TWI690545B - Composition for forming peeling layer - Google Patents

Abstract

According to the present invention, it is possible to provide adhesion to a glass substrate provided with a peeling layer without peeling at the interface with the glass substrate. In addition, the layer or layer group formed above the peeling layer can The composition for forming the peeling layer is simply peeled from the peeling layer. The present invention provides a composition for forming a peeling layer, which contains a polyamic acid containing 50 mol% or more of monomer units represented by formula (1) and having a weight average molecular weight of 10,000 or more and an organic solvent. Here, in formula (1), X ¹ represents a tetravalent organic group, and Y ¹ represents a divalent group represented by the following formula (P).

Description

Composition for forming peeling layer

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

In recent years, electronic devices have been required to impart bending performance, thinness, and weight reduction. Therefore, it is required to use a light-weight flexible plastic substrate to replace the glass substrate which is heavy and fragile and cannot be bent in the past. In addition, the new generation of displays requires the development of an active full-color TFT display panel using a lightweight flexible plastic substrate.

Therefore, reviews of various electronic device manufacturing methods using resin films as substrates are underway, and reviews are being made to switch to existing TFT device manufacturing processes to manufacture new-generation displays.

Patent Documents 1, 2 and 3 disclose that an amorphous silicon thin film layer is formed on a glass substrate. After a plastic substrate is formed on the thin film layer, a laser is irradiated from the glass surface side, and hydrogen gas generated by crystallization of the amorphous silicon is accompanied by , The method of peeling the plastic substrate from the glass substrate.

In addition, Patent Document 4 discloses that the technique disclosed in Patent Documents 1 to 3 is used to separate the layer to be peeled (in Patent Document 4, it is described as "transferred layer") A method of sticking to a plastic film to complete a liquid crystal display device.

However, the methods disclosed in Patent Documents 1 to 4, especially the method disclosed in Patent Document 4, must use a substrate with high light transmittance to pass the substrate to provide sufficient energy in order to release hydrogen contained in amorphous silicon. Therefore, a large amount of laser light must be irradiated, which may cause damage to the peeled layer. In addition, laser processing requires a long time, and it is difficult to peel off the peeled layer having a large area, so there is also a problem that it is difficult to improve the productivity of device manufacturing.

[Prior Technical Literature] [Patent Literature]

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

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

[Patent Document 3] WO2005/050754 pamphlet.

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

[Summary of the Invention]

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

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

Moreover, the object of the present invention is in addition to the above object, or the above object In addition, it can maintain the adhesion with the glass substrate provided with the peeling layer, and there is no peeling at the interface with the glass substrate. In addition, the layer or layer group formed above the peeling layer can be easily formed by the peeling layer. The composition for forming the peeling layer is peeled off.

The inventor found the following invention. That is, the present inventor unexpectedly discovered that when a composition having a polyamide unit and an organic solvent 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 peeling layer, the The layer has a characteristic that it does not cause damage to a substrate applied to a flexible electronic device or the like, and can be peeled off. This layer can maintain the adhesion to the glass substrate provided with the peeling layer, and there is no peeling at the interface with the glass substrate. In addition, the layer or layer formed above the peeling layer opposite to the glass substrate Group, can be easily peeled by the peeling layer. The present invention is based on this knowledge.

[式中，X¹表示4價有機基，Y¹表示以下述式(P)表示之2價基：

(式中，R表示F、Cl、碳數1~3之烷基、或苯基，m表示0~4之整數，且r表示1~4之整數)]。 <1> A composition for forming a peeling layer, comprising: a polyamic acid containing 50 mol% or more of monomer units represented by the following formula (1) and having a weight average molecular weight of 10,000 or more, and an organic solvent,

[In the formula, X ¹ represents a tetravalent organic group, and Y ¹ represents a divalent group represented by the following formula (P):

(In the formula, R represents F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, m represents an integer of 0 to 4, and r represents an integer of 1 to 4)].

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

(式中，R¹、R²、R³、R⁴、R⁵及R⁶可相同或相異，表示F、Cl、碳數1~3之烷基、或苯基，m1、m2、m3、m4、m5及m6可相同或相異，表示0~4之整數)。

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, representing F, Cl, C 1-3 alkyl, or phenyl, m1, m2, m3 , M4, m5, and m6 can be the same or different, indicating an integer of 0~4).

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

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

[式中，X¹係如前述<1>所定義，Y²表示下述式(P4)表示之基：

(式中，R⁷、及R⁸可相同或相異，表示F、Cl、碳數1~3之烷基、或苯基，R’表示氫原子、碳數1~3之烷基、或苯基，l表示0~4之整數，且m係如前述<1>所定義)]。

[In the formula, X ¹ is as defined in the aforementioned <1>, and Y ² represents the base represented by the following formula (P4):

(In the formula, R ⁷ and R ⁸ may be the same or different, representing F, Cl, C 1-3 alkyl group, or phenyl group, R'represents a hydrogen atom, C 1-3 alkyl group, or Phenyl, l represents an integer from 0 to 4, and m is as defined in the aforementioned <1>)].

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

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

(式中，R^a及R^b可相同或相異，表示碳數1~4之烷基，h表示自然數)。

(In the formula, R ^a and R ^b may be the same or different, and represent a C 1-4 alkyl group, h represents a natural number).

<8> In any of the aforementioned <1> to <7>, the content of the monomer unit represented by the aforementioned formula (1) in the polyamide may be 60 mol% or less on.

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

<10> A peeling layer formed between a flexible substrate and a base substrate applied to a flexible electronic device, and produced using the composition for forming a peeling layer according to any one of the above <1> to <9> .

<11> A substrate structure suitable for a flexible electronic device, which includes: a base substrate; a peeling layer covering the base substrate with an area of 1 or 2 or more, and by the above-mentioned <1>~ <9> the peeling layer formed by the peeling layer forming composition; and the flexible substrate covering the base substrate and the peeling layer; the adhesion between the flexible substrate and the peeling layer is greater than the peeling layer and the foundation The tightness of the substrate.

<12> In the aforementioned <11>, the base substrate may contain glass.

<13> A method for manufacturing a peeling layer, which uses the composition for forming a peeling layer according to any one of the above <1> to <9>. In one preferred aspect, the method for manufacturing the peeling layer includes the steps of applying the resin composition for forming the peeling layer to the substrate and heating.

<14> A manufacturing method, which is a manufacturing method suitable for a substrate structure of a flexible electronic device, which includes the following steps: The step of preparing the base substrate; the step of using the peeling layer forming composition of any one of the above <1> to <9> to prepare a peeling layer covering the base substrate with an area of 1 or more; and the base substrate The step of forming a flexible substrate on the peeling layer; the adhesion between the flexible substrate and the peeling layer is greater than the adhesion between the peeling layer and the base substrate.

The above-mentioned problems can be solved by the present invention.

Specifically, the present invention can provide a composition for forming a peeling layer that can be peeled without causing damage to a substrate applied to a flexible electronic device or the like without causing damage.

In addition, according to the present invention, in addition to the above objects, or in addition to the above objects, it is possible to provide adhesion to a glass substrate provided with a peeling layer without peeling at the interface with the glass substrate. The upper layer or layer group can be easily peeled from the peeling layer to form the composition for the peeling layer.

[Forms for carrying out the invention]

The present invention will be described in detail below.

Composition for forming peeling layer

The composition for forming a peeling layer of the present invention is as described above, which contains: There are more than 50 mole% of the polyamic acid in the monomer unit represented by the formula (1), and the polyamic acid and organic solvent having a weight average molecular weight of 10,000 or more.

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

Moreover, in formula (P), R represents F, Cl, or a C1-C3 alkyl group, or a phenyl group, Preferably it represents F and Cl. Similarly, in the aforementioned formula (P), m represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0. In addition, in the aforementioned formula (P), r represents an integer of 1 to 3.

The alkyl group having 1 to 3 carbons includes methyl, ethyl, n-propyl, and i-propyl groups. Preferably, the alkyl group having 1 to 3 carbons is methyl, and more preferably methyl.

The weight average molecular weight of the polyamic acid having the monomer unit represented by formula (1) used in the present invention must be 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, and still more preferably 30,000 or more. on. In addition, the upper limit of the weight average molecular weight of the polyamic acid used in the present invention is usually 2,000,000 or less. However, when it is considered that the viscosity of the resin composition becomes excessively high or the reproducibility is good, a resin film with high flexibility is obtained. It is preferably 1,000,000 or less, and 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 formula (1) above the ear %. By using polyamide having 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 polyamic acid contained in the composition for forming a peeling layer of the present invention is a polymer composed of only monomer units represented by formula (1), that is, formula ( 1) The indicated monomer unit contains 100 mol% of polymer. At this time, as long as the monomer unit in such a polyamic acid is represented by formula (1), only one kind may be specified, or two or more kinds may be used. In the latter case, the number of monomer units of the formula (1) contained in the polyamic acid is preferably 2 to 4, more preferably 2 to 3.

In the present invention, the group represented by formula (P) preferably contains a divalent group represented by any of formulas (P1) to (P3), and more preferably contains a divalent group represented by formula (P1) or (P3) , And more preferably, contains a divalent group represented by 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, indicating F, Cl, carbon number 1~3 The alkyl group or 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 integers of 0~4, preferably 0-2, more preferably 0-1, and particularly preferably Is 0.

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

Examples of such other monomer units include monomer units of formula (2).

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

In formula (P4), R ⁷ and R ⁸ may be the same or different, and represent F, Cl, a C 1-3 alkyl group, 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 represents a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, and more preferably represents a hydrogen atom.

In addition, l and m may be the same or different, and represent integers of 0 to 4, preferably represent 0 to 2, more preferably represent 0 to 1, and particularly preferably represent 0.

Such other monomer units include, in addition to the monomer unit of the aforementioned formula (2), 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-(tri (Fluoromethyl)-1,3-phenylenediamine and 4-(trifluoromethyl)-1,3-phenylenediamine, benzidine, 2,2'-dimethylbenzidine, 3,3'-di Methyl benzidine, 2,3'-dimethyl benzidine, 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'-diaminobenzyl Diamine and trimellitic anhydride of aniline (benzanilide), 5-amino-2-(3-aminophenyl)-1H-benzimidazole, 9,9-bis(4-aminophenyl) stilbene, etc. (PMDA), 2,3,6,7-naphthalene tetra Structure derived from acid dianhydride such as carboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3', 4,4'-benzophenone tetracarboxylic anhydride, etc.

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

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

That is, trimellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2 ,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid Acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4- Dicarboxyphenoxy) diphenylpropane dianhydrate, 4,4'-hexafluoroisopropylidene phthalic anhydride, p-phenylene phthalic dianhydride, 2,2-bis-(( 3,4-dicarboxyphenyl)-hexafluoropropane dianhydrate, 9,9-bis(3,4-dicarboxyphenyl) stilbene anhydrate, 9,9'-bis(4-(3,4 -Dicarboxyphenoxy)phenyl] stilbene dihydrate, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-Perylenetetracarboxylic dianhydride, 4,4'-sulfonyl diphthalic 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-tetramethyldisilaxane dihydrate, 1-(2,3-dicarboxyphenyl)-3-(3,4 -Dicarboxyphenyl)-1,1,3,3-tetramethyldisilazane Alkane dianhydrate, 3,3',4,4'-hydroquinone dibenzoate tetracarboxylic dianhydride, 2,2'-bis(4-hydroxyphenyl)propane dibenzoate-3, 3',4,4'-tetracarboxylic acid, etc.

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

(式中，R₃係具有至少1個芳香環之2價有機基，較佳為苯基、聯苯基、具有萘骨架之基)。

(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 the preferred aspect of the present invention, the tetravalent aromatic group that X ¹ can adopt has any one of a benzene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a terphenyl skeleton, more preferably a benzene skeleton , Any of the naphthalene skeleton and the biphenyl skeleton is more preferably any one having a benzene skeleton and a biphenyl skeleton.

According to the preferred aspect of the present invention, the polyamic acid used in the present invention is 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) (formula (4 )) with p-phenylenediamine (pPDA) (formula (5)) and 4,4”-diamino-p-terphenyl (DATP) (formula (6)) as diamines, or as acid di Anhydride trimellitic dianhydride (PMDA) (formula (7)) and pPDA (formula (5)) as a diamine can be obtained by reacting.

In the above reaction, 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (pPDA) and 4,4"-diamino-p-terphenyl (DATP) The input ratio of diamine, trimellitic dianhydride (PMDA) and pPDA (mol ratio), consider the desired polymerization The molecular weight of the amide acid, the ratio of monomer units, and the like can be appropriately set, but the acid anhydride component is usually set to about 0.7 to 1.3, preferably about 0.8 to 1.2 relative to the amine component 1.

In addition, for the input ratio of pPDA and DATP of the diamine, when the material mass (m ² ) of DATP is set to 1, the material mass (m ¹ ) of pPDA can usually be set to about 1.7-20, preferably 2.1-20 , Better is 2.2~20, yet better is 2.3~19, and even better is 2.3~18. 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, and even more preferably 2.3 to 18.

The above reaction is carried out in an organic solvent. That is, the composition for peeling layer formation of this invention contains this organic solvent. The organic solvent that can be used here can be any solvent as long as it does not adversely affect the aforementioned reaction.

Specific examples include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethyl Ethylacetamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropylamide, 3-ethoxy-N,N-dimethylpropylamide Amine, 3-propoxy-N,N-dimethylpropylamide, 3-isopropoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-di Methylpropylamide, 3-sec-butoxy-N,N-dimethylpropylamide, 3-tert-butoxy-N,N-dimethylpropylamide, γ-butane Protic solvents such as lactones. These can be used alone or in combination of two or more.

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

In, R ^a and R ^b may be the same as the formula (A) and formula (B) or different and represent an alkyl group having 1 to 4 carbon atoms, the carbon atoms preferably 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 used, and is usually about 0 to 100°C. However, in order to prevent the imidization of the resulting polyamic acid, the unit of the polyamic acid is maintained At a high content, it is preferably about 0 to 70°C, more preferably about 0 to 60°C, and still more preferably about 0 to 50°C.

The reaction time depends on the reaction temperature or the reactivity of the raw materials, so it cannot be limited in general, but is usually about 1 to 100 hours.

By the method described above, a reaction solution containing the target polyamic acid can be obtained.

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

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

Among these, the solvent used when obtaining a resin film with high flatness and good reproducibility is preferably N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ-butyrolactone.

The concentration of the polyamic acid with respect to the total mass of the composition for forming the peeling layer is suitably set considering the thickness of the film (peeling layer) produced or the viscosity of the composition, but it is usually about 0.5 to 30% by mass, preferably It is about 5-25% by mass.

In addition, the viscosity of the composition for forming the peeling layer is also suitably set considering the thickness of the film to be produced, especially when the resin film with a thickness of about 0.05 to 5 μm is obtained with good reproducibility, usually 10 at 25°C ~10,000mPa. Around s, preferably 20~1000mPa. Around s, more preferably 20~200mPa. s or so.

Here, the viscosity of the composition for peeling layer formation can be measured at a temperature of 25°C using a commercially available viscometer for measuring the viscosity of liquids, for example, referring to the procedure described in JIS K7117-2. It is preferable to use a cone-plate rotary viscometer for the viscometer, preferably to use a standard cone rotor 1° 34'×R24 with the same type of viscometer, and the composition for forming the peeling layer may be Measured at 25°C. Examples of such a rotary viscometer include TVE-25H manufactured by Toki Industries Co., Ltd.

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

Examples of the aforementioned crosslinkable compound include compounds containing two or more epoxy groups, melamine derivatives having a hydrogen atom having an amine group substituted with a methylol group, an alkoxymethyl group, or both, benzoguanamine Derivatives, glycolurils, etc., but not limited to this.

Specific examples of the cross-linkable compound are listed below, but it is not limited thereto.

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

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

By applying the composition for forming a peeling layer of the present invention described above to a substrate, a film made of polyimide having high heat resistance, moderate flexibility, and moderate linear expansion coefficient can be obtained by heating ( Peel layer).

The base substrate (substrate) includes, for example, glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triethyl cellulose, ABS, AS, Camphene resins, etc.), metals (silicon wafers, etc.), wood, paper, asbestos, etc.

The coating method is not particularly limited, and examples thereof include a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, and a printing method (Relief, gravure, lithography, screen printing, etc.) etc.

In addition, the method for producing imidate in the polyamic acid contained in the composition for forming a peeling layer of the present invention includes, for example, thermal imidate in which the composition applied on the substrate is directly heated, and A catalyst is added to the composition, and the heated catalyst is imidized.

Polyimide acid catalyst imidization is added to the composition for forming a peeling layer of the present invention, a catalyst is added, and after adding the composition by preparing the catalyst, it is coated on a substrate and a resin film can be obtained by heating (Peeling layer). The amount of catalyst is 0.1 to 30 mole times of the amide acid group, preferably 1 to 20 mole times. In addition, in the catalyst addition composition, acetic anhydride or the like as a dehydrating agent may be added, and the amount thereof is 1 to 50 mole times of the amide acid group, preferably 3 to 30 mole times.

The amide imidization catalyst preferably uses a tertiary amine. The tertiary amine is preferably pyridine, substituted pyridines, imidazole, substituted imidazoles, picoline, quinoline, isoquinoline and the like.

The heating temperature during thermal imidization and catalyst imidization is preferably 450°C or lower. When the temperature exceeds 450°C, the resulting resin film becomes brittle, and a resin film suitable for the intended use may not be obtained.

In addition, when considering the heat resistance and linear expansion coefficient characteristics of the resulting resin film, the coated composition is heated at 50°C to 100°C for 5 minutes to 2 hours. In this state, stepwise heating increases the temperature Finally, it is better to heat at more than 375℃~450℃ for 30 minutes~4 hours.

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

Examples of appliances used for heating include hot plates and ovens. The heating environment can be under air, under inert gas, under normal pressure, or under reduced pressure.

The thickness of the resin film, especially when used as a peeling layer, is usually about 0.01 to 10 μm, preferably about 0.05 to 5 μm, and the thickness of the coating film before heating is adjusted to form a resin film of a desired thickness.

The film described above is most suitable for use as a peeling layer for peeling a substrate suitable for a flexible electronic device without causing damage.

With the composition of this case, a peeling layer provided between a flexible substrate and a base substrate suitable for flexible electronic devices can be formed. The base substrate preferably contains glass or silicon wafers, and more preferably contains glass.

For example, the composition of this case is applied to a glass substrate by a conventionally known method, and the resulting coating film is heated at a specific temperature to form a peeling layer.

In addition, the layer to be peeled may be formed on the peeling layer. The layer to be peeled may be one layer or plural layers. When making various devices, there are actually multiple layers.

Among the layers to be peeled, the layer directly above the peeling layer depends on the peeling layer used, but those having better peelability with the peeling layer can be used, in other words, those with poor adhesion to the peeling layer used.

The other aspect of this case is to provide a method for manufacturing the stripped body.

In this method, the peeled body can be obtained by having the following steps.

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

In addition, in the "removed body", the layer directly above the peeling layer depends on the peeling layer used, but the peelability of the peeling layer can be used better, in other words, the adhesion with the peeling layer used is not The best.

According to other preferred aspects of the present invention, a substrate structure may be provided, which is suitable for flexible electronic device substrate structures, and includes: a base substrate; and an area of 1 or more, covering the aforementioned base substrate A peeling layer, and a peeling layer formed by the peeling layer forming composition of the present invention; and a flexible substrate covering the base substrate and the peeling layer, the adhesion of the flexible substrate and the peeling layer is greater than that of the peeling layer and the above Dense focus on the base substrate. The magnitude of the adhesion force here can be confirmed by, for example, the grid test shown in the embodiment of the present invention.

The present invention will be described below based on embodiments, but the present invention is not limited to those of the embodiments.

[Example]

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

<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 (pyromellitic acid monoester anhydride).

PMDA: trimellitic 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 molecular weight distribution were determined using a GPC device (Shodex (registered trademark) columns KF803L and KF805L) manufactured by Nippon Spectroscopy Co., Ltd., and dimethylformamide as the elution solvent , Flow rate 1ml/min, column temperature The measurement is performed under the condition of 50°C. In addition, Mw is a polystyrene conversion value.

<Synthesis example> <Synthesis Example 1 Synthesis of Polyimide Precursor P1> BPDA(98)//p-PDA(90)/DATP(10)

After dissolving p-PDA 17.8g (0.164 mol), DATP 2.38g (0.009 mol) and APAB 2.05g (0.009 mol) in NMP 425g, and adding BPDA 52.8g (0.179 mol), add NMP again Under a nitrogen environment, 7.4g was allowed to react at 23°C for 24 hours. The obtained polyimide precursor P1 had an Mw of 63000 and a molecular weight distribution of 9.9.

<Synthesis Example 2 Synthesis of Polyimide Precursor P2> BPDA(98)/DATP(100)

After dissolving 30.8 g (0.118 mol) of DATP in 425 g of NMP and simultaneously adding 34.1 g (0.116 mol) of BPDA, 10 g of NMP was added again, and the reaction was performed at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polyimide precursor P2 was 70,700, and the molecular weight distribution was 9.7.

<Synthesis Example 3 Synthesis of Polyimide 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, and after cooling to 15°C, PMDA 50.112g (0.2298 mol) was added under nitrogen atmosphere at 50 React for 48 hours at ℃. The Mw of the obtained polyimide precursor P3 is 82,100, molecular weight distribution is 2.7.

<Synthesis Example 4 Synthesis of Polyimide 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 440 g of NMP, 49.2 g (0.092 mol) of BP-TME was added, and the mixture was allowed to react at room temperature for 24 hours under a nitrogen atmosphere. The obtained polyimide precursor P4 had an Mw of 57,000 and a molecular weight distribution of 9.3.

<Synthesis Example 5 Synthesis of Polyimide Precursor P5> BPDA(98)//p-PDA(100)

After dissolving 3.176 g (0.02937 mol) of p-PDA in 88.2 g of NMP and adding 8.624 g (0.02931 mol) of BPDA, the reaction was carried out at 23° C. for 24 hours under a nitrogen atmosphere. The obtained polyimide precursor P5 had an Mw of 107,300 and a molecular weight distribution of 4.6.

<Synthesis Example 6 Synthesis of polybenzoxazole precursor (P6)> IHPA(98)//6FAP(100)

After dissolving 3.18 g (0.059 mol) of 6FAP in 70 g of NMP and adding 7.92 g (0.060 mol) of IPHA, the reaction was carried out at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 107,300 and the molecular weight distribution was 4.6.

<Synthesis Example 7 Synthesis of Polyimide 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 resulting solution, 19.922 g (91 mmol) of PMDA was added, and the reaction was carried out at 23°C for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 55,900 and the molecular weight distribution was 3.1.

<Fabrication of the peeling layer substrate>

P1~P7 obtained in the above Synthesis Examples 1~7 were diluted with NMP to 4wt%, and then applied on a 100mm×100mm glass substrate (OA-10G alkali-free glass) or silicon wafer using a spin coater. Under hardening conditions A to C, it is baked in an oven to produce a peeling layer.

Hardening condition A: 120°C, 30 minutes → temperature rise → 300°C, 60 minutes → temperature rise → 400°C, 60 minutes. In addition, the temperature increase rate is 10°C/min.

Hardening condition B: 120°C, 30 minutes → temperature rise → 180°C, 20 minutes → temperature rise → 240°C, 20 minutes → temperature rise → 300°C, 20 minutes → temperature rise → 400°C, 20 Minutes → temperature rise → 450°C for 60 minutes. In addition, the temperature increase rate is 10°C/min.

Hardening condition C: at 80°C, 10 minutes → temperature rise → 300°C, 30 minutes → temperature rise → 400°C, 30 minutes. In addition, the temperature increase rate is 10°C/min.

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

Table 1 shows the used P1~P7 precursors, coated substrates, curing conditions, and the film thickness of the produced release layer.

<Cross-cut test I>

For the substrates with peeling layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the adhesive force of the substrate (glass or silicon wafer)/peeling layer was confirmed by the square test I.

The grid test I was performed as follows.

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

(2) Then, stick the adhesive tape (Selicate tape (registered trademark)) to the above square, and then perform the peeling step.

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

<Indicator of Results of Grid Test I>

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

5B: No peeling.

4B: Peel below 5%.

3B: 5~15% peeling.

2B: 15~35% peeling.

1B: 35~65% peeling.

0B: 65%~80% peeling.

B: 80%~95% peeling.

A: 95%~less than 100% peeling.

AA: 100% peeling.

Unlike the above-mentioned grid test I, for the substrates with peeling layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the characteristics of the components constituting the peeling layer were measured, that is, (1) showed heating The weight change at the time reduces the temperature by 1% by weight, (2) the refractive index at a wavelength of 1000 nm, (3) the birefringence at a wavelength of 1000 nm, and (4) the surface energy. The measurement conditions of each characteristic are shown below.

<(1) Temperature at which the weight change during heating is reduced by 1% by weight>

Using TD-DTA2000ST manufactured by Bruker Co., Ltd., thermogravimetric (TG) measurement was carried out in a nitrogen environment, and the temperature at which the weight was reduced by 1% was determined.

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

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

<(4) Surface energy>

Using a fully automatic contact angle meter DM-701 (made by Kyowa Interface Science Co., Ltd.), the surface energy of each component is measured. In addition, the solvent used for the measurement is water and methylene iodide, and the contact angle of the solvent is calculated.

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

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

<<Production of the peeled body layer>>

On the peeling layer of the substrate provided with the peeling layer, a polyimide layer as a peeled body is formed.

Specifically, as shown in Table 1, the precursor obtained in Synthesis Example 5 or Synthesis Example 1 above was coated with a coating bar on the peeling layers of the substrates having peeling layers in Examples 1 to 5 and Comparative Examples 1 to 3.物P5 or P1. Then, the oven is maintained at 120°C for 30 minutes → temperature rise → 180°C for 20 minutes → temperature rise → 240°C/maintain 20 minutes → temperature rise → 300°C for 20 minutes → temperature rise → 400°C for 20 Minutes → temperature rise → 450° C., maintaining for 60 minutes (any temperature rise rate is 10° C./minute) and hardening, to produce a 15 μm-thick peeled body layer composed of polyimide.

<<Square Test II>>

For the substrate with peeled body layer and peeling layer obtained above, The square test II confirmed the adhesion between the peeled body layer and the peeled layer.

The grid test II was conducted in the same way as the grid test I.

Table 2 shows (1) the temperature at which the weight change during heating is reduced by 1% by weight (in Table 2, "denoted by (1)"), and (2) the refractive index at a wavelength of 1000 nm (in Table 2, "denoted by ( 2)"), (3) the difference between the refractive index and birefringence of (2) (in Table 2, "denoted by (3)"), (4) surface energy (in Table 2, denoted by "(4) "Means. However, the unit is dyne/cm), the polyimide precursor used in the peeled body layer, and the results of grid tests I and II.

*: The birefringence of Comparative Example 2 cannot be measured.

**: The square test II of Comparative Example 1 and Comparative Example 3 was unable to measure because of the low adhesion to the peeling layer and the substrate.

Table 2 shows the following situation. The result of the test I of the peeling layer of Examples 1 to 5 is 5B, so it is known that the peeling layer will not peel off from the substrate, and the result of the test II is AA, so it is known that only the peeling layer The peeling layer peels off. In other words, it is known that the peeling layer formed from the composition for peeling layer of the present invention produces a desired peeling result.

In addition, the result of Test I of Comparative Example 1 and Comparative Example 3 is AA, so it is known that the peeling layer can be peeled off from the substrate. In other words, it is understood that Comparative Example 1 and Comparative Example 3 cannot obtain the desired peeling result. In addition, since both Test I and Test II of Comparative Example 2 are 5B, it is understood that even at the interface between the peeling layer and the substrate, or the interface between the peeling layer and the object layer to be peeled off, the desired peeling result cannot be obtained .

Claims (3)

A substrate structure suitable for a flexible electronic device, which includes: a base substrate of a glass substrate; a peeling layer, and a flexible substrate covering the base substrate and the peeling layer, wherein the peeling layer is 1 or 2 The above area covers the peeling layer of the base substrate and is formed by the following peeling layer forming composition comprising the following formula containing 50 mole% or more ( 1) The monomer unit represented, the polyamic acid having a weight average molecular weight of 10,000 or more, and an organic solvent, the adhesion of the peeling layer to the base substrate is greater than the adhesion of the flexible substrate to the peeling layer,

[In the formula, X ¹ represents an aromatic group having at least one kind selected from a benzene skeleton, a naphthalene skeleton and a biphenyl skeleton, and Y ¹ is a divalent group represented by any of the following formulas (P1) to (P3), And at least contains the divalent group represented by formula (P2),

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, representing F, Cl, C 1-3 alkyl, or phenyl, m1, m2, m3 , M4, m5, and m6 may be the same or different, indicating an integer of 0~4). According to the substrate structure of the first item of the patent application scope, wherein the aforementioned polyamic acid further includes a monomer unit represented by the following formula (2),

[In the formula, X ¹ is as defined in item ¹ of the patent application, and Y ² represents a group represented by the following formula (P4):

(In the formula, R ⁷ and R ⁸ may be the same or different, representing F, Cl, C 1-3 alkyl group, or phenyl group, R'represents a hydrogen atom, C 1-3 alkyl group, or Phenyl, l represents an integer from 0 to 4, and m is as defined in item 1 of the patent application scope)]. For example, in the substrate structure of claim 1, the content of the monomer unit represented by the aforementioned formula (1) in the polyamide is 60 mol% or more.