TW201708394A - Composition for forming release layer, and release layer - Google Patents

Abstract

Provided is a composition for forming a release layer that contains a polyamic acid obtained by introducing anchor groups at one or both ends of the polymer chain, and an organic solvent.

Description

Release layer forming composition and release layer

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 flexibility and performance such as thinning and weight reduction. Therefore, in order to replace the conventional bulky, fragile and inflexible glass substrate, it is required to use a lightweight flexible plastic substrate. In addition, in the case of new generation displays, the development of active full-color TFT display panels using lightweight flexible plastic substrates is required.

Therefore, some people have begun to investigate various methods of manufacturing electronic devices using a resin film as a substrate. For the new generation of displays, research has been conducted on a process that can be transferred to an existing TFT device. Patent Documents 1, 2 and 3 disclose that an amorphous germanium film layer is formed on a glass substrate, and after a plastic substrate is formed on the film layer, a laser is irradiated from the glass surface side by crystallization of the amorphous germanium. A method in which hydrogen gas strips a plastic substrate from a glass substrate.

Further, Patent Document 4 discloses disclosure using Patent Documents 1 to 3. The technique of adhering a peeled layer (referred to as "transfer layer" in the patent document 4) to a plastic film and completing a liquid crystal display device.

However, the methods disclosed in Patent Documents 1 to 4, in particular, the method disclosed in Patent Document 4, it is necessary to use a substrate having high light transmittance, in order to impart sufficient transparency to the substrate and to further release hydrogen contained in the amorphous germanium. Energy, but it is necessary to illuminate the laser light with a large amount of energy, thereby causing damage to the peeled layer. Further, since the laser treatment requires a long time and it is difficult to peel off the peeled layer having a large area, there is a problem that it is difficult to improve the productivity of the apparatus.

[Previous Technical Literature] [Patent Literature]

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

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

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

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

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a release layer which can be peeled off without causing damage to a resin substrate of a flexible electronic device, and the release layer.

In order to solve the above-mentioned problems, the inventors of the present invention have made a lot of research and have found that a polyglycine which is obtained by introducing an anchor group to either or both of the polymer chain ends, and an organic solvent composition. The present invention can be completed by forming a release layer having excellent adhesion to a substrate and moderate adhesion to a resin substrate used in a flexible electronic device and moderate peelability.

That is, the present invention provides a composition for forming a release layer comprising a polylysine obtained by introducing an anchor group to either or both of the polymer chain ends, and an organic solvent; The composition for forming a release layer according to 1, wherein the anchor group is a decyl group or a carboxylic acid group; 3. The composition for forming a release layer according to 1 or 2, wherein the polyamic acid is an aromatic diamine. a poly-proline which is obtained by reacting a diamine component with an acid dianhydride component containing an aromatic tetracarboxylic dianhydride; 4. A composition for forming a release layer according to 3, wherein the aromatic diamine comprises 1 to 5 An aromatic diamine of a benzene nucleus; 5. A composition for forming a release layer according to 3 or 4, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride comprising 1 to 5 benzene nucleuses; A release layer formed using the composition for forming a release layer according to any one of 1 to 5; 7. A manufacturer of a flexible electronic device including a resin substrate And a method of manufacturing the substrate, wherein the resin substrate is a substrate composed of polyimide.

By using the composition for forming a release layer of the present invention, a release layer having excellent adhesion to a substrate, moderate adhesion to a resin substrate, and appropriate peelability can be obtained with good reproducibility. Therefore, by using the composition for forming a release layer of the present invention, in the manufacturing process of the flexible electronic device, it is possible to prevent damage to the resin substrate formed on the substrate, or even the circuit provided thereon. The resin substrate is separated from the substrate by a circuit or the like. Therefore, the composition for forming a release layer of the present invention can contribute to the simplification of the manufacturing procedure of the flexible electronic device including the resin substrate, the improvement in yield thereof, and the like.

[Formation of the Invention]

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

The composition for forming a release layer of the present invention comprises a polylysine obtained by introducing an anchor group to either or both of the polymer chain ends, and an organic solvent. Here, the release layer in the present invention refers to a layer which is provided directly above the glass substrate for a predetermined purpose, and as a typical example thereof, in the manufacturing process of the flexible electronic device, in order to form a matrix, The resin substrate is defined between the resin substrates of the flexible electronic device composed of a resin such as sulfimine. In order to fix the resin substrate, the resin substrate can be easily peeled off from the substrate after the formation of an electronic circuit or the like on the resin substrate.

The polyaminic acid used in the present invention is not particularly limited as long as it has an anchor group at the terminal of the polymer chain, and the obtained polyamine can be obtained by reacting the diamine component with the tetracarboxylic dianhydride component. It is obtained by reacting an amine having an anchor group or an acid anhydride having an anchor group. That is, the polylysine obtained herein is one in which one or both of the molecular chain ends are blocked by a compound containing an anchor group described later.

Examples of such an anchor group include a carboxylic acid group, a decyl group (for example, an alkyl decyl group, an alkoxy decyl group, a vinyl decyl group, and an allyl fluorenyl group), a vinyl group, and a maleimide group. The phenolic hydroxyl group or the like is preferably a carboxylic acid group or a decyl group (especially a group selected from the group consisting of an alkoxy group, a vinyl group and an allyl group having at least one fluorenyl group bonded to a ruthenium atom). By using such an anchoring base, the difference between the flexible substrate and the skeleton used in the upper layer can be expressed, and the function of the obtained film as a peeling layer can be improved.

In the present invention, as long as an anchor group is present at any of the polymer chain ends of the polyamic acid, it is preferred that an anchor group is present at both ends of the polymer chain.

Further, in the polyamine and the anchoring group obtained from the diamine component and the tetracarboxylic dianhydride component, an alkyl group having a carbon number of about 1 to 10 and having a carbon number which does not significantly lower the peeling property or heat resistance may be present. A spacer such as a group or an aryl group may have an ether bond, a thioether bond, an ester bond or the like in these spacers.

Specific examples of the amine having an anchor group include 4-amine Phenoxy 3-methyl decane, 4-aminophenoxydimethyl vinyl decane, 4-aminophenoxymethyl divinyl decane, 4-aminophenoxy trivinyl decane, 4 -Aminophenoxydimethylallyl decane, 4-aminophenoxymethyldiallyldecane, 4-aminophenoxytriallyl decane, 4-aminophenoxyl Methyl phenyl decane, 4-aminophenoxymethyl diphenyl decane, 4-aminophenoxy triphenyl decane, 4-aminophenoxy trimethoxy decane, 4-aminophenoxy Dimethoxyvinyl decane, 4-aminophenoxymethoxydivinyl decane, 4-aminophenoxytrivinyl decane, 4-aminophenoxydimethoxyallyl Decane, 4-aminophenoxymethoxy diallyl decane, 4-aminophenoxydimethoxyphenyl decane, 4-aminophenoxymethoxy diphenyl decane, 4- Aminophenoxytriethoxydecane, 4-aminophenoxydiethoxyvinylnonane, 4-aminophenoxyethoxydivinylnonane, 4-aminophenoxytriethylene Baseline, 4-aminophenoxydiethoxyallyl decane, 4-aminophenoxy ethoxydiene Propyl decane, 4-aminophenoxydiethoxyphenyl decane, 4-aminophenoxyethoxy diphenyl decane, 3-aminophenoxy trimethyl decane, 3-amino group Phenoxydimethyl vinyl decane, 3-aminophenoxymethyl divinyl decane, 2-aminophenoxy trivinyl decane, 2-aminophenoxy trimethyl decane, 2- Aminophenoxy dimethyl vinyl decane, 2-aminophenoxymethyl divinyl decane, 2-aminophenoxy trivinyl decane, 3-aminopropyl triethyl decane, 3 -Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2- Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-ethoxycarbonyl-3- Aminopropyl three Methoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxyallylpropyltrisethylenetriamine, N-trimethoxyallylpropyl Triamethylenetriamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, etc., but are not limited thereto.

Specific examples of the acid anhydride having an anchor group include trimellitic anhydride, vinyl maleic anhydride, 4-vinylnaphthalene-1,2-dicarboxylic anhydride, maleic anhydride, and 2,3-dimethylmaleic anhydride. 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, and the like, but are not limited thereto.

Moreover, as a function of improving the function of the obtained film as a release layer, the diamine component and the acid dianhydride component used for producing a polyamic acid are preferably a diamine component containing an aromatic diamine. Polylysine obtained by reacting an acid dianhydride component of an aromatic tetracarboxylic dianhydride.

The aromatic diamine is not particularly limited as long as it has two amine groups in the molecule and has an aromatic ring, and 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-phenylene). 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-pair Phenylenediamine, m-xylenediamine, p-xylenediamine, 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5- a benzene nucleus such as bis(trifluoromethyl)benzene-1,2-diamine is a diamine; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine, 1,7- Naphthalene diamine, 1,8-naphthalenediamine, 2,3-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-biphenyldiamine, 2,2'-bis(trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diamino Diphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminobenzimidamide, 3,3'- Dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2- Bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3, 3-hexafluoropropane, 3,3'-diaminodiphenylarylene, 3,4'-diaminodiphenylarylene, 4,4'-diaminodiphenylarylene, 3, 3'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 3,3',5,5'-tetrafluorobiphenyl-4,4'-diamine, 4,4'-di a benzene nucleus such as amino octafluorobiphenyl, 2-(3-aminophenyl)-5-aminobenzimidazole or 2-(4-aminophenyl)-5-aminobenzoxazole 2 Diamine; 1,5-diaminoguanidine, 2,6-diaminoguanidine, 9,10-diaminoguanidine, 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 sulfide)benzene, 1,3-double (4 -aminophenyl sulfide) benzene, 1,4-bis(4-aminophenyl sulfide) benzene, 1,3-bis(3-aminophenyl fluorene) benzene, 1,3-double (4 -aminophenylhydrazine)benzene, 1,4-bis(4-aminophenylphosphonium)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, 4,4"-diamino-m-triphenyl, etc. The benzene nucleus is a diamine or the like, but is not limited thereto. These may be used alone or in combination of two or more. Further, in the present invention, the aromatic diamine is preferably one which does not contain an ether bond or an ester bond.

In view of the function of the release layer as a function of the release layer, it is preferably composed of an aromatic ring and a heteroaromatic ring which do not have a substituent such as a methyl group on the aromatic ring and the hetero ring to which it is condensed. Aromatic diamine. Specifically, p-phenylenediamine, m-phenylenediamine, 2-(3-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-5-amine are preferred. Benzooxazole, 4,4"-diamino-p-triphenyl, and the like.

The aromatic tetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has an aromatic ring, and 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, Indole-1,2,3,4-tetracarboxylic dianhydride, indole-1,2,5,6-tetracarboxylic dianhydride, indole-1,2,6,7-tetracarboxylic dianhydride, hydrazine- 1,2,7,8-tetracarboxylic dianhydride, indole-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 acid The dianhydride, phenanthrene-3,4,9,10-tetracarboxylic dianhydride, etc. are not limited thereto. These may be used alone or in combination of two or more.

Among them, from the viewpoint of improving the function of the film obtained as a release layer, the benzene nucleus is preferably one or two aromatic carboxylic dianhydrides. Specifically, the aromatic tetracarboxylic dianhydride represented by any one of the formulae (C1) to (C12) is more preferably a formula (C1) to (C7) or (C9) to (C11). Any of the aromatic tetracarboxylic dianhydrides shown.

Moreover, the diamine component used in the present invention may contain a diamine other than the aromatic diamine, and the tetracarboxylic dianhydride component used in the present invention may also be used in view of improving the flexibility and heat resistance of the release layer obtained. A tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride may be contained.

In the present invention, the amount of the 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, and still more preferably 95 mol%. More than or equal to the ear, preferably 100% by mole. Further, the amount of the aromatic tetracarboxylic dianhydride in the tetracarboxylic acid component is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol%. More than %, more preferably 95% by mole or more, and most preferably 100% by mole. By using such an amount, a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate peelability can be obtained with good reproducibility.

By reacting the diamine component described above with a tetracarboxylic dianhydride component, the obtained polyglycolic acid, an amine having an anchor group or an acid anhydride having an anchor group is reacted to obtain a release layer of the present invention. The composition contains a polylysine having an anchor group at the end of its polymer chain.

The organic solvent used in the 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-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-propoxy-N,N-dimethylpropanamide, 3-isopropyl Oxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-secondary butoxy-N,N-dimethylpropanamide, 3-tertiary butoxy-N,N-dimethylpropanamide, γ-butyrolactone, and the like. In addition, the organic solvent may be used alone or in combination of two or more.

Since the feed ratio of the diamine component to the tetracarboxylic dianhydride component is appropriately determined depending on the molecular weight and molecular weight distribution of the target, the type of the diamine, or the type of the tetracarboxylic dianhydride, it cannot be uniformly defined with respect to the tetracarboxylic acid. The dianhydride component 1 and the diamine component are about 0.7 to 1.3, preferably about 0.8 to 1.2, more preferably about 0.9 to 1.1.

Further, an amine having an anchor group and an acid anhydride having an anchor group The amount of the amine having an anchor group is from about 0.01 to about 0.6, preferably from about 0.05 to about 0.4, more preferably from about 0.1 to about 0.2, relative to the tetracarboxylic dianhydride component; or having an anchoring group relative to the diamine component. The acid anhydride is from about 0.01 to about 0.52, preferably from about 0.05 to about 0.32, more preferably from about 0.1 to about 0.2.

The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C. However, in order to prevent the obtained polyaminic acid from being imidized in the solution, the polyamido acid unit is maintained. The high content is preferably about 0 to 70 ° C, more preferably 0 to 60 ° C, and even more preferably about 0 to 50 ° C.

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

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

The composition for forming a release layer of the present invention contains an organic solvent. The organic solvent is the same as the specific example of the reaction solvent of the above reaction. Among them, a composition which can sufficiently dissolve poly-proline and easily prepare high uniformity is preferably N,N-dimethylformamide, N,N-dimethylacetamide, N-A. Base-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ-butyrolactone, more preferably N-methyl-2- Pyrrolidone.

Further, the solvent which cannot dissolve the polyamic acid when used alone is used, but it can be used for the preparation of the composition as long as it does not precipitate in the polyamic acid. In particular, it is possible to moderately blend ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2 -propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol -1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate A solvent having a low surface tension such as ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate. Accordingly, it is known that the uniformity of the coating film can be improved when applied to a substrate, and it can be suitably used in the present invention.

The method for preparing the composition for forming a release layer of the present invention is any. As a preferable example of the preparation method, a method of filtering a reaction solution containing the target polylysine obtained by the above-described method is exemplified. At this time, it is possible to adjust the concentration or the like, and if necessary, dilute or concentrate the filtrate. By using such a method, it is possible to reduce the incorporation of impurities which may cause deterioration of adhesion and peeling properties of the release layer produced from the obtained composition, and to effectively obtain a composition for forming a release layer. The solvent to be used for the dilution is not particularly limited, and specific examples thereof are the same as the specific examples of the reaction solvent of the above reaction. The solvent to be used for the dilution may be used singly or in combination of two or more.

The concentration of the polylysine in the composition for forming a release layer of the present invention depends on the thickness of the release layer to be produced, the viscosity of the composition, and the like. It is preferably set to be about 1 to 30% by mass, preferably about 1 to 20% by mass. By adjusting 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 acid dianhydride component as a raw material of the polyamic acid or adjusting the amount of the separated polylysine when it is dissolved in a solvent.

The viscosity of the composition for forming a release layer of the present invention is suitably set depending on the thickness of the release layer to be produced, and the like, in particular, for the purpose of obtaining a film having a thickness of about 0.05 to 5 μm with good reproducibility, usually at 25 ° C. It is 10~10,000mPa. s or so, preferably 20~5,000mPa. s or so.

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

Further, in addition to the polylysine and the organic solvent, the composition for forming a release layer of the present invention may contain a crosslinking agent or the like in order to enhance the film strength, for example.

By coating the above-described composition for forming a release layer of the present invention on a substrate, and heating the obtained coating film to thermally amidize the polyglycine, it is possible to obtain excellent adhesion to the substrate and to the resin. Adhesiveness consisting of a polyimide film with moderate adhesion and moderate peelability of the substrate Floor.

When such a 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 state in which a peeling layer is formed on a part of the surface of the substrate, a peeling layer is formed only in a predetermined range among the surfaces of the substrate, and the peeling layer is formed into a dot pattern, a line and a space pattern on the entire surface of the substrate surface. The shape of the pattern shape and so on. Further, in the present invention, the base system means a composition for forming a release layer of the present invention, and may be used in a manufacturer of a flexible electronic device or the like.

Examples of the substrate (substrate) include glass and plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, cellulose triacetate, ABS, AS, and lower). A terpene resin or the like, a metal (such as a ruthenium wafer), wood, paper, or slate, and the like, in particular, the release layer of the present invention has a sufficient adhesion to the glass, and is preferably glass. Further, the surface of the substrate can be composed of a single material, and can also be composed of two or more materials. As a state in which the surface of the substrate is composed of two or more kinds of materials, a certain range of the surface of the substrate is formed of a certain material, and the other surfaces are formed of other materials, and a certain material is used as a dot pattern on the surface of the substrate. Pattern shapes such as type, line and space patterns exist in other materials.

The method of applying the composition for forming a release layer of the present invention to a substrate is not particularly limited, and examples thereof include a casting coating method, a spin coating method, a knife coating method, a dip coating method, a roll coating method, and a rod. Coating method, die coating method, inkjet method, printing method (embossing, gravure, lithography, screen printing) Brush, etc.).

The heating temperature for the imidization is usually suitably determined in the range of 50 to 550 ° C, preferably more than 150 ° C to 510 ° C. By setting the heating temperature in this manner, the resulting film can be prevented from being weakened, and the ruthenium imidization reaction can be sufficiently performed. The heating time varies depending on the heating temperature, so it cannot be specified in general, and is usually 5 minutes to 5 hours. Further, the ruthenium amination rate may be in the range of 50 to 100%.

As a preferred example of the heating aspect in the present invention, after heating at 50 to 150 ° C for 5 minutes to 2 hours, the heating temperature is directly increased stepwise, and finally heated at 150 ° C to 510 ° C for 30 minutes to 4 minutes. Hours of the way. In particular, as a preferred example of the heating state, heating at 50 to 100 ° C for 5 minutes to 2 hours, heating at 100 ° C to 375 ° C for 5 minutes to 2 hours, and finally exceeding 375 ° C to 450 ° C Heat for 30 minutes to 4 hours. Further, as a further example of the heating state, heating at 50 to 150 ° C for 5 minutes to 2 hours, heating at 150 ° C to 350 ° C for 5 minutes to 2 hours, and then exceeding 350 ° C to 450 °C heating for 30 minutes to 4 hours, and finally heating at 450 ° C ~ 510 ° C for 30 minutes ~ 4 hours.

The means for heating may, for example, be a heating plate, an oven or the like. The heating environment may be under air or under an inert gas; or it may be under normal pressure or under reduced pressure.

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

The release layer described above has excellent adhesion to a substrate, particularly a glass substrate, and an appropriate adhesion to a resin substrate and moderate peelability. Therefore, the release layer of the present invention can be suitably used in a manufacturing process of a flexible electronic device, and the resin substrate and the circuit formed on the resin substrate are simultaneously peeled off from the substrate without causing damage to the resin substrate of the device. .

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

Using the composition for forming a release layer of the present invention, a release layer is formed on a glass substrate according to the above method. A resin solution for forming a resin substrate is applied onto the release layer, and the coating film is heated to form a resin substrate to which the release layer of the present invention is fixed to the glass substrate. At this time, in order to cover the entire peeling layer, the substrate is formed in an area larger than the area of the peeling layer. Examples of the resin substrate include a resin substrate composed of polyimine which is a typical resin substrate of a flexible electronic device, and a resin solution for forming the resin substrate may be a polyimine solution or a polyfluorene. Amino acid solution. The method of forming the resin substrate can be carried out by following a usual method.

Next, a desired circuit is formed on the resin substrate which is fixed to the substrate via the release layer of the present invention, and thereafter, for example, the resin substrate is cut along the peeling layer, and the resin substrate is peeled off from the peeling layer together with the loop, and the resin is removed. The substrate is separated from the substrate. At this time, a part of the substrate may also be cut along with the peeling layer.

In addition, it is reported in Japanese Laid-Open Patent Publication No. 2013-147599 that it has been widely used in the manufacture of high-intensity LEDs or three-dimensional semiconductor packages. The widely used laser lift-off method (LLO method) is applied to the manufacture of flexible displays. The LLO method is characterized in that light of a specific wavelength, for example, light having a wavelength of 308 nm, is irradiated from the glass substrate side on the surface opposite to the surface on which the circuit or the like is formed. The irradiated light can penetrate the glass substrate, and only the polymer (polyimine) in the vicinity of 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 release layer of the present invention can be used as a sacrificial layer of the LLO method because it has a characteristic that the above-mentioned LLO method can sufficiently absorb light of a specific wavelength (for example, 308 nm). Therefore, if a desired circuit is formed on the resin substrate which is fixed to the glass substrate by using the release layer formed by using the composition of the present invention, then the light of 308 nm is irradiated by the LLO method, and only the release layer absorbs the light. Light evaporates (sublimation). Thereby, the peeling layer is sacrificed (acting as a sacrificial layer), and the resin substrate can be selectively peeled off from the glass substrate.

[Examples]

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

[1] Abbreviation of compound

p-PDA: p-phenylenediamine

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

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

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

PMDA: pyromellitic dianhydride

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

LS-3280: 4-aminophenoxydimethyl vinyl decane

LS-3150: 3-Aminopropyltriethoxydecane

TMA: trimellitic anhydride

IHPA: isophthalaldehyde

NMP: N-methyl-2-pyrrolidone

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

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

[3] Synthesis of polymers <Synthesis Example F1 Synthesis of Polylysine (F1)>

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

<Synthesis Example F2 Synthesis of Polyuric Acid (F2)>

3.218 g (30 mmol) of p-PDA was dissolved in 88.2 g of NMP. To the obtained solution, 8.581 g (29 mmol) of BPDA was added, and the mixture was reacted at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 107,300 and a molecular weight distribution of 4.6.

<Synthesis Example L1 Synthesis of Polylysine (L1)>

2.66 g (24.6 mmol) of P-PDA and 0.18 g (0.6 mmol) of TFMB were dissolved in 90 g of NMP. To the obtained solution, 6.09 g (27.9 mmol) of PMDA was added, and after reacting for 24 hours at 23 ° C under a nitrogen atmosphere, 1.08 g (5.6 mmol) of LS-3280 was further added and reacted for 24 hours to give two polylysines. The terminal is introduced into a decyl group. The obtained polymer had an Mw of 62,700 and a molecular weight distribution of 2.7.

<Synthesis Example L2 Synthesis of Polylysine (L2)>

2.96 g (27.3 mmol) of p-PDA and 0.19 g (0.6 mmol) of TFMB were dissolved in 90 g of NMP. To the obtained solution, 6.34 g (29.1 mmol) of PMDA was added, and after reacting for 24 hours at 23 ° C under a nitrogen atmosphere, 0.52 g (2.3 mmol) of LS-3150 was further added and reacted for 24 hours to give two poly-proline acids. The terminal is introduced into a decyl group. The obtained polymer had a Mw of 51,100 and a molecular weight distribution of 2.8.

<Synthesis Example L3 Synthesis of Polylysine (L3)>

3.06 g (28.3 mmol) of p-PDA was dissolved in 90 g of NMP. To the obtained solution, 6.42 g (29.4 mmol) of PMDA was added, and after reacting for 24 hours at 23 ° C under a nitrogen atmosphere, 0.52 g (2.4 mmol) of LS-3150 was further added and reacted for 24 hours to give two polylysines. The terminal is introduced into a decyl group. The obtained polymer had a Mw of 47,800 and a molecular weight distribution of 2.8.

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

0.78 g (7.2 mmol) of p-PDA was dissolved in 17.6 g of NMP. 1.51 g (6.9 mmol) of PMDA was added to the obtained solution, and after reacting for 24 hours at 23 ° C under a nitrogen atmosphere, 0.11 g (0.3 mmol) of TMA was further added and reacted for 24 hours to introduce both ends of the polyamic acid.矽alkyl. The obtained polymer had Mw of 48,000 and a molecular weight distribution of 3.1.

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

3.18 g (0.059 mol) of 6FAP was dissolved in 70 g of NMP. To the resulting solution, 7.92 g (0.060 mol) of IHPA was added, and the mixture was reacted at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 107,300 and a molecular weight distribution of 4.6.

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

The reaction liquids obtained in Synthesis Examples F1 and F2 were used as the resin substrate-forming composition W and X, respectively.

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

To 10 g of the reaction liquid obtained in Synthesis Example L1, 6 g of NMP and 4 g of butyl cellosolve were added, and the mixture was stirred at room temperature for 24 hours to obtain a composition for forming a release layer.

[Examples 1-2 to 1-3]

A composition for forming a release layer was obtained in the same manner as in Example 1-1 except that the reaction liquid obtained in Synthesis Example L2 to L3 was used instead of the reaction liquid obtained in Synthesis Example L1.

[Examples 1-4]

To 10 g of the reaction liquid obtained in Synthesis Example L4, 9.4 g of NMP and 4.6 g of butyl cellosolve were added, and the mixture was stirred at room temperature for 24 hours to obtain a composition for forming a release layer.

[Comparative Example 1-1]

The reaction liquid obtained in Comparative Synthesis Example 1 was diluted with NMP to have a polymer concentration of 5 wt% to obtain a composition.

[6] Formation and evaluation of the peeling layer [Example 2-1]

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

Then, the obtained coating film was heated at 80 ° C for 10 minutes using a hot plate, and thereafter, heated at 300 ° C for 30 minutes using an oven, and the heating temperature was raised to 400 ° C (10 ° C / min), further at 400 The film was heated at ° C for 30 minutes to form a release layer having a thickness of about 0.1 μm on the glass substrate. Further, during the temperature rise, the substrate with the film attached was not taken out from the oven and heated in an oven.

[Example 2-2~2-4]

The same procedure as in Example 2-1 was carried out except that the composition for forming a release layer obtained in Examples 1-2 to 1-4 was used instead of the composition for forming a release layer obtained in Example 1-1. A release layer is formed.

[Comparative Example 2-1]

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

[7] Evaluation of peelability [Examples 3-1 to 3-4, Comparative Example 3-1]

The substrate was produced in such a manner that the combination of the release layer shown in Table 1 and the resin substrate was carried out according to the following method, and the peeling property was evaluated.

The peeling layer and the glass base obtained in Examples 2-1 to 2-4 were confirmed in advance. The peeling property of the board and the peeling property of this peeling layer (resin film) and a resin substrate. Further, as the resin substrate, a resin substrate made of polyimide is used.

First, by performing the cross-cutting of the peeling layer on the glass substrate with the peeling layer obtained in Examples 2-1 to 2-4 (1 mm in the vertical and horizontal directions, the same below), and the resin substrate. Resin substrate on the glass substrate of the peeling layer. The cross-cut of the peeling layer was cut and the block of 100 bars was cut. That is, by this cross cutting, 100 squares of 1 mm square are formed.

Thereafter, the tape was pasted to the 100-piece cut portion, and 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 3-4). Further, according to the above method, the same test (Comparative Examples 3 to 1) was carried out using the glass substrate with the resin film obtained in Comparative Example 2-1. The results are shown in Table 1.

5B: 0% peeling (no peeling)

4B: Less than 5% stripped

3B: 5~ less than 15% stripping

2B: 15~ less than 35% stripping

1B: 35~ less than 65% stripping

0B: 65%~ not up to 80% stripping

B: 80%~ not up to 95% stripping

A: 95%~ not up to 100% stripping

AA: 100% peeling (all peeling)

Further, the resins of Examples 3-1 to 3-4 and Comparative Example 3-1 The substrate was formed in the following manner.

The resin substrate forming composition W or X was applied onto a release layer (resin film) on a glass substrate by a bar coater (gap: 250 μm). Then, the obtained coating film was heated at 80 ° C for 10 minutes using a hot plate, and then heated at 140 ° C for 30 minutes using an oven to raise the heating temperature 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 heating 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 Polyimine substrate. During the temperature rise, the film-attached substrate was not taken out of the oven and heated in an oven.

As shown in Table 1, it was found that the release layer of the example was excellent in adhesion to a glass substrate and excellent in peelability from a resin substrate. On the other hand, the resin film of the comparative example can be understood that the adhesion between the glass substrate and the release layer is low, or when the adhesion is high, the resin layer is in close contact with the resin layer and is not peeled off at all.

Claims (8)

A composition for forming a release layer comprising a polyamic acid obtained by introducing an anchor group to either or both of polymer polymer terminal ends, and an organic solvent. The composition for forming a release layer according to claim 1, wherein the anchor group is a decyl group or a carboxylic acid group. The composition for forming a release layer according to claim 1 or 2, wherein the polyamic acid is a polymerization obtained by reacting a diamine component containing an aromatic diamine with an acid dianhydride component containing an aromatic tetracarboxylic dianhydride. Proline. The composition for forming a release layer according to claim 3, wherein the aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei. The composition for forming a release layer according to claim 3 or 4, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei. A release layer formed using the composition for forming a release layer according to any one of claims 1 to 5. A method of producing a flexible electronic device comprising a resin substrate, characterized in that the release layer of claim 6 is used. The manufacturing method of claim 7, wherein the resin substrate is a substrate composed of polyimide.