KR20190100228A - Composition for Forming Substrate Protective Layer - Google Patents

Abstract

After forming a resin substrate on a base, when peeling the said resin substrate and manufacturing a resin substrate, it interposes between the said base and a resin substrate, has peeling property from the said base, and the resin substrate after peeling As a composition for substrate protective layer formation which functions as a protective layer of the present invention, a composition for substrate protective layer formation containing a polyamic acid and an organic solvent is provided.

Description

Composition for Forming Substrate Protective Layer

The present invention relates to a composition for forming a substrate protective layer.

In recent years, in addition to the characteristics of being thin and light, electronic devices have been required to be bent. In this respect, it is desired to use lightweight flexible plastic substrates in place of conventional heavy, fragile and unbending glass substrates.

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 manufacturing existing TFT display panels can be dedicated is advanced in the new generation display.

For example, in Patent Literatures 1, 2 and 3, after forming an amorphous silicon thin film layer on a glass substrate, forming a plastic substrate on the thin film layer, and irradiating a laser from the glass substrate side, amorphous silicon is crystallized and the crystallization thereof The method of peeling a plastic substrate from a glass substrate with the hydrogen gas which generate | occur | produces is disclosed.

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

However, in the methods disclosed in Patent Literatures 1 to 4, in particular, the method disclosed in Patent Literature 4, it is essential to use a highly transmissive substrate in order to transmit laser light, and to pass hydrogen through the substrate and release hydrogen contained in amorphous silicon. There is such a problem that irradiation of laser light with a relatively large energy sufficient to make it necessary is necessary and damage to the layer to be peeled off by irradiation of the laser light is caused.

In addition, when the layer to be peeled is large, laser processing requires a long time, and therefore, it is difficult to increase the productivity of device fabrication.

As a means to solve such a problem, Patent Document 5 uses a current glass substrate as a base (hereinafter referred to as a glass base), and forms a release layer on the glass base using a polymer such as a cyclic olefin copolymer. After forming heat-resistant resin films (resin substrates), such as a polyimide film, on the peeling layer, and forming and sealing an ITO transparent electrode, TFT, etc. by the vacuum process on the film, finally peeling and removing a glass substrate The manufacturing process to make is employ | adopted.

By the way, as the TFT, a low temperature polysilicon TFT having a mobility twice as fast as an amorphous silicon TFT is used. The low temperature polysilicon TFT needs to be dehydrogenated at 400 ° C. or higher after amorphous silicon deposition, irradiated with a pulsed laser to crystallize silicon (hereinafter, these are referred to as TFT processes), and the temperature of the dehydrogenated annealing process is It is above the glass transition temperature (hereinafter Tg) of the existing polymer.

However, when the existing polymer is heated to a temperature of Tg or more, it is known that the adhesion becomes high (see Patent Document 6, for example), and the adhesion between the release layer and the substrate and the resin substrate is increased after the heat treatment, and the resin substrate is vaporized. It may become difficult to peel off from.

Moreover, although the heat resistant polymer applicable to such a process is limited to some high heat resistant high molecular compounds, such as a polyimide, it cannot be dissolved in a general solvent. For this reason, when the said polyimide was used for a peeling layer, it was difficult to remove the peeling layer which remained in the glass base after peeling a resin substrate, and to reuse a glass base.

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 Japanese Patent Application Laid-Open No. 2010-111853 Japanese Patent Laid-Open No. 2008-188792

This invention is made | formed in view of the said situation, and can make reuse of a base material easy, can peel from a base | substrate together with the resin substrate of a flexible electronic device, and also damages a resin substrate, and changes a characteristic significantly. An object of the present invention is to provide a composition for forming a substrate protective layer that is not allowed to be made.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, when forming a resin substrate on a base, when peeling the said resin substrate and manufacturing a resin substrate, this inventor interposes between the said base and a resin substrate, By using the composition containing a polyamic acid and an organic solvent as a composition for substrate protective layer formation which has peeling property from the said gas, and functions as a protective layer of the resin substrate after peeling, The present invention was completed by finding that it is possible to form a substrate protective layer having suitable adhesiveness, suitable peelability, and excellent adhesion with a resin substrate used in a flexible electronic device.

That is, the present invention

1. After forming a resin substrate on a base, when peeling the said resin substrate together with the said resin substrate from the said base, it interposes between the said base and the said resin substrate, and has exfoliation property from the said base | substrate. And a composition for forming a substrate protective layer functioning as a protective layer of the resin substrate after peeling, comprising a polyamic acid and an organic solvent.

2. Composition for formation of substrate protective layer of 1 containing polyamic acid and organic solvent represented by following formula (1),

(In formula, X represents the aromatic group represented by following formula (2), Y represents the bivalent aromatic group which has a fluorine atom, and n represents a natural number.)

3. The composition for substrate protective layer formation of 2 whose Y is an aromatic group represented by following formula (3),

4. The composition for 2 or 3 board | substrate protective layer formation whose said Y is an aromatic group represented by following formula (4),

5. The composition for forming a substrate protective layer in any one of 1 to 4, wherein the organic solvent is at least one selected from those having a structure represented by the following formulas (S1) to (S7):

(In formula, R <^1> -R <^8> represents a hydrogen atom or a C1-C10 alkyl group independently of each other, R <^9> and R <^10> represents a hydrogen atom, a C1-C10 alkyl group, or C1-C10 independently of each other Represents an acyl group of b and n represent a natural number)

6. When an electronic device is further manufactured on the said resin substrate, and an electronic device is peeled from the said base material with the said resin substrate, it has the peelability from the said base, and functions as a protective layer of the resin substrate after peeling. 1 composition for forming a substrate protective layer,

7. Substrate protective layer obtained from composition for substrate protective layer formation in any one of 1-6,

8. Process of apply | coating the composition for 6 substrate protective layer formation on a base material, baking at the maximum temperature of 500 degreeC or more, and forming the board | substrate protective layer which has the peelability from the said base material,

Apply | coating the composition for resin substrate formation on this board | substrate protective layer, baking at the maximum temperature of 500 degreeC or more, and forming a resin substrate,

A step of producing an electronic device on the resin substrate,

A method of manufacturing a flexible electronic device, comprising the step of peeling the electronic device together with the substrate protective layer and the resin substrate from the substrate,

9. The manufacturing method of 8 flexible electronic device whose said resin substrate is a polyimide resin substrate,

10. Apply the composition for forming a substrate protective layer of any one of 1 to 5 on a substrate, and bake at a maximum temperature of 500 ° C. or higher to form a substrate protective layer, and then apply the composition for forming a resin substrate onto the substrate protective layer. After coating and baking at the maximum temperature of 500 degreeC or more, and forming a resin substrate, the said resin substrate is peeled from a base material with the said board | substrate protective layer, The manufacturing method of the resin substrate with a protective layer,

11. The manufacturing method of 10 whose said resin substrate is a polyimide resin substrate.

To provide.

By using the composition for substrate protective layer formation of this invention, the board | substrate protective layer which has suitable adhesiveness with a base material, appropriate peelability, and the outstanding adhesiveness with a resin substrate can be obtained reproducibly. Therefore, by using the composition for substrate protective layer formation of this invention, in the manufacturing process of a flexible electronic device, it does not damage the resin substrate formed on the base | substrate, the circuit further provided on it, etc., and the said circuit etc. It is possible to separate the resin substrate and the substrate protective layer from the substrate. Accordingly, the composition for forming a substrate protective layer of the present invention can promote the reuse of gas, and can contribute to simplifying the manufacturing process of the flexible electronic device including the resin substrate, improving its yield, and the like.

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

The composition for substrate protective layer formation of this invention contains a polyamic acid and an organic solvent. Here, the board | substrate protective layer in this invention is a layer provided directly on a glass base for a predetermined purpose, and the typical example of the flexible electronic device which consists of a base and resin like polyimide in the manufacturing process of a flexible electronic device is mentioned. The layer provided in order to fix the said resin substrate in a predetermined process between resin substrates is mentioned. Moreover, after forming an electronic circuit etc. on the said resin substrate, this board | substrate protective layer differs from the conventional peeling layer in the point which peels from the said base material with the said resin substrate.

As the diamine component and the acid dianhydride component used when producing the polyamic acid, the above-described manufacturing process has the property of being peeled off from the gas together with the resin substrate, that is, the peeling property from the gas, and the adhesiveness with the resin substrate. Although it will not specifically limit, if it gives a polyimide membrane, From a viewpoint of fully exhibiting the property of the peeling property from the said base and adhesiveness with respect to a resin substrate, the diamine component containing aromatic diamine, and aromatic tetracarboxylic dianhydride are included. The polyamic acid obtained by making an acid dianhydride component react is preferable, and the polyamic acid obtained using the biphenyl tetracarboxylic dianhydride and the aromatic diamine which have a fluorine atom especially as represented by following formula (1) is Suitable.

In Formula (1), X represents the aromatic group derived from biphenyl tetracarboxylic acid represented by following formula (2), and Y represents the bivalent fluorine atom containing aromatic group derived from aromatic diamine which has a fluorine atom.

n represents a natural number, but an integer of 2 or more is preferable.

As biphenyl tetracarboxylic dianhydride which gives the bivalent group derived from biphenyl tetracarboxylic acid represented by said Formula (2), what is represented by following formula (C1)-(C3) is mentioned, In this invention, Especially the 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride represented by Formula (C1) is suitable. In addition, (C1)-(C3) may be used independently, respectively and may be used in combination of 2 or more type.

Moreover, in this invention, in addition to the said biphenyl tetracarboxylic dianhydride, other tetracarboxylic dianhydride can also be used.

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, anthracene-1,2 , 3,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2,6,7-tetracarboxylic dianhydride, anthracene-1, 2,7,8-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,3,4-tetracarboxylic dianhydride, phenanthrene -1,2,5,6-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride Water, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, phenanthrene-2,3,5,6-tetra Carboxylic acid dianhydride, phenanthrene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-2,3,9,10-tetracarboxylic dianhydride, phenanthrene-3,4,5 And 6-tetracarboxylic dianhydride and phenanthrene-3,4,9,10-tetracarboxylic dianhydride and the like, and these may be used alone or in combination of two or more thereof.

In the polyamic acid used in the present invention, the amount of the biphenyltetracarboxylic dianhydride in the tetracarboxylic acid component is 70 mol% in consideration of achieving both the peeling property from the above-described gas and the adhesion to the resin substrate. The above is preferable, 80 mol% or more is more preferable, 90 mol% or more is further more preferable, 95 mol% or more is more preferable, 100 mol% is the most preferable.

In addition, as a specific example of the aromatic diamine which has the said fluorine atom which gives said Y, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5-bis ( Trifluoromethyl) benzene-1,2-diamine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-bis (trifluoromethyl) benzidine) , 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3,3'-bis (trifluoromethyl) benzidine), 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 '-Bis (trifluoromethyl) biphenyl-4,4'-diamine, 3,3', 5,5'-tetrafluorobiphenyl-4,4'-diamine, 4,4'-diaminooctafluoro Roviphenyl etc. are mentioned, These may be used independently and may be used in combination of 2 or more type.

Among them, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2) in consideration of making both the peeling property from the above-mentioned gas and adhesiveness with respect to the resin substrate compatible '-Bis (trifluoromethyl) benzidine), 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3,3'-bis (trifluoromethyl) benzidine) Preferably, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-bis (trifluoromethyl) benzidine) is more preferable.

Therefore, as suitable Y in Formula (1), the bivalent aromatic group represented by Formula (3) and (4) is mentioned.

Moreover, in this invention, other diamine can also be used in addition to the aromatic diamine which has the said fluorine atom.

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- Diamines having one benzene nucleus such as xylylenediamine; 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, 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, 3,3'-diaminodiphenylsulfoxide, 3,4'-diaminodiphenylsulfoxide, Two benzene nuclei such as 4,4'-diaminodiphenylsulfoxide, 2- (3-aminophenyl) -5-aminobenzimidazole, and 2- (4-aminophenyl) -5-aminobenzooxazole Diamine; 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- Aminophenylsulfide) 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, diamine having three benzene nuclei such as 4,4 ''-diamino-p-terphenyl and 4,4 ''-diamino-m-terphenyl; You may use and combine two or more kinds You can use it.

In the polyamic acid to be used in the present invention, the amount of the aromatic diamine having a fluorine atom in the diamine component is preferably 70 mol% or more in consideration of making both the exfoliation from the above-mentioned gas and the adhesion to the resin substrate compatible. 80 mol% or more is more preferable, 90 mol% or more is more preferable, 95 mol% or more is more preferable, and 100 mol% is the most preferable.

By making the diamine component and tetracarboxylic dianhydride component demonstrated above react in an organic solvent, the polyamic acid contained in the composition for substrate protective layer formation of this invention can be obtained.

The organic solvent used in this reaction is not particularly limited as long as it does not adversely affect the reaction, and specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and 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, an organic solvent can be used individually by 1 type or in combination of 2 or more type.

Since the introduction ratio (molar ratio) of the diamine component and the tetracarboxylic dianhydride component is appropriately determined in consideration of the target molecular weight, the molecular weight distribution, the kind of the diamine, the kind of the tetracarboxylic dianhydride, etc., it cannot be specified collectively. It is about 0.7-1.3 diamine component, Preferably it is about 0.8-1.2, More preferably, it is about 0.9-1.1 with respect to the tetracarboxylic dianhydride component 1.

What is necessary is just to set reaction temperature suitably in the range from the melting point of a solvent to boiling point, and it is about 0-100 degreeC normally, but in order to prevent the imidation in the solution of the obtained polyamic acid, and to maintain high content of a polyamic acid unit, Is about 0-70 degreeC, More preferably, it is about 0-60 degreeC, More preferably, it is about 0-50 degreeC.

Since the reaction time depends on the reaction temperature and the reactivity of the raw materials, it cannot be specified collectively, but is usually about 1 to 100 hours.

Although the weight average molecular weight of the polyamic acid obtained in this way is about 5,000-500,000 normally, From a viewpoint of improving the function as a board | substrate protective layer of the film | membrane obtained, Preferably it is about 10,000-200,000, More preferably, it is about 30,000-150,000. In addition, in this invention, a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography (GPC) measurement.

In addition, the polyamic acid used by this invention may be made to react one or both of the polymer chain terminal with the amine which has an anchor group, or the acid anhydride which has an anchor group further.

Examples of such anchor groups include carboxylic acid groups, silyl groups (eg, alkylsilyl groups, alkoxysilyl groups, vinylsilyl groups and allylsilyl groups, etc.), vinyl groups, maleimide groups, phenolic hydroxyl groups, and the like. Among them, a carboxylic acid group and a silyl group (particularly, a silyl group in which one or more groups selected from an alkoxy group, a vinyl group and an allyl group are bonded to a silicon atom) are preferable.

Moreover, spacer groups, such as a C1-C10 alkyl group and an aryl group, which do not significantly reduce the peelability and heat resistance of about 1-10 carbon atoms, may exist between the polyamic acid obtained from a diamine component and the tetracarboxylic dianhydride component, and an anchor group. .

Specific examples of the amine having an anchor group include 4-aminophenoxytrimethylsilane, 4-aminophenoxydimethylvinylsilane, 4-aminophenoxymethyldivinylsilane, 4-aminophenoxytrimethylvinylsilane, and 4-aminophenoxydimethylallyl. Silane, 4-aminophenoxymethyldiallylsilane, 4-aminophenoxycitriallylsilane, 4-aminophenoxydimethylphenylsilane, 4-aminophenoxymethyldiphenylsilane, 4-aminophenoxycitriphenylsilane, 4- Aminophenoxytrimethoxysilane, 4-aminophenoxydimethoxyvinylsilane, 4-aminophenoxymethoxydivinylsilane, 4-aminophenoxytrivinylsilane, 4-aminophenoxydimethoxyallylsilane, 4-amino Phenoxymethoxydiallylsilane, 4-aminophenoxydimethoxyphenylsilane, 4-aminophenoxymethoxydiphenylsilane, 4-aminophenoxytriethoxysilane, 4-aminophenoxydiethoxyvinylsilane, 4-aminophenoxy Ethoxydivinylsilane, 4-aminophenoxytrivinylsilicone , 4-aminophenoxy diethoxyallyl silane, 4-aminophenoxy ethoxy diallyl silane, 4-amino phenoxy diethoxy phenyl silane, 4-amino phenoxy ethoxy diphenyl silane, 3-amino phenoxy citrimethyl silane , 3-aminophenoxydimethylvinylsilane, 3-aminophenoxymethyldivinylsilane, 2-aminophenoxytriethylvinylsilane, 2-aminophenoxytrimethylsilane, 2-aminophenoxydimethylvinylsilane, 2-aminophenoxy Methyldivinylsilane, 2-aminophenoxytriethylsilane, 3-aminopropyltriethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-ethoxycar Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N -Triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 2-aminophenol, 3-aminophenol, 4-aminophenol and the like can be mentioned, but not limited thereto.

Specific examples of the acid anhydride having an anchor group include trimellitic anhydride, vinylmaleic anhydride, 4-vinylnaphthalene-1,2-dicarboxylic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, and 4-hydroxy Phthalic anhydride, 3-hydroxyphthalic anhydride, etc. are mentioned, It is not limited to these.

The amount of the amine having an anchor group and the acid anhydride having the anchor group is about 0.01 to 0.6, preferably about 0.05 to 0.4, and more preferably about 0.1 to 0.2 of the amine having an anchor with respect to the tetracarboxylic dianhydride component 1 in molar ratio. Or about 0.01 to 0.52 of acid anhydride having an anchor group with respect to diamine component 1, preferably about 0.05 to 0.32, and more preferably about 0.1 to 0.2.

The composition for substrate protective layer formation of this invention contains an organic solvent in addition to the polyamic acid mentioned above. Although it does not specifically limit as this organic solvent, The solvent chosen from the following is preferable.

(In formula, R <^1> -R <^8> represents a hydrogen atom or a C1-C10 alkyl group independently of each other, R <^9> and R <^10> represents a hydrogen atom, a C1-C10 alkyl group, or C1-C10 independently of each other Represents an acyl group, b and m represent a natural number)

b and m represent 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, a C1-C3 alkyl group is preferable and a C1-C2 alkyl group is more preferable.

Examples of the acyl group having 1 to 10 carbon atoms include alkanoyl groups having 1 to 8 carbon atoms (for example, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, pivaloyl group, etc.) 6 cycloalkylcarbonyl group (for example, cyclopropylcarbonyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, etc.), a benzoyl group, etc. are mentioned, An acetyl group is preferable.

Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3 in terms of easily dissolving polyamic acid and preparing a composition having high uniformity. -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 a polyamic acid independently, it can be used for preparation of a composition as long as it is a range in which a polyamic acid does not precipitate. 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 mixed as appropriate. . Thereby, it is known that coating film uniformity improves at the time of application | coating to a board | substrate, and it can use suitably also in this invention.

The preparation method of the composition for substrate protective layer formation of this invention is arbitrary. As a preferable example of a preparation method, the method of filtering the reaction solution containing the target polyamic acid obtained by the method demonstrated above is mentioned. At this time, if necessary for the purpose of concentration adjustment or the like, the filtrate may be diluted or concentrated. By adopting such a method, not only the mixing of impurities which may cause deterioration of adhesion, peelability, etc. of the substrate protective layer manufactured from the composition obtained can be reduced, but also the composition for forming the substrate protective layer can be efficiently obtained. Can be. It does not specifically limit as a solvent used for dilution, 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 can be used individually by 1 type or in combination of 2 or more type.

Although the density | concentration of the polyamic acid in the composition for board | substrate protective layer formation of this invention is set suitably in consideration of the thickness of the board | substrate protective layer to manufacture, the viscosity of a composition, etc., it is about 1-30 mass% normally, Preferably it is 1- It is about 20 mass%. By setting it as such a density | concentration, the board | substrate protective layer of thickness about 0.05-5 micrometers can be obtained reproducibly. The concentration of the polyamic acid can be adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride which are raw materials of the polyamic acid, or by adjusting the amount thereof when the isolated polyamic acid is dissolved in a solvent.

Although the viscosity of the composition for board | substrate protective layer formation of this invention sets it suitably in consideration of the thickness of the board | substrate protective layer to produce, etc., when aiming at obtaining the film | membrane of thickness of about 0.05-5 micrometers with good reproducibility normally, it is 25 degreeC normally. At about 10 to 10,000 mPa · s, preferably about 20 to 5,000 mPa · s.

Here, a viscosity can be measured on the conditions of the temperature of 25 degreeC of a composition using the viscosity meter for measuring the viscosity of a commercially available liquid, and referring the procedure of JISK7117-2, for example. Preferably, a conical flat plate (corn plate) rotational viscometer is used, and a homogeneous viscometer is preferably used at a temperature of 25 ° C. in a composition of 1 ° 34 ′ × R 24 as a standard cone rotor. Can be. As such a rotational viscometer, TVE-25L by Toki Sangyo Co., Ltd. is mentioned, for example.

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

After apply | coating the composition for peeling layer formation demonstrated above on a base | substrate, heat | fever imidating a polyamic acid by the baking method containing the process of baking at the maximum temperature of 500 degreeC or more, and the peeling property with a base and a resin substrate The resin substrate protective layer which consists of a polyimide film which has the outstanding adhesiveness can be obtained.

In this invention, if the maximum temperature at the time of the said baking is a range below 500 degreeC and the heat resistance temperature of a polyimide, it will not specifically limit. Moreover, the upper limit is about 550 degreeC normally, Preferably it is 520 degreeC, More preferably, it is about 510 degreeC. By making heating temperature into the said range, it becomes possible to fully advance imidation reaction, preventing the weakening of the film | membrane obtained.

Since heating time changes with heating temperature, it cannot be prescribed | regulated collectively, but is 5 minutes-5 hours normally. Moreover, imidation ratio should just be 50 to 100% of range.

Moreover, 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 in steps as it is, and finally heating at 500 degreeC or more is mentioned. Especially as a more preferable example of a heating aspect, the method of heating at 50-100 degreeC, heating more than 100 degreeC-less than 500 degreeC, and heating at 500 degreeC or more is mentioned. Moreover, as another preferable example of a heating aspect, the method of heating at 50-100 degreeC, heating at 200-300 degreeC, heating at more than 300 degreeC-less than 500 degreeC, and finally heating at 500-510 degreeC is mentioned. .

Moreover, as a preferable example of the heating aspect in case of considering a baking time, the method of heating for 1 minute-2 hours at 50-150 degreeC, then raising a heating temperature in steps as it is, and finally heating at 500 degreeC or more for 30 minutes-4 hours is mentioned. Can be. Especially as a more preferable example of a heating aspect, it heats at 50-100 degreeC for 1 minute-2 hours, heats more than 100 degreeC-less than 500 degreeC for 5 minutes-2 hours, and heats at 500 degreeC or more for 30 minutes-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, it is 5 minutes-2 hours at 200-300 degreeC, 5 minutes-2 hours at 300 degreeC-less than 500 degreeC, and finally 500 The method of heating at -510 degreeC for 1 minute-2 hours is mentioned.

When forming the board | substrate protective layer of this invention on a base, the board | substrate protective layer may be formed in one surface of a base, and may be formed in the whole surface. As an aspect in which the substrate protective layer is formed on a part of the surface of the substrate, the substrate protective layer is formed in a pattern shape such as a dot pattern, a line-and-space pattern on the entire surface of the substrate, and an embodiment in which the substrate protective layer is formed only in a predetermined range of the substrate surface. Such as the sun. In the present invention, the substrate is coated with the composition for forming a substrate protective layer of the present invention on the surface thereof, which means that the substrate is used for production of a flexible electronic device or the like.

Examples of the base material include glass and plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene-based resin, etc.), metal (silicon wafer) Etc.), wood, paper, slate, and the like, and glass is particularly preferable in that the substrate protective layer of the present invention has sufficient adhesiveness thereto. 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 any material, and the rest of the surface is made of other materials. In the shape, there is an aspect in which a material is present in other materials.

Although the method of apply | coating the composition for substrate protective layer formation of this invention to a base is not specifically limited, For example, the cast coat method, the spin coat method, the blade coat method, the dip coat method, the roll coat method, the bar coat method, the 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, inert gas, normal pressure or reduced pressure.

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

Although the resin substrate formed on the said board | substrate protective layer is not specifically limited, It is suitable that the 1% weight loss temperature in thermal gravimetric analysis is 500 degreeC or more from a heat resistant viewpoint.

As such a resin substrate, the resin substrate using the wholly aromatic polymer, such as a wholly aromatic polyimide, polybenzoxazole, polybenzothiazole, and polybenzoimidazole, is mentioned. Moreover, the hybrid film which silica sol, titania sol, etc. were added to the said polymer may be sufficient.

Hereinafter, an example of the manufacturing method of the flexible electronic device using the board | substrate protective layer of this invention is demonstrated.

The substrate protective layer is formed on a glass base by the method mentioned above using the composition for substrate protective layer formation of this invention. The resin substrate formation solution for forming a resin substrate is apply | coated on this board | substrate protective layer, and this coating film is baked, and the resin substrate fixed to glass base is formed through the board | substrate protective 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 into 500 degreeC or more. Moreover, although the upper limit is about 550 degreeC normally, Preferably it is 520 degreeC, More preferably, it is about 510 degreeC.

By making the maximum temperature at the time of baking at the time of resin substrate manufacture into this range, the peelability of a protective layer which is a base and a base body, and the appropriate adhesiveness and peelability of a board | substrate protective 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 at 500 degreeC or more is mentioned. Especially as a more preferable example of a heating aspect, the method of heating at 50-100 degreeC, heating more than 100 degreeC-less than 500 degreeC, and heating at 500 degreeC 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, heats more than 200 degreeC-300 degreeC, heats more than 300 degreeC-less than 500 degreeC, and finally The method of heating at 500-510 degreeC is mentioned.

Moreover, as a preferable example of the heating aspect in case of considering a baking time, the method of heating for 1 minute-2 hours at 50-150 degreeC, then raising a heating temperature in steps as it is, and finally heating at 500 degreeC or more for 30 minutes-4 hours is mentioned. Can be. Especially as a more preferable example of a heating aspect, it heats at 50-100 degreeC for 1 minute-2 hours, heats more than 100 degreeC-less than 500 degreeC for 5 minutes-2 hours, and heats at 500 degreeC or more for 30 minutes-4 hours. Can be mentioned. Moreover, as another more preferable example of a heating aspect, after heating for 1 minute-2 hours at 50-100 degreeC, 5 minutes-2 hours at 100 degreeC-200 degreeC, 5 minutes-2 hours at 200 degreeC-300 degreeC, 300 degreeC 5 minutes-2 hours at the excess-less than 500 degreeC, and the method of heating at 500-510 degreeC for 30 minutes-4 hours lastly is mentioned.

Subsequently, a desired circuit is formed on the resin substrate fixed to the substrate via the substrate protective layer of the present invention, and then the resin substrate is cut along the substrate protective layer, for example, and the resin substrate together with the circuit. And the substrate protective layer is peeled off from the substrate to separate the resin substrate, the substrate protective layer from the substrate. At this time, a part of the substrate may be cut together with the substrate protective 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 and three-dimensional semiconductor packages, to the manufacture of flexible displays. The LLO method is characterized by irradiating a light of a specific wavelength, for example, a light 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 a board | substrate protective layer from glass base, without affecting the circuit etc. provided on the resin substrate which determines the performance of a display.

Since the composition for substrate protective layer formation of this invention has the characteristic to absorb the light of the specific wavelength (for example, 308 nm) which the said LLO method can apply to, 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 the glass substrate via the board | substrate protective layer formed using the composition for this invention, and then irradiated with the light of 308 nm by LLO method, this board | substrate will be provided. Only the protective layer absorbs this light and evaporates (sublimes). Thereby, the said board | substrate protective layer becomes a sacrifice (acts as a sacrificial layer), and it becomes possible to selectively peel a resin substrate from a glass substrate.

(Example)

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

[1] abbreviations for compounds

p-PDA: p-phenylenediamine

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

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

PMDA: pyromellitic dianhydride

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

PGME: Propylene Glycol Monomethyl Ether

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

Measurement of the weight average molecular weight of the polymer (hereinafter referred to as Mw) and the molecular weight distribution were carried out using a GPC device (column: Shodex KD801 and KD805; eluent: dimethylformamide / LiBr.H ₂ O (29.6 mM) / H ₃ PO ₄ (29.6 mM) / THF (0.1 wt%); flow rate: 1.0 mL / min; column temperature: 40 ° C .; Mw: standard polystyrene conversion value).

[3] polymer synthesis

Polyamic acid was synthesize | combined by the following method.

Moreover, the composition for resin substrate formation or the composition for board | substrate protective layer formation was prepared by diluting a reaction liquid as mentioned later, 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)

23.7 g (74.2 mmol) of TFMB was dissolved in 352 g of NMP. BPDA24.2g (82.5mmol) was added to the obtained solution, and it was made to react at 23 degreeC by nitrogen atmosphere for 24 hours. Obtained polymer Mw was 76,400 and molecular weight distribution 2.2. The obtained solution was soluble in PGME.

Synthesis Example Synthesis of L2 Polyamic Acid (L2)

9.89 g (30.9 mmol) of TFMB was dissolved in 380 g of PGME. 10.0 g (34.3 mmol) of BPDA was added to the obtained solution, and it was made to react at 50 degreeC for 72 hours in nitrogen atmosphere. Obtained polymer Mw was 76,400 and molecular weight distribution 2.2.

Comparative Synthesis Example Synthesis of HL1 Polyamic Acid (HL1)

2.73 g (8.53 mmol) of TFMB were dissolved in 38.5 g of NMP. PMDA 2.06g (9.47mmol) was added to the obtained solution, and it was made to react at 23 degreeC by nitrogen atmosphere for 24 hours. Obtained polymer Mw was 76,400 and molecular weight distribution 2.2. The obtained solution was soluble in PGME.

Comparative Synthesis Example Synthesis of HL2 Polyamic Acid (HL2)

2.86 g (8.91 mmol) of TFMB were dissolved in 35.2 g of NMP. CBDA 1.94g (9.91mmol) was added to the obtained solution, and it was made to react at 23 degreeC by nitrogen atmosphere for 24 hours. Obtained polymer Mw was 69,200 and molecular weight distribution 2.2. The obtained solution was soluble in PGME.

[4] Preparation of Composition for Forming Resin Substrate

Preparation Example 1

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

[5] Preparation of Composition for Forming Substrate Protective Layer

Example 1-1

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

Example 1-2

The reaction solution obtained in the synthesis example L2 was used as the composition for substrate protective layer formation as it is.

Comparative Example 1-1

BCS and NMP were added to the reaction liquid obtained by the comparative synthesis example HL1, and it diluted so that a polymer concentration might be 5 wt% and 20 mass% of BCS, and the composition for substrate protective layer formation was obtained.

Comparative Example 1-2

BCS and NMP were added to the reaction liquid obtained by the comparative synthesis example HL2, and it diluted so that a polymer concentration might be 5 wt% and 20 mass% of BCS, and the composition for substrate protective layer formation was obtained.

[6] substrate protective layers and resin substrates

Example 2-1

The composition for substrate protective layer formation obtained in Example 1-1 was apply | coated on the 100 mm x 100 mm glass substrate (hereafter same) as a glass base | substrate using the spin coater (condition: about 30 second at 3,000 rpm).

And the obtained coating film was heated at 80 degreeC for 10 minutes using a hotplate, and after that, it heated at 300 degreeC for 30 minutes and 400 degreeC for 30 minutes using an oven, and further heated at 500 degreeC for 10 minutes, and glass The board | substrate protective layer of thickness about 0.1 micrometer was formed on the board | substrate, and the glass substrate with a board | substrate protective layer was obtained. In addition, the temperature increase rate between each heating temperature was 5 degree-C / min, and it heated in the oven, without taking out the board | substrate with a film from the oven, while raising temperature.

The composition for resin substrate formation was apply | coated on the board | substrate protective layer (resin thin film) on the glass substrate obtained above using the bar coater (gap: 250 micrometers). And the obtained coating film was heated at 80 degreeC for 40 minutes using a hotplate, and after that, it heated at 140 degreeC, 210 degreeC, 300 degreeC, and 400 degreeC, respectively for 30 minutes using an oven, and further at 500 degreeC 60 It heated for minutes, formed the polyimide resin substrate of thickness about 10 micrometers on the board | substrate protective layer, and obtained the glass substrate with a resin substrate and a board | substrate protective layer. In addition, the temperature increase rate between each heating temperature was 2 degree-C / min, and it heated in the oven, without taking out the board | substrate with a film from the oven, while raising temperature.

Example 2-2

A substrate protective layer and a polyimide resin substrate in the same manner as in Example 2-1 except that the composition for forming a substrate protective layer obtained in Example 1-2 was used instead of the composition for forming a substrate protective layer obtained in Example 1-1. Was formed and the glass substrate with a board | substrate protective layer and the glass substrate with a resin substrate and a board | substrate protective layer were obtained.

[Comparative Example 2-1 ~ 2-2]

Substrate protective layer in the same manner as in Example 2-1 except for using the composition for forming a substrate protective layer obtained in Comparative Examples 1-1 to 1-2 instead of the composition for forming a substrate protective layer obtained in Example 1-1, respectively. And a polyimide resin substrate were formed to obtain a glass substrate with a substrate protective layer and a glass substrate with a resin substrate and a substrate protective layer.

[7] evaluation of peelability

Strip shape of width 2cm and length 5cm using the cutter for the resin substrate and board | substrate protective layer of the glass substrate with a resin substrate and a board | substrate protective layer obtained in Examples 2-1-2-2 and Comparative Examples 2-1-2-2. Cut into. And the adhesive tape was affixed on the edge part of the cut resin substrate, and this was made into the test piece. A peel test was performed for this test piece so that a peel angle might be 170 degrees using the push pull tester made by Atonic Co., Ltd., and peelability was evaluated based on the following reference | standard. The results are shown in Table 1.

<Evaluation criteria of peelability of glass substrate and substrate protective layer>

(Circle): A board | substrate protective layer peels all from glass substrate.

(Triangle | delta): Although a resin substrate can be peeled off, a board | substrate protective layer remains on some glass substrates.

X: The resin substrate and the substrate protective layer cannot be peeled from the glass substrate.

Moreover, the surface of the glass surface of the peeled part was scraped off with the cutter, and the residual film property was evaluated based on the following criteria. The results are shown in Table 1.

<Residual Evaluation Criteria of Substrate Protective Layer to Glass Substrate>

(Circle): There is no residual film of a board | substrate protective layer.

(Triangle | delta): Some board | substrate protective layer remains.

X: The substrate protective layer remains.

-: Evaluation failed because the resin substrate did not peel off.

Board protective layer Peelability of Glass Substrate and Substrate Protective Layer Residual property of the substrate protective layer on the glass substrate Example 2-1 L1 ○ ○ Example 2-2 L2 ○ ○ Comparative Example 2-1 HL1 × - Comparative Example 2-2 HL2 × -

As shown in Table 1, the board | substrate protective layers of Examples 2-1 to 2-2 were peeled easily with a resin substrate, and it was confirmed that there is no residual film of a board | substrate protective layer in a glass substrate. On the other hand, the resin substrate of Comparative Examples 2-1 to 2-2 was stuck firmly to the glass substrate through the board | substrate protective layer, and was not able to peel from glass substrate.

[9] properties of resin film

The mechanical properties of the resin substrate obtained in Example 2-1 were measured. In addition, the resin substrate produced by apply | coating and baking resin composition S1 for resin substrate formation directly on a base | substrate, without forming a board | substrate protective layer as a comparison was used. At that time, the substrate was changed from a glass substrate to a silicon substrate, and a resin substrate was formed in the same manner as in Example 2-1 except for that. The obtained resin film was made into SF1.

<Linear expansion coefficient>

A 20 mm x 5 mm strip-shaped test piece was produced from the film obtained above, and the linear expansion coefficient from 50 degreeC to 500 degreeC was measured using TMA-4000SA (made by Brooke AX Corporation). The results are shown in Table 2.

<Weight reduction>

A strip-shaped test piece of 20 mm x 3 mm was made from the film obtained above, and the weight loss from 50 degreeC to 600 degreeC was measured using TGA-DTA-2000SR (made by Brooker AX Corporation), , 1% of the weight loss was confirmed. The results are shown in Table 2.

Board protective layer Coefficient of linear expansion
(ppm / ℃) 1% weight reduction
(℃) SF1 - -15 550 Example 2-1 L1 -9 548

As shown in Table 2, in the resin substrate with a board | substrate protective layer produced in the Example, and the resin substrate produced without forming a board | substrate protective layer, it was confirmed that there is no difference in a mechanical characteristic. From the above result, it was confirmed that the board | substrate protective layer does not affect the mechanical characteristic of the resin substrate produced.

Claims (11)

After forming a resin substrate on a base, when peeling the said resin substrate together with the said resin substrate from the said base, it interposes between the said base and the said resin substrate, and has peeling property from the said base, A composition for forming a substrate protective layer functioning as a protective layer of the resin substrate after peeling, comprising a polyamic acid and an organic solvent. The composition for forming a substrate protective layer according to claim 1, comprising a polyamic acid represented by the following formula (1) and an organic solvent.

(In formula, X represents the aromatic group represented by following formula (2), Y represents the bivalent aromatic group which has a fluorine atom, and n represents a natural number.)

The composition for forming a substrate protective layer according to claim 2, wherein Y is an aromatic group represented by the following formula (3).

The composition for forming a substrate protective layer according to claim 2 or 3, wherein Y is an aromatic group represented by the following formula (4).

The composition for forming a substrate protective layer according to any one of claims 1 to 4, wherein the organic solvent is at least one selected from those having a structure represented by the following formulas (S1) to (S7). .

(In formula, R <^1> -R <^8> represents a hydrogen atom or a C1-C10 alkyl group independently of each other, R <^9> and R <^10> represents a hydrogen atom, a C1-C10 alkyl group, or C1-C10 independently of each other Represents an acyl group of b and n represent a natural number) The method according to claim 1, wherein when the electronic device is further fabricated on the resin substrate, and the electronic device is peeled from the substrate together with the resin substrate, the resin substrate has a peeling property from the substrate. It functions as a protective layer, The composition for substrate protective layer formation characterized by the above-mentioned. The board | substrate protective layer obtained from the composition for substrate protective layer formation as described in any one of Claims 1-6. Applying the composition for substrate protective layer formation of Claim 6 on a base material, baking at the maximum temperature of 500 degreeC or more, and forming the board | substrate protective layer which has the peelability from the said base material,
Apply | coating the composition for resin substrate formation on this board | substrate protective layer, baking at the maximum temperature of 500 degreeC or more, and forming a resin substrate,
A step of producing an electronic device on the resin substrate,
And a step of peeling the electronic device together with the substrate protective layer and the resin substrate from the substrate. The method of manufacturing a flexible electronic device according to claim 8, wherein the resin substrate is a polyimide resin substrate. After apply | coating the composition for board | substrate protective layer formation as described in any one of Claims 1-5 on a base material, baking at the maximum temperature of 500 degreeC or more, and forming a board | substrate protective layer, a resin substrate is formed on this board | substrate protective layer. After apply | coating the composition for formation, baking at the maximum temperature of 500 degreeC or more, and forming a resin substrate, the said resin substrate is peeled from a base material with the said board | substrate protective layer, The manufacturing method of the resin substrate with a protective layer characterized by the above-mentioned. The production method according to claim 10, wherein the resin substrate is a polyimide resin substrate.