8 g (6.03 mmol) of CHMI, 4.32 g (5.02 mmol) of MAA and 2.46 g (1.50 mmol) of AIBN were dissolved in 46.9 g of PGMEA, Deg.] C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 40% by mass). The acrylic polymer thus obtained had an Mw of 7,300 and a molecular weight distribution of 1.9.

Synthesis Example L1 Synthesis of Polyamic acid (L1)

5.24 g (15.05 mmol) of BPTP was dissolved in 88.0 g of NMP. 6.76 g (14.75 mmol) of TAHQ 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 85,900 and a molecular weight distribution of 3.0.

Synthesis Example L2 Synthesis of polyamic acid (L2)

4.04 g (17.71 mmol) of APAB-E were dissolved in 88.0 g of NMP. 7.96 g (17.37 mmol) of TAHQ 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 33,100 and the molecular weight distribution was 1.8.

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

3.64 g (15.96 mmol) of APAB-E was dissolved in 88.0 g of NMP. 8.36 g (15.64 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 41,600 and a molecular weight distribution of 3.5.

Synthesis Example L4 Synthesis of polyamic acid (L4)

0.96 g (2.75 mmol) of BPTP was dissolved in 17.6 g of NMP. 1.44 g (2.70 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 112,800 and a molecular weight distribution of 3.6.

Synthesis Example L5 Synthesis of polyamic acid (L5)

1.77 g (8.82 mmol) of DDE was dissolved in 10.5 g of NMP. 2.74 g (8.82 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 obtained had Mw of 46,400 and a molecular weight distribution of 2.2.

Synthesis Example L6 Synthesis of polyamic acid (L6)

0.93 g (8.61 mmol) of p-PDA was dissolved in 35.2 g of NMP. 3.87 g (8.44 mmol) of TAHQ 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 obtained polymer had a Mw of 45,000 and a molecular weight distribution of 2.7.

Synthesis Example L7 Synthesis of polyamic acid (L7)

17.41 g (86.96 mmol) of DDE was dissolved in 264.0 g of NMP. 18.59 g (85.22 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 52,800 and a molecular weight distribution of 2.4.

&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 >

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 resin composition for forming a substrate F2.

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

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 F3.

[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 1-7]

Except for using the reaction solutions obtained in Synthesis Examples L2 to L7 instead of the reaction solution obtained in Synthesis Example L1, the compositions L2 to L7 for forming a release layer were obtained in the same manner as in Example 1-1.

[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 resin substrate was applied on the release layer (resin thin film) on the glass substrate obtained above 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 2-7]

Except that the release layer forming compositions L2 to L7 obtained in Examples 1-2 to 1-7 were used in place of the release layer forming composition L1 obtained in Example 1-1, And a resin substrate were formed to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and peeling layer.

[Example 2-8]

Using the release layer forming composition L6 obtained in Example 1-6, 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 resin composition F2 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 2-9]

A release layer and a resin substrate were prepared in the same manner as in Example 2-8 except that the release layer forming composition L7 obtained in Example 1-7 was used in place of the release layer formation composition L6 obtained in Example 1-6 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were obtained.

[Example 2-10]

Using the release layer forming composition L6 obtained in Example 1-6, 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 F3 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 2-11]

A release layer and a resin substrate were prepared in the same manner as in Example 2-10 except that the release layer forming composition L7 obtained in Example 1-7 was used in place of the release layer formation composition L6 obtained in Example 1-6 , A glass substrate with a release layer, and a glass substrate with a resin substrate and release layer were obtained.

[Comparative Examples 2-1 and 2-2]

Except that the release layer-forming compositions HL1 and HL2 obtained in Comparative Examples 1-1 and 1-2 were used in place of the release layer-forming composition L1 obtained in Example 1-1, the release layer and the resin A substrate was formed to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[7] Evaluation of peelability

The peelability of the peeling layer and the glass substrate on the glass substrate with the peeling layer obtained in Examples 2-1 to 2-11 and Comparative Examples 2-1 and 2-2 was evaluated by peeling off the glass substrate with the resin substrate and peeling layer Layer and the resin substrate were confirmed by the following method.

&Lt; Evaluation of Peelability of Release Layer and Glass Substrate &

The peeling layer on the glass substrate with the peeling layer obtained in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-2 and the peeling layer and the resin substrate on the glass substrate with the resin substrate and peeling layer were cut in a cross- Vertical 2 mm intervals, the same is applied hereinafter). In other words, 25 checkerboards of 2 mm in each side were formed by the cross skirt.

Adhesive tapes were attached to the 25 checkerboard cut portions, the tape was peeled off, and the degree of peeling was evaluated 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 2-8 to 2-11. 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 (trademark registered, Nichiban CT-24) was attached to the fabricated strip, and then, using Autograph AG-500N (manufactured by Shimadzu Seisakusho Co., Ltd.) , And the peel force was measured. The peel strength was 100% peel (all peel), and the peel force was less than 0.1 N / 25 mm as AAA.

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

<Evaluation of Peelability of Release Layer and Resin Substrate>

The releasability of the glass substrates with resin substrates and release layers obtained in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-2 was evaluated in the same manner as the peelability evaluation described above. The results are shown in Table 1.

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 F1 5B AA Examples 2-7 L7 F1 5B AA Examples 2-8 L6 F2 5B AAA Examples 2-9 L7 F2 5B AAA Examples 2-10 L6 F3 5B AAA Examples 2-11 L7 F3 5B AAA Comparative Example 2-1 HL1 F1 5B 5B Comparative Example 2-2 HL2 F1 5B 5B

As shown in Table 1, it was confirmed that the peeling layers of Examples 2-1 to 2-11 had excellent adhesion to the glass substrate and easily peeled off from the transparent resin substrate.

On the other hand, it was confirmed that the peeling layers of Comparative Examples 2-1 to 2-2 had good adhesion to the glass substrate, but had poor peelability from the resin substrate.

Claims (9)

A composition for forming a release layer for a transparent resin substrate comprising a polyamic acid as a reaction product of a diamine component and a tetracarboxylic acid dianhydride component and an organic solvent,
Wherein the diamine component comprises at least one of an aromatic diamine having an ester bond and / or an ether bond, and an aromatic diamine having no ester bond and no ether bond, wherein the tetracarboxylic dianhydride component has an ester bond and / And at least one of an aromatic tetracarboxylic acid dianhydride having no ester bond and an ether bond,
Wherein at least one of the diamine component and the tetracarboxylic acid dianhydride component comprises a component having an ester bond and / or an ether bond. The composition for forming a release layer for a transparent resin substrate according to claim 1, wherein the aromatic diamine having an ester bond and / or an ether bond is at least one selected from the group consisting of formulas (A1) to (A39).

The transparent resin substrate according to claim 1 or 2, wherein the aromatic tetracarboxylic dianhydride having an ester bond and / or an ether bond is at least one selected from the group consisting of the formulas (B1) to (B16) (2).

The composition for forming a release layer for a transparent resin substrate according to any one of claims 1 to 3, wherein the aromatic diamine having no ester bond or ether bond is an aromatic group containing 1 to 5 benzene rings . The composition for forming a release layer for a transparent resin substrate according to claim 4, wherein the aromatic diamine having no ester bond or ether bond is p-phenylenediamine. 6. The transparent resin substrate according to any one of claims 1 to 5, wherein the aromatic tetracarboxylic acid dianhydride having no ester bond or ether bond is an aromatic group containing 1 to 5 benzene rings / RTI &gt; The transparent resin substrate for a transparent resin substrate according to any one of claims 1 to 6, wherein the organic solvent comprises at least one selected from amides represented by formulas (S1) to (S3) / RTI &gt;

(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 for a transparent resin substrate according to any one of claims 1 to 7. A method for manufacturing a flexible electronic device comprising a transparent resin substrate, characterized by using the release layer according to claim 8.