TWI746611B - Composition for forming peeling layer, and laminate containing the same - Google Patents

Abstract

The present invention provides a composition for forming a release layer, which is characterized by comprising: a polyamide acid represented by the following formula (1), a polyamide acid represented by the following (2), and the following formula (3) The polyamide acid or the polyamide represented by the following formula (4), and an organic solvent.

(In the formula, X ₁ represents a tetravalent aromatic group without a fluorine atom, X ₂ represents a tetravalent aromatic group _{with a fluorine atom, and X 3} represents a divalent aromatic group without a fluorine atom. , Y ₁ represents a divalent aromatic group having a fluorine atom, Y ₂ represents a divalent aromatic group without a fluorine atom, and m represents a natural number)

Description

Composition for forming peeling layer, and laminate containing the same

The present invention relates to a composition for forming a peeling layer, and in detail, it is a composition for forming a peeling layer provided on a substrate.

In recent years, in addition to characteristics such as thinning and weight reduction, electronic devices are also required to provide functions such as flexibility. Therefore, it is required to use a lightweight flexible plastic substrate to replace the conventional heavy, fragile and inflexible glass substrate.

In particular, the new-generation display system requires the development of an active array type full-color TFT display panel that uses a lightweight, flexible plastic substrate (hereinafter referred to as a resin substrate). The technology of this new-generation display is expected to be applied to various fields such as flexible displays, flexible smartphones, and mirror displays.

Here, various reviews have been conducted on the manufacturing methods of electronic devices using resin films as substrates, and process reviews that can apply existing TFT display panel manufacturing equipment to new-generation displays are being conducted. In addition, with regard to touch panel displays, resin substrates for transparent electrodes of touch panels used in combination with display panels have already been used. Review the countermeasures used to efficiently manufacture the resin substrate. Generally speaking, resin substrates used in touch panels are the same as TFT display panels. Polyimide resin substrates or acrylic resin substrates and polyterephthalene resin substrates with the same degree of transparency as glass are used. Film substrates such as ethylene formate (PET) resin substrates and cycloolefin resin substrates.

For example, Patent Documents 1, 2 and 3 disclose a method of forming an amorphous silicon thin film layer on a glass substrate, forming a plastic substrate on the thin film layer, and then irradiating a laser from the glass surface side by being accompanied by The hydrogen generated by the crystallization of amorphous silicon peels the plastic substrate from the glass substrate. In addition, Patent Document 4 discloses a method that uses the techniques disclosed in Patent Documents 1 to 3 to attach a peeled layer (described as "transferred layer" in Patent Document 4) to a plastic film to complete a liquid crystal display device. .

However, the methods disclosed in Patent Documents 1 to 4, especially the method disclosed in Patent Document 4, have the following problems: in order to make the laser light penetrate, a substrate with high light transmittance must be used; The substrate and further release the hydrogen contained in the amorphous silicon must be irradiated with sufficient and relatively high-energy laser light; the laser light may cause damage to the peeling layer.

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

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-125929

[Patent Document 2] Japanese Patent Application Laid-Open No. 10-125931

[Patent Document 3] International Publication No. 2005/050754

[Patent Document 4] Japanese Patent Application Laid-Open No. 10-125930

The present invention is an invention in view of the above circumstances, and its object is to provide a composition for forming a release layer, which can provide a resin substrate (especially polyimide resin, acrylic resin, or cycloolefin polymer) that does not damage flexible electronic devices. It is a peeling layer that is peeled from a resin substrate formed by a resin or the like.

In order to solve the above-mentioned problems, the inventors have conducted intensive studies and found that a composition containing polyamide acid or polyamide and an organic solvent having a specific structure can impart excellent adhesion and adhesion to substrates such as glass substrates. The resin substrate used as a flexible electronic device is a peeling layer with moderate adhesion and moderate releasability, and thus the present invention has been completed.

That is, the present invention provides the following inventions.

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

(In the formula, X ₁ represents a tetravalent aromatic group without a fluorine atom, X ₂ represents a tetravalent aromatic group _{with a fluorine atom, and X 3} represents a divalent aromatic group without a fluorine atom. , Y ₁ represents a divalent aromatic group having a fluorine atom, Y ₂ represents a divalent aromatic group having no fluorine atom, and m represents a natural number).

2. The composition for forming a release layer according to the above 1, wherein the 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 according to the above 2, wherein the 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 above, wherein the above 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 above, wherein the X ₁ is an aromatic group containing 1 to 5 benzene rings.

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

8. The composition for forming a release layer according to any one of 1 to 7, the organic solvent, wherein the organic solvent contains amides selected from the group consisting of amides represented by formula (S1) and amides represented by formula (S2) At least one of amines and amides represented by formula (S3),

(In the formula, R ¹ and R ² independently represent an alkyl group having 1 to 10 carbons, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbons, and h represents a natural number).

9. A peeling layer formed using the composition for forming a peeling layer in any one of 1 to 8 above.

10. A method for manufacturing a flexible electronic device with a resin substrate, which is characterized by using the peeling layer of 9;

11. A method for manufacturing a touch panel sensor with a resin substrate, characterized by using the peeling layer of 9 above.

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

By using the composition for forming a release layer of the present invention, a film having excellent adhesion to the substrate and moderate adhesion and moderate releasability to the resin substrate can be obtained with good reproducibility. By using the composition of the present invention, in the manufacturing process of flexible electronic devices, the resin substrate formed on the substrate or the circuit provided on it will not be damaged, and the resin substrate can be combined with The circuit and the like from the substrate at the same time Carry out separation. Therefore, the composition for forming a release layer of the present invention can contribute to the simplification of the manufacturing process of the flexible electronic device provided with the resin substrate, the improvement of the yield, and the like.

[Best form to implement the invention]

The present invention will be described in more detail below.

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

In the present invention, the so-called peeling layer is a layer provided directly above the substrate (glass substrate, etc.) that will form the resin substrate. As a typical example, in the manufacturing process of flexible electronic devices, among the resin substrates of flexible electronic devices formed with the above-mentioned matrix, polyimide resin, acrylic resin, cycloolefin polymer resin, etc. In order to fix the resin substrate in a specified manufacturing process, and to form an electronic circuit or the like on the resin substrate, the release layer is provided to make the resin substrate easily peelable from the base.

In the above formulas (1) to (4), X ₁ represents a tetravalent aromatic group without a fluorine atom, X ₂ represents a tetravalent aromatic group _{with a fluorine atom, and X 3} represents a tetravalent aromatic group without a fluorine atom. Y ₁ represents a divalent aromatic group _{having a fluorine atom, Y 2} represents a divalent aromatic group having no fluorine atom, and m represents a natural number.

The above-mentioned X ₁ is preferably an aromatic group that does not have a fluorine atom and contains 1 to 5 benzene rings. Furthermore, the above-mentioned X ₁ system may also include one or both of an ester bond and an ether bond.

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

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

The above-mentioned Y ₂ is preferably an aromatic group that does not have a fluorine atom and contains 1 to 5 benzene rings, and more preferably contains 1 to 3 aromatic groups. Furthermore, the above-mentioned Y ₂ system may also include one or both of an ester bond and an ether bond.

The above-mentioned 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 more preferably a biphenyl group .

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

[Polyamide 1]

The polyamide acid represented by the above formula (1) is obtained by reacting an aromatic tetracarboxylic dianhydride having no fluorine atom and an aromatic diamine having a fluorine atom. Hereinafter, the aromatic tetracarboxylic dianhydride and aromatic diamine which can be used for synthesizing the polyamide acid represented by the above formula (1) will be described in detail.

In the present invention, the above-mentioned aromatic tetracarboxylic dianhydride is not particularly limited as long as it does not have a fluorine atom and has two dicarboxylic anhydride sites in the molecule. However, it is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene rings. Acid dianhydride is preferred.

Specific examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic acid dianhydride Acid dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride Anhydride, naphthalene-2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, Biphenyl-2,2',3,3'-tetracarboxylic dianhydride, biphenyl-2,3,3',4'-tetracarboxylic dianhydride, biphenyl-3,3',4 ,4'-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, phenanthrene-1,2,7,8-tetracarboxylic Acid 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 it is not limited to these. These systems may be used individually by 1 type, and may be used in combination of 2 or more types.

On the other hand, as the aromatic diamine, it is not particularly limited as long as it has a fluorine atom and has two amine groups directly bonded to the aromatic ring in the molecule, and it is an aromatic containing 1 to 5 benzene rings. Group diamines are preferred. Furthermore, those having a fluoroalkyl group or a perfluoroalkyl group are more preferable, and a perfluoroalkyl group is more preferable. Examples of the perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl, i-heptafluoropropyl, and the like.

Specific examples of the above-mentioned aromatic diamines include 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 2-trifluoromethylbenzene -1,4-diamine, 3,5-bis(trifluoromethyl)benzene-1,2-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diamino Benzene, 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'-diaminooctafluorobiphenyl, aromatic diamines represented by the following formulas (A1)~(A5), etc., but are not limited to these . These systems may be used individually by 1 type, and may be used in combination of 2 or more types.

[Polyamic acid 2]

The polyamide acid represented by the above formula (2) is obtained by reacting an aromatic tetracarboxylic dianhydride having a fluorine atom with an aromatic diamine having no fluorine atom. Hereinafter, the aromatic tetracarboxylic dianhydride and aromatic diamine which can be used for synthesizing the polyamide acid represented by the above formula (2) will be described in detail.

The aromatic tetracarboxylic dianhydride is not particularly limited as long as it has a fluorine atom and has two dicarboxylic anhydride sites in the molecule. Furthermore, those having a fluoroalkyl group or a perfluoroalkyl group are more preferable, and a perfluoroalkyl group is more preferable. Examples of the perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl, i-heptafluoropropyl, and the like.

As specific examples of the above-mentioned aromatic tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylene) diphthalic anhydride, N,N'-[2,2'-bis(tri Fluoromethyl)biphenyl-4,4'-diyl)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carbamide), 3,6-difluorocoke Melstone dianhydride, 3,6-bis(trifluoromethyl) pyromellitic dianhydride, 3,6-bis(trifluoromethoxy) pyromellitic dianhydride, 3-fluoropyromellitic acid Dianhydride, 3-trifluoromethyl pyromellitic dianhydride, 3-trifluoromethoxy pyromellitic dianhydride, 9,9-bis-(trifluoromethyl) xanthene tetracarboxylic dianhydride, 9-Phenyl-9-(trifluoromethyl)xanthenetetracarboxylic dianhydride, 3,3',5,5',6,6'-hexafluorooxy-4,4'-diphthalic acid Dianhydride and so on. These systems may be used individually by 1 type, and may be used in combination of 2 or more types.

On the other hand, the aromatic diamine is not particularly limited as long as it does not have a fluorine atom and has two amine groups directly bonded to the aromatic ring in the molecule, and it is an aromatic containing 1 to 5 benzene rings. Group diamines are preferred.

As a specific example of aromatic diamine, 1,4-diamino group Benzene (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-xylene Diamine, p-xylene diamine and other diamines containing one benzene ring; 1,2-naphthalene diamine, 1,3-naphthalene diamine, 1,4-naphthalene diamine, 1,5-naphthalene diamine Amine, 1,6-naphthalenediamine, 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2,3-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-biphenyldiamine Amine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3', 5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminobenzaniline, 3,3'-dichlorobenzidine, 3,3'- Dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamine Diphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 3,3'-diaminodiphenyl sulfene, Diamines containing 2 benzene rings such as 3,4'-diaminodiphenyl sulfene and 4,4'-diaminodiphenyl sulfene; 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-aminophenylsulfonic acid)benzene, 1,3-bis(4-aminophenylsulfonic acid)benzene, 1,4-bis(4 -Aminophenylsulfonic acid)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, etc. Containing 3 benzene rings Diamines, aromatic diamines represented by the following formulas (A6) to (A44), etc. are not limited to these. These systems may be used individually by 1 type, and may be used in combination of 2 or more types.

[Polyamic acid 3]

The polyamide acid represented by formula (3) is based on an aromatic having a fluorine atom It is obtained by reacting tetracarboxylic dianhydride with an aromatic diamine having a fluorine atom.

As the aromatic tetracarboxylic dianhydride, it is possible to use the same aromatic tetracarboxylic dianhydride having a fluorine atom as that which can be used to synthesize the polyamide represented by the above formula (2).

As the aromatic diamine, the same aromatic diamine having a fluorine atom that can be used for synthesizing the polyamide represented by the above formula (1) can be used.

[Polyamide]

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

In the present invention, the above-mentioned 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 derivatives thereof in the molecule, but it may contain 1 to 5 benzene rings, In particular, 1 to 2, and more preferably 2 aromatic dicarboxylic acids or derivatives thereof are preferred.

Specific examples of aromatic dicarboxylic acids or their derivatives include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, and 5-tert-butylisophthalic acid. Formic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 1, 6-Naphthalenedicarboxylic acid, 2,5-Naphthalenedicarboxylic acid, 2,6- Naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-onion dicarboxylic acid, 1,6-onion dicarboxylic acid, 2,6-onion dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid , 2,5-Biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 1,5-diphenyldicarboxylic acid Phenyl dicarboxylic acid, 4,4"-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'- Diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-bibenzyl dicarboxylic acid, 4,4 '-Stilbene dicarboxylic acid, 4,4'-diphenylacetylene dicarboxylic acid (4,4'-tolandicarboxylic acid), 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 4,4'-Dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylene dipropionic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid, 3,3' -[4,4'-(methylenebis-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)] dibutyric acid, (isopropylidene bis-p-phenylene dioxy) dibutyric acid, bis(p-carboxyl) Phenyl) Dimethyl silane and other dicarboxylic acids; isophthalic acid dichloride, terephthalic acid dichloride, 3-chloroisophthalic acid dichloride, 3-methoxyisophthalic acid dichloride Dichloride, 2,5-dichloroterephthalic acid dichloride, trichloroterephthalic acid dichloride, tetrachloroterephthalic acid dichloride, 1,4-naphthalene dicarboxylic acid dichloride, 2 ,6-Naphthalenedicarboxylic acid dichloride, 3,3'-biphenyldicarboxylic acid dichloride, 4,4'-biphenyldicarboxylic acid dichloride, 2,2'-biphenyldicarboxylic acid dichloride Halides of the above-mentioned various dicarboxylic acids, such as dichloride, 3,4'-biphenyl dicarboxylic acid dichloride, etc. These systems may be used singly or in combination of two or more. Various dicarboxylic acids can also be anhydrides structurers.

As the aromatic diamine, an aromatic diamine having the same fluorine atom as can be used to synthesize the polyamide acid represented by the above formula (1) can be used. amine.

The number of moles of all tetracarboxylic dianhydride components and the number of moles of all diamine components when synthesizing the polyamide acid represented by the above formula (1) and the polyamide acid represented by the above formula (2) The ratio is preferably tetracarboxylic acid component/diamine component=0.8 to 1.2. In addition, the ratio of the molar number of all dicarboxylic acid components to the molar number of all diamine components when synthesizing the polyamide represented by the above formula (4) is dicarboxylic acid component/diamine component=0.8~1.2 For better.

By reacting the aromatic diamine described above with the aromatic tetracarboxylic dianhydride, the polyamide acid represented by the formula (1) and the formula ( 2) The polyamide represented by the formula (3) and the polyamide represented by the formula (3). Furthermore, by reacting the above-mentioned aromatic diamine and aromatic dicarboxylic acid, the polyamide represented by formula (4) contained in the composition for forming a peeling layer according to the present invention is obtained.

[Organic solvents]

The organic solvent used in such a reaction is not particularly limited as long as it does not adversely affect the reaction. Specific examples thereof include m-cresol, 2-pyrrolidone, and N-methyl- 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 3-Methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-propoxy-N,N-dimethylpropanamide , 3-isopropoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-sec-butoxy-N,N-dimethyl Propyl propionamide, 3-tert-butoxy-N,N-dimethyl propionamide, γ-butyrolactone, etc. Still, the organic solvent system can be one alone or also Two or more types can be used in combination.

In particular, the organic solvent used in the reaction sufficiently dissolves the above-mentioned diamine, tetracarboxylic dianhydride, dicarboxylic acid, polyamide acid and polyamide, so it is selected from the amides represented by formula (S1) At least one of the amides represented by (S2) and the amides represented by formula (S3) is preferred.

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

Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and n-pentyl. Group, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. Among them, an alkyl group having 1 to 3 carbon atoms is preferred, and an alkyl group having 1 or 2 carbon atoms is more preferred.

The reaction temperature may be appropriately set within the range of the melting point to the boiling point of the solvent used, and is usually about 0 to 100°C. For example, to prevent the imidization of the obtained polyamide acid in the solution. To maintain a high content of polyamide units, it is preferably about 0 to 70°C, more preferably about 0 to 60°C, and still more preferably about 0 to 50°C.

Still, in the production of polyamides, polymerization catalysts can also be used in order to increase the efficiency of polymerization. Examples of the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid or their salts, and pyridine. The addition amount of the polymerization catalyst is generally preferably 2 mol% or less with respect to all monomers constituting the polyamide.

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

According to the method described above, the target reaction solution containing polyamide acid or polyamide can be obtained.

The weight average molecular weight of the polyamide acid or polyamide is preferably 5,000 to 1,000,000, more preferably 6,000 to 500,000, and more preferably 7,000 to 200,000 from the viewpoint of operability. Furthermore, in the present invention, the weight average molecular weight is the average molecular weight obtained by gel permeation chromatography (GPC) analysis and converted from standard polystyrene.

In the present invention, normally, after filtering the above-mentioned reaction solution, the filtrate or the solution obtained after dilution or concentration can be used as the composition for forming a peeling layer of the present invention. With such a method, it is possible not only to reduce the mixing of impurities that cause deterioration of the adhesion and peelability of the obtained peeling layer, but also to efficiently obtain the composition for forming the peeling layer. Moreover, after isolating polyamide acid or polyamide from the said reaction solution, it can melt|dissolve in a solvent again and use as the composition for peeling layer formation. As a solvent in this case, the organic solvent used in the reaction mentioned above, etc. are mentioned.

The solvent used in the dilution is not particularly limited, and specific examples thereof include those that are the same as the specific examples of the reaction solvent of the above-mentioned reaction. dilute The solvent used in the release can be used alone or in combination of two or more. Among them, because polyamide acid or polyamide is fully dissolved, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1 , 3-Dimethyl-2-imidazolinone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone is even more preferred.

In addition, even if it is a solvent that cannot dissolve polyamide acid or polyamide when used alone, as long as it is a range in which polyamide acid or polyamide does not precipitate, it can be mixed with the release layer forming composition of the present invention. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propane can be mixed appropriately Alcohol, 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, lactic acid Solvents with low surface tension such as ethyl ester, n-propyl lactate, n-butyl lactate, and isoamyl lactate. According to this, it is known that the uniformity of the coating film can be improved when it is applied to a substrate, and it can also be suitably used in the composition for forming a release layer of the present invention.

The concentration of polyamide 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 produced, the viscosity of the composition, etc., and is usually about 1 to 30% by mass. Preferably it is about 1-20 mass %. By setting such a concentration, a peeling layer with a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. Still, the concentration of polyamide acid or polyamide can be adjusted as the amount of diamine and tetracarboxylic dianhydride or dicarboxylic acid used as the raw materials. After filtering the above reaction solution, the filtrate is diluted It may be concentrated or adjusted by adjusting the amount when dissolving the isolated polyamide acid or polyamide in a solvent.

In addition, the viscosity of the release layer forming composition is appropriately set in consideration of the thickness of the release layer to be produced. In particular, when a film with a thickness of about 0.05 to 5 μm with good reproducibility is targeted, it is usually 25°C. 10~10,000mPa. s, preferably 20~5,000mPa. s around. Here, the viscosity can be measured using a commercially available viscometer for measuring the viscosity of a liquid, referring to, for example, the procedure described in JIS K7117-2, and measuring the temperature of the composition under the condition of 25°C. It is preferable to use a cone-and-plate rotary viscometer as a viscometer, and it is preferable to use the same type of viscometer, using 1°34'×R24 as a standard cone rotor, and The measurement is performed under the condition of the temperature of the composition at 25°C. As such a rotary viscometer. For example, TVE-25L manufactured by Toki Sangyo Co., Ltd. can be cited.

In addition, the composition for forming a release layer according to the present invention may contain components such as a crosslinking agent in addition to polyamide acid or polyamide and an organic solvent 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 resulting coating film, it can be obtained that it has excellent adhesion to the substrate and moderate adhesion to the resin substrate It is a peeling layer with good releasability and moderate releasability.

When the release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface. As a way to form a peeling layer on a part of the surface of the substrate, there are only The peeling layer is formed in a specified range on the surface of the substrate, and the peeling layer is formed into a pattern such as a dot pattern, a line and space pattern, etc., on the entire surface of the substrate. Style and so on. In addition, in the present invention, the so-called base system refers to those that can coat the release layer forming composition of the present invention on the surface thereof, which means that it can be used for manufacturers of flexible electronic devices and the like.

As the matrix (substrate), for example, glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetate cellulose, ABS, AS, and Camphene-based resins, etc.), metals (silicon wafers, etc.), wood, paper, slate, etc., especially since the peeling layer obtained from the composition for forming the peeling layer of the present invention has sufficient adhesion to them Therefore, glass is preferred. Furthermore, the surface of the substrate can be composed of a single material or more than 2 materials. As the surface of the substrate is composed of 2 or more materials, a certain range of the surface of the substrate is composed of a certain material, and the rest of the surface is composed of other materials, on the entire surface of the substrate A certain kind of material exists in other materials in pattern shapes such as dot pattern, line and space pattern, etc.

The coating method is not particularly limited, and examples include cast coating, spin coating, knife coating, dip coating, roll coating, rod coating, die coating, and inkjet methods. , Printing methods (relief, intaglio, lithography, screen printing, etc.), etc.

The heating temperature for imidization is usually in the range of 50 to 550°C to make an appropriate decision, preferably 200°C or higher, and more preferably Below 500°C. By setting the heating temperature in this way, the fragility of the obtained film can be prevented, and at the same time, the imidization reaction can proceed sufficiently. The heating time varies depending on the heating temperature, so it cannot be specified uniformly, and it is usually 5 minutes to 5 hours. In addition, the imidization rate may be in the range of 50 to 100%.

As a preferable example of the heating aspect in the present invention, it can be mentioned that after heating at 50~100℃ for 5 minutes~2 hours, the heating temperature is directly increased step by step, and the final heating is over 375℃~450℃ 30 minutes to 4 hours of technique. Especially after heating at 50~100℃ for 5 minutes~2 hours, heating at over 100℃~375℃ for 5 minutes~2 hours, and finally heating at over 375℃~450℃ for 30 minutes~4 hours .

Examples of the appliance system used for heating include a hot plate, an oven, and the like. The heating environment can be under air or under inert gas, and can be under normal pressure or under reduced pressure.

The thickness of the peeling layer is usually about 0.01-50μm. From the viewpoint of productivity, it is preferably about 0.05-20μm, and more preferably about 0.05-5μm. Adjust the thickness of the coating film before heating to achieve the desired thickness .

The peeling layer described above has excellent adhesion to a substrate (especially a glass substrate), and moderate adhesion and moderate releasability to the resin substrate. Therefore, the peeling layer system of the present invention can be applied to the flexible electronic device manufacturing process, without causing damage to the resin substrate of the device, the resin substrate and the circuit formed on the resin substrate, etc. at the same time The substrate is peeled off.

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

Using the composition for forming a peeling layer of the present invention, a peeling layer is formed on a glass substrate according to the aforementioned method. The resin solution for forming the resin substrate is applied on the release layer and the coating film is heated to form the resin substrate fixed to the glass substrate via the release layer related to the present invention. At this time, in order to cover the entire release layer, the resin substrate is formed with an area larger than the area of the release layer. As the above-mentioned resin substrate, a resin substrate made of polyimide resin, acrylic resin, or cycloolefin polymer resin, which is representative of resin substrates for flexible electronic devices, can be cited as the resin used to form it. The solution includes a polyimide solution, a polyamide acid solution, an acrylic polymer solution, and a cycloolefin polymer solution. The method of forming the resin substrate may be based on a common method. In addition, as a resin substrate system with high transparency, a resin substrate formed of an acrylic resin or a cycloolefin polymer resin can be exemplified. In particular, a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm is preferable.

Next, a desired circuit is formed on the resin substrate fixed to the base via the peeling layer related to the present invention, and then, for example, the resin substrate is cut along the peeling layer, and the resin substrate is removed from the peeling layer together with the circuit. Peeling is performed to separate the resin substrate from the base. At this time, it is also possible to cut a part of the substrate together with the release layer.

On the other hand, in the manufacture of flexible displays, it is reported that a laser lift-off method (LLO method), which has been widely used in the manufacture of high-brightness LEDs or three-dimensional semiconductor packages, can be used to remove polymers from glass carriers. The substrate is preferably peeled off (Japanese Patent Application Laid-Open No. 2013-147599). In the manufacture of flexible displays, a polymer substrate made of polyimide, etc. is placed on a glass carrier. Next, a circuit including electrodes, etc., is formed on the substrate, and finally it must be combined with the circuit, etc. Peel the substrate from the glass carrier. In this peeling step, the LLO method is used, that is, when light with a wavelength of 308 nm is irradiated on the glass carrier from the surface opposite to the surface on which the circuit etc. are formed, the light with this wavelength penetrates the glass carrier and only the polymer near the glass carrier The material (polyimide resin) absorbs this light and evaporates (sublimates). As a result, it is reported that it is possible to selectively perform peeling of the substrate from the glass carrier without affecting the circuit or the like provided on the substrate that determines the performance of the display.

The resin substrate is fixed to the base via the peeling layer related to the present invention to form a desired circuit. Then, when the LLO method is used, only the peeling layer absorbs the light and evaporates (sublimates). In other words, the peeling layer will become a protective layer (playing a role as a protective layer), and the substrate can be selectively peeled from the glass carrier. Since the composition for forming a release layer of the present invention has the characteristic of being able to sufficiently absorb light of a specific wavelength (for example, 308 nm), which is applicable to the LLO method, it can be used as an LLO method.

[Example]

Hereinafter, synthesis examples, comparative synthesis examples, examples, and comparative examples are given to explain the present invention in more detail, but the present invention is not limited to these examples.

[1] Abbreviation of compound

p-PDA: p-phenylenediamine

DDE: 4,4’-oxodiphenylamine

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)aniline]

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

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

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

a-ODPA: 3,4’-oxobisphthalic anhydride

6FDA: 4,4’-(hexafluoroisopropylene) 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-diox-1,3-di Hydroisobenzofuran-5-carbamide)

BTDA: 3,3’,4,4’-benzophenone tetracarboxylic dianhydride

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

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

MMA: methyl methacrylate

MAA: Methacrylic acid

HEMA: 2-hydroxyethyl methacrylate

AIBN: Azobisisobutyronitrile

CHMI: Cyclohexylmaleimide

EPOLEAD GT-401: Epoxidized butane tetracarboxylic acid 4-(3-cyclohexylmethyl) modified ε-caprolactone, manufactured by DAICEL (stock)

NMP: N-methyl-2-pyrrolidone

PGMEA: Propylene Glycol Monomethyl Ether Acetate

BCS: Butyl cellosolve

[2] Measuring method of weight average molecular weight and molecular weight distribution

The polymer's weight average molecular weight (hereinafter referred to as Mw) and molecular weight distribution were measured using a GPC device manufactured by JASCO Corporation (column: KD801 and KD805 manufactured by Shodex; eluate: dimethylformamide/LiBr.H) ₂ O (29.6 mM)/H ₃ PO ₄ (29.6 mM)/THF (0.1% by mass); flow rate: 1.0 mL/min; column temperature: 40° C.; Mw: standard polystyrene conversion value).

[3] Synthesis of polymers

The various polymers used in the examples and comparative examples were synthesized according to the following methods.

In addition, the polymer does not separate from the obtained reaction liquid containing the polymer, but the composition for forming a resin substrate or the composition for forming a release layer can be prepared by diluting the reaction liquid as described later.

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

MMA7.20g (0.0719mol), HEMA7.20g (0.0553mol), CHMI10.8g (0.0603mol), MAA4.32g (0.0502mol), AIBN2.46g (0.0150mol) are dissolved in PGMEA46.9g, by It was made to react at 60-100 degreeC for 20 hours, and the acrylic polymer solution (solid content concentration 40 mass %) was obtained. The Mn of the obtained acrylic polymer was 3,800 and the Mw was 7,300.

<Synthesis Example S2 Synthesis of Polyamide Acid (S2)>

20.3g (188mmol) of p-PDA and 12.2g (46.9mmol) of TPDA were dissolved in NMP617g, after cooling to 15°C, PMDA50.1g (230mmol) was added, and the reaction was carried out at 50°C for 48 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 82,100 and the molecular weight distribution was 2.7.

<Synthesis Example S3 Synthesis of Polyamide (S3)>

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

<Synthesis Example L1 Synthesis of Polyamide Acid (L1)>

Dissolve 1.74 g (8.70 mmol) of DDE in 14.0 g of NMP. Add 1.17 g (1.74 mmol) of CF3-BP-TMA and 6.09 g (6.96 mmol) of CF3-BP-TMA to the resulting solution, and let it react at 23°C for 24 hours under a nitrogen environment Time. The Mw of the obtained polymer was 19,600, and the molecular weight distribution was 2.1.

<Synthesis Example L2 Synthesis of Polyamide 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. for 24 hours in a nitrogen atmosphere. The Mw of the obtained polymer was 33,800, and the molecular weight distribution was 2.0.

<Synthesis Example L3 Synthesis of Polyamide (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. for 24 hours in a nitrogen atmosphere. The Mw of the obtained polymer was 56,600 and the molecular weight distribution was 1.8.

<Synthesis Example L4 Synthesis of Polyamide (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 allowed to react at 23° C. for 24 hours in a nitrogen environment. The Mw of the obtained polymer was 38,300 and the molecular weight distribution was 2.3.

<Synthesis Example L5 Synthesis of Polyamide 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 it was allowed to react at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer is 7,300, molecular weight distribution is 1.9.

<Synthesis Example L6: Synthesis of Polyamide (L6)>

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

<Synthesis Example L7 Synthesis of Polyamide 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 allowed to react at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 16,000 and the molecular weight distribution was 1.6.

<Synthesis Example L8: Synthesis of Polyamide (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 allowed to react at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 70,300, and the molecular weight distribution was 1.7.

<Synthesis Example L9 Synthesis of Polyamide Acid (L9)>

Dissolve 1.18 g (3.7 mmol) of TFMB and 0.93 g (8.6 mmol) of p-PDA in 35.2 g of NMP. Add 2.69 g (12.3 mmol) of PMDA to the obtained solution, and make it react at 23°C for 24 hours in a nitrogen environment Time. The Mw of the obtained polymer was 60,700, and the molecular weight distribution was 3.3.

<Synthesis Example L10 Synthesis of Polyamide Acid (L10)>

2.16 g (5.04 mmol) of 6FAPB was dissolved in 35.2 g of NMP. 2.64 g (4.94 mmol) of BPTME was added to the obtained solution, and it was allowed to react at 23° C. for 24 hours in a nitrogen environment. The Mw of the obtained polymer was 87,700, and the molecular weight distribution was 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. To the obtained solution, 1.26 g (4.51 mmol) of DPDOC was added, and the reaction was carried out at 23° C. for 24 hours in a nitrogen environment. After that, the obtained solution was poured into 500 mL of pure water. After filtering the obtained precipitate, it dried under reduced pressure at 70 degreeC for 24 hours, and obtained the target polyamide P1. The Mw of the obtained polymer was 88,200, and the molecular weight distribution was 1.8.

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

Dissolve FDA1.56g (4.47mmol) in NMP7.0g. 1.44 g (4.47 mmol) of BTDA was added to the obtained solution, and it was allowed to react at 23° C. for 24 hours in a nitrogen environment. The Mw of the obtained polymer was 67,300, and the molecular weight distribution was 2.0.

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

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

[4] Preparation of composition for resin substrate formation

The composition for forming a resin substrate was prepared according to the following method.

<Preparation example 1 Composition F1 for resin substrate formation>

To 10 g of the reaction liquid obtained in Synthesis Example S1, 0.61 g of GT-401 and 5.06 g of PGMEA were added, and the mixture was stirred at 23° C. for 24 hours to prepare composition F1 for forming a resin substrate.

<Preparation example 2 Composition F2 for forming resin substrate>

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

<Preparation example 3 Composition F3 for resin substrate formation>

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

<Preparation example 4 Composition F4 for forming resin substrate>

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

<Preparation Example 5 Composition F5 for Forming Resin Substrate>

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

[5] Preparation of composition for forming peeling layer [Example 1-1]

To the reaction solution obtained in Synthesis Example L1, BCS and NMP were added to dilute the polymer concentration to 5 mass% and BCS to 20 mass% to obtain a release layer forming composition L1.

[Examples 1-2~1-10]

Except that the reaction solutions obtained in Synthesis Examples L2 to L10 were used instead of the reaction solutions obtained in Synthesis Example L1, the same method as in Example 1-1 was used to obtain release layer forming compositions L2 to L10.

[Example 1-11]

To 0.5 g of the polyamide obtained in Synthesis Example P1, BCS and NMP were added and dissolved, and diluted so that the polymer concentration became 5 mass% and BCS 20 mass%, to obtain a release layer formation Composition P1.

[Comparative Example 1-1]

To the reaction solution obtained in Comparative Synthesis Example HL1, BCS and NMP were added, and the polymer concentration was diluted so that the polymer concentration was 5 mass% and BCS was 20 mass%, thereby obtaining a release layer forming composition HL1.

[Comparative Example 1-2]

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

[6] Production of peeling layer and resin substrate [Example 2-1]

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

Then, use a hot plate to heat the obtained coating film at 80°C for 10 minutes, and then use an oven to heat at 300°C for 30 minutes, and increase the heating temperature to 400°C (10°C/min), and then heat it at 400°C In 30 minutes, a peeling layer with a thickness of about 0.1 μm was formed on the glass substrate, and a glass substrate with a peeling layer was obtained. Still, during the temperature rise, the glass substrate is not taken out from the oven, but is heated in the oven.

Using a spin coater (condition: about 10 seconds at a rotation speed of 500 rpm), the composition F1 for forming a resin substrate was coated on the glass substrate On the release layer (resin film). Then, use a hot plate to heat the resulting coating film at 80°C for 10 minutes, and then use a hot plate to heat at 230°C for 30 minutes to form a resin substrate with a thickness of about 5 μm on the release layer, and obtain a resin substrate with peeling Layer of glass substrate. After that, using an ultraviolet visible spectrophotometer (Shimadzu Corporation UV-2600) to measure the light transmittance, the resin substrate showed a transmittance of 80% or more at 400 nm.

[Examples 2-2~2-5]

Except that the release layer forming composition L2 to L5 obtained in Examples 1-2 to 1-5 were used instead of the release layer forming composition L1 obtained in Example 1-1, the same as in Example 2-1 The method to form a peeling layer and a resin substrate to produce a glass substrate with a peeling layer and a glass substrate with a resin substrate ˙ peeling layer.

[Example 2-6]

The release layer was formed in the same manner as in Example 2-1 except that the release layer forming composition L6 obtained in Example 1-6 was used instead of the release layer forming composition L1 obtained in Example 1-1. , And obtain a glass substrate with a peeling layer.

Next, using a bar coater (gap: 250 μm), the resin substrate forming composition F2 was applied on the release layer (resin film) on the glass substrate obtained above. Then, use a hot plate to heat the obtained coating film at 80°C for 30 minutes, and then use an oven to heat at 140°C for 30 minutes to increase the heating temperature to 210°C (10°C/min, the same below), and Heating at 210°C for 30 minutes, raising the heating temperature to 300°C, then heating at 300°C for 30 minutes, raising the heating temperature to 400°C, and heating at 400°C for 60 minutes to form a resin substrate with a thickness of about 20μm on the release layer. Obtained a glass substrate with a resin substrate and a peeling layer. Still, during the temperature rise, the glass substrate is not taken out from the oven, but is heated in the oven.

[Example 2-7]

The release layer was formed in the same manner as in Example 2-1 except that the release layer forming composition L7 obtained in Example 1-7 was used instead of the release layer forming composition L1 obtained in Example 1-1 , And obtain a glass substrate with a peeling layer.

Next, using a bar coater (gap: 250 μm), the composition F3 for forming a resin substrate was applied on the release layer (resin film) on the glass substrate obtained above. Then, the obtained coating film was heated at 80°C for 30 minutes using a hot plate, and then heated at 140°C for 30 minutes in an oven, and the heating temperature was increased to 210°C (2°C/min, the same below), and then heated to 210°C. Heating at ℃ for 30 minutes, raising the heating temperature to 300°C, then heating at 300°C for 30 minutes, raising the heating temperature to 400°C, heating at 400°C for 60 minutes, forming a resin substrate with a thickness of about 20μm on the release layer, The result is a glass substrate with a resin substrate and a peeling layer. Still, during the temperature rise, the glass substrate is not taken out from the oven, but is heated in the oven.

[Example 2-8]

Except for using the release layer forming composition L8 obtained in Examples 1-8 In place of the release layer forming composition L1 obtained in Example 1-1, the release layer and the resin substrate were formed in the same manner as in Example 2-6 to produce a glass substrate with a release layer and a resin substrate. Substrate ˙ The glass substrate of the peeling layer.

[Example 2-9]

The release layer was formed in the same manner as in Example 2-7, except that the release layer forming composition L8 obtained in Example 1-8 was used instead of the release layer forming composition L1 obtained in Example 1-1. And a resin substrate to produce a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[Example 2-10]

The release layer was formed in the same manner as in Example 2-7, except that the release layer forming composition L9 obtained in Example 1-9 was used instead of the release layer forming composition L1 obtained in Example 1-1. And a resin substrate to produce a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[Example 2-11]

The release layer was formed in the same manner as in Example 2-6, except that the release layer forming composition L10 obtained in Example 1-10 was used instead of the release layer forming composition L1 obtained in Example 1-1. And resin substrate to produce glass substrate with peeling layer and resin substrate with peeling Separate glass substrate.

[Example 2-12]

The release layer was formed in the same manner as in Example 2-7, except that the release layer forming composition L10 obtained in Example 1-10 was used instead of the release layer forming composition L1 obtained in Example 1-1. And a resin substrate to produce a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[Example 2-13]

Using a spin coater (condition: about 30 seconds at a rotation speed of 3,000 rpm), the composition P1 for forming a peeling layer obtained in Example 1-11 was coated on a glass substrate of 100 mm×100 mm 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 in an oven to form a peeling layer with a thickness of about 0.1 μm on the glass substrate, thereby obtaining a glass with a peeling layer Substrate.

Next, a resin substrate was formed by the same method as in Example 2-1, and a glass substrate with a resin substrate ˙ peeling layer was obtained.

[Example 2-14]

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

Immediately after that, using a spin coater (condition: about 15 seconds at a rotation speed of 200 rpm), the resin substrate forming composition F4 was applied on the release layer (resin film) on the glass substrate. Use a hot plate to heat the obtained coating film at 80°C for 2 minutes, and then use a hot plate to heat at 230°C for 30 minutes to form a resin substrate with a thickness of about 3 μm on the release layer, and obtain a resin substrate with a release layer Glass base board. After that, using an ultraviolet visible spectrophotometer (Shimadzu Corporation UV-2600) to measure the light transmittance, the resin substrate showed a transmittance of 80% or more at 400 nm.

[Example 2-15]

The release layer was produced in the same manner as in Example 2-14, except that the release layer forming composition L9 obtained in Example 1-9 was used instead of the release layer forming composition L8 obtained in Example 1-8. And a resin substrate to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[Example 2-16]

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

Immediately after that, using a spin coater (condition: about 15 seconds at a rotation speed of 200 rpm), the resin substrate forming composition F5 was applied on the release layer (resin film) on the glass substrate. Use a hot plate to heat the obtained coating film at 80°C for 2 minutes, and then use a hot plate to heat at 230°C for 30 In minutes, a resin substrate with a thickness of about 3μm is formed on the peeling layer, and a glass substrate with a resin substrate ˙ peeling layer is obtained. After that, using an ultraviolet visible spectrophotometer (Shimadzu Corporation UV-2600) to measure the light transmittance, the resin substrate showed a transmittance of 80% or more at 400 nm.

[Example 2-17]

The release layer was produced in the same manner as in Example 2-16, except that the release layer forming composition L9 obtained in Example 1-9 was used instead of the release layer forming composition L8 obtained in Example 1-8. And a resin substrate to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[Comparative Example 2-1]

The release layer was formed in the same manner as in Example 2-1 except that the release layer forming composition HL1 obtained in Comparative Example 1-1 was used instead of the release layer forming composition L1 obtained in Example 1-1 And a resin substrate to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[Comparative Example 2-2]

The release layer was formed in the same manner as in Example 2-7, except that the release layer forming composition HL1 obtained in Comparative Example 1-1 was used instead of the release layer forming composition L1 obtained in Example 1-1. And a resin substrate to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate ˙ peeling layer Glass substrate.

[Comparative Example 2-3]

The release layer was formed in the same manner as in Example 2-1 except that the release layer forming composition HL2 obtained in Comparative Example 1-2 was used instead of the release layer forming composition L1 obtained in Example 1-1 And a resin substrate to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[7] Evaluation of peelability

The peelability of the peeling layer and the glass substrate was confirmed for the glass substrates with the peeling layer obtained in the foregoing Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2-3 by the following method; For glass substrates with resin substrates and peeling layers, check the peelability of the peeling layer and the resin substrate.

<Resin film peelability evaluation by cross-cut test>

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 the resin substrate is cross-cut (2mm in vertical and horizontal, the same below), and 25 blocks are cut. That is, by this cross cutting, 25 square meshes of 2 mm square are formed.

Then, attach the adhesive tape to the 25-block cut part, and peel off the tape to evaluate the degree of peeling based on the following benchmarks (5B~0B, B, A, AA).

Furthermore, among all the peeled substrates, the glass substrates with the resin substrates and peeling layers produced in Examples 2-14 to 2-17 were used to perform a peeling force evaluation test. The test method is to use a blade to cut through the back of the resin substrate to make the resin substrate of the glass substrate with the resin substrate ˙ peeling layer into a rectangle with a width of 25 mm × 50 mm to form a long strip. Furthermore, after pasting Nichiban CT-24 on the manufactured strip, using Autograph AG-500N (manufactured by Shimadzu Corporation), it was peeled off at 90 degrees with respect to the surface of the substrate, that is, in the vertical direction. The peeling force was measured, and 100% peeling (full peeling), and the peeling force was less than 0.1N/25mm as AAA.

The above results are shown in Table 1.

<Judgment Criteria>

5B: 0% peeling (no peeling)

4B: Less than 5% peel

3B: 5 to less than 15% peeling

2B: 15 to less than 35% peeling

1B: 35 to less than 65% peeling

0B: 65% to less than 80% peeling

B: 80% to less than 95% peeling

A: 95% to less than 100% peeling

AA: 100% peeling (all peeling)

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

As shown in Table 1, it was confirmed that the peeling layer system of Examples 2-1 to 2-17 had excellent adhesion to the glass substrate and easily peeled off from the resin film. On the other hand, it can be confirmed that the peeling layer of Comparative Examples 2-1 to 2-3 has excellent adhesion to the glass substrate, but poor peelability to the resin substrate.

Claims (10)

A laminate characterized by sequentially layering a base, a release layer, and a resin substrate, wherein the release layer is formed of a composition for forming a release layer, and the composition for forming a release layer includes the following formula (1 ), the polyamide represented by the following formula (2), the polyamide represented by the following formula (3), or the polyamide represented by the following formula (4), And an organic solvent; the resin substrate is formed of a transparent resin, and the transparent resin is selected from polyimide resin, acrylic resin or cycloolefin polymer;

(In the formula, X ₁ represents a tetravalent aromatic group without a fluorine atom, X ₂ represents a tetravalent aromatic group _{with a fluorine atom, and X 3} represents a divalent aromatic group without a fluorine atom. , Y ₁ represents a divalent aromatic group having a fluorine atom, Y ₂ represents a divalent aromatic group having no fluorine atom, and m represents a natural number). Such as the laminate of claim 1, wherein the above Y ₁ is an aromatic group selected from the group consisting of the following formulas (5) to (9),

The laminate of claim 1, wherein the above Y ₁ is an aromatic group represented by the following formula (10),

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

Such as the laminate of claim 1, wherein the above X ₁ is an aromatic group containing 1 to 5 benzene rings. Such as the laminate of claim 1, wherein the above-mentioned X ₃ is an aromatic group containing 1 to 5 benzene rings. Such as the laminate of claim 1, wherein the Y ₂ is an aromatic group containing 1 to 5 benzene rings. The layered body of claim 1, wherein the organic solvent is selected from the group consisting of amides represented by formula (S1), amides represented by formula (S2), and amides represented by formula (S3) At least one,

(In the formula, R ¹ and R ² independently represent an alkyl group having 1 to 10 carbons, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbons, and h represents a natural number). A method for manufacturing a flexible electronic device provided with a resin substrate, characterized by the laminated body of any one of claims 1-8. A method for manufacturing a touch panel sensor with a resin substrate, which is characterized by the laminated body of any one of claims 1-8.