TW201610036A - Composition for forming releasing layer - Google Patents

Abstract

The present invention provides a composition for forming a releasing layer that enables easy separation of a layer or layers from the releasing layer, said layer or layers being formed on top of the releasing layer, while preventing separation at the interface with a glass substrate by maintaining good adhesion to the glass substrate on which the releasing layer is provided. The present invention provides a composition for forming a releasing layer, which contains an organic solvent and a polyamic acid containing 50% by mole or more of a monomer unit represented by formula (1) and having a weight average molecular weight of 10,000 or more. In formula (1), X1 represents a tetravalent organic group; and Y1 represents a divalent group represented by formula (P).

Description

Release layer forming composition

The present invention relates to a composition for forming a release layer provided directly above a glass substrate.

In recent years, electronic devices have been required to impart performance such as bending function or thinning and weight reduction. Therefore, it is required to use a lightweight soft plastic substrate instead of a glass substrate that is heavy and fragile and cannot be bent. In addition, the new generation of displays requires the development of an active full-color TFT display panel using a lightweight, flexible plastic substrate.

For this reason, we began to review various methods of manufacturing electronic devices using resin films as substrates, and we are reviewing processes that can be converted to existing TFT devices to create new generation displays.

Patent Documents 1, 2 and 3 disclose that an amorphous germanium film layer is formed on a glass substrate, and after forming a plastic substrate on the film layer, a laser is irradiated from the glass surface side, and hydrogen gas generated by crystallization of the amorphous germanium is formed. A method of peeling a plastic substrate from a glass substrate.

Moreover, in the patent document 4, the peeling layer is described using the technique disclosed by the patent documents 1-3 (patent document 4, it is described as "transfer layer"). A method of adhering to a plastic film to complete 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 to pass the substrate, and to provide sufficient energy for releasing hydrogen contained in the amorphous germanium. Therefore, it is necessary to irradiate a large amount of laser light, which causes a problem of damage to the peeled layer. Further, since the laser treatment takes a long time and it is difficult to peel off the peeled layer having a large area, it is difficult to improve the productivity of the device production.

[Previous Technical Literature] [Patent Literature]

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

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

[Patent Document 3] WO2005/050754 pamphlet.

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

[Summary of the Invention]

Therefore, the object of the present invention is to solve the above problems.

Specifically, an object of the present invention is to provide a composition for forming a release layer for peeling without causing damage to a substrate suitable for a flexible electronic device.

Further, the object of the present invention is in addition to the above object, or the above object In addition, it is provided that the adhesion to the glass substrate provided with the release layer can be maintained, and no peeling occurs at the interface with the glass substrate, and the layer or layer group formed above the release layer can be easily formed by the release layer. The composition for the release layer is formed by peeling.

The inventors have found the following invention. That is, the inventors have unexpectedly found that when a composition having a monomer unit having a specific structure of 50 mol% or more and a weight average molecular weight of a certain value or more is used to form a release layer, The layer has a property of being applied to a substrate suitable for a flexible electronic device or the like without causing damage and allowing peeling. This layer can maintain the adhesion to the glass substrate provided with the release layer, and does not peel off at the interface with the glass substrate, and is formed on a layer or layer formed on the upper side of the release layer opposite to the glass substrate. The group can be simply peeled off by the peeling layer. The present invention is based on the invention of this insight.

<1> A composition for forming a release layer, which comprises a monomeric unit represented by the following formula (1): 50 mol% or more, and a polyamine and an organic solvent having a weight average molecular weight of 10,000 or more. [wherein, X ¹ represents a tetravalent organic group, and Y ¹ represents a divalent group represented by the following formula (P): (wherein R represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and m represents an integer of 0 to 4, and r represents an integer of 1 to 4)].

<2> In the above <1>, the Y ¹ may be a divalent group represented by any one of the following formulae (P1) to (P3).

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, m1, m2, m3 , m4, m5, and m6 may be the same or different, indicating an integer from 0 to 4.

<3> In the above <2>, the Y ¹ may contain at least a divalent group represented by the formula (P1).

<4> In any one of <1> to <3>, the polyamic acid may further contain a monomer unit represented by the following formula (2).

[wherein X ¹ is as defined in the above <1>, and Y ² represents a group represented by the following formula (P4): (wherein R ⁷ and R ⁸ may be the same or different and each represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group; and R' represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or Phenyl group, l represents an integer of 0 to 4, and m is as defined in the above <1>).

<5> In any one of <1> to <4>, X ¹ may be a tetravalent aromatic group.

<6> In the above <5>, the tetravalent aromatic group may be at least one selected from the group consisting of a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton.

<7> In any one of <1> to <6>, the organic solvent may be a solvent represented by the following formula (A) or (B).

(wherein R ^a and R ^b may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and h represents a natural number).

<8> In any one of <1> to <7>, the content of the monomer unit represented by the above formula (1) in the polyamic acid may be 60 mol%. on.

<9> In any one of the above <1> to <8>, the composition for forming a release layer of the present invention may be a layer for forming a release layer provided directly above the glass substrate.

<10> A release layer formed on a release layer formed between the flexible substrate and the base substrate of the flexible electronic device, which is produced by using the composition for forming a release layer of any one of <1> to <9> .

<11> A substrate structure which is applied to a substrate structure of a flexible electronic device, comprising: a base substrate; and a peeling layer covering the base substrate in a region of 1 or 2 or more, and by the above <1>~ <9> a release layer formed of the composition for forming a release layer; and a flexible substrate covering the base substrate and the release layer; and a adhesion force between the flexible substrate and the release layer is larger than the separation layer and the foundation The tightness of the substrate.

<12> In the above <11>, the base substrate may be glass-containing.

<13> A method for producing a release layer, which is the composition for forming a release layer according to any one of <1> to <9>. In a preferred embodiment, the method for producing the release layer includes a step of applying the resin composition for forming a release layer to a substrate and heating the substrate.

<14> A manufacturing method, which is applied to a method of fabricating a substrate structure of a flexible electronic device, comprising the steps of: a step of preparing a base substrate; a step of forming a release layer of the base substrate in a region of 1 or 2 or more by using the composition for forming a release layer of any one of <1> to <9>; and the base substrate a step of forming a flexible substrate on the release layer; and a adhesion between the flexible substrate and the release layer is greater than a adhesion between the release layer and the base substrate.

The above problems can be solved by the present invention.

Specifically, according to the present invention, it is possible to provide a composition for forming a release layer which can be peeled off without causing damage to a substrate which is applied to a flexible electronic device or the like.

Moreover, according to the present invention, in addition to the above object or the above object, it is possible to provide adhesion to a glass substrate provided with a release layer, and to prevent peeling from occurring at the interface with the glass substrate, and to form a specific release layer. The upper layer or the layer group can be formed by simply peeling off the release layer to form the composition for the release layer.

[Formation of the Invention]

The invention is described in detail below.

Release layer forming composition

The composition for forming a release layer of the present invention is as described above, and it contains: 50% by mole or more of the monomeric polyamine acid represented by the formula (1), and a polyglycine having a weight average molecular weight of 10,000 or more and an organic solvent.

Further, in the above formula (1), X ¹ represents a tetravalent organic group, and Y ¹ represents a divalent group represented by the following formula (P).

Further, in the formula (P), R represents F, Cl, or an alkyl group having 1 to 3 carbon atoms or a phenyl group, and preferably represents F and Cl. Similarly, in the above formula (P), m represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0. Further, in the above formula (P), r represents an integer of 1 to 3.

The alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. Preferably, the alkyl group having 1 to 3 carbon atoms is a methyl group, and more preferably a methyl group.

The weight average molecular weight of the polyamic acid having the monomer unit represented by the formula (1) used in the present invention must be 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, still more preferably 30,000. on. In addition, the upper limit of the weight average molecular weight of the polyamic acid to be used in the present invention is usually 2,000,000 or less. However, when it is considered that the viscosity of the resin composition is too high or the reproducibility is good, a resin film having high flexibility is obtained. It is preferably 1,000,000 or less, more preferably 200,000 or less.

The polyamic acid used in the present invention contains 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and even more preferably 90 mol. The monomer unit represented by the formula (1) above the ear %. By using the polyaminic acid in such a monomer unit content, a resin film having characteristics suitable for a release film can be obtained with good reproducibility.

According to a preferred aspect of the present invention, the polylysine contained in the composition for forming a release layer of the present invention is a polymer composed only of the monomer unit represented by the formula (1), that is, a formula ( 1) The monomer unit represented contains 100 mol% of the polymer. In this case, the monomer unit in the polyamic acid may be one specific or two or more types as long as it is represented by the formula (1). In the latter case, the number of monomer units of the formula (1) contained in the polyamic acid is preferably from 2 to 4, more preferably from 2 to 3.

In the present invention, the group represented by the formula (P) preferably contains a divalent group represented by any one of the formulae (P1) to (P3), and more preferably contains a divalent group represented by the formula (P1) or (P3). More preferably, it contains a divalent group represented by the formula (P3).

In the above formula (P1), formula (P2) and formula (P3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, and represent F, Cl, and carbon number 1-3. The alkyl group or the phenyl group preferably represents F or Cl.

Similarly, in this equation, m1, m2, m3, m4, m5, and m6 may be the same or different, and represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, especially excellent. To indicate 0.

The polyamic acid used in the present invention may contain other monomer units in addition to the monomer unit represented by the formula (1). The content of such other monomer units must be less than 50% by mole, preferably less than 40% by mole, more preferably less than 30% by mole, and even more preferably less than 20% by mole. More preferably, it is less than 10% by mole.

Such other monomer unit may, for example, be a monomer unit of the formula (2).

In the formula (2), X ¹ represents a tetravalent organic group, and Y ² represents a group represented by the above formula (P4).

In the formula (P4), R ⁷ and R ⁸ may be the same or different and each represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. R ⁷ preferably represents F or Cl. R ⁸ preferably represents F or Cl.

R' represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

Further, l and m may be the same or different, and represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0.

Such other monomer units, in addition to the monomer unit of the above formula (2), may be exemplified by o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-methyl-1,4-benzene. Diamine, 5-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2-(three Fluoromethyl)-1,3-phenylenediamine and 4-(trifluoromethyl)-1,3-phenylenediamine, benzidine, 2,2'-dimethylbenzidine, 3,3'-di Methyl benzidine, 2,3'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,3' - bis(trifluoromethyl)benzidine, 4,4'-diphenyl ether, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminobenzimidazole An amine such as benzanilide, 5-amino-2-(3-aminophenyl)-1H-benzimidazole, 9,9-bis(4-aminophenyl)anthracene or trimellitic anhydride (PMDA), 2,3,6,7-naphthalene A structure derived from an acid dianhydride such as carboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, 3,3' or 4,4'-benzophenonetetracarboxylic anhydride.

In the formulae (1) and (2), as described above, X ¹ represents a tetravalent organic group, and preferably a tetravalent aromatic group.

The tetravalent aromatic group which can be used for X ¹ can be produced by using the aromatic tetracarboxylic dianhydride as follows when producing the polyamic acid used in the present invention.

That is, trimellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2 ,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dihydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylate Acid dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis (3,4- Dicarboxyphenoxy)diphenylpropane dihydrate, 4,4'-hexafluoroisopropylidene dianhydride, p-phenylenediphthalic dianhydride, 2,2-bis-(( 3,4-Dicarboxyphenyl)-hexafluoropropane di-anhydrous, 9,9-bis(3,4-dicarboxyphenyl)phosphonium anhydrate, 9,9'-bis[4-(3,4 -Dicarboxyphenoxy)phenyl]anthracene anhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, p-terphenyl--3,4,3',4'-tetracarboxylic dianhydride , meta terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldioxine Alkanedihydrate, 1-(2,3-dicarboxyphenyl)-3-(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldioxine Alkanedihydrate, 3,3',4,4'-hydroquinone dibenzoate tetracarboxylic dianhydride, 2,2'-bis(4-hydroxyphenyl)propane dibenzoate-3, 3', 4, 4'-tetracarboxylic acid, and the like.

Preferably, the preferred aromatic tetracarboxylic dianhydride is selected from the group consisting of the following compounds.

(In the formula, R ₃ is a divalent organic group having at least one aromatic ring, preferably a phenyl group, a biphenyl group, or a group having a naphthalene skeleton).

Therefore, according to a preferred aspect of the present invention, the tetravalent aromatic group which X ¹ may have may have any one of a benzene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a terphenyl skeleton, and more preferably has a benzene skeleton. Any one of a naphthalene skeleton and a biphenyl skeleton is more preferably a benzene skeleton or a biphenyl skeleton.

According to a preferred aspect of the present invention, the polyaminic acid used in the present invention is a 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) as an acid dianhydride (Formula (4) )) with p-phenylenediamine (pPDA) as a diamine (formula (5)) and 4,4"-diamino-p-terphenylphenyl (DATP) (formula (6)), or as acid The anhydride trimellitic acid dianhydride (PMDA) (formula (7)) is obtained by reacting with pPDA (formula (5)) as a diamine.

In the above reaction, 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (pPDA) and 4,4"-diamino-p-terphenyl (DATP) of the diamine, or trimesic acid dianhydride (PMDA) and pPDA ratio (Mo Erbi), consider the desired The molecular weight of the proline acid or the ratio of the monomer unit can be appropriately set. However, the acid anhydride component is usually about 0.7 to 1.3, preferably about 0.8 to 1.2, based on the amine component 1.

Further, in the case of the ratio of the pPDA of the diamine to the DATP, when the mass of the DATP (m ² ) is set to 1, the mass of the pPDA (m ¹ ) can be usually set to about 1.7 to 20, preferably 2.1 to 20. More preferably, it is 2.2 to 20, more preferably 2.3 to 19, and even more preferably 2.3 to 18. That is, m ¹ and m ² are usually m ¹ /m ² =1.7 to 20, preferably 2.1 to 20, more preferably 2.2 to 20, still more preferably 2.3 to 19, still more preferably 2.3 to 18.

The above reaction is carried out in an organic solvent. That is, the composition for forming a release layer of the present invention contains the organic solvent. The organic solvent which can be used herein can be used as long as it does not adversely affect the above reaction.

Specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethyl Ethyl amide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropyl decylamine, 3-ethoxy-N,N-dimethylpropyl hydrazine Amine, 3-propoxy-N,N-dimethylpropyl decylamine, 3-isopropoxy-N,N-dimethylpropyl decylamine, 3-butoxy-N,N-di Methylpropyl decylamine, 3-sec-butoxy-N,N-dimethylpropyl decylamine, 3-tert-butoxy-N,N-dimethylpropyl decylamine, γ-butyl A protic solvent such as a lactone. These may be used alone or in combination of two or more.

According to a preferred embodiment of the present invention, the organic solvent is a solvent represented by the formula (A) or (B).

In the formulae (A) and (B), R ^a and R ^b may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, preferably a carbon number of 1 to 3. Here, h represents a natural number, preferably 1 to 3.

The reaction temperature may be appropriately set within 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 imidization of the obtained polyglycine, the polyamine unit is maintained. When the content is high, it is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and even more preferably about 0 to 50 ° C.

The reaction time depends on the reaction temperature or the reactivity of the starting material, and therefore cannot be uniformly defined, and is usually about 1 to 100 hours.

According to the method described above, a reaction solution containing the target polyglycine can be obtained.

In the present invention, after the above reaction solution is usually filtered, the filtrate is directly or diluted or concentrated to be used as a composition for forming a release layer. In this way, not only impurities which may cause deterioration in heat resistance, flexibility, or linear expansion coefficient characteristics of the obtained resin film can be reduced, and a composition can be obtained efficiently.

The solvent to be used for the dilution or concentration is not particularly limited, and examples thereof include the same as the specific examples of the reaction solvent of the above reaction, and they may be used alone or in combination of two or more.

Among these, when a resin film having high flatness is obtained in consideration of good reproducibility, a solvent to be used is preferably N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl. Phen-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ-butyrolactone.

The concentration of the polyamine acid relative to the total mass of the composition for forming the release layer is preferably set in consideration of the thickness of the produced film (release layer) or the viscosity of the composition, but is usually about 0.5 to 30% by mass, preferably It is about 5 to 25 mass%.

In addition, the viscosity of the composition for forming a release layer is appropriately set in consideration of the thickness of the film to be produced, and the like, and particularly, when the resin film having a thickness of about 0.05 to 5 μm is obtained with good reproducibility, it is usually 10 at 25 ° C. ~10,000mPa. s or so, preferably 20~1000mPa. s or so, more preferably 20~200mPa. s or so.

Here, the viscosity of the composition for forming a release layer is measured using a commercially available viscosity measuring instrument for viscosity measurement of a liquid, for example, by referring to the procedure described in JIS K7117-2, and the composition for forming a release layer can be measured at a temperature of 25 °C. Preferably, the viscosity meter uses a cone-type rotary viscometer, preferably a homo-type viscometer, using a standard conical rotor (cone Rotor) 1° 34'×R24, and the composition for forming a peeling layer can be used. Measured at a temperature of 25 °C. As such a rotary viscometer, for example, TVE-25H manufactured by Toki Sangyo Co., Ltd. can be cited.

Further, the composition of the present invention may contain various components in addition to the polyamic acid and the organic solvent. For example, a crosslinking agent (hereinafter also referred to as a crosslinkable compound) is exemplified, but it is not limited thereto.

The crosslinkable compound may, for example, be a melamine derivative or a benzoguanamine containing a compound having two or more epoxy groups, a hydrogen atom having an amine group substituted with a methylol group, an alkoxymethyl group or both. A derivative or glycoluril or the like, but is not limited thereto.

Specific examples of the crosslinkable compound are listed below, but are not limited thereto.

Examples of the compound containing two or more epoxy groups include Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celloxide 2021, and Celloxide 3000 (the above is manufactured by Daicel Co., Ltd.). Oxygen cyclohexene structure epoxy compound; Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (above: Japan Epoxy Resin) (now: Mitsubishi Chemical Corporation) Bisphenol A type epoxy compound such as JER (registered trademark) series); bisphenol F type epoxy compound such as Epikote 807 (made by Japan Epoxy Resin Co., Ltd.); Epikote 152, Epikote 154 (above Japan) Epoxy Resin Co., Ltd., EPPN201, EPPN202 (above, Nippon Chemical Co., Ltd.), etc.; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 Novolac-type ring of EOCN-1027 (the above is manufactured by Nippon Kayaku Co., Ltd.) and Epikote 180S75 (Japan Epoxy Resin (produced by Mitsubishi Chemical Corporation, jER (registered trademark) series)) Oxygen compound; naphthalene type epoxy such as V8000-C7 (made by DIC Corporation) Compound; Denacol EX-252 (NagaseChemtex), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, BASF), Epiclon 200, Epiclon 400 (above DIC) , Epikote 871, Epikote 872 (above is made by Japan Epoxy Resin Co., Ltd. (currently: manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series)), ED-5661, ED-5662 (the above is Celanese coating) An alicyclic epoxy compound such as exe); Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX- 421. An aliphatic polyglycidyl ether compound such as Denacol EX-313, Denacol EX-314, and Denacol EX-312 (manufactured by Nagase Chemtex Co., Ltd.).

A melamine derivative, a benzoguanamine derivative or a glycoluril having a hydrogen atom of an amine group substituted with a methylol group, an alkoxymethyl group or both, and, for example, a triazine ring, a methoxy group The average methyl group of 3.7 substituted MX-750, one triazine ring, MW-30 substituted by an average of 5.8 methoxymethyl groups (above is the joint company Sanhe Chemical); Cymel 300, Cymel 301 Methoxymethylated melamine of Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc.; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254 Methoxymethylated butoxymethylated melamine; butoxymethylated melamine of Cymel 506, Cymel 508, etc.; such as Cymel 1141 a methoxymethylated isobutoxymethylated melamine containing a carboxyl group; a methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123; a methoxymethylation of Cymel 1123-10 Butoxymethylated benzoguanamine; butoxymethylated benzoguanamine such as Cymel 1128; methoxymethylated ethoxymethyl benzoguanamine containing a carboxyl group such as Cymel 1125-80; Butyloxymethylated glycoluril of Cymel 1170; hydroxymethylated glycoluril such as Cymel 1172 (above, manufactured by Mitsui Cyanamid Co., Ltd. (present: Japan Cytec Industries Co., Ltd.).

The composition for forming a release layer of the present invention described above is applied to a substrate, and a film composed of polyimine having high heat resistance, moderate flexibility, and a moderate coefficient of linear expansion can be obtained by heating ( Peel layer).

Examples of the base substrate (substrate) include glass and plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triethyl cellulose, ABS, AS, and lower). Terpene resin, etc., metal (such as silicon wafer), wood, paper, asbestos, and the like.

The method of coating 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, a bar coating method, a die coating method, an inkjet method, and a printing method. (embossing, gravure, lithography, screen printing, etc.), etc.

In addition, the method of producing a ruthenium imidization by the polyglycine contained in the composition for forming a release layer of the present invention may, for example, be a hydrazine imidization in which the composition coated on the substrate is directly heated, and A catalyst is added to the composition, and the heated catalyst is imidized.

In the composition for forming a release layer of the present invention, a catalyst is added to the composition for forming a release layer of the present invention, and a composition is added by a modulation catalyst, and then applied to a substrate, and a resin film can be obtained by heating. (peeling layer). The amount of the catalyst is 0.1 to 30 moles, preferably 1 to 20 moles, of the valerine group. Further, in the catalyst addition composition, acetic anhydride or the like as a dehydrating agent may be added in an amount of from 1 to 50 moles, preferably from 3 to 30 moles, per mole of the amidate group.

The ruthenium imidization catalyst preferably uses a tertiary amine. The tertiary amine is preferably pyridine, substituted pyridine, imidazole, substituted imidazole, picoline, quinoline, isoquinoline or the like.

The heating temperature in the case of the heat imidization and the imidization of the catalyst is preferably 450 ° C or lower. When the temperature exceeds 450 ° C, the obtained resin film becomes brittle, and a resin film suitable for the intended purpose may not be obtained.

Further, in consideration of heat resistance and linear expansion coefficient characteristics of the obtained resin film, the composition after coating is heated at 50 ° C to 100 ° C for 5 minutes to 2 hours, and in this state, the stepwise heating causes the temperature to rise. It is better to heat for more than 30 minutes to 4 hours at temperatures above 375 ° C to 450 ° C.

In particular, the coated composition is heated at 50 ° C ~ 100 ° C for 5 minutes to 2 hours, then heated at more than 100 ° C ~ 200 ° C for 5 minutes to 2 hours, and then heated at more than 200 ° C ~ 375 ° C 5 minutes to 2 hours, and finally more than 375 ° C ~ 450 ° C, heating for 30 minutes to 4 hours is preferred.

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

The thickness of the resin film is usually about 0.01 to 10 μm, preferably about 0.05 to 5 μm, in the case of being used as a release layer, and the thickness of the coating film before heating is adjusted to form a resin film having a desired thickness.

The film described above is most suitably used as a release layer for peeling off a substrate applied to a flexible electronic device without causing damage.

With the composition of the present invention, a release layer provided between a flexible substrate suitable for a flexible electronic device and a base substrate can be formed. The base substrate is preferably one containing glass or tantalum wafer, more preferably glass.

For example, on the glass substrate, the composition of the present invention is applied by a conventionally known method, and the obtained coating film is heated at a specific temperature to form a release layer.

Further, the peeled body layer may be formed on the peeling layer. The layer to be peeled off may be one layer or a plurality of layers. When making various devices, it is actually a plurality of layers.

Among the peeled body layers, the layer directly above the peeling layer depends on the peeling layer to be used, but the peeling property with the peeling layer is preferably used, in other words, the adhesion to the peeling layer to be used is not good.

Another aspect of the present invention is to provide a method of manufacturing a stripped body.

This method can obtain a peeled body by having the following steps.

a) a step of forming a release layer after applying the composition of the present invention on a glass substrate; b) a step of forming a peeled body on the release layer; c) a step of peeling off the object to be peeled off at the interface between the peeling layer and the object to be peeled; and in the step b), the layer to be peeled may be one layer or a plurality of layers.

Further, in the "exfoliated body", the layer directly above the release layer depends on the peeling layer to be used, but the peeling property with the peeling layer can be preferably used, in other words, the adhesion to the peeling layer to be used is not Good.

According to another preferred aspect of the present invention, there is provided a substrate structure suitable for a substrate structure of a flexible electronic device, comprising: a base substrate; covering the base substrate in a region of 1 or more a release layer formed of the composition for forming a release layer of the present invention; and a flexible substrate covering the base substrate and the release layer, wherein the adhesion between the flexible substrate and the release layer is greater than the release layer and the The adhesion of the foundation matrix. The magnitude of the so-called adhesion force can be confirmed, for example, by the square test shown in the examples of the present invention.

The invention is described below based on the examples, but the invention is not limited to the examples.

[Examples]

The abbreviations used in this embodiment are listed below and explained.

<solvent>

NMP: N-methylpyrrolidone.

<amines>

p-PDA: p-phenylenediamine.

APAB: 2-(3-Aminophenyl)-5-aminobenzimidazole.

DATP: 4,4'-diamino-p-terphenyl.

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

<acid dianhydride>

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

BA-TME: 4,4-biphenylene bis(benzenetetracarboxylic acid monoester anhydride).

PMDA: trimellitic acid dianhydride.

<aldehyde>

IPHA: isophthalaldehyde.

[Measurement of number average molecular weight and weight average molecular weight]

The weight average molecular weight of the polymer (hereinafter referred to as "Mw") and the molecular weight distribution, using a GPC apparatus (Shodex (registered trademark) column KF803L and KF805L) manufactured by JASCO Corporation, in the dimethylformamide as a dissolution solvent , with a flow rate of 1 ml / min, column temperature The measurement was carried out at 50 °C. Further, Mw is a value in terms of polystyrene.

<Synthesis Example>

<Synthesis Example 1 Synthesis of Polyimine Precursor P1>

BPDA(98)//p-PDA(90)/DATP(10)

17.8g (0.164 mol), DATP 2.38g (0.009 mol) and APAB 2.05g (0.009 mol) of p-PDA were dissolved in NMP 425g, and BPDA 52.8g (0.179 mol) was added, and NMP was added again. 7.4 g was reacted at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polyimine precursor P1 had a Mw of 63,000 and a molecular weight distribution of 9.9.

<Synthesis Example 2 Synthesis of Polyimine Precursor P2>

BPDA(98)/DATP(100)

30.8 g of DATP (0.118 mol) was dissolved in 425 g of NMP, and 34.1 g (0.116 mol) of BPDA was added thereto, and 10 g of NMP was further added thereto, and the mixture was reacted at 23 ° C for 24 hours in a nitrogen atmosphere. The obtained polyimine precursor P2 had a Mw of 70,700 and a molecular weight distribution of 9.7.

<Synthesis Example 3 Synthesis of Polyimine Precursor P3>

PMDA(98)/p-PDA(80)/DATP(20)

P-PDA 20.261g (0.1875 mol) and TPDA 12.206g (0.0469 mol) were dissolved in NMP 617.4g, cooled to 15 ° C, added PMDA 50.112g (0.2298 mol), under nitrogen, to 50 The reaction was carried out at ° C for 48 hours. The Mw of the obtained polyimine precursor P3 is 82,100, molecular weight distribution is 2.7.

<Synthesis Example 4 Synthesis of Polyimine Precursor P4>

BP-TME(98)//p-PDA(95)/APAB(5)

9.66 g (0.089 mol) of p-PDA and 1.05 g (0.005 mol) of APAB were dissolved in NMP 440 g, and BP-TME 49.2 g (0.092 mol) was added, and the mixture was allowed to react at room temperature for 24 hours under a nitrogen atmosphere. The obtained polyimine precursor P4 had a Mw of 57,000 and a molecular weight distribution of 9.3.

<Synthesis Example 5 Synthesis of Polyimine Precursor P5>

BPDA(98)//p-PDA(100)

3.176 g (0.02937 mol) of p-PDA was dissolved in 88.2 g of NMP, and 8.624 g (0.02931 mol) of BPDA was added, and then reacted at 23 ° C for 24 hours in a nitrogen atmosphere. The obtained polybendimimine precursor P5 had a Mw of 107,300 and a molecular weight distribution of 4.6.

<Synthesis Example 6 Synthesis of Polybenzoxazole Precursor (P6)>

IHPA(98)//6FAP(100)

6.18 g (0.059 mol) of 6FAP was dissolved in 70 g of NMP, and 7.92 g (0.060 mol) of IPHA was added, and then 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 7 Synthesis of Polyimine Precursor P7>

PMDA(98)//p-PDA(100)

10.078 g (93 mmol) of p-PDA was dissolved in 220.0 g of NMP. To the obtained solution, 19.922 g (91 mmol) of PMDA was added, and the mixture was reacted at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 55,900 and a molecular weight distribution of 3.1.

<Production of peeling layer substrate>

P1 to P7 obtained in the above Synthesis Examples 1 to 7 were diluted to 4 wt% with NMP, and applied onto a 100 mm × 100 mm glass substrate (OA-10G alkali-free glass) or a tantalum wafer using a spin coater, and then In the curing conditions A to C, the mixture was fired in an oven to prepare a release layer.

Hardening condition A: maintained at 120 ° C for 30 minutes → temperature rise → 300 ° C, maintained for 60 minutes → temperature rise → 400 ° C, maintained for 60 minutes. Further, the temperature increase rate was 10 ° C / min.

Hardening condition B: maintained at 120 ° C for 30 minutes → temperature rise → 180 ° C, maintained for 20 minutes → temperature rise → 240 ° C, maintained for 20 minutes → temperature rise → 300 ° C, maintained for 20 minutes → temperature rise → 400 ° C, maintain 20 Minutes → warming → 450 ° C, maintained for 60 minutes. Further, the temperature increase rate was 10 ° C / min.

Hardening condition C: maintained at 80 ° C for 10 minutes → temperature rise → 300 ° C, maintained for 30 minutes → temperature rise → 400 ° C, maintained for 30 minutes. Further, the temperature increase rate was 10 ° C / min.

The film thickness of the obtained coating film was measured using a contact film thickness measuring instrument (Dektak 3ST, manufactured by the company ULVAC).

Table 1 shows the film thickness of the P1 to P7 precursor, the coated substrate, the curing conditions, and the produced release layer.

<Cross-cut test I>

With respect to the substrates having the release layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the adhesion of the substrate (glass or germanium wafer)/release layer was confirmed by the check test I.

The checker test I was carried out as follows.

(1) 100 squares of 1 mm square were produced on the film.

(2) Then, it is adhered to the above square with an adhesive tape (赛路玢 tape (registered trademark)), and then a peeling step is performed.

(3) After the stripping step, the square remaining on the substrate is calculated.

<Indicators of the results of the square test I>

The results of the square test and the degree of peeling are indicated by the following indicators.

5B: Not peeled off.

4B: Peeling of 5% or less.

3B: 5~15% peeling.

2B: 15~35% peeling.

1B: 35~65% peeling.

0B: 65% to 80% peeling.

B: 80% to 95% peeling.

A: 95%~ not 100% off.

AA: 100% stripping.

Unlike the above-described checker test I, the properties of the components constituting the peeling layer were measured for the substrates having the peeling layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, that is, (1) showing heating The weight change is reduced by a temperature of 1% by weight, (2) a refractive index at a wavelength of 1000 nm, (3) a birefringence at a wavelength of 1000 nm, and (4) a surface energy. Moreover, the measurement conditions of each characteristic are as follows.

<(1) shows a change in weight change by 1% by weight when heated>

The TD-DTA2000ST manufactured by Bruker Co., Ltd. was used to measure the thermal weight (TG) in a nitrogen atmosphere, and the temperature was reduced by 1%.

<(2) Refractive index at a wavelength of 1000 nm and (3) birefringence>

The refractive index and birefringence were measured using a high-speed spectroscopic thickness gauge M-2000 (manufactured by J.A. Woollam Japan Co., Ltd.). Further, the refractive index is an in-plane refractive index of a value of 1000 nm, and the birefringence is a difference between an in-plane refractive index and an out-of-plane refractive index.

<(4) Surface energy>

The surface energy of each member was measured using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). Further, the solvent used for the measurement was water and a methylene iodide, and the contact angle of the solvent was calculated.

<Formation of the peeled body and peeling test (square test II)>

On the substrates having the release layers of Examples 1 to 5 and Comparative Examples 1 to 3, the object to be peeled off was formed, and the degree of peeling was confirmed by the square test II.

<<Production of peeled body layer>>

On the release layer of the substrate having the release layer, a polyimide layer as a release body is formed.

Specifically, as shown in Table 1, the precursors obtained in the above Synthesis Example 5 or Synthesis Example 1 were coated on the release layer of the substrate having the release layer of Examples 1 to 5 and Comparative Examples 1 to 3 with a coating bar. P5 or P1. Then, in an oven at 120 ° C for 30 minutes → temperature rise → 180 ° C, maintained for 20 minutes → temperature rise → 240 ° C / maintain 20 minutes → temperature rise → 300 ° C, maintained for 20 minutes → temperature rise → 400 ° C, maintain 20 In the minute → temperature rise → 450 ° C, the film was cured for 60 minutes (any temperature increase rate was 10 ° C / minute), and a peeled body layer made of polyimide polyimide having a film thickness of 15 μm was produced.

<<square test II>>

The substrate having the peeled body layer and the peeled layer obtained as described above is The check test II confirmed the adhesion between the peeled body layer/release layer.

The checker test II was carried out in the same manner as the checker test I.

Table 2 shows (1) the temperature at which the weight change during heating is reduced by 1% by weight (in Table 2, "indicated by (1)"), and (2) the refractive index at a wavelength of 1000 nm (in Table 2, "I" 2)" indicates), (3) the difference between the refractive index and the birefringence of (2) (in Table 2, "indicated by (3)"), and (4) the surface energy (in Table 2, "(4) "Yes, but the unit is dyne/cm), the polyimide precursor used in the stripped layer, and the results of the checkers I and II.

The following cases are known from Table 2. The result of the test I of the peeling layers of Examples 1 to 5 was 5B, so that the peeling layer was not peeled off from the substrate, and the result of the test II was AA, and therefore, it was found that only the peeled body layer was self-exposed. The peeling layer is peeled off. In other words, it was found that the release layer formed of the composition for a release layer of the present invention produced a desired peeling result.

Further, the results of Test I of Comparative Example 1 and Comparative Example 3 were AA, and it was found that the release layer was peeled off from the substrate. In other words, it was found that Comparative Example 1 and Comparative Example 3 failed to obtain a desired peeling result. Further, in Tests 1 and II of Comparative Example 2, both of them were 5B. Therefore, even if the interface between the release layer and the substrate or the interface between the release layer and the release layer was not peeled off, the desired peeling result could not be obtained. .

Claims (14)

A composition for forming a release layer, comprising: a monomeric unit represented by the following formula (1): 50 mol% or more, and a polyglycine and an organic solvent having a weight average molecular weight of 10,000 or more. [wherein, X ¹ represents a tetravalent organic group, and Y ¹ represents a divalent group represented by the following formula (P): (wherein R represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and m represents an integer of 0 to 4, and r represents an integer of 1 to 4)]. The composition for forming a release layer according to the first aspect of the invention, wherein the Y ¹ is a divalent group represented by any one of the following formulae (P1) to (P3), (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, m1, m2, m3 , m4, m5, and m6 may be the same or different, indicating an integer from 0 to 4. The composition for forming a release layer according to the second aspect of the invention, wherein the Y ¹ contains at least a divalent group represented by the formula (P1). The composition for forming a release layer according to any one of claims 1 to 3, wherein the polyamic acid further contains a monomer unit represented by the following formula (2). [wherein, X ¹ is as defined in the first item of the patent application scope, and Y ² represents a base represented by the following formula (P4): (wherein R ⁷ and R ⁸ may be the same or different and each represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group; and R' represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or Phenyl, l represents an integer from 0 to 4, and m is as defined in item 1 of the patent application). The composition for forming a release layer according to any one of claims 1 to 4, wherein the X ¹ is a tetravalent aromatic group. The composition for forming a release layer according to claim 5, wherein the tetravalent aromatic group has at least one selected from the group consisting of a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton. The composition for forming a release layer according to any one of claims 1 to 6, wherein the organic solvent is a solvent represented by the following formula (A) or (B). (wherein R ^a and R ^b may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and h represents a natural number). The composition for forming a release layer according to any one of the items 1 to 7, wherein the content of the monomer unit represented by the above formula (1) in the polyamic acid is 60 mol% or more. The composition for forming a release layer according to any one of claims 1 to 8, which is for forming a release layer provided directly above the glass substrate. A peeling layer which is formed on a peeling layer which is applied between a flexible substrate and a base substrate of a flexible electronic device, and which is produced by using the composition for forming a release layer according to any one of claims 1 to 9. A substrate structure suitable for a substrate structure of a flexible electronic device, comprising: a base substrate; a release layer formed by covering the release layer of the base substrate in a region of 1 or 2 or more, and a release layer forming composition according to any one of claims 1 to 9; and covering In the flexible substrate of the base substrate and the release layer, the adhesion between the flexible substrate and the release layer is greater than the adhesion between the release layer and the base substrate. The substrate structure of claim 11, wherein the base substrate contains glass. A method for producing a release layer, which is a composition for forming a release layer according to any one of claims 1 to 9. A manufacturing method for a substrate structure for a flexible electronic device, comprising the steps of: preparing a base substrate; and using the composition for forming a release layer according to any one of claims 1 to 9. a step of forming a peeling layer covering the base substrate in a region of 1 or 2 or more; and a step of forming a flexible substrate on the base substrate and the peeling layer; and the adhesion between the flexible substrate and the peeling layer is greater than The adhesion of the release layer to the aforementioned base substrate.