KR102467105B1 - Composition for forming releasing layer - Google Patents

Abstract

According to the present invention, adhesion to the glass substrate on which the release layer is formed is maintained, and peeling does not occur at the interface with the glass substrate, while the layer or layer group formed above the release layer can be easily separated from the release layer. A composition for forming the exfoliation layer, which can be provided. The present invention provides a composition for forming a release layer comprising a polyamic acid containing 50 mol% or more of the monomer unit 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 a release layer {COMPOSITION FOR FORMING RELEASING LAYER}

The present invention relates to a composition for forming a release layer formed directly on a glass substrate.

BACKGROUND OF THE INVENTION [0002] In recent years, electronic devices have been required to have functions such as bending, thinning, and light weight. From this, it is demanded to use a lightweight flexible plastic substrate instead of the conventional heavy, brittle and unbendable glass substrate. Further, in a new generation display, development of an active full-color TFT display panel using a lightweight flexible plastic substrate is required.

Then, various methods of manufacturing electronic devices using a resin film as a substrate have begun to be examined, and in a new generation display, manufacturing examination is progressing with a process capable of diverting existing TFT facilities.

Patent Literatures 1, 2 and 3 form an amorphous silicon thin film layer on a glass substrate, form a plastic substrate on the thin film layer, and then irradiate a laser from the glass surface side to generate the crystallization of the amorphous silicon. Disclosed is a method of peeling a plastic substrate from a glass substrate by hydrogen gas.

In addition, in Patent Document 4, a layer to be peeled (referred to as "layer to be transferred" in Patent Document 4) is attached to a plastic film using the techniques disclosed in Patent Documents 1 to 3 to complete a liquid crystal display device. Introduce how to do it.

However, in the method disclosed in Patent Literatures 1 to 4, particularly the method disclosed in Patent Literature 4, it is essential to use a substrate having high light transmission properties, and energy sufficient to pass through the substrate and release hydrogen contained in amorphous silicon is required. Because of the cycle, there is a problem that irradiation with a relatively large laser beam is required, which damages the layer to be separated. In addition, since laser processing requires a long time and it is difficult to peel a layer to be separated having a large area, there is also a problem that it is difficult to increase productivity in device manufacturing.

Japanese Unexamined Patent Publication No. 10-125929. Japanese Unexamined Patent Publication No. 10-125931. Pamphlet WO2005/050754. Japanese Unexamined Patent Publication No. 10-125930.

Then, the objective of this invention exists to solve the said subject.

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

Further, an object of the present invention is, in addition to the above object or other than the above object, to maintain adhesion to the glass substrate on which the release layer is formed and to prevent separation at the interface with the glass substrate, while at the top of the release layer. It is an object of the present invention to provide a composition for forming a release layer that can easily separate a layer or group of layers to be formed from the release layer.

This inventor discovered the following invention this time. That is, when the present inventor forms a release layer using a composition containing a polyamic acid containing 50 mol% or more of a monomer unit having a specific structure and having a weight average molecular weight of a certain value or more and an organic solvent, the layer is flexible. It was unexpectedly found that it has suitable characteristics that can be peeled off without damaging a substrate applied to an electronic device or the like. This layer maintains adhesion to the glass substrate on which the release layer is formed, and peeling at the interface with the glass substrate does not occur easily, while being formed on a layer or layer group formed above the release layer on the opposite side to the glass substrate. For the case, it was a thing that could be easily peeled from the peeling layer. The present invention is based on these findings.

<1> A composition for forming a release layer comprising a polyamic acid having a weight average molecular weight of 10,000 or more and containing 50 mol% or more of the monomer unit represented by the following formula (1), and an organic solvent.

[Formula 1]

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

[Formula 2]

(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 above <1>, it is preferable that the Y ¹ is a divalent group represented by any of the following formulas (P1) to (P3).

[Formula 3]

(In the expression,

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 and represent an integer of 0 to 4).

It is good that <3> said <2> said Y< ¹ > contains at least the divalent group represented by Formula (P1).

<4> In any one of said <1>-<3>, it is good that a polyamic acid further contains the monomer unit represented by following formula (2).

[Formula 4]

[during expression,

X ¹ is as defined in <1> above, and Y ² represents a group represented by the following formula (P4):

[Formula 5]

(In the expression,

R ⁷ and R ⁸ may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group;

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

l represents an integer of 0 to 4, and

m is as defined in <1> above)].

<5> In any one of said <1>-<4>, it is preferable that X< ¹ > is a tetravalent aromatic group.

<6> In the above <5>, it is preferable that the tetravalent aromatic group has at least one selected from a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton.

<7> In any one of said <1>-<6>, it is good that the said organic solvent is a solvent represented by following formula (A) or (B).

[Formula 6]

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

<8> In any one of said <1>-<7>, it is preferable that content of the monomer unit represented by the said Formula (1) in the said polyamic acid is 60 mol% or more.

<9> In any one of <1> to <8>, the composition for forming a release layer according to the present invention is preferably for forming a release layer formed directly on a glass substrate.

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

<11> As a substrate structure applied to a flexible electronic device,

a base substrate;

A release layer formed of the release layer-forming composition of any one of the above <1> to <9> as a release layer covering the base substrate in one or two or more regions;

A flexible substrate covering the base substrate and the exfoliation layer

including,

The substrate structure, characterized in that the adhesion between the flexible substrate and the release layer is greater than the adhesion between the release layer and the base substrate.

<12> In the above <11>, it is preferable that the base substrate contains glass.

<13> A method for producing a release layer characterized by using the composition for forming a release layer according to any one of the above <1> to <9>. In one preferable aspect, the manufacturing method of the said peeling layer includes the process of apply|coating the said resin composition for peeling layer formation to a board|substrate, and heating.

<14> As a manufacturing method of a substrate structure applied to a flexible electronic device,

A process of preparing a base substrate;

A step of producing a release layer covering the base substrate in one or two or more regions using the composition for forming a release layer according to any one of the above <1> to <9>;

A step of forming a flexible substrate on the base substrate and the release layer;

The manufacturing method, characterized in that the adhesion between the flexible substrate and the release layer is greater than the adhesion between the release layer and the base substrate.

The above problem can be solved by the present invention.

Specifically, according to the present invention, a composition for forming a peeling layer for peeling without damaging a substrate applied to a flexible electronic device can be provided.

In addition, according to the present invention, in addition to the above effects or in addition to the above effects, adhesion to the glass substrate on which the release layer is formed is maintained, and peeling at the interface with the glass substrate does not occur, while formed above the release layer. It is an object of the present invention to provide a composition for forming a release layer capable of easily peeling a layer or group of layers to be formed from the release layer.

Hereinafter, the present invention will be described in detail.

Composition for forming release layer

As described above, the composition for forming a release layer of the present invention comprises a polyamic acid containing 50 mol% or more of the monomer unit represented by formula (1), a polyamic acid having a weight average molecular weight of 10,000 or more, and an organic solvent. will be.

[Formula 7]

As 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).

[Formula 8]

In formula (P), R represents F, Cl, or an alkyl group having 1 to 3 carbon atoms or a phenyl group, and preferably represents F or 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. Moreover, in said formula (P), r represents the integer of 1-3.

In addition, the C1-C3 alkyl group includes methyl, ethyl, n-propyl, and i-propyl, preferably the C1-C3 alkyl group is methyl, more preferably methyl.

The weight average molecular weight of the polyamic acid having a monomer unit represented by formula (1) used in the present invention needs to be 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more. . On the other hand, 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, but in consideration of suppressing excessive increase in the viscosity of the resin composition and obtaining a highly flexible resin thin film with good reproducibility, etc. , 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 of the monomer unit represented by Formula (1). , more preferably 90 mol% or more. By using a polyamic acid having such a monomer unit content, a resin thin 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 release layer of the present invention is a polymer composed only of monomer units represented by formula (1), that is, 100 mol% of monomer units represented by formula (1) It is a polymer that contains At this time, as long as it is represented by Formula (1), only a specific 1 type may be sufficient as the monomer unit in such a polyamic acid, and 2 or more types may be sufficient as it. In the case of the latter, the number of monomer units of formula (1) included 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 includes a divalent group represented by any of formulas (P1) to (P3), more preferably a divalent group represented by formula (P1) or (P3) A group is included, and more preferably a divalent group represented by the formula (P3) is included.

[Formula 9]

In the above formulas (P1), formulas (P2) and formulas (P3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, and F, Cl, carbon number represents an alkyl group of 1 to 3 or a phenyl group, preferably F or Cl.

Similarly, in these formulas, 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 , and particularly preferably represents 0.

The polyamic acid used in the present invention may also contain other monomer units other than the monomer unit represented by Formula (1). The content of such other monomer units needs to be less than 50 mol%, preferably less than 40 mol%, more preferably less than 30 mol%, still more preferably less than 20 mol%, and even more preferably less than 10 mol%. desirable.

As such another monomer unit, the monomer unit of Formula (2) is mentioned, for example.

[Formula 10]

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

[Formula 11]

In formula (P4), R ⁷ and R ⁸ may be the same or different and represent 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 of 1 to 3 carbon atoms, or a phenyl group, preferably a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, more preferably a hydrogen atom.

In addition, 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.

As such other monomer units, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 5 -Methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2-(trifluoromethyl)-1 ,3-phenylenediamine and 4-(trifluoromethyl)-1,3-phenylenediamine, benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 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'-diaminobenzanilide, 5-amino-2-(3-aminophenyl)-1H-benzoimidazole, 9,9- diamines such as bis(4-aminophenyl)fluorene, pyromellitic anhydride (PMDA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3, and structures derived from acid dianhydrides such as 3',4,4'-benzophenone tetracarboxylic acid anhydride.

In Formulas (1) and (2), as described above, X ¹ is a tetravalent organic group, but is preferably a tetravalent aromatic group.

When manufacturing the polyamic acid used by this invention, the tetravalent aromatic group which X< ¹ > can take can manufacture by using the following aromatic tetracarboxylic dianhydride.

That is, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3, 3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , 1,2,5,6-naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3, 3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) Diphenylpropane dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride, paraphenylenediphthalic dianhydride, 2,2-bis-((3,4-dicarboxyphenyl)-hexafluoropropane 2 Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9'-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,3 ',4,4'-biphenylethertetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, paraterphenyl-3,4,3',4'-tetracarboxylic dianhydride, metaterphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 1-(2,3-dicarboxyphenyl)-3-(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 3,3',4,4 '-hydroquinone dibenzoate tetracarboxylic dianhydride, 2,2'-bis(4-hydroxyphenyl)propane dibenzoate-3,3',4,4'-tetracarboxylic acid, etc. have.

Preferably, the aromatic tetracarboxylic dianhydride preferred herein is selected from the following compound groups.

[Formula 12]

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

Therefore, according to a preferred aspect of the present invention, the tetravalent aromatic group that X ¹ can take has any of a benzene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a terphenyl skeleton, more preferably a benzene skeleton, a naphthalene skeleton, It has any of biphenyl skeletons, More preferably, it has any of a benzene skeleton and a biphenyl skeleton.

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

[Formula 13]

In the above reaction, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), p-phenylenediamine (pPDA) and 4,4″-diamino-p-terphenyl ( DATP), or pyromellitic dianhydride (PMDA), and the addition ratio (molar ratio) of pPDA can be appropriately set in consideration of the molecular weight of the desired polyamic acid, the ratio of monomer units, etc. , The acid anhydride component can usually be about 0.7 to 1.3, preferably about 0.8 to 1.2.

On the other hand, the input ratio of pPDA and DATP, which are diamines, when the amount of substance (m ² ) of DATP is 1, the substance amount (m ¹ ) of pPDA can be usually about 1.7 to 20, but preferably 2.1 to 20 , More preferably from 2.2 to 20, still more preferably from 2.3 to 19, still more preferably from 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, and still more Preferably it is 2.3-18.

The above reaction is carried out in an organic solvent. That is, the composition for forming a release layer according to the present invention contains such an organic solvent. As the organic solvent that can be used here, various solvents can be used as long as they do not adversely affect the reaction.

Specific examples include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethyl Acetamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropylamide, 3-ethoxy-N,N-dimethylpropylamide, 3-propoxy-N,N-dimethylpropylamide, 3-isopropoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-dimethylpropylamide, 3-sec-butoxy-N,N-dimethylpropylamide, 3-tert-butoxy-N , protonic solvents such as N-dimethylpropylamide and γ-butyrolactone; and the like. You may use these individually or in combination of 2 or more types.

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

[Formula 14]

In the formulas (A) and (B), R ^a and R ^b may be the same or different and represent an alkyl group having 1 to 4 carbon atoms, preferably having 1 to 3 carbon atoms. Moreover, h represents a natural number here, Preferably it is 1-3.

The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ° C., but in order to prevent imidation of the obtained polyamic acid and maintain a high content of polyamic acid units, preferably It is preferably about 0 to 70°C, more preferably about 0 to 60°C, even more preferably about 0 to 50°C.

The reaction time cannot be uniformly defined because it depends on the reaction temperature or the reactivity of the raw materials, 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, usually, after filtering the reaction solution, the filtrate is used as a composition for forming a release layer as it is or after being diluted or concentrated. By doing in this way, not only can the mixing of impurities which can cause deterioration of the heat resistance, flexibility, or linear expansion coefficient characteristics of the thin resin film obtained can be reduced, but also the composition can be obtained efficiently.

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

Among these, in view of obtaining a resin thin film with high flatness with good reproducibility, as solvents to be used, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1 ,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferred.

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

In addition, the viscosity of the composition for forming a release layer is also set appropriately in consideration of the thickness of the thin film to be produced, etc., but especially when the purpose is to obtain a resin thin film having a thickness of about 0.05 to 5 μm with good reproducibility, usually at 25 ° C. It is about 10 to 10,000 mPa·s, preferably about 20 to 1000 mPa·s, and more preferably about 20 to 200 mPa·s.

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

Moreover, the composition of this invention may have various components other than a polyamic acid and an organic solvent. For example, although a crosslinking agent (henceforth also referred to as a crosslinkable compound) is mentioned, it is not limited to these.

Examples of the cross-linkable compound include compounds containing two or more epoxy groups, melamine derivatives, benzoguanamine derivatives, and glycolurils having a group in which the hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both. may, but are not limited to these.

Although the specific example of a crosslinkable compound is given below, it is not limited to this.

Examples of the compound containing two or more epoxy groups include Epolyd GT-401, Epolid GT-403, Epolid GT-301, Epolid GT-302, Celoxide 2021, and Celoxide 3000 (above, Daicel) Epoxy compounds having a cyclohexene structure; Bisphenol A type epoxy compounds such as Resin Co., Ltd. (current: Mitsubishi Chemical Co., Ltd., jER (registered trademark) series)); Bisphenol F type epoxy compounds such as Epicoat 807 (Japan Epoxy Resin Co., Ltd.); Epicoat 152, Epicoat Coat 154 (above, manufactured by Japan Epoxy Resin Co., Ltd. (currently: manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series)), EPPN201, EPPN202 (above, manufactured by Nippon Kayaku Co., Ltd.), and other phenol novolak-type epoxy compounds; ECON-102 , ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy Resin Co., Ltd. (currently: manufactured by Mitsubishi Chemical Corporation, jER (registered trademark)) series); cresol novolac type epoxy compounds such as; V8000-C7 (manufactured by DIC Corporation); naphthalene type epoxy compounds such as; CY-182, Araldite CY-192, Araldite CY-184 (above, manufactured by BASF), Epiklon 200, Epiklon 400 (above, manufactured by DIC Corporation), Epicoat 871, Epicoat 872 (above, Alicyclic epoxy compounds such as Japan Epoxy Resin Co., Ltd. (current: manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series)), ED-5661, ED-5662 (above, manufactured by Celanese Coatings); Denacol EX-611 , Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol and aliphatic polyglycidyl ether compounds such as EX-314 and Denacol EX-312 (above, manufactured by Nagase ChemteX Co., Ltd.).

Examples of melamine derivatives, benzoguanamine derivatives, or glycolurils in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both, MX-750 in which an average of 3.7 methoxymethyl groups are substituted per triazine ring; MW-30 having an average of 5.8 methoxymethyl groups substituted per triazine ring (above, 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, etc. Methylated butoxymethylated melamine; Butoxymethylated melamine such as Cymel 506 and Cymel 508; Carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141; Methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123; Methoxymethylated butoxymethylated benzoguanamines such as Cymel 1123-10; Butoxymethylated benzoguanamines such as Cymel 1128; Carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamines such as Cymel 1125-80; Cymel Butoxymethylation glycoluril like 1170; methylolation glycoluril like Cymel 1172 (above, manufactured by Mitsui Cyanamid Co., Ltd. (present: Nippon Cytec Industries, Ltd.), etc. are mentioned.

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

As the base substrate (substrate), for example, glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene-based resin, etc.), metal (silicon wafer, etc.), wood, paper, slate, etc. are mentioned.

The coating method is not particularly limited, but examples 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 version , intaglio, plate, screen printing, etc.).

In addition, as a method of imidizing the polyamic acid contained in the composition for forming a release layer of the present invention, thermal imidation in which the composition applied on the substrate is heated as it is, and catalyst imidation in which a catalyst is added to the composition and heated can be heard

Catalyst imidation of polyamic acid is carried out by adding a catalyst to the composition for forming a release layer of the present invention and adjusting the catalyst-added composition by stirring, then applying to a substrate and heating to obtain a thin resin film (release layer). The amount of the catalyst is 0.1 to 30 mole times, preferably 1 to 20 mole times the amount of the amide acid group. Also, acetic anhydride or the like may be added as a dehydrating agent in the catalyst-added composition, and the amount is 1 to 50 mole times, preferably 3 to 30 mole times the amount of the amic acid group.

It is preferable to use a tertiary amine as an imidation catalyst. As a tertiary amine, pyridine, substituted pyridine, imidazole, substituted imidazole, picoline, quinoline, isoquinoline, etc. are preferable.

As for the heating temperature at the time of thermal imidation and catalyst imidation, 450 degreeC or less is preferable. When 450 degreeC is exceeded, the obtained resin thin film becomes brittle, and the resin thin film suitable for the intended use may not be obtained.

In addition, considering the heat resistance and linear expansion coefficient characteristics of the obtained resin thin film, after heating the applied composition at 50 ° C. to 100 ° C. for 5 minutes to 2 hours, the heating temperature is raised stepwise as it is, and finally over 375 ° C. to 450 ° C. It is preferable to heat from 30 minutes to 4 hours.

In particular, the applied composition is heated at 50 ° C. to 100 ° C. for 5 minutes to 2 hours, then higher than 100 ° C. to 200 ° C. for 5 minutes to 2 hours, then higher than 200 ° C. to 375 ° C. for 5 minutes to 2 hours, Finally, it is preferable to heat at over 375°C to 450°C for 30 minutes to 4 hours.

As for the mechanism used for heating, a hot plate, an oven, etc. are mentioned, for example. The heating atmosphere may be air or an inert gas, and may be normal pressure or reduced pressure.

The thickness of the resin thin film is usually about 0.01 to 10 μm, preferably about 0.05 to 5 μm, especially when used as a release layer, and a resin thin film having a desired thickness is formed by adjusting the thickness of the coating film before heating.

The thin film described above is optimal for use as a peeling layer for peeling without damaging a substrate applied to a flexible electronic device.

With the composition of the present application, a peeling layer formed between a flexible substrate applied to a flexible electronic device and a base substrate can be formed. As the base substrate, it is preferable to include glass or a silicon wafer, and more preferably, glass is included.

For example, a peeling layer can be formed by applying the composition of the present application to a glass substrate by a conventionally known method and heating the obtained coating film to a predetermined temperature.

In addition, the layer to be peeled off can be formed on the peeling layer. The layer of the body to be peeled off may be one layer or a plurality of layers. To manufacture various devices, it is realistic to have multiple layers.

Among the layers of the body to be released, the layer directly above the release layer depends on the release layer used, but it is preferable to use a layer having good peelability with the release layer, in other words, a layer with poor adhesion to the release layer used.

As another aspect of the present application, a method for producing a body to be separated is provided.

that way,

a) a step of forming a release layer after applying the composition of the present application onto a glass substrate;

b) forming a body to be separated on the release layer; and

c) Step of peeling the body to be separated at the interface between the release layer and the body to be separated;

By having, a body to be separated can be obtained.

In the step b), the "object to be peeled" may be one layer or a plurality of layers. In addition, the layer directly above the release layer among the "substances to be separated" is dependent on the release layer used, but it is said that the release property with the release layer is good, in other words, the adhesion with the release layer used is poor. good night.

According to another preferred aspect of the present invention, as a substrate structure applied to a flexible electronic device,

a base substrate;

A release layer formed of the composition for forming a release layer according to the present invention as a release layer covering the base substrate in one or two or more areas;

A flexible substrate covering the base substrate and the exfoliation layer

including,

A substrate structure is provided in which adhesion between the flexible substrate and the exfoliation layer is greater than adhesion between the exfoliation layer and the base substrate. The size of the adhesive force referred to herein can be confirmed by, for example, a cross-cut test shown in Examples of the present application.

Hereinafter, the present invention will be described according to examples, but the present invention is not limited to the examples.

Example

The abbreviations used in this embodiment are enumerated 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 (trimellitic acid monoester acid anhydride).

PMDA: Pyromellitic dianhydride.

<aldehyde>

IPHA: isophthalaldehyde.

[Measurement of Number Average Molecular Weight and Weight Average Molecular Weight]

The weight average molecular weight (hereinafter abbreviated as "Mw") and molecular weight distribution of the polymer were measured using a GPC apparatus (Shodex (registered trademark) column KF803L and KF805L) manufactured by Nippon Spectroscopy Co., Ltd., using dimethylformamide as an elution solvent at a flow rate of 1 ml. /min, column temperature was measured under the condition of 50 degreeC. In addition, Mw was taken as a polystyrene conversion value.

<Synthesis example>

<Synthesis Example 1 Synthesis of Polyimide Precursor P1>

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

17.8 g (0.164 mol) of p-PDA, 2.38 g (0.009 mol) of DATP, and 2.05 g (0.009 mol) of APAB were dissolved in 425 g of NMP, 52.8 g (0.179 mol) of BPDA was added simultaneously, and NMP 7.4 was added again. g was added, and it was made to react at 23 degreeC for 24 hours by nitrogen atmosphere. Mw of the obtained polyimide precursor P1 was 63000 and molecular weight distribution 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 adding 34.1 g (0.116 mol) of BPDA at the same time, 10 g of NMP was added again and it was made to react under nitrogen atmosphere at 23 degreeC for 24 hours. Mw of obtained polyimide precursor P2 was 70700 and molecular weight distribution 9.7.

<Synthesis Example 3 Synthesis of Polyimide Precursor P3>

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

20.261 g (0.1875 mol) of p-PDA and 12.206 g (0.0469 mol) of TPDA were dissolved in 617.4 g of NMP, and after cooling to 15°C, 50.112 g (0.2298 mol) of PMDA was added and the mixture was stirred at 48°C at 50°C under a nitrogen atmosphere. time reacted. Mw of obtained polyimide precursor P3 was 82,100, and molecular weight distribution was 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 reacted under a nitrogen atmosphere at room temperature for 24 hours. Mw of obtained polyimide precursor P4 was 57000, and molecular weight distribution was 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, it was made to react by nitrogen atmosphere at 23 degreeC for 24 hours. Mw of obtained polyimide precursor P5 was 107,300 and molecular weight distribution 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, it was made to react at 23 degreeC by nitrogen atmosphere for 24 hours. Mw of the obtained polymer was 107,300 and molecular weight distribution 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. PMDA 19.922g (91mmol) was added to the obtained solution, and it was made to react at 23 degreeC by nitrogen atmosphere for 24 hours. Mw of the obtained polymer was 55,900 and molecular weight distribution 3.1.

<Manufacture of release layer substrate>

P1 to P7 obtained in Synthesis Examples 1 to 7 were diluted to 4 wt% with NMP and coated on a 100 mm × 100 mm glass substrate (OA-10G alkali-free glass) or silicon wafer using a spin coater, Under curing conditions A to C, it was baked in an oven to prepare a release layer.

Cure conditions A : Maintained at 120 ° C for 30 minutes → Raised temperature → Maintained at 300 ° C for 60 minutes → Raised temperature → Maintained at 400 ° C for 60 minutes. In addition, the heating rate was 10 deg. C/min.

Cure conditions B : hold at 120 ° C for 30 minutes → raise the temperature → hold at 180 ° C for 20 minutes → raise the temperature → hold at 240 ° C for 20 minutes → raise the temperature → hold at 300 ° C for 20 minutes → raise the temperature → hold at 400 ° C for 20 minutes → raise the temperature → 450°C hold 60 minutes at °C. In addition, the heating rate was 10 deg. C/min.

Cure conditions C : hold at 80°C for 10 minutes → raise the temperature → hold for 30 minutes at 300°C → raise the temperature → hold for 30 minutes at 400°C. In addition, the heating rate was 10 deg. C/min.

The film thickness of the obtained coating film was measured using the contact-type film thickness meter (Dektak 3ST by ULVAC Co., Ltd.).

In Table 1, the precursors of P1 to P7 used, the applied substrate, curing conditions, and the film thickness of the produced release layer are shown.

＜Crosscut Test I＞

For the substrates provided with the release layer of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, adhesion between the substrate (glass or silicon wafer)/release layer was confirmed in cross-cut test I.

Crosscut test I was conducted as follows.

(1) On a film, 100 squares of 1 mm square were prepared.

(2) After that, the square was affixed with an adhesive tape (Cellotape (registered trademark)), and a peeling step was performed.

(3) After the peeling step, the squares remaining on the substrate were counted.

<Indices of results of crosscut test I>

As a result of the cross-cut test, the degree of peeling is represented by the following indexes.

5B: No peeling.

4B: Peeling of 5% or less.

3B: 5 to 15% peeling.

2B: 15 to 35% peeling.

1B: 35 to 65% peeling.

0B: 65% - 80% peeling.

B: 80% - 95% of peeling.

A: Peeling less than 95% - 100%.

AA: 100% peeling.

Apart from the cross-cut test I, for the substrates provided with the release layer of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the properties of the components constituting the release layer, namely (1) Heating Temperature indicating a 1% weight loss in weight change with time, (2) refractive index at a wavelength of 1000 nm, (3) birefringence at a wavelength of 1000 nm, and (4) surface energy were measured. In addition, measurement conditions, etc. of each characteristic are shown below.

<(1) Temperature showing 1% weight loss in weight change upon heating>

Thermogravimetric (TG) measurement was performed in a nitrogen atmosphere using TD-DTA2000ST manufactured by Bruker Corporation, and the temperature at which the weight decreased by 1% was determined.

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

The refractive index and birefringence were measured using a high-speed spectroscopic ellipsometer M-2000 (manufactured by J.A. Ulam Japan Co., Ltd.). In addition, the refractive index was made into the in-plane refractive index of the value of 1000 nm, and the birefringence was made into the difference of the in-plane refractive index and the 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.). In addition, the solvent used for the measurement was water and methylene iodide, and it calculated from the contact angle of these solvents.

<Formation of body to be peeled off and peeling test (crosscut test II)>

In Examples 1 to 5 and Comparative Examples 1 to 3, bodies to be peeled were formed on the substrates provided with the peeling layer, and the degree of peeling was confirmed by cross-cut test II.

<<Manufacture of layer to be released>>

On the release layer of the substrate provided with the release layer, a polyimide layer was formed as a body to be separated.

Specifically, the precursor P5 or P1 obtained in Synthesis Example 5 or Synthesis Example 1 was added to the release layer of the substrate provided with the release layer of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1. It was applied with a bar coater. After that, hold in the oven for 30 minutes at 120 ℃ → temperature increase → hold for 20 minutes at 180 ℃ → temperature rise → hold at 240 ℃ / 20 minutes → raise the temperature → hold for 20 minutes at 300 ℃ → raise the temperature → hold for 20 minutes at 400 ℃ → increase the temperature → Curing was performed at 450°C for 60 minutes (the speed was 10°C/minute at any temperature increase) to prepare a layer to be released with a film thickness of 15 µm made of polyimide.

＜＜Crosscut Test II＞＞

With respect to the board|substrate provided with the to-be-released body layer and the release layer obtained above, the adhesive force between the to-be-released body layer/released layer was confirmed by the cross-cut test II.

Cross-cut test II was carried out in the same way as cross-cut test I.

In Table 2, (1) temperature showing 1% weight loss in weight change during heating (in Table 2, it is indicated as "(1)"), (2) refractive index at a wavelength of 1000 nm (in Table 2) . (4)". However, the unit is dyne/cm), the polyimide precursor used in the layer to be peeled off, and the results of crosscut tests I and II are shown.

*: The birefringence of Comparative Example 2 could not be measured.

**: The cross-cut test II of Comparative Example 1 and Comparative Example 3 was not able to measure because the adhesion between the release layer and the substrate was low.

From Table 2, the following can be seen. In the release layers of Examples 1 to 5, since the result of test I was 5B, the release layer was not peeled off from the substrate, while the result of test II was AA, so only the layer to be released from the release layer. can be known to be In short, it is understood that the release layer formed from the composition for a release layer of the present invention brings about the desired release results.

On the other hand, in Comparative Example 1 and Comparative Example 3, since the result of Test I was AA, it was found that the release layer was separated from the substrate. In short, it turns out that Comparative Example 1 and Comparative Example 3 cannot obtain the desired peeling result. Further, in Comparative Example 2, since both Test I and Test II were 5B, neither peeling occurred at the interface between the peeling layer and the substrate nor between the peeling layer and the layer to be peeled off, and the desired peeling result could not be obtained. Able to know.

Claims (11)

A composition for forming a release layer containing a polyamic acid having a weight average molecular weight of 10,000 or more and containing 50 mol% or more of the monomer unit represented by the following formula (1), and an organic solvent.

[Wherein, X ¹ represents a tetravalent organic group, Y ¹ is a divalent group represented by any of the following formulas (P1) to (P3), and includes at least a divalent group represented by formula (P2):

(In the expression,
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 and represent an integer of 0 to 4)]. According to claim 1,
The composition for forming a release layer in which the polyamic acid further contains a monomer unit represented by the following formula (2).

[during expression,
X ¹ is as defined in claim 1, and Y ² represents a group represented by the following formula (P4):

(In the expression,
R ⁷ and R ⁸ may be the same or different and represent F, Cl, an alkyl group having 1 to 3 carbon atoms, or a phenyl group;
R' represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group;
l represents an integer of 0 to 4, and
m represents an integer of 0 to 4)]. According to claim 1,
The composition for forming a release layer, wherein X ¹ is a tetravalent aromatic group. According to claim 3,
The composition in which the said tetravalent aromatic group has at least 1 sort(s) chosen from a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton. According to claim 1,
A composition in which the organic solvent is a solvent represented by the following formula (A) or (B).

(In the formula, R ^a and R ^b may be the same or different, represent an alkyl group having 1 to 4 carbon atoms, and h represents a natural number). According to claim 1,
A composition for forming a release layer for forming a release layer formed directly on a glass substrate. A peeling layer formed between a flexible substrate applied to a flexible electronic device and a base substrate,
A release layer manufactured using the composition for forming a release layer according to any one of claims 1 to 6. As a substrate structure applied to flexible electronic devices,
A base substrate that is a glass substrate;
a release layer formed of the composition for forming a release layer according to any one of claims 1 to 6, as a release layer covering the base substrate in one or two or more regions;
Including the base substrate and a flexible substrate covering the exfoliation layer,
The substrate structure, characterized in that the adhesion between the release layer and the base substrate is greater than the adhesion between the flexible substrate and the release layer. According to claim 8,
A substrate structure in which the base substrate includes glass. A method for producing a release layer characterized by using the composition for forming a release layer according to any one of claims 1 to 6. As a manufacturing method of a substrate structure applied to a flexible electronic device,
A step of preparing a base substrate, which is a glass substrate;
A step of producing a release layer covering the base substrate in one or two or more regions using the composition for forming a release layer according to any one of claims 1 to 6;
A step of forming a flexible substrate on the base substrate and the release layer;
The manufacturing method, characterized in that the adhesion between the release layer and the base substrate is greater than the adhesion between the flexible substrate and the release layer.