TWI758244B - Manufacturing method of flexible electronic device - Google Patents

Abstract

The present invention provides a composition for forming a release layer comprising a polyamic acid, an organosilane compound, and an organic solvent.

Description

Manufacturing method of flexible electronic device

The present invention relates to a composition for forming a release layer and a release layer.

In recent years, electronic devices have been required to provide functions such as flexibility, thinning, and weight reduction. Therefore, in order to replace the conventional glass substrate which is bulky, fragile and inflexible, it is required to use a light-weight flexible plastic substrate. In addition, for the new generation display, development of an active full-color TFT display panel using a lightweight flexible plastic substrate is required.

Therefore, some people have begun to study various methods of manufacturing electronic devices using resin films as substrates. For new-generation displays, some people have conducted research on manufacturing processes that can be converted to existing TFT equipment. Patent Documents 1, 2, and 3 disclose that an amorphous silicon thin film layer is formed on a glass substrate, and a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side, resulting in crystallization accompanying the crystallization of amorphous silicon. A method of peeling a plastic substrate from a glass substrate with hydrogen.

Further, Patent Document 4 discloses the disclosure using Patent Documents 1 to 3 The technique is a method in which a peeled layer (referred to as "transferred layer" in Patent Document 4) is adhered to a plastic film to complete a liquid crystal display device.

However, the methods disclosed in Patent Documents 1 to 4, and particularly the method disclosed in Patent Document 4, must use a substrate with high light transmittance, and in order to impart sufficient energy to penetrate the substrate and further release hydrogen contained in amorphous silicon Therefore, it is necessary to irradiate laser light with high energy, which causes damage to the peeled layer. Furthermore, the laser treatment requires a long time, and it is difficult to peel off the peeled layer having a large area, so there is a problem that it is difficult to improve the productivity of the device fabrication.

[Prior Art 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 has been made in view of the above-mentioned facts, and an object of the present invention is to provide a composition for forming a peeling layer and the peeling layer for forming a peeling layer that can be peeled off without causing damage to a resin substrate of a flexible electronic device.

The inventors of the present invention, as a result of repeated studies to solve the above-mentioned problems, have found that a composition comprising a polyamide acid, an organosilane compound, and an organic solvent can form a composition having excellent adhesion to the substrate and compatibility with the substrate. The present invention has been accomplished with a release layer having moderate adhesiveness and moderate releasability of a resin substrate used in a flexible electronic device.

That is, the present invention provides 1. a composition for forming a peeling layer, which comprises a polyamide acid, an organosilane compound, and an organic solvent; 2. the composition for forming a peeling layer according to 1, wherein the aforementioned organosilane The compound is an alkoxysilane compound containing a reactive functional group; 3. The release layer forming composition according to 1 or 2, wherein the above-mentioned polyamic acid is a diamine component containing an aromatic diamine and an aromatic tetramine-containing diamine component. A polyamide acid obtained by reacting an acid dianhydride of a carboxylic dianhydride; 4. The peeling layer forming composition according to 3, wherein the aforementioned aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei; 5 . The composition for forming a peeling layer according to 3 or 4, wherein the aforementioned aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride comprising 1 to 5 benzene nuclei; 6. according to any one of 3 to 5 A composition for forming a peeling layer, wherein the diamine component further comprises a diamine represented by formula (S);

(In formula (S), each L independently represents an alkanediyl group having 1 to 20 carbon atoms, an alkenediyl group having 2 to 20 carbon atoms, or an alkynediyl group having 2 to 20 carbon atoms, and each R' independently represents each other. alkyl group with 1 to 20 carbon atoms, alkenyl group with 2 to 20 carbon atoms or alkynyl group with 2 to 20 carbon atoms); 8. A method for manufacturing a flexible electronic device having a resin substrate, characterized by using the release layer as described in 7. 9. The manufacturing method as described in 8, wherein the resin substrate is made of polyimide substrate.

By using the composition for forming a peeling layer of the present invention, a peeling layer having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate releasability can be obtained with good reproducibility. Therefore, by using the composition for forming a peeling layer of the present invention, in the manufacturing process of the flexible electronic device, the resin substrate formed on the base body, the circuit provided thereon, etc. can be not damaged, together with the A circuit or the like separates the resin substrate from the base. Therefore, the composition for forming a peeling 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.

[Form of implementing the invention]

Hereinafter, the present invention will be described in more detail.

The composition for forming a release layer of the present invention contains a polyamic acid, an organosilane compound, and an organic solvent. Here, the peeling layer in the present invention refers to a layer provided just above the glass substrate for a predetermined purpose, and a typical example thereof includes, in the manufacturing process of flexible electronic devices, in order to separate the substrate, The resin substrates of the flexible electronic device made of resin such as imide are fixed and installed in a predetermined program, and the resin substrates are installed in order to form electronic circuits on the resin substrates. A release layer provided that can be easily peeled off from the base.

The polyamic acid used in the present invention is not particularly limited, and can be obtained by reacting a diamine component with a tetracarboxylic dianhydride component, but from the viewpoint of improving the function of the obtained film as a release layer, it is preferable to include an aromatic A polyamide acid obtained by reacting a diamine component of a family diamine with an acid dianhydride containing an aromatic tetracarboxylic dianhydride.

The aromatic diamine is not particularly limited as long as it has two amine groups in the molecule and an aromatic ring, but is preferably an aromatic diamine containing 1 to 5 benzene nuclei.

Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), and 1,2-diaminobenzene (o-phenylenediamine). amine), 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 Phenylenediamine, m-xylenediamine, p-xylenediamine, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5- Bis(trifluoromethyl) 1,2-naphthalene diamine, 1,3-naphthalene diamine, 1,4-naphthalene diamine, 1,5-naphthalene diamine Diamine, 1,6-naphthalenediamine, 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2,3-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-biphenyl Diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3 ,3'-Dicarboxy-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4 '-Diaminobenzidine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminobenzidine Diphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2- Bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amine phenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylene, 3,4'-diaminodiphenylene, 4 ,4'-Diaminodiphenylene, 3,3'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 3,3',5,5'-tetrafluorobiphenyl -4,4'-diamine, 4,4'-diaminooctafluorobiphenyl, 2-(3-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl) )-5-aminobenzoxazole and other benzene cores are two diamines; 1,5-diaminoanthracene, 2,6-diaminoanthracene, 9,10-diaminoanthracene, 1, 8-Diaminophenanthrene, 2,7-Diaminophenanthrene, 3,6-Diaminophenanthrene, 9,10-Diaminophenanthrene, 1,3-bis(3-aminophenyl)benzene, 1 ,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(3-aminophenyl)benzene 3-Aminophenyl sulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis (3-aminophenyl benzene) benzene, 1,3-bis(4-aminophenyl benzene) benzene, 1,4-bis(4-aminophenyl benzene) 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, 4,4"-diamino-p-triphenyl, 4 , The benzene nucleus of 4"-diamino-m-triphenyl etc. is 3-diamine etc., but it is not limited to these. These can be used alone or in combination of two or more.

Among them, from the viewpoint of improving the function of the obtained film as a release layer, it is preferably composed of only an aromatic ring and a heteroaromatic ring which do not have substituents such as methyl groups on the aromatic ring and the heterocyclic ring condensed therewith. Aromatic diamines. Specifically, p-phenylenediamine, m-phenylenediamine, 2-(3-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-5-amine are preferred benzoxazole, 4,4"-diamino-p-triphenyl, etc.

The aromatic tetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic acid anhydride moieties in the molecule and has an aromatic ring, but is preferably an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei.

Specific examples thereof 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 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 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 Acid dianhydride, etc., but not limited to these. These can be used alone or in combination of two or more.

Among them, from the viewpoint of enhancing the function of the obtained film as a release layer, an aromatic carboxylic dianhydride having one or two benzene cores is preferred. Specifically, aromatic tetracarboxylic dianhydrides represented by any one of formulae (C1) to (C12) are preferred, and those of formulae (C1) to (C7) and (C9) to (C11) are more preferred. Aromatic tetracarboxylic dianhydride represented by any one.

Moreover, from the viewpoint of improving the flexibility, heat resistance, etc. of the obtained release layer, the diamine component of the present invention may contain diamines other than aromatic diamines, and a preferable example thereof includes those represented by the formula (S). shown as diamine.

In formula (S), each L independently represents an alkanediyl group having 1 to 20 carbon atoms, an alkenediyl group having 2 to 20 carbon atoms, or an alkynediyl group having 2 to 20 carbon atoms, and each R' independently represents a carbon group. Alkyl with 1 to 20 carbons, alkenyl with 2 to 20 carbons or alkynyl with 2 to 20 carbons.

The carbon number of such an alkanediyl group, an alkenediyl group, and an alkynediyl group is preferably 10 or less, and more preferably 5 or less.

Among them, L is preferably an alkanediyl group, more preferably a -(CH ₂ ) _n - group (n= 1~10), more preferably -(CH ₂ ) _m - group (m=1~5), and if further consideration is given to the ease of obtaining, it is more preferably propylidene.

As a specific example of the alkyl group having 1 to 20 carbon atoms, any of linear, branched and cyclic may be used, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tertiary butyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. straight or branched chain with 1 to 20 carbon atoms Alkyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, dicyclobutyl, dicyclopentyl, dicyclohexyl, bicyclo Cyclic alkyl groups having 3 to 20 carbon atoms, such as heptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl, etc.

Specific examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, n-1-propenyl, n-2-propenyl, 1-methylvinyl, n-1-butenyl, n- 2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl , 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n-1-eicosenyl, etc.

Specific examples of the alkynyl group having 2 to 20 carbon atoms include ethyl Alkynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2- Propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl yl-n-butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n -1-pentadeynyl, n-1-eicosynyl, etc.

Among them, as R', if considering the balance between the solubility of the obtained polyamide acid to the organic solvent and the heat resistance of the obtained film, it is preferably an alkyl group with 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group .

Considering the ease of acquisition, the function of the obtained film as a release layer, and the like, the diamine represented by the formula (S) is preferably 1,3-bis(3-aminopropyl)tetramethyldisiloxane alkyl.

In addition, the diamine represented by formula (S) can be obtained as a commercial item, and can also be synthesized by a known method (for example, the method described in International Publication No. WO 2010/108785).

In the present invention, the amount of aromatic diamine in the diamine component is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% ear % or more. Moreover, especially when the diamine represented by formula (S) is used together with the aromatic diamine, the amount of the aromatic diamine in the total amount of the aromatic diamine and the diamine represented by the formula (S) is preferable It is 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 97 mol% or more. By adopting such an amount of use, a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate releasability can be obtained with good reproducibility.

In the present invention, the amount of aromatic tetracarboxylic dianhydride used in Among the total tetracarboxylic dianhydrides, it is preferably 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, and most preferably 100 mol% or more. Mol%.

By adopting such an amount of use, a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate releasability can be obtained with good reproducibility.

The polyamic acid contained in the composition for peeling layer formation of this invention can be obtained by making the diamine component demonstrated above and a tetracarboxylic dianhydride component react.

The organic solvent used in 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, and N-methyl-2-pyrrolidone. , N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 3-methoxy -N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-propoxy-N,N-dimethylpropionamide, 3-isopropyl Oxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 3-secondary butoxy-N,N-dimethylpropionamide, 3-tertiary butoxy-N,N-dimethylpropionamide, γ-butyrolactone, etc. Moreover, an organic solvent can be used individually by 1 type or in combination of 2 or more types.

Since the feeding ratio of the diamine component and the tetracarboxylic dianhydride component is appropriately determined in consideration of the target molecular weight and molecular weight distribution, the type of diamine or the type of tetracarboxylic dianhydride, etc., it cannot be specified uniformly. 1. The tetracarboxylic dianhydride component is about 0.7 to 1.3, preferably about 0.8 to 1.2.

The reaction temperature can 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, but the polyamic acid unit is maintained in order to prevent imidization of the obtained polyamic acid in the solution. The high content is preferably about 0~70℃, more preferably about 0~60℃, still more preferably about 0~50℃.

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

The weight average molecular weight of the polyamic acid thus obtained is usually about 5,000 to 500,000, and from the viewpoint of improving the function of the obtained film as a release layer, it is preferably about 10,000 to 200,000, more preferably about 30,000 to 150,000. In addition, in this invention, the weight average molecular weight is the polystyrene conversion value obtained by gel permeation chromatography (GPC).

The organosilane compound contained in the composition for forming a release layer of the present invention is not particularly limited, and specific examples thereof include alkoxysilane compounds such as dialkoxysilane compounds and trialkoxysilane compounds.

Moreover, it is preferable that the organosilane compound contained in the composition for peeling layer formation of this invention contains a reactive functional group from a viewpoint of improving the function as a peeling layer of the obtained film.

Specific examples of such reactive functional groups include vinyl groups, epoxy groups, styryl groups, methacryloyl groups, acryl groups, amine groups, isocyanurate groups, urea groups, and mercapto groups. , a thioether group, and an isocyanate group, among which, an epoxy group is preferred.

From the above facts, an alkoxysilane compound having an epoxy group can be mentioned as an example of a preferable organosilane compound in the present invention.

Specific examples of the organosilane compound having a reactive functional group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltri(2-methoxysilane) ethoxy)silane, vinylmethyldimethoxysilane, allyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxy Dipropylmethyldimethoxysilane, 3-glycidoxydipropyltrimethoxysilane, 3-glycidoxydipropylmethyldiethoxysilane, 3-glycidoxy Dipropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane Silane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3 -aminopropyltriethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyl Triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl triethene Ethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1, 4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonylethyl acid ester, N-benzyl-3-aminopropyltrimethoxysilane, N- Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -Bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, 4-aminophenoxydimethylvinyl Silane, 3-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethyl Oxysilane, etc., but not limited to these.

The ratio of the polyamide acid to the organosilane compound in the composition for forming a peeling layer of the present invention is about 0.001~0.2, preferably 0.005~ About 0.1, more preferably about 0.007~0.07.

The composition for forming a peeling layer of the present invention contains an organic solvent. As this organic solvent, the same as the specific example of the reaction solvent of the said reaction can be mentioned. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylacetamide yl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ-butyrolactone, more preferably N-methyl-2-pyrrole pyridone.

In addition, even if it is a solvent which cannot dissolve polyamic acid when used alone, it can be used for preparation of a composition as long as it is a range in which polyamic acid does not precipitate. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol can be blended moderately Alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetic acid Esters, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropane) oxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and other solvents with low surface tension. Thereby, 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 present invention.

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

The concentration of the polyamide in the composition for forming a peeling layer of the present invention is appropriately set in consideration of the thickness of the peeling layer to be produced, the viscosity of the composition, etc., and is usually about 1 to 30% by mass, preferably 1 to 20% by mass. mass% or so. By adjusting to such a concentration, a peeling layer having a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. The concentration of the polyamic acid can be adjusted by adjusting the amount of the diamine component and the tetracarboxylic dianhydride component as the raw material of the polyamic acid. Alternatively, it can be adjusted by adjusting the amount thereof when dissolving the isolated polyamic acid in a solvent.

In addition, the viscosity of the composition for forming a peeling layer of the present invention is appropriately set in consideration of the thickness of the peeling layer to be produced, and the like; in particular, when the purpose of obtaining a film with a thickness of about 0.05 to 5 μm with good reproducibility is made, usually, the viscosity is 25 μm. It is about 10-10,000 mPa·s at ℃, preferably about 20-5,000 mPa·s.

Here, the viscosity can be measured under the condition of the temperature of the composition of 25° C. with reference to, for example, the procedure described in JIS K7117-2 using a commercially available viscometer for measuring the viscosity of a liquid. Preferably, as the viscometer, a conical-plate type (cone-plate type) rotational viscometer is used, and preferably a viscometer of the same type, using 1°34'×R24 as a standard conical rotor, in the composition. Measured at a temperature of 25°C. As such a rotational viscometer, TVE-25L by Toki Sangyo Co., Ltd. is mentioned, for example.

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

By applying the above-described composition for forming a peeling layer of the present invention to a substrate, and heating the obtained coating film to thermally imidize the polyamic acid, it is possible to obtain excellent adhesion to the substrate and excellent adhesion to the resin. A release layer composed of a polyimide film with moderate adhesion to the substrate and moderate releasability.

When the peeling layer of the present invention is formed on the substrate, the peeling layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface. As a form of forming a peeling layer on a part of the surface of the substrate, there is a method in which only the surface of the substrate is formed. A form in which a peeling layer is formed in a predetermined range on the surface, a form in which the peeling layer is formed in a pattern shape such as a dot pattern, a line and space pattern, etc. on the entire surface of the substrate. In addition, in this invention, a base system means the thing which can apply|coat the composition for peeling layer formation of this invention to the surface, that is, can be used for the manufacture of a flexible electronic device etc..

Examples of substrates (substrates) include glass, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, cellulose triacetate, ABS, AS, polystyrene, etc.) Camphene resin, etc.), metal (silicon wafer, etc.), wood, paper, slate, etc., in particular, glass is preferable because the peeling layer of the present invention has sufficient adhesiveness to it. In addition, the surface of the base body may be composed of a single material, or may be composed of two or more materials. As an aspect in which the surface of the substrate is composed of two or more kinds of materials, there is an aspect in which a certain area of the substrate surface is composed of a certain material, and the rest of the surface is composed of other materials. Patterns such as patterns, line and space patterns, etc., exist in other materials, etc.

The method for applying the composition for forming a release layer of the present invention to the substrate is not particularly limited, and examples thereof include cast coating, spin coating, knife coating, dip coating, roll coating, bar coating, etc. Coating method, die coating method, ink jet method, printing method (relief, gravure, lithography, screen printing, etc.), etc.

The heating temperature for imidization is usually appropriately determined in the range of 50 to 550°C, and preferably over 150 to 510°C. By setting the heating temperature in this way, while preventing the weakening of the obtained film, it is possible to sufficiently The imidization reaction was carried out. The heating time varies depending on the heating temperature, so it cannot be specified uniformly, but it is usually 5 minutes to 5 hours. In addition, the imidization rate should just be in the range of 50 to 100%.

As a preferable example of the heating aspect in the present invention, after heating at 50°C to 150°C for 5 minutes to 2 hours, the heating temperature is directly increased in stages, and finally heated at more than 150°C to 510°C for 30 minutes to 4 hour method. It is particularly preferable to heat at 50~150°C for 5 minutes to 2 hours, then heat at over 150°C to 350°C for 5 minutes to 2 hours, and finally heat at over 350°C to 450°C for 30 minutes to 4 hours.

A hotplate, an oven, etc. are mentioned, for example as the apparatus used for heating. The heating environment may be under air or under inert gas, and may also be under normal pressure or reduced pressure.

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

The peeling layer described above has excellent adhesiveness with a substrate, particularly a glass substrate, and moderate adhesiveness and moderate releasability with a resin substrate. Therefore, the peeling layer of the present invention can be applied to a device in which the resin substrate and the circuits formed on the resin substrate are simultaneously peeled off from the substrate without causing damage to the resin substrate of the device in the manufacturing process of the flexible electronic device. .

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 peeling layer of the present invention, according to the above method method to form a peeling layer on the glass substrate. On the peeling layer, a resin solution for forming a resin substrate is applied, and the coating film is heated to form a resin substrate fixed to a glass substrate via the peeling layer of the present invention. At this time, in order to cover the whole peeling layer, the board|substrate is formed in the area larger than the area of the peeling layer. As the resin substrate, a resin substrate made of polyimide, which is a representative resin substrate of a flexible electronic device, can be mentioned; as a resin solution for forming the resin substrate, a polyimide solution or a polyimide Amino acid solution. The formation method of this resin substrate should just follow a usual method.

Next, a desired loop is formed on the resin substrate fixed to the base via the peeling layer of the present invention. After that, the resin substrate is cut along the peeling layer, for example, and the resin substrate is peeled from the peeling layer together with the loop, and the resin The substrate is separated from the base. At this time, a part of the base body may be cut together with the release layer.

Furthermore, Japanese Patent Laid-Open No. 2013-147599 reports that a laser lift-off method (LLO method), which has hitherto been widely used in the manufacture of high-brightness LEDs, three-dimensional semiconductor packages, and the like, is applied to the manufacture of flexible displays. The above-mentioned LLO method is characterized by irradiating a light beam of a specific wavelength, for example, a light beam having a wavelength of 308 nm, from the glass substrate side from the surface opposite to the surface on which the circuit and the like are formed. The irradiated light can penetrate the glass substrate, and only the polymer (polyimide) near the glass substrate absorbs the light and evaporates (sublimates). As a result, the resin substrate can be selectively peeled off from the glass substrate without affecting the circuit or the like provided on the resin substrate which determines the performance of the display.

The composition for forming a peeling layer of the present invention has the so-called The characteristics of the above-mentioned LLO method that can fully absorb light of a specific wavelength (eg, 308 nm) can be applied, so it can be used as a sacrificial layer of the LLO method. Therefore, if a desired circuit is formed on a resin substrate fixed to a glass base via a peeling layer formed by using the composition of the present invention, and then irradiated with light of 308 nm by the LLO method, only the peeling layer will absorb the Light evaporates (sublimates). Thereby, the said peeling layer becomes sacrificial (functions as a sacrificial layer), and can peel a resin substrate selectively from a glass substrate.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[1] Explanation of abbreviations

p-PDA: p-phenylenediamine

m-PDA: m-phenylenediamine

DATP: 4,4"-diamino-p-triphenyl

H-PAM: 1,3-bis(3-aminopropyl)tetramethyldisiloxane

6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

PMDA: pyromellitic dianhydride

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

NTCDA: Naphthalene-2,3,6,7-tetracarboxylic dianhydride

IHPA: Isophthalaldehyde

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

LS-4668: 3-Glycidoxypropyltriethoxysilane

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

The weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of the polymer were measured using a GPC apparatus manufactured by JASCO Corporation (column: OHpak SB803-HQ and OHpak SB804-HQ manufactured by Shodex; eluent: dimethyl Carboxamide/LiBr·H ₂ O (29.6mM)/H ₃ PO ₄ (29.6mM)/THF (0.1wt%); flow rate: 1.0mL/min; column temperature: 40°C; Mw: standard polyphenylene ethylene conversion value)

[3] Synthesis of polymers <Synthesis Example S1 Synthesis of Polyamic Acid (S1)>

20.261 g (187 mmol) p-PDA and 12.206 g (47 mmol) DATP were dissolved in 617.4 g NMP. The obtained solution was cooled to 15° C., 50.112 g (230 mmol) of PMDA was added thereto, and the temperature was raised to 50° C. under a nitrogen atmosphere for 48 hours to react. The Mw of the obtained polymer was 82,100 and the molecular weight distribution was 2.7.

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

3.218 g (30 mmol) of p-PDA were dissolved in 88.2 g of NMP. 8.581 g (29 mmol) of BPDA was added to the obtained solution, and it was made to react under nitrogen atmosphere at 23 degreeC for 24 hours. The Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.

<Synthesis example L1: Synthesis of polyamic acid (L1)>

10.078 g (93 mmol) p-PDA was dissolved in 220.0 g NMP. 19.922 g (91 mmol) of PMDA was added to the obtained solution, and it was made to react under nitrogen atmosphere at 23 degreeC for 24 hours. The Mw of the obtained polymer was 55,900, and the molecular weight distribution was 3.1.

<Synthesis Example L2 Polyamide (L2) Synthesis>

9.934 g (92 mmol) p-PDA and 0.042 g (93 mmol) H-PAM were dissolved in 220.0 g NMP. 19.835 g (91 mmol) of PMDA was added to the obtained solution, and it was made to react under nitrogen atmosphere at 23 degreeC for 24 hours. The Mw of the obtained polymer was 48,000, and the molecular weight distribution was 2.9.

<Synthesis example L3: Synthesis of polyamide (L3)>

1.474 g (14 mmol) p-PDA and 0.843 g (3 mmol) DATP and 0.042 g (0.2 mmol) H-PAM were dissolved in 34.0 g NMP. 3.641 g (17 mmol) of PMDA was added to the obtained solution, and it was made to react under nitrogen atmosphere at 23 degreeC for 24 hours. The Mw of the obtained polymer was 45,100, and the molecular weight distribution was 2.5.

<Synthesis Example L4 Synthesis of Polyamic Acid (L4)>

1.588 g (15 mmol) of p-PDA was dissolved in 35.2 g of NMP. To the obtained solution, 2.818 g (13 mmol) of PMDA and 0.393 g (2 mmol) of NTCDA were added, and the reaction was carried out at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 21,000, and the molecular weight distribution was 2.7.

<Synthesis Example L5 Synthesis of Polyamic Acid (L5)>

1.432 g (13 mmol) p-PDA and 0.159 g (2 mmol) m-PDA were dissolved in 35.2 g NMP. 3.209 g (15 mmol) of PMDA was added to the obtained solution, and it was made to react under nitrogen atmosphere at 23 degreeC for 24 hours. The Mw of the obtained polymer was 106,100, and the molecular weight distribution was 3.6.

<Comparative Synthesis Example 1 Synthesis of Polybenzoxazole Precursor (B1)>

3.18 g (0.059 moles) of 6FAP were dissolved in 70 g of NMP. 7.92 g (0.060 mol) of IHPA was added to the obtained solution, and it was made to react under nitrogen atmosphere at 23 degreeC for 24 hours. The Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.

[4] Preparation of resin substrate forming composition and silane solution [Preparation example 1, 2]

The reaction liquids obtained in Synthesis Examples S1 and S2 were used as the resin substrate-forming compositions W and X as they were, respectively.

[Preparation Example 3]

Using LS-4668 and NMP, a silane solution having a concentration of LS-4668 of 10 mass % was prepared.

[5] Preparation of the composition for forming a release layer [Example 1-1]

Using the reaction solution obtained in Synthesis Example L1, the silane solution obtained in Preparation Example 3, BCS and NMP, a polymer concentration of 5 mass %, LS-4668 concentration of 1 mass %, and BCS concentration of 20 mass % were obtained. A composition for forming a layer.

[Examples 1-2 to 1-5]

A composition for forming a peeling layer was obtained in the same manner as in Example 1-1, except that the reaction liquids obtained in Synthesis Examples L2 to L5 were used instead of the reaction liquids obtained in Synthesis Example L1, respectively.

[Example 1-6]

Using the reaction solution obtained in Synthesis Example L1, the silane solution obtained in Preparation Example 3, BCS and NMP, a polymer concentration of 5 mass %, LS-4668 concentration of 0.25 mass %, and BCS concentration of 20 mass % were obtained. A composition for forming a layer.

[Comparative Example 1]

The reaction solution obtained in Comparative Synthesis Example 1 was diluted with NMP so that the polymer concentration was 5 wt % to obtain a composition.

[6] Formation of peeling layer [Example 2-1]

Using a spin coater (conditions: number of rotations: 3,000 rpm, about 30 seconds), the composition for forming a release layer obtained in Example 1-1 was applied on On a 100 mm×100 mm glass substrate (the same below) as a glass substrate.

Then, the obtained coating film was heated at 80°C for 10 minutes using a hot plate, then heated at 300°C for 30 minutes using an oven, the heating temperature was raised to 400°C (10°C/min), and further heated at 400°C. The peeling layer with a thickness of about 0.1 μm was formed on the glass substrate by heating for 30 minutes. In addition, during the heating period, the film-attached substrate was heated in the oven without being taken out of the oven.

[Examples 2-2 to 2-6]

The same method as in Example 2-1 was carried out, except that the composition for forming a peeling layer obtained in Examples 1-2 to 1-6 was used instead of the composition for forming a peeling layer obtained in Example 1-1, respectively. A release layer is formed.

[Comparative Example 2]

A resin film was formed in the same manner as in Example 2-1, except that the composition obtained in Comparative Example 1 was used instead of the composition for forming a release layer obtained in Example 1-1.

[7] Evaluation of peelability [Examples 3-1 to 3-12, Comparative Example 3]

According to the following method, a board|substrate was produced so that it might become the combination of the peeling layer shown in Table 1, and a resin board|substrate, and the evaluation of peelability was performed.

The peelability of the peeling layers obtained in Examples 2-1 to 2-6 from the glass substrate and the peeling of the peeling layer (resin film) from the resin substrate were confirmed in advance sex. In addition, as the resin substrate, a resin substrate made of polyimide was used.

First, by performing cross-cutting of the peeling layers on the glass substrates with peeling layers obtained in Examples 2-1 to 2-6 (at a distance of 1 mm in length and breadth, the same below), and, by carrying out the resin substrate and peeling layers. For the cross-cutting of the resin substrate and the peeling layer on the glass substrate, 100-square block cutting is performed. That is, by this cross-cutting, 100 squares of 1 mm square are formed.

Then, the tape was affixed to the cut portion of the 100 blocks, the tape was peeled off, and the degree of peeling was evaluated based on the following criteria (5B to 0B, B, A, AA) (Examples 3-1 to 3-12). Moreover, according to the said method, using the glass substrate with the resin film obtained in the comparative example 2, the same test was performed (comparative example 3). The results are shown in Table 1.

5B: 0% peel (no peel)

4B: less than 5% peeling

3B: 5~ less than 15% peel off

2B: 15~ less than 35% peel off

1B: 35~ less than 65% peeling

0B: 65% to less than 80% peeling off

B: 80% ~ less than 95% peeling

A: 95% ~ less than 100% peeling

AA: 100% peel (full peel)

In addition, the resin substrates of Examples 3-1 to 3-12 and Comparative Example 3 were formed by the following methods.

Using a bar coater (gap: 250 μm), either of the resin substrate-forming compositions W or X was applied on the release layer (resin film) on the glass substrate. Then, the obtained coating film was heated at 80°C for 30 minutes using a hot plate, then heated at 140°C for 30 minutes using an oven, and the heating temperature was raised to 210°C (10°C/min, the same below), Heating at 210°C for 30 minutes, raising the heating temperature to 300°C, heating at 300°C for 30 minutes, then raising the heating temperature to 400°C, heating at 400°C for 60 minutes, and forming a thickness of about 20 μm on the peeling layer. Polyimide substrate. During the heating period, the film-attached substrate was heated in the oven without being taken out of the oven.

As shown in Table 1, it turned out that the peeling layer of an Example was excellent in the adhesiveness with a glass substrate, and was excellent in the peelability with a resin substrate. On the other hand, although the resin film of the comparative example was excellent in the peelability from the resin substrate, the adhesiveness to the glass was low, and peeling occurred in the cross-cut test.

Claims (8)

A method of manufacturing a flexible electronic device, which is a method of manufacturing a flexible electronic device including a resin substrate, wherein the resin substrate is fixed on a glass base via a peeling layer, and comprising: using a peeling layer forming composition , to form a peeling layer on the glass substrate, on the peeling layer, apply a resin solution for forming a resin substrate, and by heating the obtained coating film, the resin substrate is separated from the peeling layer and fixed on the glass substrate and forming a circuit on the resin substrate, peeling the resin substrate from the peeling layer together with the circuit, and separating the resin substrate and the glass substrate, and the peeling layer forming composition is substantially composed of a polymer The aramidic acid, the organosilane compound, and the organic solvent are formed, and in terms of mass ratio, the organosilane compound is 0.05-0.2 relative to the polyamide 1 . The method for manufacturing a flexible electronic device according to claim 1, wherein the organosilane compound is an alkoxysilane compound containing a reactive functional group. The method for producing a flexible electronic device according to claim 1 or 2, wherein the polyamic acid is obtained by reacting a diamine component containing an aromatic diamine and an acid dianhydride containing an aromatic tetracarboxylic dianhydride Polyamide. The manufacturing method of a flexible electronic device according to claim 3, wherein the aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei. The manufacturing method of a flexible electronic device according to claim 3, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic acid containing 1 to 5 benzene nuclei Dianhydride. The manufacturing method of a flexible electronic device according to claim 4, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei. The manufacturing method of a flexible electronic device according to claim 3, wherein the diamine component further comprises a diamine represented by formula (S);

(In formula (S), each L independently represents an alkanediyl group having 1 to 20 carbon atoms, an alkenediyl group having 2 to 20 carbon atoms, or an alkynediyl group having 2 to 20 carbon atoms, and each R' independently represents each other. Alkyl with 1 to 20 carbons, alkenyl with 2 to 20 carbons or alkynyl with 2 to 20 carbons). The manufacturing method of a flexible electronic device according to claim 1, wherein the resin substrate is a substrate made of polyimide.