KR102340689B1 - Composition for forming releasing layer - Google Patents

Abstract

According to the present invention, the adhesiveness with 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 group of layers formed above the release layer can be easily peeled from the release layer. A composition for forming the release layer thereof is provided. This invention contains 50 mol% or more of the monomer unit represented by Formula (1), A weight average molecular weight provides the composition for peeling layer formation containing 10,000 or more polyamic acid, and an organic solvent. In Formula (1), X<^1> represents a tetravalent organic group here, and Y<^1> represents a divalent group represented by a 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 to be formed directly on a glass substrate.

In recent years, performance, such as provision of a bending function, and thickness reduction and weight reduction, is calculated|required by an electronic device. From this, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, brittle and inflexible glass substrate. Moreover, in a new-generation display, development of the active full-color TFT display panel using a lightweight flexible plastic substrate is calculated|required.

Then, various examinations of the manufacturing method of the electronic device which used the resin film as a board|substrate were started, and in a new-generation display, manufacturing examination is advancing in the process which can divert existing TFT equipment.

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

Moreover, in patent document 4, the to-be-released layer (in Patent Document 4, it is described as a "transfer to-be-transferred layer") is affixed to a plastic film using the technique of patent documents 1 - 3 indication, and a liquid crystal display device is completed. disclose how to do it.

However, in the method disclosed in Patent Documents 1 to 4, particularly the method disclosed in Patent Document 4, it is essential to use a substrate with high light transmittance, and sufficient energy to pass through the substrate and release hydrogen contained in the amorphous silicon Therefore, there is a problem that relatively large laser light irradiation is required and damage to the layer to be peeled is caused. Moreover, since laser processing requires a long time and it is difficult to peel the to-be-released layer which has a large area, there also exists a problem that it is difficult to raise the productivity of device manufacture.

Japanese Patent Laid-Open No. 10-125929. Japanese Patent Application Laid-Open No. 10-125931. WO2005/050754 pamphlet. Japanese Patent Application Laid-Open No. 10-125930.

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

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

Further, an object of the present invention is, in addition to or in addition to the above object, adhesiveness with 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 upper portion of the release layer is not It is to provide the composition for forming the peeling layer which can peel easily the layer or layer group to be formed from a peeling layer.

The present inventors discovered the following invention this time. That is, when the present inventor forms a peeling layer using the composition containing 50 mol% or more of monomer units of a specific structure, a weight average molecular weight is a fixed value or more, and a composition containing an organic solvent, the layer is flexible It was unexpectedly discovered that it has suitable properties that can be peeled off without damaging a substrate applied to electronic devices or the like. While this layer maintains adhesion to the glass substrate on which the release layer is formed and peels off easily at the interface with the glass substrate, it is a layer or group of layers formed above the release layer on the opposite side to the glass substrate. About it, it was a thing which could peel easily from a peeling layer. This invention is based on this knowledge.

The composition for peeling layer formation containing 50 mol% or more of the monomer unit represented by <1> following formula (1), and a weight average molecular weight of 10,000 or more polyamic acid, 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]

(wherein, 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>, wherein Y ¹ is preferably a bivalent group represented by any one of formulas (P1) ~ (P3) below.

[Formula 3]

(during the meal,

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 the integer of 0-4).

<3> The <2> wherein Y is ^1, preferably comprises a divalent group represented by at least formulas (P1).

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

[Formula 4]

[During the ceremony,

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

[Formula 5]

(during the meal,

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, a C1-C3 alkyl group, or a phenyl group,

l represents an integer of 0 to 4, and

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

<5> The method according to any one of the above <1> ~ <4>, X 1 is, preferably a tetravalent aromatic group.

<6> In <5>, it is preferable that the said tetravalent aromatic group has at least 1 sort(s) chosen 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 a following formula (A) or (B).

[Formula 6]

(In formula, R ^a and R ^b may be the same or different, and represent a C1-C4 alkyl group, and h represents a natural number).

<8> In any one of said <1>-<7>, it is good 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 said <1>-<8>, it is good that the composition for peeling layer formation by this invention is for forming the peeling layer formed directly on a glass substrate.

A release layer formed between the flexible substrate applied to a <10> flexible electronic device, and a base substrate, Comprising: The release layer manufactured using the composition for release layer formation in any one of said <1>-<9>.

<11> A substrate structure applied to a flexible electronic device, comprising:

base board,

In one or two or more regions, as a release layer covering the base substrate, a release layer formed of the composition for forming a release layer according to any one of <1> to <9>;

The base substrate and the flexible substrate covering the release layer

including,

A substrate structure, characterized in that the adhesive force between the flexible substrate and the release layer is greater than the adhesion force 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, wherein the composition for forming a release layer according to any one of <1> to <9> is used. 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> A method for manufacturing a substrate structure applied to a flexible electronic device, the method comprising:

The process of preparing the 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 <1> to <9>;

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

Adhesive force between the flexible substrate and the release layer is greater than the adhesion force between the release layer and the base substrate, the manufacturing method.

The present invention can solve the above problems.

Specifically, according to the present invention, it is possible to provide a composition for forming a release layer for peeling without damaging a substrate applied to a flexible electronic device.

Further, according to the present invention, in addition to or in addition to the above effects, adhesion to the glass substrate on which the release layer is formed is maintained, so that peeling at the interface with the glass substrate does not occur, while forming above the release layer It is to provide the composition for forming the peeling layer which can peel easily the layer or layer group used as a peeling layer from a peeling layer.

Hereinafter, the present invention will be described in detail.

Composition for forming a release layer

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

[Formula 7]

Moreover, as mentioned above, in Formula (1), X<^1> represents a tetravalent organic group, and Y<^1> represents a divalent group represented by a following formula (P).

[Formula 8]

Moreover, in Formula (P), R represents F, Cl, or a C1-C3 alkyl group, or a phenyl group, Preferably F, Cl is represented. Similarly, in said formula (P), m represents the integer of 0-4, Preferably it shows 0-2, More preferably, it shows 0-1, Especially preferably, it shows 0. Moreover, in said Formula (P), r represents the integer of 1-3.

Moreover, methyl, ethyl, n-propyl, and i-propyl are contained as a C1-C3 alkyl group, Preferably a C1-C3 alkyl group is methyl, More preferably, it is 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 considering that the viscosity of the resin composition becomes excessively high and that a resin thin film with high flexibility is obtained with good reproducibility, etc. , Preferably it is 1,000,000 or less, More preferably, it is 200,000 or less.

The polyamic acid used by this invention is 50 mol% or more of the monomer unit represented by Formula (1), Preferably it is 60 mol% or more, More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more. , more preferably 90 mol% or more. By using the polyamic acid which is content of such a monomer unit, the resin thin film which has the characteristic suitable for a peeling film can be obtained with favorable 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 comprising only the monomer unit represented by formula (1), that is, the monomer unit represented by formula (1) is 100 mol%. contained polymer. At this time, as long as it is represented by Formula (1), 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 latter case, the number of the monomer units of Formula (1) which a polyamic acid contains becomes like this. Preferably it is 2-4, More preferably, it is 2-3.

In the present invention, the group represented by the formula (P) preferably includes a divalent group represented by any of the formulas (P1) to (P3), and more preferably a divalent group represented by the formula (P1) or (P3). group, and still more preferably, a divalent group represented by the formula (P3) is included.

[Formula 9]

In the above formulas (P1), (P2) and (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 A 1-3 alkyl group or a phenyl group is shown, Preferably F or Cl is shown.

Similarly, in these formulas, m1, m2, m3, m4, m5 and m6 may be the same or different, and represent the integer of 0-4, Preferably it represents 0-2, More preferably, 0-1 , and particularly preferably 0.

The polyamic acid used by this 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 still 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, Y<^2> represents group represented by said Formula (P4).

[Formula 11]

In the 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 having 1 to 3 carbon atoms, or a phenyl group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In addition, l and m may be the same or different, and represent the integer of 0-4, Preferably it shows 0-2, More preferably, it shows 0-1, Especially preferably, it shows 0.

As such other monomer units, in addition to the monomer units of formula (2), 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 and 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'-benzophenonetetracarboxylic anhydride.

In Formulas (1) and (2), although X<^1> is a tetravalent organic group as above-mentioned, Preferably it is a tetravalent aromatic group.

When producing 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 acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3, 3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , 1,2,5,6-naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic 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 acid 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 '-hydroquinonedibenzoate tetracarboxylic dianhydride, 2,2'-bis(4-hydroxyphenyl)propanedibenzoate-3,3',4,4'-tetracarboxylic acid, etc. are mentioned. have.

Preferably, the aromatic tetracarboxylic dianhydride preferable here is selected from the following compound group.

[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 embodiment 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 a biphenyl skeleton, 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 comprises 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) (formula (4)) as acid dianhydride; p-phenylenediamine (pPDA) (formula (5)) and 4,4″-diamino-p-terphenyl (DATP) (formula (6)) as diamines, or pyromellitic dianhydride as acid dianhydride It can obtain by making (PMDA) (Formula (7)) and pPDA (Formula (5)) as diamine react.

[Formula 13]

In the above reaction, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (pPDA) and 4,4″-diamino-p-terphenyl ( DATP) or pyromellitic dianhydride (PMDA), and the input 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., but with respect to the amine component 1 , Usually, an acid anhydride component can be made into about 0.7-1.3, Preferably it is about 0.8-1.2.

On the other hand, the diamine of tuipbi of pPDA and DATP, in the case when the amount of substance (m ²⁾ of a DATP to 1, the amount of substance (m ¹⁾ of pPDA, can typically about 1.7 ~ 20, but, preferably 2.1 ~ 20 , More preferably, it is 2.2-20, More preferably, it is 2.3-19, More preferably, it 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 further 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. Various solvents can be used as the organic solvent that can be used here as long as it does 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 and protic solvents such as ,N-dimethylpropylamide and γ-butyrolactone. These may be used individually or in combination of 2 or more type.

According to a preferable aspect of this invention, an organic solvent is a solvent represented by a formula (A) or (B).

[Formula 14]

In formulas (A) and (B), R ^a and R ^b may be the same or different, represent a C1-C4 alkyl group, Preferably it is C1-C3. In addition, h represents a natural number here, Preferably it is 1-3.

The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C. In order to prevent imidization of the obtained polyamic acid and maintain a high content of the polyamic acid unit, it is preferable Preferably it is about 0-70 degreeC, More preferably, it is about 0-60 degreeC, More preferably, it is about 0-50 degreeC.

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

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

In this invention, after filtering the said reaction solution normally, the filtrate is used as it is, or diluted or concentrated and used as a composition for peeling layer formation. 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 characteristic of the resin thin film obtained be reduced, but a composition can be obtained efficiently.

The solvent used for dilution or concentration is not specifically limited, For example, the thing similar to the specific example of the reaction solvent of the said reaction is mentioned, These may be used individually or in combination of 2 or more types.

Among these, in consideration of obtaining a resin thin film with high flatness with good reproducibility, examples of the solvent to be used include 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 with respect 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, etc., but is usually about 0.5 to 30 mass%, preferably 5 to It is about 25 mass %.

In addition, the viscosity of the composition for forming a release layer is also appropriately set in consideration of the thickness of the thin film to be manufactured. It is about 10-10,000 mPa*s, Preferably it is about 20-1000 mPa*s, More preferably, it is about 20-200 mPa*s.

Here, the viscosity of the composition for forming a release layer is measured using a commercially available viscometer for measuring the viscosity of a liquid, for example, referring to the procedure described in JIS K7117-2, under the condition that the temperature of the composition for forming the release layer is 25°C. can be measured Preferably, as the viscometer, a conical flat plate type (cone plate type) rotational viscometer is used, preferably the same type viscometer and 1°34'×R24 as a standard cone rotor, the composition for forming a release layer can be measured under the condition of a temperature of 25 °C. As such a rotational viscometer, TVE-25H by Toki Sangyo Co., Ltd. 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 a crosslinking compound is also mentioned.) is mentioned, It is not limited to these.

Examples of the crosslinkable compound include compounds containing two or more epoxy groups, melamine derivatives, benzoguanamine derivatives, glycoluril, and the like, in which the hydrogen atom of the amino group has a methylol group, an alkoxymethyl group, or a group substituted with both. can, but is 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 EPOLID GT-401, EPOLID GT-403, EPOLID GT-301, EPOLID GT-302, CELOXIDE 2021, CELOXIDE 3000 (above, Co., Ltd.) Epoxy compound having a cyclohexene structure such as Daicel); Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, Japan Epoxy) Bisphenol A epoxy compounds such as Resin Corporation (current: Mitsubishi Chemical Corporation, jER (registered trademark) series)); Bisphenol F epoxy compounds such as Epicoat 807 (manufactured by Japan Epoxy Resin Corporation); 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.), etc. phenol novolac 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. (current: manufactured by Mitsubishi Chemical Co., Ltd., jER (registered trademark)) series), cresol novolak-type epoxy compounds such as); naphthalene-type epoxy compounds such as V8000-C7 (manufactured by DIC Corporation); Denacol EX-252 (manufactured by Nagase Chemtex Corporation), CY175, CY177, CY179, and Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, manufactured by BASF), Epiclone 200, Epiclone 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 Co., Ltd., jER (registered trademark) series)), ED-5661, ED-5662 (above, manufactured by Celanese Coatings Co., Ltd.); 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.).

As a melamine derivative, benzoguanamine derivative or glycoluril, in which the hydrogen atom of the amino group has a methylol group, an alkoxymethyl group, or a group substituted with both, MX-750 in which an average of 3.7 methoxymethyl groups are substituted per triazine ring; MW-30 in which an average of 5.8 methoxymethyl groups are substituted per triazine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel 771 Methoxymethylated melamines, such as Cymel 325, Cymel 327, Cymel 703, Cymel 712; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Methoxy, such as Cymel 254. 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 benzoguanamine such as Cymel 1123-10; Butoxymethylated benzoguanamine such as Cymel 1128; Carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80; Cymel A butoxymethylation glycoluril like 1170; A methylolation glycoluril like Cymel 1172 (above, the Mitsui Cyanamide Co., Ltd. product (current: Nippon Cytec Industries Co., 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 (releasable layer) made of polyimide having high heat resistance, moderate flexibility, and a suitable 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 application method is not particularly limited, but for example, 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, a printing method (embossed plate) , intaglio, flat plate, screen printing, etc.) and the like.

In addition, as a method for imidizing the polyamic acid contained in the composition for forming a release layer of the present invention, thermal imidization by heating the composition applied on the substrate as it is, and catalytic imidization by heating by adding a catalyst to the composition. can be heard

Catalyst imidation of polyamic acid adds a catalyst in the composition for peeling layer formation of this invention, and adjusts a catalyst addition composition by stirring, Then, a resin thin film (release layer) is obtained by apply|coating to a board|substrate and heating. The amount of the catalyst is 0.1 to 30 mole times of the amic acid group, preferably 1 to 20 mole times. In addition, acetic anhydride or the like may be added as a dehydrating agent to the catalyst addition composition, and the amount thereof is 1 to 50 mole times, preferably 3 to 30 mole times of the amic acid group.

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

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

In addition, in consideration of the heat resistance and coefficient of linear expansion characteristics of the resulting resin thin film, the applied composition is heated at 50°C to 100°C for 5 minutes to 2 hours, then the heating temperature is raised stepwise as it is, and finally exceeds 375°C to 450°C It is preferable to heat for 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 at more than 100°C to 200°C for 5 minutes to 2 hours, then at more than 200°C to 375°C for 5 minutes to 2 hours; Finally, it is preferable to heat over 375 degreeC - 450 degreeC for 30 minutes - 4 hours.

As an apparatus used for heating, a hot plate, an oven, etc. are mentioned, for example. The heating atmosphere may be air or inert gas, and may be under 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 the thickness of the coating film before heating is adjusted to form a resin thin film having a desired thickness.

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 this application, the peeling layer formed between the flexible substrate applied to a flexible electronic device, and a base substrate can be formed. As a base substrate, it is preferable to contain glass or a silicon wafer, More preferably, glass is contained.

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

Moreover, the to-be-released body layer can be formed on a peeling layer. One layer may be sufficient as the to-be-released body layer, and multiple layers may be sufficient as it. In order to manufacture various devices, it is realistic that there are multiple layers.

Among the layers to be removed, the layer immediately above the release layer depends on the release layer to be used, but it is preferable to use one having good releasability with the release layer, in other words, those having poor adhesion to the release layer to be used.

As another aspect of the present application, there is provided a method for producing an object to be removed.

That way,

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

b) a step of forming an object to be removed on the release layer; and

c) at the interface between the release layer and the object to be peeled, a step of peeling the object to be peeled;

By having it, a to-be-released body can be obtained.

b) Step WHEREIN: One layer or multiple layers may be sufficient as "to-be-released body". In addition, although the layer immediately above the release layer in the "subject to be peeled" depends on the release layer to be used, it is necessary to have good releasability with the release layer, in other words, those with poor adhesion to the release layer to be used. good.

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

base board,

In one or two or more regions, as a release layer covering the base substrate, a release layer formed by the composition for forming a release layer according to the present invention;

The base substrate and the flexible substrate covering the release layer

including,

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

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Example

Abbreviations used in the present Examples are listed and described 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-biphenylenebis (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 manufactured by Nippon Spectroscopy Co., Ltd. (Shodex (registered trademark) columns KF803L and KF805L), and dimethylformamide as the elution solvent at a flow rate of 1 ml It measured on conditions of /min and the column temperature of 50 degreeC. In addition, Mw was made into polystyrene conversion value.

<Synthesis example>

<Synthesis example 1 synthesis|combination 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 were simultaneously added, and then NMP 7.4 again g was added, and it was made to react in nitrogen atmosphere at 23 degreeC for 24 hours. Mw of the obtained polyimide precursor P1 was 63000 and molecular weight distribution 9.9.

<Synthesis example 2 synthesis|combination 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 simultaneously, 10 g of NMP was added again, and reaction was performed at 23° C. under a nitrogen atmosphere for 24 hours. Mw of the obtained polyimide precursor P2 was 70700, and molecular weight distribution 9.7.

<Synthesis example 3 synthesis|combination 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 thereto, and 48 at 50°C in a nitrogen atmosphere. time was reacted. Mw of the obtained polyimide precursor P3 was 82,100, and molecular weight distribution was 2.7.

<Synthesis example 4 synthesis|combination 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 thereto, and the reaction was carried out at room temperature in a nitrogen atmosphere for 24 hours. Mw of the obtained polyimide precursor P4 was 57000, and molecular weight distribution was 9.3.

<Synthesis example 5 synthesis|combination 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 at 23°C under a nitrogen atmosphere for 24 hours. Mw of the 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 reacted at 23° C. under a nitrogen atmosphere for 24 hours. The obtained polymer had a Mw of 107,300 and a molecular weight distribution of 4.6.

<Synthesis example 7 synthesis|combination 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. 19.922 g (91 mmol) of PMDA was added to the obtained solution, and it was made to react at 23 degreeC in nitrogen atmosphere for 24 hours. The obtained polymer had a Mw of 55,900 and a molecular weight distribution of 3.1.

<Manufacture of a release layer substrate>

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

Cure condition A : Hold at 120 °C for 30 minutes → Increase in temperature → Hold at 300 °C for 60 minutes → Increase in temperature → Hold at 400 °C for 60 minutes. In addition, the temperature increase rate was 10 degreeC/min.

Cure condition B : Hold for 30 minutes at 120 °C → Increase temperature → Hold at 180 °C for 20 minutes → Increase temperature → Hold at 240 °C for 20 minutes → Increase temperature → Hold at 300 °C for 20 minutes → Increase temperature → Hold at 400 °C for 20 minutes → Increase temperature → 450 Hold for 60 minutes at °C. In addition, the temperature increase rate was 10 degreeC/min.

Cure condition C : Hold for 10 minutes at 80°C → Increase in temperature → Hold at 300°C for 30 minutes → Increase in temperature → Hold at 400°C for 30 minutes. In addition, the temperature increase rate was 10 degreeC/min.

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

In Table 1, the precursors of P1-P7 used, the coating substrate, curing conditions, and the film thickness of the produced peeling layer are shown.

<Cross Cut Test I>

About the board|substrate with a peeling layer of Examples 1-5 and Comparative Examples 1-3 shown in Table 1, the adhesive force of the board|substrate (glass or silicon wafer) / peeling layer was confirmed in the crosscut test I.

The crosscut test I was implemented as follows.

(1) On the film, 100 1 mm squares were manufactured.

(2) Then, the said square was affixed with the adhesive tape (Cellotape (trademark)), and the peeling process was implemented.

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

<Indices of results of cross-cut test I>

As a result of the crosscut test, the degree of peeling is shown with the following index|index.

5B: It does not peel.

4B: Peeling of 5% or less.

3B: 5 to 15% of peeling.

2B: 15 to 35% of peeling.

1B: 35 to 65% of peeling.

0B: 65% to 80% of peeling.

B: 80% to 95% of peeling.

A: 95% - less than 100% peeling.

AA: 100% peeling.

Separately from the cross-cut test I, for the substrates with a release layer in Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the characteristics of the components constituting the release layer, that is, (1) heating The temperature showing a 1% weight loss with respect to the weight change at 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, the measurement conditions of each characteristic, etc. are shown below.

<(1) Temperature at which 1% weight loss in weight change during heating>

Thermogravimetric (TG) measurement was performed in nitrogen atmosphere using TD-DTA2000ST by Bruker Corporation, and the temperature at which weight decreases 1% was calculated|required.

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

The refractive index and the birefringence were measured using 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 a value of 1000 nm, and the birefringence was made into the difference between the in-plane refractive index and the out-of-plane refractive index.

<(4) surface energy>

The surface energy of each member was measured using the fully automatic contact angle meter DM-701 (made by Kyowa Interface Science Co., Ltd.). In addition, the solvent used for the measurement was water and methylene iodide, Computation was carried out from the contact angle of these solvents.

<Formation of object to be removed and its peel test (Crosscut Test II)>

The body to be peeled was formed on the board|substrate with a peeling layer of Examples 1-5 and Comparative Examples 1-3, and the degree of the peeling was confirmed by the crosscut test II.

<<Preparation of layer to be removed>>

On the release layer of the substrate provided with the release layer, a polyimide layer was formed as an object to be released.

Specifically, the precursor P5 or P1 obtained in Synthesis Example 5 or Synthesis Example 1 above on 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, in an oven, keep at 120 ℃ for 30 minutes → raise the temperature → maintain at 180 ℃ for 20 minutes → increase the temperature → keep at 240 ℃/20 min → increase the temperature → hold at 300 ℃ for 20 minutes → increase the temperature → keep at 400 ℃ for 20 minutes → increase the temperature → Curing was performed at 450 degreeC for 60 minutes (in any temperature increase, the rate was 10 degreeC/min), the to-be-released body layer with a film thickness of 15 micrometers which consists of polyimide was manufactured.

<<Crosscut Test II>>

About the board|substrate provided with the to-be-released body layer and peeling layer obtained above, the adhesive force between to-be-released body layer/peelable layers was confirmed by crosscut test II.

Crosscut test II was implemented similarly to crosscut test I.

In Table 2, (1) a temperature at which a weight loss by 1% in a weight change upon heating (in Table 2, it is denoted as “(1)”), (2) a refractive index at a wavelength of 1000 nm (in Table 2) , "(2)"), (3) the difference between the refractive index and birefringence (in Table 2, "(3)"), (4) surface energy (in Table 2, " (4)". However, the unit is dyne/cm), the polyimide precursor used for the layer to be removed, and the results of crosscut tests I and II are shown.

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

**: Since adhesiveness with a peeling layer and a board|substrate was low in the crosscut test II of the comparative example 1 and the comparative example 3, it was not able to measure.

Table 2 shows the following. As for the release layers of Examples 1 to 5, since the result of Test I was 5B, the release layer did not peel off from the substrate, while the result of Test II was AA, so only the release layer peeled from the release layer. it can be seen that That is, it turns out that the peeling layer formed from the composition for peeling layers of this invention brings a desired peeling result.

On the other hand, in Comparative Example 1 and Comparative Example 3, since the result of Test I is AA, it turns out that the peeling layer peels from a board|substrate. That is, it turns out that the comparative example 1 and the comparative example 3 cannot obtain the desired peeling result. Further, in Comparative Example 2, since Test I and Test II were both 5B, there was no peeling at the interface between the release layer and the substrate, nor at the interface between the release layer and the layer to be peeled, so that the desired peeling result could not be obtained. Able to know.

Claims (14)

The composition for peeling layer formation which contains 50 mol% or more of monomer units represented by following formula (1), and contains a polyamic acid with a weight average molecular weight of 10,000 or more, 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 the formula (P1):

(during the meal,
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 the integer of 0-4)]. delete delete The method of claim 1,
The composition for peeling layer formation in which the said polyamic acid further contains the monomer unit represented by following formula (2).

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

(during the meal,
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)]. The method of claim 1,
The composition for forming a release layer wherein X ^{1 is a tetravalent aromatic group.} 6. The method of claim 5,
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. The method of claim 1,
The composition in which the said organic solvent is a solvent represented by a following formula (A) or (B).

(In formula, R ^a and R ^b may be the same or different, and represent a C1-C4 alkyl group, and h represents a natural number). The method of claim 1,
The composition for peeling layer formation whose content of the monomer unit represented by the said Formula (1) in the said polyamic acid is 60 mol% or more. The method of claim 1,
A composition for forming a release layer for forming a release layer to be formed directly on a glass substrate. A release layer formed between a flexible substrate applied to a flexible electronic device and a base substrate, comprising:
A release layer produced by using the composition for forming a release layer according to any one of claims 1 to 9. A substrate structure applied to a flexible electronic device, comprising:
base board,
In one or two or more regions, a release layer covering the base substrate, the release layer formed of the composition for forming a release layer according to any one of claims 1 to 9;
A flexible substrate covering the base substrate and the release layer,
A substrate structure, characterized in that the adhesive force between the flexible substrate and the release layer is greater than that between the release layer and the base substrate. 12. The method of claim 11,
A substrate structure wherein the base substrate comprises glass. 10. A method for producing a release layer, wherein the composition for forming a release layer according to any one of claims 1 to 9 is used. A method of manufacturing a substrate structure applied to a flexible electronic device, comprising:
The process of preparing the 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 claims 1 and 4 to 9;
a step of forming a flexible substrate on the base substrate and the release layer;
A manufacturing method, characterized in that the adhesive force between the flexible substrate and the release layer is greater than that of the release layer and the base substrate.