KR102376154B1 - Composition for forming a release layer - Google Patents

Abstract

A polyamic acid represented by the following formula (1), a polyamic acid represented by the following formula (2), a polyamic acid represented by the following formula (3) or a polyamide represented by the following formula (4), and an organic solvent A composition for forming a release layer is provided. (Wherein, X ₁ represents a tetravalent aromatic group having no fluorine atom, X ₂ represents a tetravalent aromatic group having a fluorine atom, X ₃ represents a divalent aromatic group not having a fluorine atom, Y ₁ is a fluorine atom represents a divalent aromatic group having , Y ₂ represents a divalent aromatic group having no fluorine atom, and m represents a natural number.)

Description

Composition for forming a release layer

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

In recent years, in addition to the characteristics of thickness reduction and weight reduction, it is calculated|required to provide the function of being bendable to an electronic device. In this regard, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, brittle and inflexible glass substrate.

In particular, 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 for a new generation display. This new-generation display technology is expected to be diverted to various fields such as flexible displays, flexible smart phones, and mirror displays.

Then, the manufacturing method of the electronic device which used the resin film as a board|substrate variously began to be examined, and examination of the process which can divert the existing equipment for TFT display panel manufacturing in a new-generation display is progressing. Moreover, in a touch panel type display, the method for efficiently manufacturing the resin substrate for transparent electrodes of a touch panel used in combination with a display panel, etc. is examined. In general, resin substrates used in touch panels are film substrates such as polyimide resin substrates or acrylic resin substrates, polyethylene terephthalate (PET) resin substrates, cycloolefin resin substrates, and the like, having transparency equivalent to glass, similar to TFT display panels. this is being used

For example, in Patent Documents 1, 2 and 3, an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side, A method of peeling a plastic substrate from a glass substrate by hydrogen gas is disclosed. Moreover, in Patent Document 4, a method of affixing a layer to be peeled (in Patent Document 4, it is described as a "transferred layer") to a plastic film using the technique disclosed in Patent Documents 1 to 3 to complete a liquid crystal display device. has been disclosed.

However, in the methods disclosed in Patent Documents 1 to 4, particularly in the method disclosed in Patent Document 4, it is essential to use a substrate with high light transmittance in order to transmit laser light, allowing the substrate to pass through, and also releasing hydrogen contained in amorphous silicon. There are problems such as that it is necessary to irradiate a laser beam with a relatively large energy sufficient to cause the fusion, and that the layer to be peeled may be damaged by the irradiation of the laser beam.

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

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

The present invention has been made in view of the above circumstances, and a release layer that can be peeled off without damaging a resin substrate of a flexible electronic device, particularly a resin substrate formed of a polyimide resin, an acrylic resin, a cycloolefin polymer resin, etc. is provided. An object of the present invention is to provide a composition for forming a release layer.

As a result of repeated studies to solve the above problems, the present inventors have found that a composition containing a polyamic acid or polyamide having a specific structure and an organic solvent has excellent adhesion to a substrate such as a glass substrate and is used as a flexible electronic device. This invention was completed by discovering providing the peeling layer which has suitable adhesiveness with a resin substrate, and suitable peeling property.

That is, the present invention

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

(Wherein, X ₁ represents a tetravalent aromatic group having no fluorine atom, X ₂ represents a tetravalent aromatic group having a fluorine atom, X ₃ represents a divalent aromatic group not having a fluorine atom, Y ₁ is a fluorine atom represents a divalent aromatic group having , Y ₂ represents a divalent aromatic group having no fluorine atom, and m represents a natural number.)

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

3. The composition for forming a release layer of 2 wherein Y ₁ is an aromatic group represented by the following formula (10);

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

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

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

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

8. Any one of 1 to 7 wherein the organic solvent contains at least one selected from amides represented by formula (S1), amides represented by formula (S2), and amides represented by formula (S3) composition for forming a release layer of

(Wherein, 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 represents a natural number.)

9. A release layer formed using the composition for forming a release layer according to any one of 1 to 8;

10. A method for manufacturing a flexible electronic device comprising a resin substrate comprising the use of the release layer of 9;

11. Method of manufacturing a touch panel sensor having a resin substrate, characterized in that using the release layer of 9;

12. The manufacturing method of 10 or 11, wherein the resin substrate is a polyimide resin substrate or a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm

provides

By using the composition for forming a release layer of the present invention, it is possible to obtain a film having excellent adhesion to a substrate, appropriate adhesion to a resin substrate, and appropriate peelability, with good reproducibility. By using the composition of the present invention, in the manufacturing process of a flexible electronic device, the resin substrate formed on the substrate or the circuit installed thereon is not damaged, and the resin substrate is separated from the substrate together with the circuit etc. thing becomes possible Therefore, the composition for forming a release layer of the present invention can contribute to simplification of the manufacturing process of a flexible electronic device including a resin substrate, improvement of its yield, and the like.

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

The composition for forming a release layer of the present invention is a polyamic acid represented by the following formula (1), a polyamic acid represented by the following formula (2), a polyamic acid represented by the following formula (3) or a polyamic acid represented by the following formula (4) It contains polyamide and an organic solvent.

In the present invention, the release layer is a layer provided directly on the substrate (eg, glass substrate) on which the resin substrate is formed. As a typical example thereof, in a manufacturing process of a flexible electronic device, the resin substrate is transferred between the substrate and a resin substrate of a flexible electronic device formed of a polyimide resin, an acrylic resin, a cycloolefin polymer resin, or the like in a predetermined process. A peeling layer provided in order to be fixed and provided in order to be able to peel the said resin substrate from the said base|substrate easily after forming an electronic circuit etc. on the said resin substrate is mentioned.

In the formulas (1) to (4), X ₁ represents a tetravalent aromatic group having no fluorine atom, X ₂ represents a tetravalent aromatic group having a fluorine atom, and X ₃ is a divalent aromatic group having no fluorine atom. group, Y ₁ represents a divalent aromatic group having a fluorine atom, Y ₂ represents a divalent aromatic group not having a fluorine atom, and m represents a natural number.

Said X< ₁ > does not have a fluorine atom, and the aromatic group which contains 1-5 benzene rings is preferable. Moreover, said X< ₁ > may contain either or both of an ester bond and an ether bond.

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

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

Y ₂ is preferably an aromatic group that does not have a fluorine atom and contains 1 to 5 benzene rings, more preferably an aromatic group containing 1 to 3 benzene rings. Moreover, said Y2 may contain either or both _of an ester bond and an ether bond.

X ₃ is preferably an aromatic group that does not have a fluorine atom and contains 1 to 5 benzene rings, more preferably an aromatic group containing 1 to 2 benzene rings, and still more preferably a biphenyl group.

Although m may be a natural number, a natural number of 100 or less is preferable, and a natural number of 2-100 is more preferable.

[Polyamic Acid 1]

The polyamic acid represented by the said Formula (1) is obtained by making the aromatic tetracarboxylic dianhydride which does not have a fluorine atom react with the aromatic diamine which has a fluorine atom. Hereinafter, the aromatic tetracarboxylic dianhydride and aromatic diamine which can be used for the synthesis|combination of the polyamic acid represented by said Formula (1) are described in detail.

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

Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, and 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 acid 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'-tetracarboxylic dianhydride, anthracene-1,2,3,4-tetracarboxylic dianhydride Water, 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, 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-3,4,5,6 -tetracarboxylic dianhydride, phenanthrene-3,4,9,10-tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride represented by the following formulas (B1) to (B12), etc., but are not limited thereto . These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

[Polyamic Acid 2]

The polyamic acid represented by the said Formula (2) is obtained by making the aromatic tetracarboxylic dianhydride which has a fluorine atom react with the aromatic diamine which does not have a fluorine atom. Hereinafter, the aromatic tetracarboxylic dianhydride and aromatic diamine which can be used for the synthesis|combination of the polyamic acid represented by said Formula (2) are described in detail.

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

Specific examples of the aromatic tetracarboxylic dianhydride include 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, N,N'-[2,2'-bis(trifluoromethyl)biphenyl-4,4' -diyl]bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carbamide), 3,6-difluoropyromellitic dianhydride, 3,6-bis(trifluoro Rhomethyl) pyromellitic dianhydride, 3,6-bis (trifluoromethoxy) pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3-trifluoromethylpyromellitic dianhydride, 3- Trifluoromethoxypyromellitic dianhydride, 9,9-bis-(trifluoromethyl)xanthenetetracarboxylic dianhydride, 9-phenyl-9-(trifluoromethyl)xanthenetetracarboxylic dianhydride, 3,3' ,5,5',6,6'-hexafluorooxy-4,4'-diphthalic dianhydride etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

On the other hand, the aromatic diamine is not particularly limited as long as it does not have a fluorine atom and has two amino groups directly linked to an aromatic ring in the molecule, but an aromatic diamine containing 1 to 5 benzene rings is preferable.

Specific examples of the aromatic diamine include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine) Min), 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- diamines containing one benzene ring, such as phenylenediamine, m-xylylenediamine, and p-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 Phosphorus, 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 diamine containing two benzene rings, such as 3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, and 4,4'-diaminodiphenyl sulfoxide; 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 ] Although diamines containing three benzene rings, such as benzene, aromatic diamines represented by following formula (A6) - (A44), etc. are mentioned, It is not limited to these. These may be used individually by 1 type, and may be used in combination of 2 or more type.

[Polyamic Acid 3]

The polyamic acid represented by the said Formula (3) is obtained by making the aromatic tetracarboxylic dianhydride which has a fluorine atom react with the aromatic diamine which has a fluorine atom.

As aromatic tetracarboxylic dianhydride, the aromatic tetracarboxylic dianhydride which has the same fluorine atom as what can be used for the synthesis|combination of the polyamic acid represented by said Formula (2) can be used.

As aromatic diamine, the aromatic diamine which has a fluorine atom similar to what can be used for the synthesis|combination of the polyamic acid represented by said Formula (1) can be used.

[Polyamide]

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

In the present invention, the aromatic dicarboxylic acid or its derivative is not particularly limited as long as it does not have a fluorine atom and has two carboxyl groups or a derivative thereof in the molecule, but 1 to 5 benzene rings, particularly 1 to 2 Aromatic dicarboxylic acids containing two or two or a derivative thereof are preferred.

Specific examples of the aromatic dicarboxylic acid or its derivative include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-di Methyl terephthalic acid, tetramethyl terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4 -Anthracendicarboxylic acid, 1,6-anthracendicarboxylic acid, 2,6-anthracendicarboxylic acid, 1,4-anthraquinonedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2 ,2'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4''-terphenyldicarboxylic acid, 4,4'-diphenylmethanedi Carboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid , 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbendicarboxylic acid, 4,4'-tolandicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4 ,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3'-[4,4' -(methylenedi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-( dicarboxylic acids such as oxydi-p-phenylene)]ibutyric acid, (isopropylidenedi-p-phenylenedioxy)dibutyric acid, and bis(p-carboxyphenyl)dimethylsilane;

Isophthalic acid dichloride, terephthalic acid dichloride, 3-chloroisophthalic acid dichloride, 3-methoxyisophthalic acid dichloride, 2,5-dichloroterephthalic acid dichloride, trichloroterephthalic acid dichloride, tetrachloroterephthalic acid dichloride, 1, 4-naphthalenedicarboxylic acid dichloride, 2,6-naphthalenedicarboxylic acid dichloride, 3,3'-biphenyldicarboxylic acid dichloride, 4,4'-biphenyldicarboxylic acid dichloride, 2,2'-biphenyldi Halides of said various dicarboxylic acids, such as carboxylic acid dichloride and 3,4'- biphenyl dicarboxylic acid dichloride, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, the said various dicarboxylic acid may be a thing of an anhydrous structure.

As aromatic diamine, the aromatic diamine which has a fluorine atom similar to what can be used for the synthesis|combination of the polyamic acid represented by said Formula (1) can be used.

When synthesizing the polyamic acid represented by the formula (1) and the polyamic acid represented by the formula (2), the ratio of the number of moles of all tetracarboxylic dianhydride components to the number of moles of all diamine components is tetracarboxylic acid component/diamine It is preferable that it is component =0.8-1.2. In addition, it is preferable that the ratio of the number of moles of the total dicarboxylic acid component to the number of moles of the total diamine component when synthesizing the polyamide represented by the formula (4) is dicarboxylic acid component/diamine component = 0.8 to 1.2.

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

[Organic solvent]

The organic solvent used for such a 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-E Toxy-N,N-dimethylpropylamide, 3-propoxy-N,N-dimethylpropylamide, 3-isopropoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-di methylpropylamide, 3-sec-butoxy-N,N-dimethylpropylamide, 3-tert-butoxy-N,N-dimethylpropylamide, γ-butyrolactone, and the like. In addition, an organic solvent may be used individually by 1 type or in combination of 2 or more type.

In particular, the organic solvent used for the reaction dissolves well the above-mentioned diamine, tetracarboxylic dianhydride, dicarboxylic acid, polyamic acid and polyamide, so the amides represented by the formula (S1), (S2) At least one selected from the amides used and the amides represented by the formula (S3) 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. Although h represents 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.

The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C. For example, to prevent imidization in the solution of the polyamic acid obtained and to maintain a high content of the polyamic acid unit Preferably it is about 0 to 70 degreeC, More preferably, it is about 0-60 degreeC, More preferably, it is about 0-50 degreeC.

Further, in the production of polyamide, a polymerization catalyst may be used in order to increase polymerization efficiency. Examples of the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid or salts thereof, and pyridine. It is preferable to use the polymerization catalyst in an amount of usually 2 mol% or less based on the total monomers constituting the polyamide.

The reaction time cannot be defined collectively because it depends on the reaction temperature or the reactivity of the raw material, but is usually about 1 to 100 hours.

By the method demonstrated above, the reaction solution containing the target polyamic acid or polyamide can be obtained.

5,000-1,000,000 are preferable, as for the weight average molecular weight of the said polyamic acid or polyamide, 6,000-500,000 are more preferable, and 7,000-200,000 are still more preferable from a handleability viewpoint. In addition, in this invention, a weight average molecular weight is the average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (GPC) analysis.

In the present invention, usually after filtering the reaction solution, the filtrate can be used as it is, or a solution obtained by diluting or concentrating can be used as the composition for forming a release layer of the present invention. By doing in this way, not only can the mixing of impurities which can cause deterioration of adhesiveness, peelability, etc. of the peeling layer obtained be reduced, but also the composition for peeling layer formation can be obtained efficiently. Moreover, after isolating a polyamic acid or a polyamide from the said reaction solution, it is good also as a composition for peeling layer formation by dissolving in a solvent again. As a solvent in this case, the organic solvent etc. used for reaction mentioned above are mentioned.

The solvent used for dilution is not specifically limited, The thing similar to the specific example of the reaction solvent of the said reaction is mentioned as the specific example. The solvent used for dilution may be used individually by 1 type or in combination of 2 or more type. Among them, from the viewpoint of dissolving polyamic acid or polyamide well, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2 -Imidazolidinone, N-ethyl-2-pyrrolidone, and (gamma)-butyrolactone are preferable, and N-methyl-2-pyrrolidone is more preferable.

Moreover, even if it is a solvent which does not dissolve polyamic acid or polyamide independently, as long as it is a range in which polyamic acid or polyamide does not precipitate, it can be mixed with the composition for release 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, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. A solvent having a low surface tension of It is known that coating-film uniformity improves at the time of application|coating to a board|substrate by this, and it is used suitably also in the composition for peeling layer formation of this invention.

The concentration of the polyamic acid or polyamide in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, etc., and is usually about 1 to 30 mass%, preferably It is about 1-20 mass %. By setting it as such a density|concentration, the peeling layer with a thickness of about 0.05-5 micrometers can be obtained with good reproducibility. In addition, the concentration of polyamic acid or polyamide is adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride or dicarboxylic acid, which are their raw materials, or diluting or concentrating the filtrate after filtering the reaction solution, or isolated polyamic acid or When dissolving a polyamide in a solvent, it can adjust by adjusting the quantity.

In addition, the viscosity of the composition for forming a release layer is appropriately set in consideration of the thickness of the release layer to be produced. In particular, when the purpose of obtaining a film with a thickness of about 0.05 to 5 μm with good reproducibility is usually 10 to 10,000 at 25°C. It is about mPa*s, Preferably it is about 20-5,000 mPa*s. Here, the viscosity can be measured using a commercially available viscometer for measuring the viscosity of a liquid, for example, referring to the procedure described in JIS K7117-2, and measuring the composition at a temperature of 25°C. Preferably, a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and 1°34'×R24 is used as a standard cone rotor as a viscometer of the same type, and the composition is measured at a temperature of 25°C. can As such a rotational viscometer, Toki Sangyo Co., Ltd. TVE-25L is mentioned, for example.

In addition to the polyamic acid or polyamide and the organic solvent, the composition for forming a release layer according to the present invention may contain components such as a crosslinking agent in order to improve film strength, for example.

By applying the release layer-forming composition of the present invention described above to a substrate and heating the obtained coating film, a release layer having excellent adhesion to the substrate, appropriate adhesion to the resin substrate, and appropriate release property can be obtained.

When the release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the surface of the substrate or may be formed on the entire surface of the substrate. As an aspect of forming the release layer on a part of the surface of the substrate, the release layer is formed only in a predetermined range on the surface of the substrate, and the release layer is formed on the entire surface of the substrate in a pattern shape such as a dot pattern, a line and space pattern, etc. There is this. In addition, in the present invention, the substrate is applied to the surface of the composition for forming a release layer according to the present invention, which means that it is used in the manufacture of a flexible electronic device or the like.

As the substrate (substrate), for example, glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS, AS, norbornene-based resin, etc.), metal (silicon wafer, etc.) ), wood, paper, slate, etc., in particular, glass is preferable because the release layer obtained from the composition for forming a release layer according to the present invention has sufficient adhesion thereto. In addition, the base|substrate surface may be comprised from a single material, and may be comprised from two or more materials. In an aspect in which the surface of the base body is composed of two or more materials, a mode in which a certain range of the base surface is constituted of a certain material and the remaining surface is constituted of other materials, a pattern such as a dot pattern, a line and space pattern, etc. on the entire surface of the base body There is an aspect in which a certain material is present among other materials as a shape, and the like.

The coating method is not particularly limited, but for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, a printing method (iron plate, intaglio, flat plate, screen printing, etc.) and the like.

The heating temperature for imidization is normally determined appropriately within the range of 50 to 550°C, but is preferably 200°C or higher, and preferably 500°C or lower. By setting the heating temperature in this way, it becomes possible to sufficiently advance the imidization reaction while preventing the resulting film from becoming brittle. Since the heating time varies depending on the heating temperature, it cannot be defined collectively, but is usually 5 minutes to 5 hours. Moreover, what is necessary is just that the imidation ratio should just be 50 to 100% of range.

As a preferred example of the heating mode in the present invention, after heating at 50 to 100°C for 5 minutes to 2 hours, the heating temperature is raised stepwise as it is, and finally heating at over 375°C to 450°C for 30 minutes to 4 hours. can be heard In particular, it is preferable to heat at 50 to 100° C. for 5 minutes to 2 hours, then at over 100° C. to 375° C. for 5 minutes to 2 hours, and finally, at more than 375° C. to 450° C. for 30 minutes to 4 hours.

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

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

The release layer described above has excellent adhesion to a substrate, particularly glass, and an appropriate adhesion to a resin substrate and an appropriate release property. Therefore, in the manufacturing process of a flexible electronic device, the release layer according to the present invention is suitably used in order to release the resin substrate from the base together with the circuit formed on the resin substrate without damaging the resin substrate of the device. can

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 forming a release layer according to the present invention, a release layer is formed on the glass substrate by the method described above. A resin solution for forming a resin substrate is applied on the release layer, and the coating film is heated to form a resin substrate fixed to the glass substrate through the release layer according to the present invention. At this time, the resin substrate is formed with a large area compared to the area of the release layer so as to cover all of the release layer. Examples of the resin substrate include resin substrates made of polyimide resins, acrylic resins, and cycloolefin polymer resins, which are typical as resin substrates for flexible electronic devices, and resin solutions for forming them include polyimide solution, polyamic acid solution, and acrylic polymer. solutions and cycloolefin polymer solutions. What is necessary is just to follow a conventional method for the formation method of the said resin substrate. Moreover, as a resin substrate with high transparency, the resin substrate formed from an acrylic resin or a cycloolefin polymer resin can be illustrated, In particular, it is preferable that the light transmittance of wavelength 400nm is 80 % or more.

Next, a desired circuit is formed on the resin substrate fixed to the base through the release layer according to the present invention, and then, for example, the resin substrate is cut along the release layer, and the resin substrate with this circuit is applied as a release layer. It is peeled from the resin substrate and the base material is separated. At this time, you may cut a part of base|substrate together with a peeling layer.

On the other hand, in the manufacture of flexible displays, it has been reported that the polymer substrate can be appropriately peeled from the glass carrier using the laser lift-off method (LLO method), which has been used in the manufacture of high-brightness LEDs and three-dimensional semiconductor packages, etc. Yes (Japanese Patent Laid-Open No. 2013-147599). In the manufacture of a flexible display, it is necessary to prepare a polymer substrate made of polyimide or the like on a glass carrier, then to form a circuit including electrodes or the like on the substrate, and finally to peel the substrate together with the circuit from the glass carrier. there is In this peeling step, the LLO method is employed, that is, when a light beam having a wavelength of 308 nm is irradiated to a glass carrier from a surface opposite to the surface on which a circuit or the like is formed, the light beam of the wavelength passes through the glass carrier and is near the glass carrier. Only the polymer (polyimide resin) of As a result, it is reported that peeling of the substrate from the glass carrier is selectively feasible without affecting the circuitry installed on the substrate, etc., which determines the performance of the display.

If a desired circuit is formed on the resin substrate fixed to the base with the release layer according to the present invention interposed therebetween, and after that, when the LLO method is employed, only the release layer absorbs this light and evaporates (sublimes). That is, this release layer becomes sacrificial (acting as a sacrificial layer), making it possible to selectively perform peeling of the substrate from the glass carrier. Since the composition for forming a release layer of the present invention has the feature of sufficiently absorbing light of a specific wavelength (eg, 308 nm) to which the LLO method can be applied, it can be used as a sacrificial layer for the LLO method.

(Example)

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

[1] Abbreviations of compounds

p-PDA: p-phenylenediamine

DDE; 4,4'-oxydianiline

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

BPTP: Bis(4-aminophenoxy)terephthalate

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

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

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

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

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

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

a-ODPA: 3,4'-oxydiphthalic anhydride

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

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

PMDA: pyromellitic dianhydride

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

BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride

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

BPTME: p-biphenylenebis (trimellitic acid monoester acid anhydride)

MMA: methyl methacrylate

MAA: methacrylic acid

HEMA: 2-hydroxyethyl methacrylate

AIBN : Azobisisobutyronitrile

CHMI: cyclohexylmaleimide

Epolide GT-401: epoxidized butanetetracarboxylic acid tetrakis-(3-cyclohexenylmethyl) modified ε-caprolactone, manufactured by Daicel Corporation

NMP: N-methyl-2-pyrrolidone

PGMEA: Propylene Glycol Monomethyl Ether Acetate

BCS : Butyl Cellosolve

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

Measurement of the polymer weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution was performed using a GPC apparatus manufactured by Nippon Bunko Co., Ltd. (Column: KD801 and KD805 manufactured by Shodex; Eluent: dimethylformamide/LiBr·H ₂ O (29.6 mM) /H ₃ PO ₄ (29.6 mM)/THF (0.1 mass %); flow rate: 1.0 mL/min; column temperature: 40° C.; Mw: standard polystyrene conversion value).

[3] Synthesis of polymers

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

Furthermore, a composition for forming a resin substrate or a composition for forming a release layer was prepared by diluting the reaction liquid as described later without isolating the polymer from the obtained polymer-containing reaction liquid.

<Synthesis Example S1 Synthesis of acrylic polymer (S1)>

MMA 7.20 g (0.0719 mol), HEMA 7.20 g (0.0553 mol), CHMI 10.8 g (0.0603 mol), MAA 4.32 g (0.0502 mol), AIBN 2.46 g (0.0150 mol) were dissolved in 46.9 g of PGMEA, 60-100 The acrylic polymer solution (solid content concentration: 40 mass %) was obtained by making it react at degreeC for 20 hours. Mn of the obtained acrylic polymer was 3,800, and Mw was 7,300.

<Synthesis Example S2 Synthesis of polyamic acid (S2)>

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

<Synthesis Example S3 Synthesis of polyamic acid (S3)>

3.22 g (29.8 mmol) of p-PDA was dissolved in 88.2 g of NMP. BPDA 8.58 g (29.2 mmol) was added to the obtained solution, and it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours. Mw of the obtained polymer was 107,300, and molecular weight distribution was 4.6.

<Synthesis Example L1 Synthesis of polyamic acid (L1)>

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

<Synthesis Example L2 Synthesis of polyamic acid (L2)>

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

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

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

<Synthesis Example L4 Synthesis of polyamic acid (L4)>

1.92 g (5.70 mmol) of BTFDPE was dissolved in 35.6 g of NMP. BPTME 2.99 g (5.59 mmol) was added to the obtained solution, and it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours. Mw of the obtained polymer was 38,300, and molecular weight distribution was 2.3.

<Synthesis Example L5 Synthesis of polyamic acid (L5)>

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

<Synthesis Example L6 Synthesis of polyamic acid (L6)>

1.70 g (3.3 mmol) of HFBAPP was dissolved in 17.6 g of NMP. To the obtained solution, 0.70 g (3.2 mmol) of PMDA was added, and the reaction was carried out at 23° C. under a nitrogen atmosphere for 24 hours. Mw of the obtained polymer was 48,300, and molecular weight distribution was 2.6.

<Synthesis Example L7 Synthesis of polyamic acid (L7)>

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

<Synthesis Example L8 Synthesis of polyamic acid (L8)>

2.86 g (8.9 mmol) of TFMB was dissolved in 35.2 g of NMP. PMDA 1.95 g (8.9 mmol) was added to the obtained solution, and it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours. Mw of the obtained polymer was 70,300, and molecular weight distribution was 1.7.

<Synthesis Example L9 Synthesis of polyamic acid (L9)>

1.18 g (3.7 mmol) of TFMB and 0.93 g (8.6 mmol) of p-PDA were dissolved in 35.2 g of NMP. PMDA 2.69 g (12.3 mmol) was added to the obtained solution, and it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours. Mw of the obtained polymer was 60,700, and molecular weight distribution was 3.3.

<Synthesis Example L10 Synthesis of polyamic acid (L10)>

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

<Synthesis Example P1 Synthesis of polyamide (P1)>

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

<Synthesis of Comparative Synthesis Example HL1 Polyamic Acid (HL1)>

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

<Synthesis of Comparative Synthesis Example HL2 Polyamic Acid (HL2)>

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

[4] Preparation of a composition for forming a resin substrate

The composition for resin substrate formation was prepared with the following method.

<Preparation Example 1 Composition F1 for forming a resin substrate>

0.61 g of GT-401 and 5.06 g of PGMEA were added to 10 g of the reaction liquid obtained by synthesis example S1, and it stirred at 23 degreeC for 24 hours, and the composition F1 for resin substrate formation was prepared.

<Preparation Example 2 Composition F2 for forming a resin substrate>

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

<Preparation Example 3 Composition F3 for forming a resin substrate>

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

<Preparation Example 4 Composition F4 for forming a resin substrate>

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

<Preparation Example 5 Composition F5 for forming a resin substrate>

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

[5] Preparation of a composition for forming a release layer

[Example 1-1]

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

[Examples 1-2 to 1-10]

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

[Example 1-11]

BCS and NMP were added to and dissolved in 0.5 g of the polyamide obtained in Synthesis Example P1, and diluted so that the polymer concentration was 5% by mass and BCS was 20% by mass to obtain a composition P1 for forming a release layer.

[Comparative Example 1-1]

BCS and NMP were added to the reaction solution obtained in Comparative Synthesis Example HL1, and the mixture was diluted so that the polymer concentration was 5% by mass and BCS was 20% by mass to obtain a composition HL1 for forming a release layer.

[Comparative Example 1-2]

BCS and NMP were added to the reaction solution obtained in Comparative Synthesis Example HL2, and the mixture was diluted so that the polymer concentration was 5% by mass and BCS was 20% by mass to obtain a composition HL2 for forming a release layer.

[6] Preparation of release layer and resin substrate

[Example 2-1]

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

Then, the obtained coating film was heated at 80°C for 10 minutes using a hot plate, and then heated at 300°C for 30 minutes using an oven, the heating temperature was raised to 400°C (10°C/min), and further 400°C was heated for 30 minutes to form a release layer with a thickness of about 0.1 µm on the glass substrate to obtain a glass substrate with a release layer. Moreover, while raising the temperature, the glass substrate was heated within the oven, without taking it out of the oven.

The composition F1 for resin substrate formation was apply|coated on the peeling layer (resin thin film) on a glass substrate using the spin coater (condition: rotation speed 500 rpm about 10 second). Then, the obtained coating film was heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 5 μm on the release layer, and a resin substrate · A glass substrate with a release layer was obtained. Thereafter, the light transmittance was measured using an ultraviolet and visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation). As a result, the resin substrate exhibited transmittance of 80% or more at 400 nm.

[Example 2-2-2-5]

The release layer was formed in the same manner as in Example 2-1 except that the compositions L2 to L5 for forming a release layer obtained in Examples 1-2 to 1-5 were used instead of the composition L1 for forming a release layer obtained in Example 1-1. And the resin substrate was formed, and the glass substrate with a peeling layer and the resin substrate and the glass substrate with a peeling layer were produced.

[Example 2-6]

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

Next, the composition F2 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). Then, the obtained coating film is heated at 80° C. for 30 minutes using a hot plate, and then heated at 140° C. for 30 minutes using an oven, and the heating temperature is raised to 210° C. (10° C./min, hereinafter the same), 210 For 30 minutes at °C, the heating temperature is increased to 300 °C, the heating temperature is increased at 300 °C for 30 minutes, the heating temperature is raised to 400 °C, and heated at 400 °C for 60 minutes to form a resin substrate having a thickness of about 20 µm on the release layer, the resin A glass substrate with a substrate and a peeling layer was obtained. Moreover, while raising the temperature, the glass substrate was heated within the oven, without taking it out of the oven.

[Example 2-7]

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

Next, the composition F3 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). Then, the obtained coating film is heated at 80° C. for 30 minutes using a hot plate, and then heated at 140° C. for 30 minutes using an oven, and the heating temperature is raised to 210° C. (2° C./min, the same hereinafter), 210 For 30 minutes at °C, the heating temperature is increased to 300 °C, the heating temperature is increased at 300 °C for 30 minutes, the heating temperature is raised to 400 °C, and heated at 400 °C for 60 minutes to form a resin substrate having a thickness of about 20 µm on the release layer, and the resin A glass substrate with a substrate and a peeling layer was obtained. Moreover, while raising the temperature, the glass substrate was heated within the oven, without taking it out of the oven.

[Example 2-8]

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

[Example 2-9]

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

[Example 2-10]

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

[Example 2-11]

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

[Example 2-12]

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

[Example 2-13]

Using a spin coater (condition: rotational speed: about 30 seconds at 3,000 rpm), the composition P1 for forming a release layer obtained in Example 1-11 was applied onto a 100 mm×100 mm glass substrate as a glass substrate.

Then, the obtained coating film was heated at 80° C. for 10 minutes using a hot plate, and then heated at 300° C. for 30 minutes using an oven to form a release layer with a thickness of about 0.1 μm on the glass substrate, and the release layer was adhered. A glass substrate was obtained.

Next, the resin substrate was formed by the method similar to Example 2-1, and the resin substrate and the glass substrate with a peeling layer were obtained.

[Example 2-14]

Using the composition L8 for peeling layer formation obtained in Example 1-8, the peeling layer was formed by the method similar to Example 2-1, and the glass substrate with a peeling layer was obtained.

Thereafter, the composition F4 for forming a resin substrate was immediately applied on the release layer (resin thin film) on the glass substrate using a spin coater (condition: about 15 seconds at 200 rpm). The resulting coating film was heated at 80°C for 2 minutes using a hot plate, and then heated at 230°C for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, and the resin substrate and peeling A glass substrate with a layer was obtained. Thereafter, the light transmittance was measured using an ultraviolet and visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation). As a result, the resin substrate exhibited a transmittance of 80% or more at 400 nm.

[Example 2-15]

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

[Example 2-16]

Using the composition L8 for peeling layer formation obtained in Example 1-8, the peeling layer was formed by the method similar to Example 2-1, and the glass substrate with a peeling layer was obtained.

Thereafter, the composition F5 for forming a resin substrate was immediately applied on the release layer (resin thin film) on the glass substrate using a spin coater (condition: about 15 seconds at 200 rpm). The resulting coating film was heated at 80°C for 2 minutes using a hot plate, and then heated at 230°C for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, and the resin substrate and peeling A glass substrate with a layer was obtained. Thereafter, the light transmittance was measured using an ultraviolet and visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation). As a result, the resin substrate exhibited a transmittance of 80% or more at 400 nm.

[Example 2-17]

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

[Comparative Example 2-1]

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

[Comparative Example 2-2]

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

[Comparative Example 2-3]

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

[7] Evaluation of peelability

About the glass substrate with a peeling layer obtained in said Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2-3, the peelability of a peeling layer and a glass substrate about the glass substrate with a resin substrate and a peeling layer The peelability of a peeling layer and a resin substrate was confirmed by the following method.

<Cross cut test peelability evaluation of resin thin film>

The peeling layer on the glass substrate with a peeling layer obtained in Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2-3, and the peeling layer on the glass substrate with a resin substrate and a peeling layer, and a resin substrate were crosscut (horizontal) At intervals of 2 mm in length, the same hereinafter) was performed, and 25 checkerboard cuts were performed. That is, 25 checkers of 2 mm square were formed by this crosscut.

And the adhesive tape was affixed on this 25 grid-cut part, the tape was peeled off, and the grade of peeling was evaluated based on the following criteria (5B-0B, B, A, AA).

Moreover, the peeling force evaluation test was done using the glass substrate with a resin substrate and peeling layer produced in Examples 2-14 - 2-17 among the board|substrates from which all were peeled. The test method put a slit so that the resin substrate of a glass substrate with a resin substrate and a peeling layer might be penetrated to the back surface of a resin substrate with a cutter knife in the rectangle of 25 mm x 50 mm width, and produced the strip. Also, after attaching Cello Tape (registered trademark, Nichiban CT-24) on the produced strip, using Autograph AG-500N (manufactured by Shimadzu Corporation), at 90°C, that is, perpendicular to the surface of the substrate The peeling force was measured by peeling in the direction, and it was 100% peeling (all peeling), and the thing of less than 0.1 N/25 mm of peeling force was made into AAA.

Table 1 shows the above results.

<Judgment Criteria>

5B: 0% peeling (no peeling)

4B: less than 5% peeling

3B: peeling less than 5-15%

2B: Peeling less than 15-35%

1B: peeling less than 35-65%

0B: Peeling less than 65% to 80%

B: 80% to less than 95% peeling

A: Peeling of 95% to less than 100%

AA: 100% peeling (all peeling)

AAA: 100% peeling and peeling force less than 0.1N/25mm

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

As shown in Table 1, the peeling layer of Examples 2-1 to 2-17 was excellent in adhesiveness with a glass substrate, and it was confirmed that it peels off easily with a resin film. On the other hand, although the peeling layer of Comparative Examples 2-1 to 2-3 was excellent in adhesiveness with a glass substrate, it was confirmed that it is inferior in peelability with a resin substrate.

Claims (12)

gas and
A polyamic acid represented by the following formula (1), a polyamic acid represented by the following formula (2), a polyamic acid represented by the following formula (3) or a polyamide represented by the following formula (4), and an organic solvent A release layer formed from the composition for forming a release layer;
A laminate in which a resin substrate formed of a transparent resin selected from a polyimide resin, an acrylic resin or a cycloolefin polymer is sequentially laminated.

(Wherein, X ₁ represents a tetravalent aromatic group having no fluorine atom, X ₂ represents a tetravalent aromatic group having a fluorine atom, X ₃ represents a divalent aromatic group not having a fluorine atom, Y ₁ is a fluorine atom represents a divalent aromatic group having , Y ₂ represents a divalent aromatic group having no fluorine atom, and m represents a natural number.) The laminate according to claim 1, wherein Y ₁ is an aromatic group selected from the group consisting of the following formulas (5) to (9).

The laminate according to claim 1, wherein Y ₁ is an aromatic group represented by the following formula (10).

The laminate according to claim 1, wherein X ₂ is an aromatic group represented by the following formula (11) or (12).

The laminate according to claim 1, wherein X ₁ is an aromatic group containing 1 to 5 benzene rings. The laminate according to claim 1, wherein X ₃ is an aromatic group containing 1 to 5 benzene rings. The laminate according to claim 1, wherein Y ₂ is an aromatic group containing 1 to 5 benzene rings. The organic solvent according to claim 1, wherein the organic solvent contains at least one selected from amides represented by formula (S1), amides represented by formula (S2), and amides represented by formula (S3). A laminate made of

(Wherein, 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 represents a natural number.) The manufacturing method of the flexible electronic device provided with the resin substrate characterized by the above-mentioned via the laminated body in any one of Claims 1-8. It passes through the laminated body in any one of Claims 1-8, The manufacturing method of the touch panel sensor provided with the resin substrate characterized by the above-mentioned. delete delete