JPWO2018025953A1 - Composition for Release Layer Formation and Release Layer - Google Patents

Abstract

Provided is a composition for forming a release layer, which comprises a polyamic acid represented by the following formula (1) and an organic solvent. (Wherein, X represents an aromatic group represented by the following formula (2a) or (2b), Y represents a divalent aromatic group having a fluorine atom, and Z represents X having the formula (2a) And when X represents an aromatic group represented by the following formula (3a) or (4a), and X is the formula (2b), they are independently from each other; (4b) represents an aromatic group, and m represents a natural number.)

Description

  The present invention relates to a release layer-forming composition and a release layer.

In recent years, in addition to the characteristics of thickness reduction and weight reduction, electronic devices are required to have a function of being able to be bent. For this reason, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, fragile, and inflexible glass substrate.
In particular, in the new-generation display, development of an active matrix full-color TFT display panel using a lightweight flexible plastic substrate (hereinafter referred to as a resin substrate) is required. Technologies related to this new generation display are expected to be diverted to various fields such as flexible displays, flexible smartphones, and mirror displays.

  Therefore, various methods of manufacturing electronic devices using resin films as substrates have begun to be studied, and in new generation displays, studies are being made on processes in which existing equipment for manufacturing TFT display panels can be diverted. Moreover, in a touch panel type display, measures for efficiently manufacturing a resin substrate or the like for a transparent electrode of a touch panel used in combination with a display panel have been studied. Generally, a resin substrate used for a touch panel is a polyimide resin substrate, an acrylic resin substrate, a polyethylene terephthalate (PET) resin substrate, a cycloolefin resin substrate having the same degree of transparency as glass as the TFT display panel etc. Film substrates are used.

  As a method of producing a flexible display, a direct method is mainly known (Non-Patent Document 1). As a direct method, a resin substrate prepared in advance is attached to a glass substrate through an adhesive layer, and a pixel circuit including a TFT and an organic EL are directly formed on the substrate, or a resin substrate on a glass substrate And a method of directly forming a pixel circuit including a TFT and an organic EL on the substrate.

  And in this direct method, the resin substrate in which the pixel circuit etc. were formed on the glass substrate is exfoliated by the various methods mentioned later, and it uses for preparation of the electronic device made into the object of a display panel etc.

  For example, in Patent Documents 1, 2 and 3, after an amorphous silicon thin film layer is formed on a glass substrate and a plastic substrate is formed on the thin film layer, laser is irradiated from the glass substrate side to crystallize amorphous silicon. There is disclosed a method of peeling a plastic substrate from a glass substrate by hydrogen gas generated along with its crystallization.

  Further, in Patent Document 4, a liquid crystal display device is obtained by attaching a layer to be peeled (described as "transferred layer" in Patent Document 4) to a plastic film using the techniques disclosed in Patent Documents 1 to 3. A method of completion is disclosed.

However, in the methods disclosed in Patent Literatures 1 to 4, in particular, the method disclosed in Patent Literature 4, it is essential to use a highly translucent substrate to transmit the laser light, and the substrate passes In addition, it is necessary to irradiate a laser beam of relatively large energy which is sufficient to release hydrogen contained in amorphous silicon, and the layer to be peeled may be damaged by the laser beam irradiation. And there is a problem.
In addition, when the layer to be peeled has a large area, it takes a long time to perform the laser treatment, so it is difficult to increase the productivity of device fabrication.

  As a means to solve such problems, Patent Document 5 uses a current glass substrate as a substrate (hereinafter referred to as a glass substrate), and forms a release layer on the glass substrate using a polymer such as cyclic olefin copolymer. After forming a heat-resistant resin film (resin substrate) such as a polyimide film on the peeling layer, forming and sealing an ITO transparent electrode or TFT on the film by a vacuum process, finally peeling off the glass substrate A manufacturing process to remove is employed.

  On the other hand, in the case of a new generation display, a large area of a substrate is required in response to a request for handling a large screen and improvement in yield. In order to apply the resin composition uniformly to a large area coated surface, a slit coating method using a slit coater or the like is generally advantageous. The slit coating method is a coating method using a slit nozzle, and since it is not necessary to rotate the substrate as in the conventional spin coating method, it is widely adopted from the viewpoint of reduction in the amount of resin composition used and process safety. There is. However, in this slit coating method, from the viewpoint of productivity improvement, speeding up of the coating process is desired. In order to realize the speeding up of the slit coating method, it is necessary to suppress the occurrence of streaks and the like at the time of coating, and for that purpose, it is necessary to reduce the viscosity of the solution which is one of the most important parameters.

  For example, Patent Documents 6 and 7 disclose a composition using a so-called low viscosity solvent such as propylene glycol monomethyl ether acetate or propylene glycol monomethyl ether as a composition for a photoresist suitable for the slit coating method. However, since a resin (or a precursor thereof) such as a polyimide resin generally used in a composition for forming a release layer is not dissolved in these low viscosity solvents, a slit coating method should be adopted for forming the release layer. Was difficult. Therefore, if it becomes possible to dissolve the resin (or its precursor) used in the composition for forming the release layer in the low viscosity solvent, not only the coating property in the conventional spin coating method is improved but also the slit It can be used suitably also as a coating system.

Japanese Patent Application Laid-Open No. 10-125929 Japanese Patent Application Laid-Open No. 10-125931 WO 2005/050754 Unexamined-Japanese-Patent No. 10-125930 gazette Unexamined-Japanese-Patent No. 2010-111853 International Publication No. 2011/030744 JP, 2008-70480, A

NHK Giken R & D / No. 145 / 2014.5

  The present invention has been made in view of the above circumstances, is also soluble in so-called low viscosity solvents such as propylene glycol monomethyl ether, can be easily applied to a slit coating method, and is a flexible electron formed thereon Provided is a composition for forming a release layer, which provides a release layer which can be released without damaging the resin substrate of a device, particularly a film substrate formed of polyimide resin, acrylic resin, cycloolefin polymer resin or the like. With the goal.

  As a result of intensive studies to solve the above problems, the present inventors have found that polyamic acid having a specific structure can be easily dissolved in a low viscosity solvent, and the polyamic acid and the organic solvent And the composition having excellent adhesion to a substrate such as a glass substrate and the like, and appropriate adhesion to a resin substrate used for a flexible electronic device, particularly a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm. The present invention has been completed by finding that a release layer having a suitable release property is provided.

（式中、Ｘは、下記式（２ａ）又は（２ｂ）で表される芳香族基を表し、Ｙは、フッ素原子を有する２価の芳香族基を表し、Ｚは、Ｘが式（２ａ）で表される芳香族基である場合、互いに独立して、下記式（３ａ）又は（４ａ）で表される芳香族基を表し、Ｘが式（２ｂ）で表される芳香族基である場合、互いに独立して、下記式（３ｂ）又は（４ｂ）で表される芳香族基を表し、ｍは、自然数を表す。）

［２］上記Ｙが、下記式（５）で表される芳香族基である［１］記載の剥離層形成用組成物。

［３］上記Ｙが、下記式（６）で表される芳香族基である［２］記載の剥離層形成用組成物。

［４］上記Ｘにおいて、上記式（２ａ）で表される芳香族基が、下記式（７ａ）又は（８ａ）で表される芳香族基であり、上記Ｚが、互いに独立して、下記式（９ａ）又は式（１０ａ）で表される芳香族基である［１］〜［３］のいずれかに記載の剥離層形成用組成物。

［５］上記Ｘにおいて、上記式（２ｂ）で表される芳香族基が、下記式（７ｂ）又は（８ｂ）で表される芳香族基であり、上記Ｚが、互いに独立して、下記式（９ｂ）又は式（１０ｂ）で表される芳香族基である［１］〜［３］のいずれかに記載の剥離層形成用組成物。

［６］上記有機溶媒が、下記式（Ｓ１）〜（Ｓ７）で表される構造を有するものから選ばれる少なくとも１種である［１］〜［５］のいずれかに記載の剥離層形成用組成物。

（式中、Ｒ¹〜Ｒ⁸は、互いに独立して、水素原子、又は炭素数１〜１０のアルキル基を表し、Ｒ⁹及びＲ¹⁰は、互いに独立して、水素原子、炭素数１〜１０のアルキル基、又は炭素数１〜１０のアシル基を表し、ｂ及びｎは自然数を表す）
［７］上記有機溶媒が、プロピレングリコールモノメチルエーテル又はプロピレングリコールモノメチルエーテルアセテートである［６］記載の剥離層形成用組成物。
［８］［１］〜［７］のいずれかに記載の剥離層形成用組成物を用いて形成される剥離層。
［９］［８］記載の剥離層を用いる樹脂基板の製造方法。
［１０］上記樹脂基板が、ポリイミド樹脂基板又は波長４００ｎｍの光透過率が８０％以上である樹脂基板である［９］記載の製造方法。Accordingly, the present invention provides the following release layer-forming composition and release layer.
[1] A composition for forming a release layer, comprising a polyamic acid represented by the following formula (1) and an organic solvent.

(Wherein, X represents an aromatic group represented by the following formula (2a) or (2b), Y represents a divalent aromatic group having a fluorine atom, and Z represents X having the formula (2a) When it is an aromatic group represented by), each of them independently represents an aromatic group represented by the following formula (3a) or (4a), and X is an aromatic group represented by the formula (2b) In some cases, each independently represents an aromatic group represented by the following formula (3b) or (4b), and m represents a natural number.)

[2] The composition for forming a release layer according to [1], wherein Y is an aromatic group represented by the following formula (5).

[3] The composition for forming a release layer according to [2], wherein Y is an aromatic group represented by the following formula (6).

[4] In the above X, the aromatic group represented by the above formula (2a) is an aromatic group represented by the following formula (7a) or (8a), and the above Z is independently from each other: The composition for peeling layer formation in any one of [1]-[3] which is an aromatic group represented by Formula (9a) or Formula (10a).

[5] In the above X, the aromatic group represented by the above formula (2b) is an aromatic group represented by the following formula (7b) or (8b), and the above Z is independently from each other: The composition for peeling layer formation in any one of [1]-[3] which is an aromatic group represented by Formula (9b) or Formula (10b).

[6] The release layer according to any one of [1] to [5], wherein the organic solvent is at least one selected from those having a structure represented by the following formulas (S1) to (S7) Composition.

(Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or 1 to 4 carbon atoms 10 alkyl groups or C1-10 acyl groups, b and n represent natural numbers)
[7] The composition for forming a release layer according to [6], wherein the organic solvent is propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate.
The peeling layer formed using the composition for peeling layer formation in any one of [8] [1]-[7].
The manufacturing method of the resin substrate using the peeling layer as described in [9] [8].
[10] The method according to [9], wherein the resin substrate is a polyimide resin substrate or a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm.

  By using the composition for release layer formation of the present invention, it is possible to obtain a release layer having excellent adhesion with a substrate, appropriate adhesion with a resin substrate, and appropriate release, with good reproducibility. In particular, since the polyamic acid used in the present invention is excellent in solubility in a low viscosity solvent, a composition that can be applied to a slit coating method can be easily prepared by using a low viscosity solvent, and a large area coated surface It is easy to apply it uniformly. Furthermore, in the process of manufacturing a flexible electronic device, the resin substrate is separated from the substrate together with the circuit without damaging the resin substrate formed on the substrate and the circuit further provided thereon. Is possible. Therefore, the composition for release layer formation of the present invention can contribute to speeding-up of the manufacturing process of a flexible electronic device provided with a resin substrate, improvement of the yield, and the like.

Hereinafter, the present invention will be described in more detail.
The composition for release layer formation of the present invention contains a polyamic acid represented by the following formula (1) and an organic solvent.

  In the present invention, the release layer is a layer provided directly on a substrate (such as a glass substrate) on which a resin substrate is formed. As a typical example, in a process of manufacturing a flexible electronic device, the resin substrate is fixed in a predetermined process between the substrate and a resin substrate of the flexible electronic device formed of polyimide resin, acrylic resin or the like. And a peeling layer provided to allow the resin substrate to be easily peeled from the base after forming an electronic circuit or the like on the resin substrate.

In the formula (1), X is an aromatic group represented by the following formula (2a) or (2b), Y is a divalent aromatic group having a fluorine atom, and Z is a formula of X When (2a) is an aromatic group represented by the following formula (3a) or (4a) independently of each other, and X is the formula (2b), they are each independently represented by the following formula (3b) Or an aromatic group represented by (4b), and m represents a natural number.

  In the above-mentioned X, the aromatic group represented by the above formula (2a) is preferably an aromatic group represented by the following formula (7a) or (8a), and the aromatic group represented by the above formula (2b) is And the aromatic group represented by following formula (7b) or (8b) is preferable.

  In the above Z, the aromatic group represented by the above formula (3a) or (4a) is preferably an aromatic group represented by the following formula (9a) or (10a), and the above formula (3b) or The aromatic group represented by 4b) is preferably an aromatic group represented by the following formula (9b) or (10b).

  Y is preferably an aromatic group having a fluorine atom and containing 1 to 5 benzene rings, more preferably an aromatic group selected from the following formula (5), and an aromatic group selected from the following formula (6) Groups are more preferred.

  Although said m should just be a natural number, 100 or less natural numbers are preferable, and 2-100 natural numbers are more preferable.

The polyamic acid represented by the said Formula (1) is obtained by making a predetermined tetracarboxylic dianhydride component and a diamine component react.
As the tetracarboxylic acid dianhydride component, benzenetetracarboxylic acid dianhydride or biphenyltetracarboxylic acid dianhydride is used. The diamine component may be any of an aliphatic chain, an alicyclic, an aromatic, and an aromatic alicyclic group as long as it has a fluorine atom, but in the present invention, the solubility in a low viscosity solvent is particularly improved. From the viewpoint of improving the function as a release layer of the obtained film, a polyamic acid obtained by reacting the above-mentioned benzenetetracarboxylic acid dianhydride or biphenyltetracarboxylic acid dianhydride with a diamine component containing the above-mentioned aromatic diamine Is preferable, and a wholly aromatic polyamic acid obtained by reacting the above-mentioned tetracarboxylic acid dianhydride with an aromatic diamine is more preferable.
Hereinafter, the benzene tetracarboxylic acid dianhydride component which can be used for the synthesis of the polyamic acid which has a structure represented by the said Formula (1), biphenyl tetracarboxylic acid dianhydride, and a diamine component are explained in full detail.

  The benzenetetracarboxylic acid dianhydride is not particularly limited as long as it has two dicarboxylic acid anhydride sites in the molecule and has a benzene ring. Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, etc. In the present invention, pyromellitic dianhydride is preferable. One of these may be used alone, or two or more of these may be used in combination.

  The biphenyltetracarboxylic acid dianhydride is not particularly limited as long as it has two dicarboxylic acid anhydride sites in the molecule and has a biphenyl group. Specific examples thereof include 2,2 ′, 3,3′-biphenyltetracarboxylic acid dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid dianhydride, 3,3 ′, 4,4. Examples thereof include '-biphenyltetracarboxylic acid dianhydride and the like, and in the present invention, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride is preferable. One of these may be used alone, or two or more of these may be used in combination.

  On the other hand, the aromatic diamine is not particularly limited as long as it has a fluorine atom and has two amino groups directly linked to the aromatic ring in the molecule, but it is not particularly limited. Preferred are aromatic diamines containing one, especially one or two, and even two. Further, those having a fluoroalkyl group or a perfluoroalkyl group are more preferable, and a perfluoroalkyl group is more preferable. Examples of the perfluoroalkyl group include trifluoromethyl group, pentafluoroethyl group, n-heptafluoropropyl group and i-heptafluoropropyl group.

  Specific examples of the above aromatic diamines include 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 2,2'-bis (trifluoromethyl) -4, 4′-Diaminobiphenyl and 3,3′-bis (trifluoromethyl) biphenyl-4,4′-diamine and the like can be mentioned, but it is not limited thereto. Among these, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl can be preferably used in the present invention. One of these may be used alone, or two or more of these may be used in combination.

  The preparation ratio of the diamine component to the tetracarboxylic acid dianhydride component can not be generally specified because it is appropriately determined in consideration of the target molecular weight and molecular weight distribution, the type of diamine and tetracarboxylic acid dianhydride, etc. In order to obtain the polyamic acid of the above formula (1), it is preferable to increase the number of moles of the tetracarboxylic dianhydride component with respect to the number of moles of the diamine component. The specific molar ratio is preferably 1.05 to 2.5 moles of tetracarboxylic acid dianhydride component, more preferably 1.07 to 1.5 moles, and more preferably 1.1 to 1.5 moles per mole of the diamine component. Even more preferred is 1.3 moles.

  By reacting the tetracarboxylic acid dianhydride component and the diamine component described above, it is possible to obtain the polyamic acid contained in the release layer-forming composition of the present invention.

  The organic solvent used in the synthesis of the polyamic acid is not particularly limited as long as it does not adversely affect the reaction, and specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N- Ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropyl Amide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethyl Propylamide, 3-tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. In addition, you may use an organic solvent individually by 1 type or in combination of 2 or more types.

  The reaction temperature at the time of synthesis of the polyamic acid 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 the imidization of the obtained polyamic acid in the solution is prevented. From the viewpoint of maintaining a high content of polyamic acid units, it is preferably about 0 to 70 ° C., more preferably about 0 to 60 ° C., and still more preferably about 0 to 50 ° C. The reaction time can not be generally defined because it depends on the reaction temperature and the reactivity of the raw material, but it is usually about 1 to 100 hours.

  The weight average molecular weight of the polyamic acid thus obtained is usually about 5,000 to 500,000, but preferably 10,000 to 200, from the viewpoint of improving the function as a release layer of the obtained film. It is about 000, more preferably about 10,000 to 150,000. In the present invention, the weight average molecular weight is a polystyrene equivalent value determined by gel permeation chromatography (GPC).

  Although the thing shown by a following formula is mentioned as a specific example of the polyamic acid which can be used suitably by this invention, It is not limited to this.

（式中、ｍ１及びｍ２は繰り返し単位の数を表し、ｍ１とｍ２の合計は上記ｍと同じである。）

(Wherein, m1 and m2 represent the number of repeating units, and the sum of m1 and m2 is the same as m above)

（式中、ｍ１及びｍ２は繰り返し単位の数を表し、ｍ１とｍ２の合計は上記ｍと同じである。）

(Wherein, m1 and m2 represent the number of repeating units, and the sum of m1 and m2 is the same as m above)

  The composition for release layer formation of the present invention contains an organic solvent. As this organic solvent, although the same one as the specific example of the reaction solvent for the above reaction can be used, it is possible to dissolve the polyamic acid of the present invention well and to easily prepare a highly uniform composition. Organic solvents selected from the group consisting of alcohols, esters, ethers and ketones are preferable, and in particular, it is preferable to contain at least one type having a structure represented by the following formulas (S1) to (S7).

In the above formulae, R ^{1 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 10, preferably 1 to 5 carbon atoms. R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or an acyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Although b represents a natural number, a natural number of 1 to 5 is preferable, and a natural number of 1 to 3 is more preferable. Although n represents a natural number, a natural number of 1 to 5 is preferable, and a natural number of 1 to 3 is more preferable.

  Specific examples of the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-Butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n- Propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2, 3-Dimethy -N-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl -N-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups etc. Be

  Specific examples of the acyl group having 1 to 10 carbon atoms include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, hexanoyl, isohexanoyl, heptanoyl, isoheptanoyl and octanoyl. Groups, isooctanoyl group, nonanoyl group, isononanoyl group, decanoyl group, isodecanoyl group, benzoyl group and the like.

Specific examples of the organic solvent represented by the above formulas (S1) to (S7) include the following.
Formula (S1): 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, N-dimethylpropylamide formula (S2): 2- Pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone Formula (S3): N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropylamide, N, N-dimethylbutane Amide formula (S4): γ-butyrolactone formula (S5): cyclopentanone, cyclohexanone, cycloheptanone (S6): methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, propyl 2-hydroxyisobutyrate, butyl 2-hydroxyisobutyrate Formula (S7): ethyl cellosolve, butyl cellosolve, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol-1-monomethyl ether 2-acetate, propylene glycol-1-monoethyl ether-2-acetate

  In the present invention, among these, N-methyl-2-pyrrolidone, butyl cellosolve, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferable, and propylene glycol monomethyl ether is more preferable. More preferable. These organic solvents may be used alone or in combination of two or more.

  In particular, when a so-called low viscosity solvent such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is used as the organic solvent, it is possible to obtain a low viscosity composition for forming a release layer suitable for slit coating. it can. In addition, when using the composition for peeling layer formation of this invention for slit coating, 60 mass% or more is preferable, and, as for the ratio of the said low viscosity solvent which occupies the whole solvent, 70 mass% or more is more preferable, 80 mass% or more Is most preferred.

  In addition, even if it is a solvent which does not dissolve polyamic acid by itself, it can be used for preparation of a composition if it is a range which polyamic acid does not precipitate. In particular, low surfaces such as ethyl carbitol, butyl carbitol, ethyl carbitol acetate, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol and the like A solvent having tension can be mixed appropriately. Thereby, it is known that the coating film uniformity is improved at the time of application to a substrate, and can be suitably used in the present invention.

  The composition for release layer formation of the present invention can be prepared by a conventional method. As a preferable example of the preparation method, the reaction solution containing the target polyamic acid obtained by the method described above is filtered, and the concentration of the obtained filtrate is made to be a predetermined concentration using the above-mentioned organic solvent. Good. By adopting such a method, it is possible not only to reduce the contamination of impurities that may cause deterioration of the adhesiveness, peelability and the like of the peelable layer produced from the composition obtained, but also to efficiently form the composition for peelable layer formation. You can get

  The concentration of the polyamic acid in the release layer-forming composition of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, etc., but usually about 1 to 30% by mass, preferably It is about 1 to 20% by mass. By setting it as such a density | concentration, the peeling layer of thickness of about 0.05-5 micrometers can be obtained with sufficient reproducibility. The concentration of the polyamic acid adjusts the amounts of the diamine component, which is the raw material of the polyamic acid, the tetracarboxylic acid dianhydride component and the aromatic monoamine, and the amount when dissolving the isolated polyamic acid in a solvent It can be adjusted equally.

  The viscosity of the release layer-forming composition of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, and in particular, the film having a thickness of about 0.05 to 5 μm is reproducible. When it is intended to be obtained well, it is usually about 10 to 10,000 mPa · s at 25 ° C., preferably about 20 to 5,000 mPa · s. Moreover, when using the composition for peeling layer formation of this invention for a slit coating system, the viscosity is good at about 2-100 mPa * s, and it is preferable from a viewpoint of productivity to be about 2-25 mPa * s.

  Here, the viscosity can be measured under the conditions of a temperature of 25 ° C. of the composition using, for example, a procedure described in JIS K7117-2 using a commercially available viscosity meter for viscosity measurement of liquid . Preferably, the temperature of the composition is 25 using a cone and plate type (cone plate type) rotational viscometer as the viscometer, preferably using 1 ° 34 ′ × R 24 as a standard cone rotor in the same type viscometer. It can measure on the conditions of ° C. As such a rotational viscometer, TVE-25L by Toki Sangyo Co., Ltd. is mentioned, for example.

  In addition to the polyamic acid and the organic solvent, the composition for forming a release layer according to the present invention may contain, for example, a crosslinking agent or the like in order to improve film strength.

  The composition for forming a release layer of the present invention described above is applied to a substrate, and the obtained coating film is heated to thermally imidize the polyamic acid, thereby achieving excellent adhesion with the substrate and appropriateness with the resin substrate. The peeling layer which consists of a polyimide film | membrane which has such adhesiveness and moderate peelability can be obtained.

  When such a release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the surface of the substrate or may be formed on the entire surface. As an embodiment in which the release layer is formed on a part of the substrate surface, an embodiment in which the release layer is formed only in a predetermined range of the substrate surface, a release layer in a pattern such as a dot pattern or line and space pattern all over the substrate surface And the like. In the present invention, the substrate means one to which the composition for forming a release layer of the present invention is applied on the surface and which is used for producing a flexible electronic device or the like.

  As the substrate (substrate), for example, glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.), Wood, paper, slate, etc. may be mentioned. In the present invention, a glass substrate can be suitably used, in particular, because the release layer has sufficient adhesion. The substrate surface may be composed of a single material or may be composed of two or more materials. As an embodiment in which the substrate surface is composed of two or more materials, an embodiment in which a certain range of the substrate surface is composed of one material and the other range is composed of another material, all over the substrate surface There is a mode in which a material in a pattern form such as a dot pattern or a line and space pattern is present in another material.

  The method for applying the release layer-forming composition of the present invention to a substrate is not particularly limited, and, for example, cast coating, spin coating, slit coating, blade coating, dip coating, roll coating Methods, bar coating methods, die coating methods, ink jet methods, printing methods (relief printing, intaglio printing, lithography, screen printing, etc.) and the like.

  Although the heating temperature for imidation is suitably determined in the range of normally 50-550 degreeC, Preferably it is more than 150 degreeC-510 degreeC. By setting the heating temperature in this manner, it is possible to sufficiently advance the imidization reaction while preventing the resulting film from being weakened. The heating time is generally 5 minutes to 5 hours, although it can not be generally defined because it varies depending on the heating temperature. Moreover, the imidation ratio should just be 50 to 100% of range.

  As a preferable example of the heating aspect in the present invention, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, the heating temperature is gradually raised as it is, and finally it is from 150 ° C. to 510 ° C. for 30 minutes to 4 hours The method of heating is mentioned. In particular, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, heating is preferably performed at more than 150 ° C. to 350 ° C. for 5 minutes to 2 hours, and finally at more than 350 ° C. to 450 ° C. for 30 minutes to 4 hours.

  The apparatus used for heating includes, for example, a hot plate, an oven, and the like. The heating atmosphere may be under air or inert gas, and may be under normal pressure or under reduced pressure.

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

  The release layer described above has excellent adhesion to a substrate, particularly to a glass substrate, moderate adhesion to a resin substrate, and moderate peelability. Therefore, in the manufacturing process of the flexible electronic device, the peeling layer of the present invention peels the resin substrate from the substrate together with the circuit and the like formed on the resin substrate without damaging the resin substrate of the device. It can be suitably used to

Hereinafter, an example of the manufacturing method of the flexible electronic device using the peeling layer of this invention is demonstrated.
The composition for release layer formation of the present invention is used to form a release layer on a glass substrate by the method described above. A resin solution for forming a resin substrate is applied onto the release layer, and the coating film is heated to form a resin substrate fixed to the glass substrate via the release layer of the present invention. At this time, the substrate is formed with a large area as compared with the area of the release layer so as to cover the entire release layer. Examples of the resin substrate include substrates made of polyimide resin, acrylic resin, and cycloolefin polymer resin that are representative of resin substrates for flexible electronic devices, and resin solutions for forming the same include polyimide solution, polyamic acid solution, Acrylic polymer solutions and cycloolefin polymer solutions may, for example, be mentioned. The formation method of the said resin substrate should just follow a conventional method. Further, as a resin substrate having high transparency, a resin substrate formed of an acrylic resin or a cycloolefin polymer resin can be exemplified, and in particular, one having a light transmittance of wavelength 400 nm of 80% or more is preferable.

  Next, a desired circuit is formed on the resin substrate fixed to the substrate via the release layer of the present invention, and then, for example, the resin substrate is cut along the release layer, and the resin substrate is It peels from a peeling layer and separates a resin substrate and a base. At this time, part of the substrate may be cut together with the release layer.

  In addition, in Unexamined-Japanese-Patent No. 2013-147599, applying the laser lift-off method (LLO method) used so far in manufacture of high-intensity LED, a three-dimensional semiconductor package, etc. to manufacture of a flexible display is reported. . The LLO method is characterized in that a light beam of a specific wavelength, for example, a light beam of a wavelength of 308 nm is irradiated from the side of the glass substrate from the surface opposite to the surface on which circuits and the like are formed. The irradiated light passes through the glass substrate, and only the polymer (polyimide resin) near the glass substrate absorbs the light and evaporates (sublimates). As a result, the resin substrate can be selectively peeled off from the glass substrate without affecting the circuits and the like provided on the resin substrate, which determines the performance of the display.

  The composition for forming a release layer of the present invention has a feature of sufficiently absorbing a light beam of a specific wavelength (for example, 308 nm) which enables the application of the LLO method, and therefore can be used as a sacrificial layer of the LLO method. Therefore, a desired circuit is formed on a resin substrate fixed to a glass substrate through a release layer formed using the composition of the present invention, and then an LLO method is performed to irradiate a light beam of 308 nm. Only the release layer absorbs this light beam and evaporates (sublimates). Thus, the release layer is sacrificed (functions as a sacrificial layer), and the resin substrate can be selectively removed from the glass substrate.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
[1] Abbreviation of compound p-PDA: p-phenylenediamine TPDA: 4,4′-diamino-p-terphenyl TFMB: 2,2′-bis (trifluoromethyl) benzidine BPDA: 3,3 ′, 4 4,4'-biphenyltetracarboxylic acid dianhydride PMDA: pyromellitic acid dianhydride DMCBDA: 1,3-dimethylcyclobutanoic acid dianhydride CBDA: cyclobutanoic acid dianhydride MMA: methyl methacrylate MAA: methacrylic acid HEMA: methacrylic Acid 2-Hydroxyethyl AIBN: Azobisisobutyro nitrile CHMI: Cyclohexylmaleimidopolyde GT-401: Butanetetracarboxylic acid, tetra (3,4-epoxycyclohexylmethyl), modified ε-caprolactone, Celoxide manufactured by Daicel Corporation 2021P: 3 ', 4'-epoxy Chlorohexyl methyl 3,4-epoxycyclohexane carboxylate, VESTAGON B 1530 manufactured by Daicel Co., Ltd. NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl Ether acetate

[2] Measurement Method of Weight Average Molecular Weight and Molecular Weight Distribution Measurement of weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of polymer is carried out by GPC apparatus manufactured by JASCO (column: KOD801 and KD805 manufactured by Shodex; eluent: Dimethylformamide / LiBr · H ₂ O (29.6 mM) / H ₃ PO ₄ (29.6 mM) / THF (0.1% by mass); Flow rate: 1.0 mL / min; Column temperature: 40 ° C .; Mw: Standard It carried out using polystyrene conversion value).

[3] Synthesis of Polymer Various polymers used in Examples and Comparative Examples were synthesized by the following method.
In addition, the polymer was not isolated from the obtained polymer containing reaction liquid, but the composition for resin substrate formation or the composition for peeling layer formation was prepared by diluting a reaction liquid as mentioned later.

Synthesis Example S1 Synthesis of Polyamic Acid (S1)
3.218 g (30 mmol) of p-PDA was dissolved in 88.2 g of NMP. To the resulting solution, 8.581 g (29 mmol) of BPDA was added, and allowed to react at 23 ° C. for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 107,300 and a molecular weight distribution of 4.6.

Synthesis Example S2 Synthesis of Polyamic Acid (S2)
20.261 g (0.1875 mol) of p-PDA and 12.206 g (0.0469 mol) of TPDA are dissolved in 617.4 g of NMP, and after cooling to 15 ° C., 50.112 g (0.2298 mol) of PMDA is added, and 50 in a nitrogen atmosphere The reaction was allowed to proceed for 48 hours at ° C. The Mw of the obtained polymer was 82, 100, and the molecular weight distribution was 2.7.

Synthesis Example S3 Synthesis of Acrylic Polymer (S3)
Dissolve 7.20 g (0.0719 mol) of MMA, 7.20 g (0.0553 mol) of HEMA, 10.8 g (0.0603 mol) of CHMI, 4.32 g (0.0502 mol) of MAA, 2.46 g (0.0150 mol) of AIBN in 46.9 g of PGMEA The reaction was carried out at 60 to 100 ° C. for 20 hours to obtain an acrylic polymer solution (solid content 40% by mass). Mn of the obtained acrylic polymer was 3,800, and Mw was 7,300.

Synthetic Example L1 Synthesis of Polyamic Acid (L1)
2.73 g (8.53 mmol) of TFMB was dissolved in 38.5 g of NMP. To the resulting solution, 2.06 g (9.47 mmol) of PMDA was added, and allowed to react at 23 ° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 17,100, and the molecular weight distribution was 1.7. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, no particular precipitation was observed.

Synthesis Example Synthesis of L2 Polyamic Acid (L2)
2.73 g (8.53 mmol) of TFMB was dissolved in 40 g of PGME. To the resulting solution, 2.06 g (9.47 mmol) of PMDA was added, and allowed to react at 23 ° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 20, 100, and the molecular weight distribution was 1.8.

Synthetic Example L3 Synthesis of Polyamic Acid (L3)
23.7 g (74.2 mmol) of TFMB were dissolved in 352 g of NMP. To the resulting solution, 24.2 g (82.5 mmol) of BPDA was added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 16,500, and the molecular weight distribution was 1.7. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, no particular precipitation was observed.

Synthetic Example L4 Synthesis of Polyamic Acid (L4)
9.89 g (30.9 mmol) of TFMB were dissolved in 380 g of PGME. To the resulting solution, 10.0 g (34.3 mmol) of BPDA was added and allowed to react at 50 ° C. for 72 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 14,700, and the molecular weight distribution was 1.7.

Comparative Synthesis Example Synthesis of HL1 Polyamic Acid (HL1)
3.90 g (3.60 mmol) of p-PDA was dissolved in 35.2 g of NMP. To the resulting solution, 9.27 g (4.00 mmol) of DMCBDA was added, and allowed to react at 23 ° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 45,000, and the molecular weight distribution was 3.9. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, polyamic acid was precipitated.

Comparative Synthesis Example HL2 Synthesis of Polyamic Acid (HL2)>
2.86 g (8.91 mmol) of TFMB were dissolved in 35.2 g of NMP. To the resulting solution, 1.94 g (9.91 mmol) of CBDA was added, and allowed to react at 23 ° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 69,200, and the molecular weight distribution was 2.2. As a result of adding 1 g of the obtained polymer solution to 10 g of PGME, no particular precipitation was observed.

[4] Preparation of Composition for Forming Resin Substrate The composition for forming a resin substrate was prepared by the following method.

Preparation Example 1 Composition F1 for Forming Resin Substrate
The reaction liquid obtained in Synthesis Example S1 was used as it is as a composition F1 for forming a resin substrate.

Preparation Example 2 Composition F2 for Forming Resin Substrate
The reaction liquid obtained in Synthesis Example S2 was used as it is as a composition F2 for forming a resin substrate.

Preparation Example 3 Composition F3 for Forming Resin Substrate
Synthesis Example S3 0.60 g of Epolide GT-401 and 11.8 g of PGMEA were added to 10 g of the reaction liquid obtained, and the mixture was stirred at 23 ° C. for 24 hours to prepare a composition F3 for forming a resin substrate.

Preparation Example 4 Composition F4 for Forming Resin Substrate
0.80 g of celloxide 2021P and 11.8 g of PGMEA were added to 10 g of the reaction liquid obtained in Synthesis Example S3, and the mixture was stirred at 23 ° C. for 24 hours to prepare a composition F4 for forming a resin substrate.

Preparation Example 5 Composition F5 for Forming Resin Substrate
0.60 g of VESTAGON B 1530 and 11.8 g of PGMEA were added to 10 g of the reaction liquid obtained in Synthesis Example S3, and the mixture was stirred at 23 ° C. for 24 hours to prepare a composition F5 for forming a resin substrate.

Preparation Example 6 Composition F6 for Forming Resin Substrate
10 g of Zeonoa (registered trademark) 1020 R (manufactured by Nippon Zeon Co., Ltd., cycloolefin polymer resin) and 3 g of GT-401 were added to an eggplant flask containing 100 g of carbon tetrachloride. The solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare a composition F6 for forming a resin substrate.

Preparation Example 7 Composition F7 for Forming Resin Substrate
10 g of Zeonoa (registered trademark) 1060 R (manufactured by Nippon Zeon Co., Ltd., cycloolefin polymer resin) was added to an eggplant flask containing 100 g of carbon tetrachloride. The solution was dissolved by stirring under a nitrogen atmosphere for 24 hours to prepare a composition F7 for forming a resin substrate.

[5] Preparation of Release Layer-Forming Composition [Example 1-1]
BCS and NMP were added to the reaction liquid obtained in Synthesis Example L1, and diluted so that the polymer concentration was 5% by mass and BCS was 20% by mass, to obtain a composition for forming a release layer.

[Example 1-2]
The reaction solution obtained in Synthesis Example L2 was used as it was as a release layer-forming composition.

[Example 1-3]
BCS and NMP were added to the reaction solution obtained in Synthesis Example L3, and diluted so that the polymer concentration was 5% by mass and BCS was 20% by mass, to obtain a composition for forming a release layer.

Example 1-4
The reaction solution obtained in Synthesis Example L4 was used as it was as a release layer-forming composition.

Comparative Example 1-1
BCS and NMP were added to the reaction solution obtained in Comparative Synthesis Example HL1, and diluted so that the polymer concentration was 5% by mass and BCS was 20% by mass, to obtain a release layer-forming composition.

Comparative Example 1-2
BCS and NMP were added to the reaction solution obtained in Comparative Synthesis Example HL2, and diluted so that the polymer concentration was 5% by mass and BCS was 20% by mass, to obtain a composition for forming a release layer.

[6] Preparation of Peeling Layer and Resin Substrate [Example 2-1]
Composition L1 for release layer formation obtained in Example 1-1 using a spin coater (conditions: about 30 seconds at a rotation speed of 3,000 rpm) was prepared using a 100 mm × 100 mm glass substrate (same below) as a glass substrate Applied on top.
Then, the obtained coating film is heated at 80 ° C. for 10 minutes using a hot plate, and then heated for 30 minutes at 300 ° C. using an oven, and the heating temperature is raised to 400 ° C. (10 ° C./minute C. and further heated at 400.degree. C. for 30 minutes to form a release layer having a thickness of about 0.1 .mu.m on the glass substrate to obtain a glass substrate with a release layer. During the temperature rise, the film-coated substrate was heated in the oven without being taken out of the oven.

  Composition F1 for resin substrate formation was apply | coated on the peeling layer (resin thin film) on the glass substrate obtained above using the bar coater (gap: 250 micrometers). Then, the obtained coating film is heated at 80 ° C. for 30 minutes using a hot plate, and then heated at 140 ° C. for 30 minutes using an oven, and the heating temperature is raised to 210 ° C. (2 ° C./minute And so on), heating temperature to 300 ° C. for 30 minutes at 210 ° C., heating temperature to 400 ° C. for 30 minutes at 300 ° C., heating for 60 minutes at 400 ° C., on release layer A resin substrate having a thickness of about 20 μm was formed to obtain a glass substrate with a resin substrate and a release layer. The film-coated substrate was not removed from the oven during heating, but was heated in the oven.

[Example 2-2]
A release layer and a resin substrate were produced in the same manner as in Example 2-1 except that the composition F2 for forming a resin substrate was used instead of the composition F1 for forming a resin substrate used in Example 2-1. A glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained.

Embodiment 2-3
Example 2-1 is the same as Example 2-1 except that the composition L2 for forming the release layer obtained in Example 1-2 is used instead of the composition L1 for forming the release layer obtained in Example 1-1. The peeling layer and the resin substrate were produced by the method, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained.

Example 2-4
Composition F2 for resin substrate formation used in Example 2-2 as a composition for resin substrate formation using composition L2 for peeling layer formation obtained in Example 1-2 as a composition for peeling layer formation The peeling layer and the resin substrate were produced using the same method as in Example 2-1, to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[Example 2-5]
Example 2- Using the composition L1 for release layer formation obtained in Example 1-1 as the composition for release layer formation and the composition F4 for resin substrate formation as the composition for resin substrate formation, Example 2- The peeling layer and the resin substrate were produced by the method similar to 1, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and peeling layer were obtained.

Example 2-6
Example 2- Using the composition L1 for release layer formation obtained in Example 1-1 as the composition for release layer formation and the composition F5 for resin substrate formation as the composition for resin substrate formation, Example 2- The peeling layer and the resin substrate were produced by the method similar to 1, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and peeling layer were obtained.

[Example 2-7]
Example 2- Using the composition L2 for release layer formation obtained in Example 1-2 as the composition for release layer formation and the composition F5 for resin substrate formation as the composition for resin substrate formation, Example 2- The peeling layer and the resin substrate were produced by the method similar to 1, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and peeling layer were obtained.

[Example 2-8]
The peeling layer was formed by the method similar to Example 2-1 using the composition L1 for peeling layer formation obtained in Example 1-1, and the glass substrate with a peeling layer was obtained.
Thereafter, using a spin coater (conditions: rotation speed: 200 rpm for about 15 seconds), the composition F6 for forming a resin substrate was applied on the release layer (resin thin film) on the glass substrate. The resulting coated film is heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A resin substrate and a glass substrate with a release layer were obtained. Thereafter, the light transmittance was measured using a UV-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and as a result, the resin substrate exhibited a transmittance of 80% or more at 400 nm.

[Example 2-9]
Example 2-8 is similar to Example 2-8 except that composition L2 for forming release layer obtained in Example 1-2 is used instead of composition L1 for forming release layer obtained in Example 1-1. The peeling layer and the resin substrate were produced by the method, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained.

Embodiment 2-10
The peeling layer was formed by the method similar to Example 2-1 using the composition L1 for peeling layer formation obtained in Example 1-1, and the glass substrate with a peeling layer was obtained.
Thereafter, using a spin coater (conditions: rotation speed: 200 rpm for about 15 seconds), the composition F7 for forming a resin substrate was applied on the release layer (resin thin film) on the glass substrate. The resulting coated film is heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A resin substrate and a glass substrate with a release layer were obtained. Thereafter, the light transmittance was measured using a UV-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and as a result, the resin substrate exhibited a transmittance of 80% or more at 400 nm.

Example 2-11
Example 2-10 is the same as Example 2-10 except that composition L2 for forming a release layer obtained in Example 1-2 is used instead of composition L1 for forming a release layer obtained in Example 1-1. The peeling layer and the resin substrate were produced by the method, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained.

[Comparative Examples 2-1 to 2-4]
Example 11 is the same as the above example except that the composition for forming a release layer obtained in Comparative Examples 1-1 to 1-2 is used instead of the composition for forming a release layer obtained in Example 1-1. The peeling layer and the resin substrate were produced by the method, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained. The combinations of the release layer and the resin substrate are as shown in Table 1.

Example 2-12
A composition L3 for release layer formation obtained in Example 1-3 using a spin coater (conditions: about 30 seconds at a rotation speed of 3,000 rpm) was subjected to 100 mm × 100 mm glass substrate as glass substrate (the same applies to the following) On top of the
Then, the obtained coating film is heated at 80 ° C. for 10 minutes using a hot plate, and then heated for 30 minutes at 300 ° C. using an oven, and the heating temperature is raised to 400 ° C. (10 ° C./minute C. and further heated at 400.degree. C. for 30 minutes to form a release layer having a thickness of about 0.1 .mu.m on the glass substrate to obtain a glass substrate with a release layer. During the temperature rise, the film-coated substrate was heated in the oven without being taken out of the oven.

  The composition F3 for resin substrate formation was applied on the release layer (resin thin film) on the glass substrate obtained above using a spin coater (conditions: about 10 seconds at a rotation speed of 800 rpm). Then, the obtained coated film was heated at 80 ° C. for 30 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using an oven to form an acrylic substrate having a thickness of about 3 μm on the release layer. . The film-coated substrate was not removed from the oven during heating, but was heated in the oven.

[Example 2-13]
A release layer and a resin substrate were produced in the same manner as in Example 2-12 except that the composition F4 for forming a resin substrate was used instead of the composition F3 for forming a resin substrate used in Example 2-12. A glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained.

Example 2-14
A release layer and a resin substrate were produced in the same manner as in Example 2-12 except that the composition F5 for forming a resin substrate was used instead of the composition F3 for forming a resin substrate used in Example 2-12. A glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were obtained.

[Example 2-15]
Example 2-12 is similar to Example 2-12 except that composition L4 for forming release layer obtained in Example 1-4 is used instead of composition L3 for forming release layer obtained in Example 1-3. The peeling layer and the resin substrate were produced by the method, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained.

[Example 2-16]
Composition F4 for resin substrate formation used in Example 2-14 as the composition for resin substrate formation using composition L4 for peeling layer formation obtained in Example 1-4 as a composition for peeling layer formation A peeling layer and a resin substrate were produced using the same method as in Example 2-12, to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[Example 2-17]
Using the composition L3 for release layer formation obtained in Example 1-3, a release layer was formed in the same manner as in Example 2-12, to obtain a glass substrate with a release layer.
Thereafter, using a spin coater (conditions: rotation speed: 200 rpm for about 15 seconds), the composition F6 for forming a resin substrate was applied on the release layer (resin thin film) on the glass substrate. The resulting coated film is heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A resin substrate and a glass substrate with a release layer were obtained. Thereafter, the light transmittance was measured using a UV-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and as a result, the resin substrate exhibited a transmittance of 80% or more at 400 nm.

[Example 2-18]
Example 2-17 is the same as Example 2-17 except that the composition L4 for forming a peeling layer obtained in Example 1-4 is used instead of the composition L3 for forming a peeling layer obtained in Example 1-3. The peeling layer and the resin substrate were produced by the method, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained.

[Example 2-19]
Using the composition L3 for release layer formation obtained in Example 1-3, a release layer was formed in the same manner as in Example 2-12, to obtain a glass substrate with a release layer.
Thereafter, using a spin coater (conditions: rotation speed: 200 rpm for about 15 seconds), the composition F7 for forming a resin substrate was applied on the release layer (resin thin film) on the glass substrate. The resulting coated film is heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A resin substrate and a glass substrate with a release layer were obtained. Thereafter, the light transmittance was measured using a UV-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and as a result, the resin substrate exhibited a transmittance of 80% or more at 400 nm.

[Example 2-20]
Example 2-19 is the same as Example 2-19 except that the composition L4 for forming a release layer obtained in Example 1-4 is used instead of the composition L3 for forming a release layer obtained in Example 1-3. The peeling layer and the resin substrate were produced by the method, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained.

[Comparative Example 2-5]
Example 2-12 is the same as Example 2-12 except that the composition for forming a release layer HL1 obtained in Comparative Example 1-1 is used instead of the composition L3 for forming a release layer obtained in Example 1-3. The peeling layer and the resin substrate were produced by the method, and the glass substrate with a peeling layer and the glass substrate with a resin substrate and a peeling layer were obtained. The combination of the release layer and the resin substrate is as shown in Table 2.

Comparative Example 2-6
Composition F4 for resin substrate formation used in Example 2-13 as a composition for resin substrate formation using composition HL2 for release layer formation obtained in Comparative Example 1-2 as a composition for peeling layer formation A peeling layer and a resin substrate were produced using the same method as in Example 2-12, to obtain a glass substrate with a peeling layer and a glass substrate with a resin substrate and a peeling layer.

[7] Evaluation of Solvent Resistance of Release Layer A pipette of NMP and PGME on the release layer of the release layer-provided glass substrate prepared in Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6 obtained 0.1 ml was dripped using. After one minute, the release layer was washed with pure water, and the state of the release layer in the portion to which the solvent was dropped was visually observed to evaluate the solvent resistance of the release layer. The judgment criteria are as follows. The results are shown in Tables 1 and 2.
<Judgment criteria>
:: No trace of droplets was observed, and no dissolution was observed.
Δ: Traces of droplets are observed, but residual film is observed.
X: dissolved
The fact that the release layer is not dissolved in the dropped solvent means that when the resin substrate is formed on the release layer, it does not dissolve in the organic solvent contained in the composition for forming a resin substrate, and from the glass substrate to the resin substrate It means that it can be peeled off without being damaged.

[8] Evaluation of releasability The releasability between the release layer and the glass substrate for the resin substrate / release layer-attached glass substrate obtained in Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6. Were confirmed by the following method. In addition, the following test was done with the same glass substrate.

<Evaluation of peelability between peelable layer and glass substrate>
The release layers on the release layer-provided glass substrates obtained in Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6 were cross cut (at intervals of 1 mm in length and width, the same applies hereinafter), and 100 mass cut was performed. . That is, 100 squares of 1 mm square were formed by this cross cut.
Then, a pressure-sensitive adhesive tape was attached to the 100 mass cut portion, the tape was peeled off, and the degree of peeling was evaluated based on the following criteria (5B to 0B, B, A, AA).
Furthermore, the peeling force evaluation test was implemented using the resin substrate * glass substrate with a peeling layer produced in Example 2-5-2-20 among the board | substrates which peeled completely. In the test method, a resin substrate of a resin substrate and a peeling substrate with a peeling layer was cut into a rectangle of 25 mm × 50 mm width so as to penetrate to the back surface of the resin substrate with a cutter knife to produce a strip. Furthermore, after putting cellophane tape (Nichiban CT-24) on the produced strip, an autograph AG-500N (manufactured by Shimadzu Corp.) is used, and it is at 90 degrees to the surface of the substrate, that is, The peeling was measured in the vertical direction, and the peeling force was measured, and the one having 100% peeling (all peeling) and having a peeling force of less than 0.1 N / 25 mm was taken as AAA.
The above results are shown in Tables 1 and 2.
<Judgment criteria>
5B: 0% peeling (without peeling)
4B: less than 5% peeling 3B: less than 5-15% peeling 2B: 15-35% peeling 1B: less than 35-65% peeling 0B: 65% to less than 80% peeling B: 80% to 95 % Peeling A: 95% to 100% peeling AA: 100% peeling (all peeling)
AAA: Peeling force less than 0.1 N / 25 mm at 100% peeling

<Evaluation of peelability between peelable layer and resin substrate>
The peelability of the glass substrates with resin substrates and peelable layers obtained in Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-6 was evaluated in the same manner as the above-described peelability evaluation. The results are shown in Tables 1 and 2.

As shown in Tables 1 and 2, it was confirmed that the peeling layers of Examples 2-1 to 2-20 were excellent in the adhesion to the glass substrate and easily peeled off with the resin film. Moreover, it was also confirmed from the result of the solubility test that it did not melt | dissolve in the organic solvent contained in the composition for resin substrate formation.
On the other hand, although the peeling layer of Comparative Examples 2-1 to 2-6 is excellent in the adhesiveness with a glass substrate, it was confirmed that it is inferior to the peelability with a resin substrate.

（式中、Ｘは、下記式（２ａ）又は（２ｂ）で表される芳香族基を表し、Ｙは、フッ素原子を有する２価の芳香族基を表し、Ｚは、Ｘが式（２ａ）で表される芳香族基である場合、互いに独立して、下記式（３ａ）又は（４ａ）で表される芳香族基を表し、Ｘが式（２ｂ）で表される芳香族基である場合、互いに独立して、下記式（３ｂ）又は（４ｂ）で表される芳香族基を表し、ｍは、自然数を表す。）

［２］上記Ｙが、下記式（５）で表される芳香族基である［１］記載の剥離層形成用組成物。

［３］上記Ｙが、下記式（６）で表される芳香族基である［２］記載の剥離層形成用組成物。

［４］上記Ｘにおいて、上記式（２ａ）で表される芳香族基が、下記式（７ａ）又は（８ａ）で表される芳香族基であり、上記Ｚが、互いに独立して、下記式（９ａ）又は式（１０ａ）で表される芳香族基である［１］〜［３］のいずれかに記載の剥離層形成用組成物。

［５］上記Ｘにおいて、上記式（２ｂ）で表される芳香族基が、下記式（７ｂ）又は（８ｂ）で表される芳香族基であり、上記Ｚが、互いに独立して、下記式（９ｂ）又は式（１０ｂ）で表される芳香族基である［１］〜［３］のいずれかに記載の剥離層形成用組成物。

［６］上記有機溶媒が、下記式（Ｓ１）〜（Ｓ７）で表される構造を有するものから選ばれる少なくとも１種である［１］〜［５］のいずれかに記載の剥離層形成用組成物。

（式中、Ｒ¹〜Ｒ⁸は、互いに独立して、水素原子、又は炭素数１〜１０のアルキル基を表し、Ｒ⁹及びＲ¹⁰は、互いに独立して、水素原子、炭素数１〜１０のアルキル基、又は炭素数１〜１０のアシル基を表し、ｂ及びｎは自然数を表す）
［７］上記有機溶媒が、プロピレングリコールモノメチルエーテル又はプロピレングリコールモノメチルエーテルアセテートである［６］記載の剥離層形成用組成物。
［８］［１］〜［７］のいずれかに記載の剥離層形成用組成物を用いて形成される剥離層。
［９］［８］記載の剥離層を用いる樹脂基板の製造方法。
［１０］上記樹脂基板が、ポリイミド樹脂基板又は波長４００ｎｍの光透過率が８０％以上である樹脂基板である［９］記載の製造方法。 Accordingly, the present invention provides the following release layer-forming composition and release layer.
[1] A composition for forming a release layer, comprising a polyamic acid represented by the following formula (1) and an organic solvent.

(Wherein, X represents an aromatic group represented by the following formula (2a) or (2b), Y represents a divalent aromatic group having a fluorine atom, and Z represents X having the formula (2a) When it is an aromatic group represented by), each of them independently represents an aromatic group represented by the following formula (3a) or (4a), and X is an aromatic group represented by the formula (2b) In some cases, each independently represents an aromatic group represented by the following formula (3b) or (4b), and m represents a natural number.)

[2] The composition for forming a release layer according to [1], wherein Y is an aromatic group represented by the following formula (5).

[3] The composition for forming a release layer according to [2], wherein Y is an aromatic group represented by the following formula (6).

[4] In the above X, the aromatic group represented by the above formula (2a) is an aromatic group represented by the following formula (7a) or (8a), and the above Z is independently from each other: The composition for peeling layer formation in any one of [1]-[3] which is an aromatic group represented by Formula (9a) or Formula (10a).

[5] In the above X, the aromatic group represented by the above formula (2b) is an aromatic group represented by the following formula (7b) or (8b), and the above Z is independently from each other: The composition for peeling layer formation in any one of [1]-[3] which is an aromatic group represented by Formula (9b) or Formula (10b).

[6] The release layer according to any one of [1] to [5], wherein the organic solvent is at least one selected from those having a structure represented by the following formulas (S1) to (S7) Composition.

(Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or 1 to 4 carbon atoms 10 alkyl groups or C1-10 acyl groups, b and n represent natural numbers)
[7] The composition for forming a release layer according to [6], wherein the organic solvent is propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate.
The peeling layer formed using the composition for peeling layer formation in any one of [8] [1]-[7].
The manufacturing method of the resin substrate using the peeling layer as described in [9] [8].
[10] The method according to [9], wherein the resin substrate is a polyimide resin substrate or a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm.

Claims (10)

The composition for peeling layer formation characterized by including the polyamic acid and organic solvent which are represented by following formula (1).

(Wherein, X represents an aromatic group represented by the following formula (2a) or (2b), Y represents a divalent aromatic group having a fluorine atom, and Z represents X having the formula (2a) When it is an aromatic group represented by), each of them independently represents an aromatic group represented by the following formula (3a) or (4a), and X is an aromatic group represented by the formula (2b) In some cases, each independently represents an aromatic group represented by the following formula (3b) or (4b), and m represents a natural number.)

The composition for release layer formation according to claim 1, wherein Y is an aromatic group represented by the following formula (5).

The composition for release layer formation according to claim 2, wherein Y is an aromatic group represented by the following formula (6).

In the above-mentioned X, the aromatic group represented by the above-mentioned formula (2a) is an aromatic group represented by the following formula (7a) or (8a), and the above-mentioned Z are independently from each other: The composition for forming a release layer according to any one of claims 1 to 3, which is an aromatic group represented by the formula (10a) or (10a).

In the above-mentioned X, the aromatic group represented by the above-mentioned formula (2b) is an aromatic group represented by the following formula (7b) or (8b), and the above-mentioned Z are independently from each other: The composition for forming a release layer according to any one of claims 1 to 3, which is an aromatic group represented by the formula (10b) or (10b).

The composition according to any one of claims 1 to 5, wherein the organic solvent is at least one selected from those having a structure represented by the following formulas (S1) to (S7).

(Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or 1 to 4 carbon atoms 10 alkyl groups or C1-10 acyl groups, b and n represent natural numbers)   The composition according to claim 6, wherein the organic solvent is propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate.   The peeling layer formed using the composition for peeling layer formation of any one of Claims 1-7.   The manufacturing method of the resin substrate using the peeling layer of Claim 8.   10. The method according to claim 9, wherein the resin substrate is a polyimide resin substrate or a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm.