KR20190094197A - Manufacturing method of release layer - Google Patents

Abstract

Polyamic acid which has both ends derived from tetracarboxylic acid, and one or both of these ends is sealed by 2-aminophenol, and the composition for peeling layer formation containing an organic solvent is apply | coated on a base, and maximum temperature It provides the manufacturing method of a peeling layer including the process of baking at 400 degreeC or more.

Description

Manufacturing method of release layer

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

In recent years, in addition to characteristics such as thinning and weight reduction, electronic devices have been required to be provided with a function that can be bent. For this reason, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, fragile and unbending glass substrate.

In particular, in the new generation display, development of an active matrix type full color TFT display panel using a lightweight flexible plastic substrate (hereinafter referred to as a resin substrate) is required. The technology of this new generation display is expected to be diversified into various fields, such as a flexible display, a flexible smart phone, and a mirror display.

Therefore, various manufacturing methods of the electronic device which used the resin film as the board | substrate are beginning to examine, and the examination of the process by which the facilities for existing TFT display panel manufactures can be dedicated is advanced in a new generation display.

For example, in patent documents 1, 2, and 3, after forming an amorphous silicon thin film layer on a glass substrate, forming a plastic substrate on this thin film layer, and irradiating a laser from the glass substrate side, amorphous silicon is crystallized, and A method of peeling a plastic substrate from a glass substrate with hydrogen gas generated by crystallization is disclosed.

Moreover, in patent document 4, using the technique disclosed by patent documents 1-3, the method of sticking a to-be-peeled layer (it describes as a "transfer layer" in patent document 4) to a plastic film and completing a liquid crystal display device is disclosed. It is.

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

In addition, in the case where the layer to be peeled is large, it is difficult to increase the productivity of device fabrication because a long time is required for laser processing.

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

This invention is made | formed in view of the said situation, and an object of this invention is to provide the manufacturing method of the peeling layer which can peel without damaging the resin substrate of a flexible electronic device.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present invention uses the composition containing the polyamic acid in which one or both of the tetracarboxylic-acid terminal is sealed by 2-aminophenol, and an organic solvent, By making the baking temperature at the time of peeling layer formation more than a predetermined | prescribed highest achieved temperature, it can form the peeling layer which has the outstanding adhesiveness with a base | substrate, moderate adhesiveness with the resin substrate used for a flexible electronic device, and moderate peelability. The present invention was completed.

That is, the present invention,

1. Applying the composition for peeling layer formation containing the polyamic acid which has both the terminal derived from tetracarboxylic acid, and one or both of these terminal is sealed by 2-aminophenol, and an organic solvent, The manufacturing method of the peeling layer characterized by including the process of baking at the maximum temperature of 400 degreeC or more,

2. The method for producing a release layer of 1, wherein the polyamic acid is a polyamic acid obtained by reacting a diamine component containing an aromatic diamine and an acid dianhydride component containing an aromatic tetracarboxylic dianhydride;

3. Manufacturing method of 2 peeling layer whose aromatic diamine is aromatic diamine containing 1-5 benzene nucleus,

4. Manufacturing method of 2 or 3 peeling layer whose aromatic tetracarboxylic dianhydride is aromatic tetracarboxylic dianhydride containing 1-5 benzene nucleus,

5. The manufacturing method of the flexible electronic device provided with the resin substrate using the peeling layer formed using the manufacturing method in any one of 1-4,

6. Flexible electron containing the process of apply | coating the composition for resin substrate formation on the peeling layer formed using the manufacturing method in any one of 1-4, and baking at the maximum temperature of 450 degreeC or more, and forming a resin substrate. Manufacturing method of the device,

7. Manufacturing method of 5 or 6 flexible electronic device whose said resin substrate is polyimide resin substrate

To provide.

By employing the manufacturing method of the peeling layer of this invention, the peeling layer which has the outstanding adhesiveness with a base material, moderate adhesiveness with a resin substrate, and moderate peelability can be obtained reproducibly. Therefore, in the manufacturing process of a flexible electronic device by implementing the manufacturing method of this invention, the said resin substrate is combined with the said circuit etc., without damaging the resin substrate formed on the base | substrate, the circuit provided on it, etc., It becomes possible to separate from the gas. Therefore, the manufacturing method of this invention can contribute to the simplification of the manufacturing process of the flexible electronic device provided with a resin substrate, its yield improvement, etc.

(Form to carry out invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The manufacturing method of the peeling layer which concerns on this invention has the both ends derived from tetracarboxylic acid, and the peeling layer formation containing the polyamic acid in which one or both of these ends are sealed by 2-aminophenol, and an organic solvent is formed. It is characterized by including the process of apply | coating a composition for gas on a base material, and baking at the maximum temperature of 400 degreeC or more.

Here, the release layer in the present invention is a layer provided directly on the glass substrate for a predetermined purpose. As a typical example, in the manufacturing process of the flexible electronic device, a flexible electronic device composed of a base and a resin such as polyimide is used. Peeling provided to fix the resin substrate in a predetermined process with the resin substrate, and further provided so that the resin substrate can be easily peeled from the substrate after an electronic circuit or the like is formed on the resin substrate. A layer is mentioned.

The polyamic acid used by this invention can be obtained by sealing either one or both of the polymer chain terminal of the polyamic acid which has both ends derived from tetracarboxylic acid by making it react with the amino group of 2-aminophenol. That is, the polyamic acid obtained here is sealed by the hydroxyl group containing phenyl group in any one or both of the molecular chain terminal.

Since the polymer terminal has a hydroxyl group, a difference between the flexible substrate and the skeleton used in the upper layer may occur, so that the function as the release layer of the resulting film can be improved.

In this invention, although the hydroxyl group derived from 2-aminophenol should exist in either one of the polymer chain terminal of a polyamic acid, it is preferable that the hydroxyl group derived from 2-aminophenol exists in both of a polymer chain terminal.

Moreover, as a diamine component and an acid dianhydride component used when manufacturing a polyamic acid, the acid dianhydride containing the diamine component containing aromatic diamine, and aromatic tetracarboxylic dianhydride from a viewpoint of improving the function as a peeling layer of the film | membrane obtained. Preference is given to polyamic acids obtained by reacting water components.

As an aromatic diamine, although it does not specifically limit as long as it has two amino groups in a molecule | numerator, and has an aromatic ring, The aromatic diamine containing 1-5 benzene nucleus is preferable.

Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), 2, 4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,6- Dimethyl-p-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine, p- Xylylenediamine, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5-bis (trifluoromethyl) benzene-1,2- Benzene nuclei such as diamines are one diamine; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine, 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2 , 3-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-biphenyldiamine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'- Diaminodiphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane , 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2 , 2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3, 3-hexafluoropropane, 3,3'-diaminodiphenylsulfoxide, 3,4'-diaminodipe Nilsulfoxide, 4,4'-diaminodiphenylsulfoxide, 3,3'-bis (trifluoromethyl) biphenyl-4,4'-diamine, 3,3 ', 5,5'-tetrafluoro Roviphenyl-4,4'-diamine, 4,4'-diaminooctafluorobiphenyl, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-amino Benzene nucleus such as benzoxazole is two diamines; 1,5-diaminoanthracene, 2,6-diaminoanthracene, 9,10-diaminoanthracene, 1,8-diaminophenanthrene, 2,7-diaminophenanthrene, 3,6-diaminophenanthrene , 9,10-diaminophenanthrene, 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1 , 4-bis (4-aminophenyl) benzene, 1,3-bis (3-aminophenylsulfide) benzene, 1,3-bis (4-aminophenylsulfide) benzene, 1,4-bis (4-aminophenyl Sulfide) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3- Bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) isopropyl ] Benzene nucleus, such as benzene, 4,4 "-diamino- p-terphenyl, and 4,4"-diamino-m-terphenyl, may mention three diamines, etc., It is not limited to these. These may be used alone or in combination of two or more thereof. In addition, in this invention, it is preferable to use the aromatic diamine which does not contain an ether bond and an ester bond.

Especially, the aromatic diamine comprised from only the aromatic ring and heteroaromatic ring which do not have substituents, such as a methyl group, on an aromatic ring and the heterocycle condensed to it from a viewpoint of improving the function as a peeling layer of the film obtained is preferable. Specifically, p-phenylenediamine, m-phenylenediamine, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzooxazole, 4, 4 ''-diamino-p-terphenyl and the like are preferred.

As an aromatic tetracarboxylic dianhydride, although it does not specifically limit as long as it has two dicarboxylic acid anhydride sites in a molecule | numerator, and also has an aromatic ring, The aromatic tetracarboxylic dianhydride containing 1-5 benzene nucleus. This is preferable.

Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,5 , 6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene-2,3, 5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, biphenyl-2, 2 ', 3,3'-tetracarboxylic dianhydride, biphenyl-2,3,3', 4'-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracar Acid dianhydride, anthracene-1,2,3,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2,6,7-tetra Carboxylic acid dianhydride, anthracene-1,2,7,8-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic acid dianhydride Water, phenanthrene-1,2,3,4-tetracarboxylic dianhydride, phenanthrene-1,2,5,6-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetra Carboxylic acid dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, phenanthrene-2,3,5 , 6-tetracarboxylic dianhydride, phenanthrene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-2,3,9,10-tetracarboxylic dianhydride, phenanthrene-3 Although, 4,5,6- tetracarboxylic dianhydride, phenanthrene-3,4,9,10- tetracarboxylic dianhydride, etc. are mentioned, It is not limited to these. These may be used alone or in combination of two or more thereof.

Especially, in the viewpoint of improving the function as a peeling layer of the film obtained, one or two aromatic carboxylic dianhydrides are preferable. Specifically, the aromatic tetracarboxylic dianhydride represented by any one of formulas (C1) to (C12) is preferable, and the aromatic represented by any one of formulas (C1) to (C7) and (C9) to (C11). Tetracarboxylic dianhydride is more preferable.

In addition, the diamine component used by this invention may contain diamines other than aromatic diamine from the viewpoint of improving the flexibility, heat resistance, etc. of the peeling layer obtained, and the tetracarboxylic dianhydride component used by this invention is aromatic tetracarbide. Tetracarboxylic dianhydrides other than the acid dianhydride may be included.

In the present invention, the amount of aromatic diamine in the diamine component 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, most preferably Is 100 mol%. The amount of the aromatic tetracarboxylic dianhydride in the tetracarboxylic acid component 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 an amount of use, a film having excellent adhesion to a substrate and proper adhesion to a resin substrate and suitable peelability can be obtained with good reproducibility.

After reacting the diamine component and the tetracarboxylic dianhydride component which were demonstrated above, the obtained polyamic acid and 2-aminophenol are made to react, and the polymer chain terminal contained in the composition for peeling layer formation of this invention is 2-amino. Polyamic acid sealed with phenol can be obtained.

Although the charge ratio of the diamine component and the tetracarboxylic dianhydride component is appropriately determined in consideration of the target molecular weight, molecular weight distribution, the type of diamine, the type of tetracarboxylic dianhydride, and the like, it cannot be uniformly defined. In order to set it as the both ends of the molecular chain derived from an acid, it is preferable to make the mole number of the tetracarboxylic dianhydride component a little more with respect to the mole number of a diamine component. As a specific molar ratio, 1.02-3.0 mol of tetracarboxylic dianhydride components are preferable with respect to 1 mol of diamine components, 1.07-2.5 mol is more preferable, Furthermore, 1.1-2.0 mol is further more preferable.

The organic solvent used in the synthesis of the polyamic acid and the sealing of the molecular chain terminal of the synthesized polyamic acid is not particularly limited as long as it does not adversely affect the reaction, but specific examples thereof include m-cresol, 2-pyrrolidone, and N-methyl-. 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N -Dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy- N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3-tert-butoxy-N, N-dimethylpropylamide, gamma -butyrolactone, etc. are mentioned. In addition, you may use an organic solvent individually by 1 type or in combination of 2 or more types.

In particular, the organic solvent used for the reaction dissolves diamine, tetracarboxylic dianhydride, and polyamic acid well, and thus is represented by the amides represented by the formula (S1), the amides represented by (S2) and the formula (S3). At least 1 sort (s) chosen from the amides used is preferable.

In the formula, R ¹ and R ² each 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 shows a natural number, Preferably it is 1-3, More preferably, it is 1 or 2.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable.

What is necessary is just to set reaction temperature at the time of the synthesis | combination of a polyamic acid suitably from the melting point of a solvent to a boiling point, and it is about 0-100 degreeC normally, but it prevents the imidation in the solution of the obtained polyamic acid, and has high content of a polyamic acid unit From the standpoint of maintaining the temperature, preferably 0 to 70 ° C, more preferably 0 to 60 ° C, still more preferably 0 to 50 ° C. Since the reaction time depends on the reaction temperature and the reactivity of the raw materials, it cannot be defined uniformly, but is usually about 1 to 100 hours.

Reaction temperature at the time of sealing the molecular chain terminal of a polyamic acid should just be set suitably in the range from melting | fusing point of a solvent to a boiling point to use similarly to the synthesis | combination of a polyamic acid, Although it is about 0-100 degreeC normally, From the viewpoint of reliably sealing the molecular chain ends of the polyamic acid, it is preferably 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 raw materials, it cannot be defined uniformly, but is usually about 1 to 100 hours.

Although the weight average molecular weight of the polyamic acid obtained in this way by which one or both of the molecular chain ends are sealed by 2-aminophenol is about 5,000-500,000 normally, from a viewpoint of improving the function as a peeling layer of the film obtained, Preferably It is about 6,000-200,000, More preferably, it is about 7,000-150,000. In addition, in this invention, a weight average molecular weight is a polystyrene conversion value by the gel permeation chromatography (GPC) measurement.

In the present invention, a solution obtained by diluting or concentrating the reaction solution after end sealing is usually used as the composition for forming a release layer of the present invention. In addition, you may filter the said reaction solution as needed. Not only can mixing of impurities which may cause deterioration of adhesiveness, peelability, etc. of the peeling layer obtained by filtering can be reduced, but the composition for peeling layer formation can be obtained efficiently. Furthermore, after isolate | separating a polyamic acid from the said reaction solution, it may melt | dissolve in a solvent again and may be set as the composition for peeling layer formation. As a solvent in this case, the organic solvent etc. which are used for the above-mentioned reaction are mentioned.

The solvent used for dilution is not specifically limited, As the specific example, the thing similar to the specific example of the reaction solvent of the said reaction is mentioned. The solvent used for dilution may be used individually by 1 type or in combination of 2 or more types. Among them, polyamic acid is well dissolved, so N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl 2-pyrrolidone and γ-butyrolactone are preferable, and N-methyl-2-pyrrolidone is more preferable.

Moreover, even if it is a solvent which does not melt | dissolve polyamic acid alone, as long as it is a range which does not precipitate a polyamic acid, it can mix with the composition for peeling layer formation of this invention. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy -2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, Solvents having low surface tension such as dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and isoamyl lactate can be appropriately mixed. . It is known that coating film uniformity improves at the time of application | coating to a board | substrate by this, It can use suitably also in the composition for peeling layer formation of this invention.

Although the density | concentration of the polyamic acid in the composition for peeling layer formation of this invention is set suitably in consideration of the thickness of the peeling layer to produce, the viscosity of a composition, etc., it is usually 1-30 mass%, Preferably it is 1-20 mass About%. By setting it as such a density | concentration, the peeling layer of thickness about 0.05-5 micrometers can be obtained reproducibly. The polyamic acid concentration is determined by adjusting the amount of diamine and tetracarboxylic dianhydride which are raw materials of the polyamic acid, diluting or concentrating the filtrate after filtering the reaction solution, or dissolving the isolated polyamic acid in a solvent. The amount can be adjusted, for example.

Although the viscosity of the composition for peeling layer formation of this invention is set suitably in consideration of the thickness of the peeling layer to produce, etc., especially when aiming at obtaining the film | membrane of thickness about 0.05-5 micrometers with good reproducibility, normally at 25 degreeC It is about 10-10,000 mPa * s, Preferably it is about 20-5,000 mPa * s.

Here, a viscosity can be measured on the conditions of 25 degreeC of composition with reference to the procedure of JISK7117-2 using the viscometer for viscosity measurement of a commercial liquid, for example. Preferably, as a viscometer, a conical flat plate type (corn plate type) rotational viscometer is used, Preferably it is a homogeneous viscometer, 1 degree 34'xR24 is used as a standard cone rotor, and it measures on the conditions of 25 degreeC of compositions. can do. As such a rotational viscometer, TVE-25L by Toki Sangyo Co., Ltd. is mentioned, for example.

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

In the baking method including the process of apply | coating the composition for peeling layer formation demonstrated above on a base | substrate, and baking at the maximum temperature of 400 degreeC or more, it is excellent in adhesiveness with a base and suitable with a resin substrate by thermally imidating a polyamic acid. The peeling layer which consists of a polyimide membrane which has adhesiveness and moderate peelability can be obtained.

In the present invention, the maximum temperature during the firing is not particularly limited as long as it is in the range of 400 ° C. or higher and the heat resistance temperature or lower of the polyimide. However, the adhesiveness with the above-described substrate and the appropriate adhesion and peelability with the resin substrate are not limited. In consideration of improving this, 450 degreeC or more is preferable and 500 degreeC or more is more preferable. In addition, although the upper limit is about 550 degreeC normally, about 510 degreeC is preferable. It is also possible to fully advance the imidation reaction, preventing the weakening of the film obtained by making heating temperature into the said range.

Since heating time changes with heating temperature, it cannot be prescribed | regulated uniformly, but is usually 1 minute-5 hours. In addition, the imidation ratio should just be 50 to 100% of range.

In addition, the temperature at the time of baking may include the process of baking at the temperature below that as long as the maximum temperature becomes the said range.

As a preferable example of the heating aspect in this invention, after heating at 50-150 degreeC, the method of raising a heating temperature stepwise as it is and finally heating at 400 degreeC or more is mentioned. In particular, as a more preferable example of the heating aspect, a method of heating at 50 to 100 ° C, heating above 100 ° C to less than 400 ° C, and heating at 400 ° C or more can be given. Moreover, as another more preferable example of a heating aspect, after heating at 50-150 degreeC, it heats at 150 degreeC-350 degreeC, and then heats it at 350 degreeC-450 degreeC, and finally heats it at 450 degreeC-510 degreeC The technique to do is mentioned.

Moreover, as a preferable example of the heating aspect in consideration of baking time, after heating at 50-150 degreeC for 1 minute-2 hours, the method of raising a heating temperature in steps as it is, and finally heating to 400 degreeC or more for 30 minutes-4 hours Can be mentioned. In particular, a more preferable example of the heating mode is a method of heating at 50 to 100 ° C. for 1 minute to 2 hours, heating at more than 100 ° C. to less than 400 ° C. for 5 minutes to 2 hours, and heating at 400 ° C. or higher for 30 minutes to 4 hours. Can be mentioned. Moreover, as another more preferable example of a heating aspect, after heating at 50-150 degreeC for 1 minute-2 hours, 5 minutes-2 hours at 150 degreeC-350 degreeC, then 30 minutes-4 hours at 350 degreeC-450 degreeC, Finally, the method of heating for 30 minutes-4 hours at over 450 degreeC-510 degreeC is mentioned.

In addition, when forming the peeling layer of this invention on a base, a peeling layer may be formed in one surface of a base, and may be formed in the whole surface. As an aspect which forms a peeling layer in the part surface of a base | substrate, the aspect which forms a peeling layer only in a predetermined range of a base surface, the aspect which forms a peeling layer in pattern shapes, such as a dot pattern and a line and space pattern, on the whole surface of a base body There is this. In addition, in this invention, a gas means that the composition for peeling layer formation of this invention is apply | coated to the surface, and is used for manufacture of a flexible electronic device.

As a base (base material), glass, a metal (silicon wafer etc.), a slate, etc. are mentioned, for example, Especially, since the peeling layer of this invention has sufficient adhesiveness to it, glass is preferable. In addition, the base surface may be comprised from a single material, and may be comprised from two or more materials. As an aspect in which the base surface is made of two or more materials, a certain range of the base surface is made of a certain material, and the rest of the surface is made of other materials, such as a dot pattern, a line-and-space pattern, etc. In the pattern shape, there is an embodiment in which a material exists among other materials.

Although the method of apply | coating the composition for peeling layer formation of this invention to a base is not specifically limited, For example, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die | dye A coating method, an inkjet method, a printing method (iron plate, intaglio, flat plate, screen printing, etc.), etc. are mentioned.

As a mechanism used for heating, a hotplate, oven, etc. are mentioned, for example. The heating atmosphere may be air or inert gas, and may be normal pressure or reduced pressure.

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

The peeling layer demonstrated above has the outstanding adhesiveness with a base material, especially glass, and the moderate adhesiveness with a resin substrate, and a suitable peelability. Therefore, in the manufacturing process of a flexible electronic device, the peeling layer of this invention is suitable for peeling the said resin substrate from a base | substrate with the circuit etc. formed on the resin substrate, without damaging the resin substrate of the said device. Can be used.

Hereinafter, an example of the manufacturing method of the flexible electronic device using the peeling layer of this invention is demonstrated.

Using the composition for release layer formation of this invention, a release layer is formed on glass base by the above-mentioned method. On this peeling layer, the resin substrate formation solution for forming a resin substrate is apply | coated, and this coating film is baked, and the resin substrate fixed to the glass base is formed through the peeling layer of this invention.

Although the baking temperature of the said coating film is set suitably according to the kind of resin, etc., in this invention, it is preferable to make the highest temperature at the time of this baking at 450 degreeC or more, It is more preferable to set it as 480 degreeC or more, More than 490 degreeC It is further more preferable, and it is more preferable to set it as 500 degreeC or more. By making the maximum temperature at the time of baking at the time of resin substrate preparation into this range, the adhesiveness of a peeling layer which is a base and a base, and the moderate adhesiveness and peelability of a peeling layer and a resin substrate can be improved more.

Also in this case, as long as the maximum temperature is within the above range, a step of firing at a temperature below that may be included.

As a preferable example of the heating aspect at the time of resin substrate preparation, after heating at 50-150 degreeC, the method of raising a heating temperature in steps as it is, and finally heating to 450 degreeC or more is mentioned. In particular, as a more preferable example of the heating aspect, a method of heating at 50 to 100 ° C, heating above 100 ° C to less than 400 ° C, and heating to 450 ° C or more is mentioned. Moreover, as another more preferable example of a heating aspect, after heating at 50-100 degreeC, it heats at more than 100 degreeC-200 degreeC, and then heats more than 200 degreeC-less than 300 degreeC, heats at 300 degreeC-less than 400 degreeC, and 400 degreeC The method of heating at less than -450 degreeC, and finally heating at 450-510 degreeC is mentioned.

Moreover, as a preferable example of the heating aspect in consideration of baking time, after heating at 50-150 degreeC for 1 minute-2 hours, the method of raising a heating temperature in steps as it is, and finally heating at 450 degreeC or more for 30 minutes-4 hours Can be mentioned. In particular, a more preferable example of the heating mode is a method of heating at 50 to 100 ° C. for 1 minute to 2 hours, heating at 100 ° C. to less than 400 ° C. for 5 minutes to 2 hours, and heating at 450 ° C. or higher for 30 minutes to 4 hours. Can be mentioned. Moreover, as another more preferable example of a heating aspect, after heating at 50-100 degreeC for 1 minute-2 hours, 5 minutes-2 hours at 100 degreeC-200 degreeC, and then 30 minutes-4 degreeC at 200 degreeC-less than 300 degreeC The method of heating for 30 minutes-4 hours at 400 degreeC-less than 400 degreeC for 30 minutes-4 hours at the time, below 300 degreeC-400 degreeC, and lasting at 450-510 degreeC for 30 minutes-4 hours is mentioned.

The resin substrate covers all the peeling layers, and forms a board | substrate with a large area compared with the area of a peeling layer. As a resin substrate, the resin substrate which consists of polyimide which is typical as a resin substrate of a flexible electronic device is mentioned, As a resin solution for forming it, a polyimide solution and a polyamic acid solution are mentioned. The formation method of the said resin substrate should just follow a conventional method.

Next, a desired circuit is formed on the resin substrate fixed to the substrate via the release layer of the present invention, and then, for example, the resin substrate is cut along the release layer, and the resin substrate is removed from the release layer together with the circuit. It peels and separates a resin substrate and gas. At this time, a part of the base may be cut together with the release layer.

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

Since the peeling layer of this invention has a characteristic that it fully absorbs the light of the specific wavelength (for example, 308 nm) which the said LLO method can apply, it can be used as a sacrificial layer of the LLO method. Therefore, when a desired circuit is formed on the resin substrate fixed to glass base through the peeling layer formed using the composition for this invention, and then irradiated with the light of 308 nm by performing the LLO method, only this peeling layer is this Absorb light and evaporate. Thereby, the said peeling layer becomes a sacrifice (acts as a sacrificial layer), and it becomes possible to selectively peel a resin substrate from a glass base.

Example

Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

[1] abbreviations for compounds

NMP: N-methylpyrrolidone

BCS: Butyl Cellosolve

p-PDA: p-phenylenediamine

2AP: 2-aminophenol

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

PMDA: pyromellitic dianhydride

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

The weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of the polymer were measured using a Nippon Bunco Co., Ltd. GPC apparatus (Shodex (R) columns KF803L and KF805L) using dimethylformamide as the elution solvent at a flow rate of 1 ml / min, It measured on the conditions of 50 degreeC of column temperature. In addition, Mw was made into the polystyrene conversion value.

[3] polymer synthesis

The polyamic acid was synthesize | combined by the following method.

Moreover, the composition for resin substrate formation or the composition for peeling layer formation was prepared by diluting a reaction liquid as follows, without isolating a polymer from the obtained polymer containing reaction liquid.

Synthesis Example S1 Synthesis of Polyamic Acid (S1)

3.176 g (0.02937 mol) of p-PDA was dissolved in 88.2 g of NMP, and after adding 8.624 g (0.02931 mol) of BPDA, it was made to react at 23 degreeC by nitrogen atmosphere for 24 hours. Obtained polymer Mw was 107,300 and molecular weight distribution 4.6.

Synthesis Example Synthesis of L1 Polyamic Acid (L1)

After 1.507 g (0.0139 mol) of p-PDAs were dissolved in 43.2 g of NMP, 3.166 g (0.01452 mol) of PMDA was added, and it was made to react at 23 degreeC under nitrogen atmosphere for 2 hours. Then, 0.12 g (0.0012 mol) of 2AP was further added, and it was made to react at 23 degreeC for 24 hours in nitrogen atmosphere. Obtained polymer Mw was 48,500 and molecular weight distribution 2.05.

Synthesis Example Synthesis of L2 Polyamic Acid (L2)

After dissolving 1.119 g (0.01103 mol) of p-PDAs in 35.2 g of NMP, and adding 3.006 g (0.01378 mol) of PMDA, it was made to react at 23 degreeC under nitrogen atmosphere for 2 hours. Then, 0.62 g (0.00551 mol) of 2AP was further added, and it was made to react at 23 degreeC for 24 hours in nitrogen atmosphere. Obtained polymer Mw was 11,700 and molecular weight distribution was 1.76.

Synthesis Example Synthesis of L3 Polyamic Acid (L3)

0.681 g (0.00629 mol) of p-PDA was dissolved in 35.2 g of NMP, and 2.746 g (0.01259 mol) of PMDA was added, followed by reacting at 23 ° C. for 2 hours under a nitrogen atmosphere. Then, 1.32 g (0.012588 mol) of 2AP was further added, and it was made to react at 23 degreeC for 24 hours in nitrogen atmosphere. Obtained polymer Mw was 8,000 and molecular weight distribution was 1.57.

Comparative Synthesis Example Synthesis of HL1 Polyamic Acid (HL1)

1.29 g (0.00107 mole) of p-PDA was dissolved in 43.2 g of NMP, and after adding 3.509 g (0.00119 mole) of BPDA, it was made to react at 23 degreeC for 24 hours in nitrogen atmosphere. Obtained polymer Mw was 34,000 and molecular weight distribution 2.03.

Comparative Example Synthesis of HL2 Polyamic Acid (HL2)

1.325 g (0.00123 mole) of p-PDA was dissolved in 36 g of NMP, and 2.674 g (0.00123 mole) of PMDA was added, followed by reacting at 23 ° C. under nitrogen atmosphere for 2 hours. Unfortunately, because it gelled, it could not be used.

[4] Preparation of Composition for Forming Resin Substrate

The reaction liquid obtained by the synthesis example S1 was used as a composition for resin substrate formation, respectively as it is.

[5] Preparation of Composition for Peeling Layer Formation

Example 1-1

BCS and NMP were added to the reaction liquid obtained by the synthesis example L1, and it diluted so that a polymer concentration might be 5 wt% and 20 mass% of BCS, and the composition for peeling layer formation was obtained.

[Examples 1-2 to 1-3]

Instead of using the reaction liquid obtained in the synthesis example L1, the composition for peeling layer formation was obtained by the method similar to Example 1-1 except having used the reaction liquid obtained by the synthesis examples L2-L3, respectively.

Comparative Example 1-1

Instead of using the reaction liquid obtained in the synthesis example L1, the composition for peeling layer formation was obtained by the method similar to Example 1-1 except having used the reaction liquid obtained by the comparative synthesis example HL1, respectively.

[6] fabrication of release layer and resin substrate

Example 2-1

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

And the obtained coating film is heated at 100 degreeC for 2 minutes using a hotplate, Then, it heats at 300 degreeC for 30 minutes using an oven, and raises heating temperature to 400 degreeC (10 degreeC / min), 400 It heated at 30 degreeC for 30 minutes, It heated up to 500 degreeC (10 degreeC / min), heated at 500 degreeC for 10 minutes, formed the peeling layer of thickness about 0.1 micrometer on the glass substrate, and obtained the glass substrate with a peeling layer. . In addition, during the temperature increase, the substrate with a film was heated in the oven without being taken out of the oven.

The composition S2 for resin substrate formation was apply | coated on the peeling layer (resin thin film) on the glass substrate obtained above using the bar coater (gap: 250 micrometers). And the obtained coating film is heated at 80 degreeC for 30 minute (s) using a hotplate, and after making into nitrogen atmosphere using an oven after that, it heats at 140 degreeC for 30 minutes and raises heating temperature to 210 degreeC (2 degreeC) / Min, the same below), heating temperature is raised to 210 ° C for 30 minutes, heating temperature to 300 ° C, heating temperature to 400 ° C for 30 minutes, and heating temperature to 400 ° C for 30 minutes at 400 ° C. It heated up, it heated at 500 degreeC for 60 minutes, formed the polyimide resin substrate of thickness about 20 micrometers on the peeling layer, and obtained the glass substrate with a resin substrate and a peeling layer. During the temperature increase, the substrate with a film was heated in the oven without being taken out of the oven.

[Examples 2-2 to 2-3]

In the same manner as in Example 2-1, except that the compositions for release layer formation L2 and L3 obtained in Examples 1-2 to 1-3 were used instead of the compositions for release layer formation L1 obtained in Example 1-1, respectively. , The peeling layer and the polyimide resin substrate were formed, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained.

Comparative Example 2-1

A release layer and a polyimide resin in the same manner as in Example 2-1 except for using the release layer formation composition HL1 obtained in Comparative Example 1-1 instead of the release layer formation composition L1 obtained in Example 1-1. The board | substrate was formed and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained.

[7] evaluation of peelability

The peeling property of a peeling layer and a glass substrate was confirmed with the following method about the glass substrate with a peeling layer obtained in the said Examples 2-1 to 2-3 and Comparative Example 2-1. In addition, the following test was done with the same glass substrate.

<Evaluation of Cross Cut Test Peelability of Resin Thin Film>

The peeling layer on the glass substrate with a peeling layer obtained by Examples 2-1 to 2-3 and Comparative Example 2-1 was cross-cut (1 mm horizontally and below) and 100 square cutting was performed. That is, 100 square pieces of 1 mm square were formed by this crosscut.

And the adhesive tape was stuck to this 100 square cutting part, the tape was peeled off, and peelability was evaluated based on the following criteria (5B-0B, B, A, AA). The results are shown in Table 1.

<Judge criteria>

5B: 0% peel (no peeling)

4B: less than 5% peeling

3B: peel less than 5-15%

2B: peel less than 15-35%

1B: less than 35-65% peeling

0B: peel less than 65% to 80%

B: peel less than 80% to 95%

A: Peeling less than 95% to 100%

AA: 100% peel (all peel)

<Evaluation of Peelability of Resin Substrate>

The resin substrate of the glass substrate with a resin substrate and a peeling layer obtained by Examples 2-1 to 2-3 and Comparative Example 2-1 was cut into strip shape of 25 mm width using the cutter. And the cellophane tape was stuck to the front-end | tip of the cut resin substrate, and this was made into the test piece. A peel test was performed for this test piece so that peeling angle might be 90 degrees using the push pull tester made by Atonic, and peelability was evaluated based on the following reference | standard. The results are shown in Table 1.

<Judge criteria>

5B: 0% peel (no peeling)

4B: less than 5% peeling

3B: peel less than 5-15%

2B: peel less than 15-35%

1B: less than 35-65% peeling

0B: peel less than 65% to 80%

B: peel less than 80% to 95%

A: Peeling less than 95% to 100%

AA: 100% peel (all peel)

Release layer Resin substrate Peelability of Resin Substrate and Peeling Layer Peelability of the Peeling Layer and Glass Substrate Example 2-1 L1 S1 AA 5B Example 2-2 L2 S1 AA 5B Example 2-3 L3 S1 AA 5B Comparative Example 2-1 HL1 S1 5B 5B

From the result of Table 1, although the peeling layer of Examples 2-1 to 2-3 was able to peel only a resin substrate, without peeling a peeling layer from a glass substrate, it was confirmed that it could not peel in Comparative Example 2-1.

Claims (7)

Polyamic acid which has both ends derived from tetracarboxylic acid, and one or both of these ends is sealed by 2-aminophenol, and the composition for peeling layer formation containing an organic solvent is apply | coated on a base, and maximum temperature The manufacturing method of the peeling layer characterized by including the process baked at 400 degreeC or more. The method of claim 1,
The polyamic acid is a polyamic acid obtained by reacting a diamine component containing an aromatic diamine with an acid dianhydride component containing an aromatic tetracarboxylic dianhydride. The method of claim 2,
Said aromatic diamine is aromatic diamine containing 1-5 benzene nuclei, The manufacturing method of the peeling layer characterized by the above-mentioned. The method according to claim 2 or 3,
Said aromatic tetracarboxylic dianhydride is aromatic tetracarboxylic dianhydride containing 1-5 benzene nucleus, The manufacturing method of the peeling layer characterized by the above-mentioned. The peeling layer formed using the manufacturing method in any one of Claims 1-4 is used, The manufacturing method of the flexible electronic device provided with the resin substrate. After apply | coating the composition for resin substrate formation on the peeling layer formed using the manufacturing method in any one of Claims 1-4, it bakes at the maximum temperature of 450 degreeC or more, and includes the process of forming a resin substrate. Method of manufacturing a flexible electronic device. The method according to claim 5 or 6,
The said resin substrate is a polyimide resin substrate, The manufacturing method of the flexible electronic device characterized by the above-mentioned.