TWI654090B - Laminated product, treatment method thereof and production method of flexible device - Google Patents

Abstract

An object of the present invention is to provide a laminate in which the polyimide film of the polyimide film is excellent in adhesion to an inorganic substrate, and the polyimide film can be easily peeled off from the inorganic substrate in a short time. The present invention provides a laminate comprising an inorganic substrate and a polyimide film formed on the inorganic substrate, and having the following characteristics: (1) the polyimide film comprises a polyimine film. The laminated film of the resin layer A and the polyimine-based resin layer B, the polyamidene-based resin layer A is in contact with the above-mentioned inorganic substrate, and the polyimine formed on the surface of the polyimide-based resin layer A One part of the resin layer B is in contact with the inorganic substrate; (2) the adhesive strength of the polyimine-based resin layer A and the inorganic substrate is 2 N/cm or less; (3) the polyimine-based resin layer B and the above The adhesive strength of the inorganic substrate exceeds 2 N/cm; and (4) the polyimide-based resin layer B that is in contact with the inorganic substrate can be peeled off from the inorganic substrate by moisture absorption treatment.

Description

Laminated body and processing method thereof and manufacturing method of flexible device

The present invention relates to a laminate in which a polyimide film is formed on an inorganic substrate, a method for treating the same, and a method for producing a flexible device. The laminate and the treatment method thereof according to the present invention are useful, for example, in the production of a flexible device or a flexible wiring board in which an electronic component is formed on the surface of a flexible substrate.

Conventionally, a flat panel display (FPD, Flat Panel Display) such as a liquid crystal display (LCD), a plasma display panel (PDP), an organic EL display (OLED, Organic Light Emitting Diode), or an electronic paper In the field of an electronic device, an electronic component is formed on a substrate (inorganic substrate) formed of an inorganic material such as a glass substrate. However, since the inorganic substrate is straight and lacks flexibility, there is a problem that it is difficult to become flexible.

Therefore, a method of using an organic polymer material such as a flexible and heat-resistant polyimine as a substrate has been proposed. In other words, the following techniques have been put into practical use: a polyimide film having a flexible heat resistance is laminated on an inorganic substrate used as a carrier, and the polyimide film is used as a substrate for forming an electronic component or Wiring substrate. Here, for example, when a glass substrate having excellent light transmittance is used as the inorganic substrate, there is an advantage that an inspection step when forming an electronic component or when a wiring substrate is formed becomes easy, and can be directly used to form an electron on a glass substrate. Flexible component Existing equipment for production.

In the inorganic substrate in which the polyimide film is laminated, since the inorganic substrate is used as the substrate for the carrier, it is necessary to form an electronic component on the surface of the polyimide film, and finally the polyimide film is used. The inorganic substrate is peeled off. However, from the viewpoint of preventing the polyimide film from peeling off from the inorganic substrate in the step of forming the electronic component, it is necessary to firmly adhere the polyimide film to the inorganic substrate, so that the peeling is not easy. For example, a method of irradiating laser light to a polyimide substrate interface with a glass substrate is proposed (for example, Patent Documents 1 and 2 and Non-Patent Document 1). Further, there has been proposed a method of performing peeling by using the following method or the like: a method in which a polyimide film which is in contact with a glass substrate is heated by Joule heat without using laser light (Patent Document 3), and a method of performing induction heating (Patent Document 3) Patent Document 4) A method of irradiating a flash from a xenon lamp (Patent Document 5). In this method, only one type of layer is in contact with the inorganic substrate at the peeling interface between the inorganic substrate and the polyimide film. However, these methods are not only complicated in steps, require a long time, but also expensive due to expensive equipment, and there is a problem that reuse of an inorganic substrate is difficult.

Therefore, as a method of peeling off the above method, Patent Document 6 proposes a method of improving the releasability of the polyimide polyimide laminate by standing for a long time in pressurized steam. Further, Patent Document 7 proposes a method of immersing the polyimide polyimide laminate in water to improve the releasability thereof. These methods utilize a case where the polyimide film is rapidly expanded due to water absorption or moisture absorption from the surface of the polyimide film, and the stress generated thereby acts on the interface between the polyimide film and the inorganic substrate. As a result, the adhesion at the interface is lowered to improve the peelability. In this method, only one type of layer is in contact with the inorganic substrate at the peeling interface between the inorganic substrate and the polyimide substrate. Further, Patent Document 8 proposes a method of forming a patterned paste on a glass substrate. The layer is formed on the surface of the adhesive layer and the surface of the glass sheet to form a flexible substrate layer such as polyimide, and then the flexible substrate layer on the surface of the adhesive layer is peeled off, and then peeled off from the glass substrate. Flexible substrate layer.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-512568

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-73001

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-189974

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2014-86451

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2014-120664

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-196243

[Patent Document 7] US Patent No. 7575983

[Patent Document 8] German Patent Publication No. 102012102131A1

[Non-patent literature]

[Non-Patent Document 1] Journal of Information Display, 2014, Vol. 15, N0.1, pp. 1~4 (issued by The Korean Information Display Society)

However, in the above method of utilizing moisture absorption or water absorption, since moisture absorption or water absorption is applied to the surface of the polyimide film, for example, a gas barrier layer is formed on the surface of the polyimide film (which is used for blocking A layer in which water vapor or oxygen penetrates is also used to prevent deterioration of electronic components formed on a polyimide film in an OLED or the like. In the case of the layer), moisture absorption or water absorption is not sufficiently performed, and the effect of sufficiently improving the peeling property cannot be obtained. Further, in the method of placing a long time in pressurized steam as disclosed in Patent Document 6, there is a problem that the polyimide is hydrolyzed to cause deterioration of the film. Further, in the method of using the patterned adhesive layer disclosed in Patent Document 8, the steps are complicated, and it is difficult to simultaneously achieve the adhesion between the member such as an electronic component and the peelability from the glass substrate after the member is formed. Further, it is difficult to peel the adhesive layer from the glass substrate, and it is difficult to reproduce the glass substrate.

Therefore, the present invention has been made in view of the above problems, and it is an object of the invention to provide a laminate in which a polyimide film of a polyimide film has good adhesion to an inorganic substrate, and the polyimide film can be easily applied to an inorganic substrate in a short time. Stripped.

Another object of the present invention is to provide a laminate in which the adhesion between the polyimide film and the inorganic substrate is good, and even if a gas barrier layer is formed on the polyimide film, it can be easily produced in a short time. The polyimide film is peeled off from the inorganic substrate.

Another object of the present invention is to provide a laminate in which the adhesion between the polyimide film and the inorganic substrate is good, and the member such as an electronic component or a wiring can be easily formed on the polyimide film. The polyimide film was peeled off from the inorganic substrate during the time.

The present inventors have made an effort to solve the above problems, and as a result, it has been found that a laminate having a polyimide film formed on an inorganic substrate (hereinafter sometimes abbreviated as "layered body") has a specific configuration. The above problems can be solved to complete the present invention.

That is, the present invention is mainly directed to the following. A laminate having an inorganic substrate and a polyimide film formed on the inorganic substrate, and having The following features: (1) Polyimide-based film comprising a laminate film of a polyimine-based resin layer A and a polyimide-based resin layer B, and the polyimide-based resin layer A is entirely in contact with the inorganic substrate And one part of the polyimine-based resin layer B formed on the surface of the polyimide-based resin layer A is in contact with the inorganic substrate; (2) the adhesion strength of the polyimide-based resin layer A to the inorganic substrate 2N/cm or less; (3) the adhesion strength of the polyimine-based resin layer B to the inorganic substrate exceeds 2 N/cm; (4) the polyimide-based resin layer B which is in contact with the inorganic substrate can be The inorganic substrate is peeled off by moisture absorption treatment.

The laminate according to the above aspect is characterized in that the inorganic substrate is a glass substrate.

The laminate according to the above aspect is characterized in that a gas barrier layer is formed on the surface of the polyamidene resin layer B.

A method for treating a laminate, wherein the laminate is subjected to moisture absorption treatment to peel the polyimide film from the inorganic substrate.

The method for treating a laminated body according to the above aspect is characterized in that the moisture absorbing treatment is carried out by dehumidifying under reduced pressure after maintaining the laminated body in an environment of a temperature of 100 ° C or lower and a relative humidity of 70% or more.

A method of producing a flexible device, wherein a flexible device is obtained by forming one or more members selected from the group consisting of an electronic component and a wiring on a surface of a polyimide film of the laminate (hereinafter sometimes abbreviated as "members such as electronic components"), the laminate is subjected to moisture absorption treatment, and the polyimide film having the above-mentioned member is peeled off from the inorganic substrate, and then cut and removed to the inorganic substrate. The polyimine-based resin layer B portion is bonded.

A method for producing a flexible device, comprising: forming one or more members selected from the group consisting of an electronic component and a wiring on a surface of the polyimide film of the laminate; Cut and cut the predetermined part of the amine film a portion of the formation region of the member in the polyimide film, and a portion of the polyimide layer B which is in contact with the inorganic substrate, and then peels off the member in the polyimide film. The region portion is formed to obtain a flexible device, and the polyimine-based resin layer B remaining on the inorganic substrate is subjected to moisture absorption treatment to be peeled off from the inorganic substrate.

The method for producing a flexible device according to the present invention is characterized in that the moisture absorbing treatment is carried out by dehumidifying under reduced pressure after maintaining the laminate at a temperature of 100 ° C or lower and a relative humidity of 70% or more.

In the laminate of the present invention, the polyimide film can be easily adhered to the inorganic substrate, and the polyimide film can be easily peeled off from the inorganic substrate by, for example, moisture absorption treatment, so that flexibility can be easily produced. Device or flexible wiring substrate. Further, even in the case where a gas barrier layer is formed on the surface of the polyimide film, good peelability can be easily obtained by moisture absorption treatment.

1‧‧‧Inorganic substrate

2‧‧‧ Polyimide film

3‧‧‧ gas barrier

21‧‧‧ Polyimine resin layer A (for example, polyimine layer A)

22‧‧‧ Polyimine resin layer B (for example, polyimine layer B)

100‧‧‧Layer

200‧‧‧ incision

210‧‧‧peripheral area

211‧‧‧Overlapping area of the polyimine-based resin layer A (21) in the surface of the polyimide layer B (22)

220‧‧‧The outer edge

250‧‧‧ Stripped scheduled area

Fig. 1(A) is a schematic view (cross-sectional view) of a laminate according to an embodiment of the present invention, and Fig. 1(B) is a schematic view showing a laminate of Fig. 1(A) viewed from above.

2(A) is a schematic view (cross-sectional view) of a laminate having an embodiment of the present invention having a gas barrier layer, and FIG. 2(B) is a schematic view of the laminate of FIG. 2(A) viewed from above in the drawing. schematic diagram.

3(A) and 3(B) are schematic views (sections) of a polyimide film which is a method for producing a flexible substrate by the method 1 for processing a laminate using the laminate of Fig. 1(A); Figure).

4(A) and (B) are schematic views (sections) of a polyimide film which is a method for producing a flexible substrate by the method 1 for processing a laminate using the laminate of Fig. 2(A) Figure).

5(A) and (B) are schematic views (sections) of a polyimide film which is a method for producing a flexible substrate by the method 2 for processing a laminate using the laminate of Fig. 1(A) Figure).

6(A) and (B) are schematic views (sections) of a polyimide film which is a method for producing a flexible substrate by the method 2 for processing a laminate using the laminate of Fig. 2(A) Figure).

Hereinafter, the present invention will be described in detail.

[layered body]

The laminated system of the present invention has a flexible substrate layer formed of a polyimide film on an inorganic substrate. The inorganic substrate to be used herein is not limited, and for example, a glass substrate, a metal substrate such as copper or aluminum, a ceramic substrate such as alumina, or the like can be preferably used. As the glass substrate, for example, soda lime glass, borosilicate glass, alkali-free glass, or the like can be used, and among these, an alkali-free glass substrate can be preferably used.

The thickness of the inorganic substrate is preferably 0.3 to 5.0 mm. If the thickness is thinner than 0.3 mm, there is a case where the substrate is rationally lowered. Moreover, when the thickness is thicker than 5.0 mm, productivity may fall. These inorganic substrates may also be subjected to a surface treatment for controlling adhesion to a polyimide film layer, for example, a decane coupling agent treatment or the like.

As shown in FIGS. 1(A) and (B), the laminate 100 of the present invention is inorganic. A polyimide film 2 is laminated on the substrate 1. The polyimine-based film 2 includes a laminated film of a polyimine-based resin layer A (21) and a polyimide-based resin layer B (22), and the polyimine-based resin layer A (21) is comprehensively The inorganic substrate 1 is in contact with each other, and a part of the polyimide-based resin layer B (22) formed on the surface of the polyimide-based resin layer A (21) is in contact with the inorganic substrate 1. Fig. 1(A) is a schematic view (cross-sectional view) showing a laminate of an embodiment of the present invention. Fig. 1(B) is a schematic view showing the laminated body of Fig. 1(A) viewed from above in the figure.

When the polyimine-based resin layer A is entirely in contact with the inorganic substrate, the polyimine-based resin layer A (21) is entirely in contact with the inorganic substrate 1 on one surface thereof as shown in FIG. 1(A).

The part of the polyimine-based resin layer B is in contact with the inorganic substrate, and the polyimine-based resin layer B (22) is formed on the polyimine as shown in FIGS. 1(A) and (B). The entire surface of the resin layer A (21) and the outer peripheral region 210 of the polyimine-based resin layer A (21) on the surface of the inorganic substrate 1, and the polyimide-based resin layer B (22) on the outer edge portion thereof 220 (hatched portion in the drawing) is in direct contact with the inorganic substrate 1. When the polyimine-based resin layer B is not formed and a part of the polyimide-based resin layer B is not bonded to the inorganic substrate, the polyimide film is applied to the inorganic substrate 1 The adhesion is reduced. Therefore, when a member such as an electronic component is formed on the polyimide film before the polyimide substrate is peeled off from the inorganic substrate, the polyimide film is peeled off and the work efficiency is lowered. When the entire surface of the polyimine-based resin layer B is in contact with the inorganic substrate, that is, when the polyimine-based resin layer A is not formed, the polyimide film is peeled off from the inorganic substrate. Sexual decline. Specifically, when a member such as an electronic component is formed on a polyimide film having a gas barrier layer formed on the surface thereof, when the polyimide film is peeled off from the inorganic substrate, the polyimide film portion directly under the member is formed. Inability to fully absorb moisture After the treatment, it is difficult to peel the polyimide film from the inorganic substrate.

The area of the polyimine-based resin layer B is preferably 110% or more with respect to the area of the polyimide-based resin layer A, from the viewpoint of the adhesion of the polyimide film to the inorganic substrate. More preferably, it is 120% or more, and further preferably 150% or more. The upper limit of the area of the polyimine-based resin layer B is not particularly limited, and the area of the polyimide-based resin layer B is larger than the area of the polyimide-based resin layer A from the viewpoint of reducing material loss. It is usually 200% or less, preferably 180% or less, more preferably 160% or less. The area of the polyimine-based resin layer A is the area of the formation region of the polyimide-based resin layer A on the surface of the inorganic substrate 1, and is equivalent to the area of the broken line region 211 in FIG. 1(B). The area of the polyimine-based resin layer B is the area of the polyimide-based resin layer A and the polyimine-based resin layer A (21) in which the polyimide-based resin layer B is directly formed on the surface of the inorganic substrate 1. The sum of the areas of the outer peripheral regions 210 is equivalent to the area of the region 22 representing the polyiminoimide-based resin layer B in Fig. 1(B).

The polyimine-based resin layer A (21) and the polyimide-based resin layer B (22) in Fig. 1 (B) have a square shape, but may be peeled off according to the laminate of the present invention. The polyimine-based film 2 has an arbitrary shape for use. The polyimine-based resin layer A and the polyimide-based resin layer B may have a circular shape or a rectangular shape, for example. In the case where the polyimine-based film 2 is used as a flexible substrate, the shape of the polyimide-based resin layer A and the polyimide-based resin layer B is generally a square shape or a rectangular shape.

In the polyimine-based resin layer B (22), the width W (see FIG. 1(B)) of the outer edge portion 220 is directly contacted with the inorganic substrate 1 (see FIG. 1(B)), and is usually 2 mm or more, particularly 2 mm or more and 100 mm or less. From the viewpoint of a better balance between the adhesion of the imide-based film 2 and the releasability, it is preferably 3 mm or more and 80 mm or less, more preferably 4 mm or more and 50 mm or less. In FIGS. 1(A) and (B), a polyimide resin layer The outer edge portion 220 of the B (22) layer is in direct contact with the inorganic substrate 1 across the entire circumference of the outer peripheral region 210 of the polyamidene-based resin layer A (21), but it is only required to be a polyimine prior to moisture absorption treatment. The film 2 has a desired adhesiveness, and the outer edge portion 220 may not directly contact the inorganic substrate 1 at a portion of the outer peripheral region 210.

The adhesion strength of the polyimine-based resin layer A to the inorganic substrate is 2 N/cm or less, preferably 1 N/cm or less, more preferably 0.5 N/cm or less. The polyimine-based resin layer A has such an adhesive strength before the moisture absorption treatment of the present invention described below, thereby ensuring good peelability of the polyimide-based resin layer A and the inorganic substrate. When the adhesion strength of the polyimine-based resin layer A to the inorganic substrate exceeds 2 N/cm, it becomes difficult to peel the polyimide film from the inorganic substrate. The lower limit of the adhesion strength of the polyimine-based resin layer A to the inorganic substrate is not particularly limited, and the lower the value, the better.

The adhesion strength of the polyimine-based resin layer B to the inorganic substrate exceeds 2 N/cm, preferably 5 N/cm or more, and more preferably 7 N/cm or more. The polyimine-based resin layer B has such an adhesive strength before the moisture absorption treatment of the present invention described below, thereby ensuring good adhesion between the polyimide-based resin layer B and the inorganic substrate, thereby ensuring integration of the laminate. The adhesion of the entire polyimide-based film to the inorganic substrate. When the adhesion strength of the polyimine-based resin layer B to the inorganic substrate is too low, the polyimine is formed on the polyimide film before the polyimine film is peeled off from the inorganic substrate. The film is peeled off and the work efficiency is lowered. The upper limit of the adhesion strength of the polyimide-based resin layer B to the inorganic substrate is not particularly limited, and the bonding strength is usually 20 N/cm or less, preferably 10 N/cm or less.

The polyimine-based resin layer B can be peeled off from the inorganic substrate by moisture absorption treatment. Specifically, the polyilylimide-based resin layer B can be peeled off by a specific peeling method such as a method of peeling off the hand from the end portion after the moisture absorption treatment described below. Jujua After the moisture absorbing treatment, the amine resin layer B exhibits, for example, the adhesive strength as shown below. The adhesive strength of the polyimine-based resin layer B after the moisture absorption treatment with the inorganic substrate is usually 2 N/cm or less, preferably 1 N/cm or less, and more preferably 0.5 N/cm or less. Since the polyimine-based resin layer B is adhered to the inorganic substrate with such a low adhesive strength by moisture absorption treatment, the polyimide film can be easily peeled off from the inorganic substrate. When the adhesion strength of the polyimide-based resin layer B to the inorganic substrate exceeds 2 N/cm after the moisture absorption treatment, it is difficult to peel the polyimide film from the inorganic substrate. The lower limit of the adhesive strength of the polyimine-based resin layer B after the moisture absorption treatment with the inorganic substrate is not particularly limited, and the lower the value, the better.

The adhesive strength in the present invention is a value obtained by measuring the adhesion strength between the layers of the polyimide film and the inorganic substrate by a 180° peel test based on JIS K6854-2.

The polyimine-based resin layer A and the polyimine-based resin layer B constituting the polyimide film are formed by thinning a polyimide film. The polyimine-based resin has a resin having a quinone bond in the main chain, and specific examples thereof include polyiminoimine, polyamidimide, polyesterimide, and the like, but are not limited thereto. Any resin can be used as long as it has a quinone bond on the main chain. These resins are usually used singly or in combination of two or more. The polyimide-based resin layer constituting the polyimine-based resin layer A and the polyimide-based resin layer B is independently selected, and any of the polyimine-based resins may be used, and it is preferred to use a polyimide. .

As the polyimine, it can be thermally hardened by using a polyimine precursor such as polylysine dissolved in a solvent to prepare a polyimine precursor or a solvent-soluble polyazide. As the amine, a precursor type polyimine can be preferably used.

The polyimine-based resin preferably has 50 mol% The constituent unit derived from the quinone imine bond (wherein the total constituent unit is set to 100 mol%).

A commercially available product can be used as the above polyimine-based resin. In other words, for example, "U imide AR", "U imide AH", "U imide BH", "U imide CR", "U imide CH" (all of which are manufactured by UNITIKA) or U varnish A can be used. Solvent-soluble polyimine varnish, Vylomax, etc. dissolved in solvent, such as polyacrylic acid varnish, "RIKACOAT SN-20" (manufactured by Nippon Chemical and Chemical Co., Ltd.) or "Matrimid 5218" (manufactured by HUNTSMAN) Polyamine amidoxime varnish such as HR-11NN (manufactured by Toyobo Co., Ltd.).

The precursor type polyimine is a polyimine precursor solution obtained by reacting a tetracarboxylic acid or a dianhydride thereof which is a raw material with a diamine in a solvent, and is coated with A polyimine layer can be obtained after drying and heat hardening (醯imination).

The reaction temperature at the time of producing the polyimide precursor solution is preferably -30 to 60 ° C, more preferably -15 to 40 ° C. Further, in the reaction, the order of addition of the monomer and the solvent is not particularly limited, and may be any order.

Here, as the tetracarboxylic acid or a dianhydride thereof, for example, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 3,3', 4 can be used in the form of a monomer or a mixture. 4'-benzophenone tetracarboxylic acid, 3,3',4,4'-diphenyltetracarboxylic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, 2,3,3 ',4'-benzophenone tetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid Acid, 3,3',4,4'-diphenylmethanetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane, 3,4,9,10-tetracarboxyindole, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane, 2,2-bis[4-( 3,4-dicarboxyphenoxy)phenyl]hexafluoropropane, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2 ,4,5-cyclohexane Tetracarboxylic acid, bicyclo[2,2,2]-7-octene-2,3,5,6-tetracarboxylic acid or such dianhydride, etc., but is not limited thereto.

Here, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid or such dianhydrides are particularly preferably used.

As the diamine, for example, p-phenylenediamine, m-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4 can be used in the form of a monomer or a mixture. 4'-Diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl Propane, 1,2-bis(anilino)ethane, diaminodiphenylanthracene, diaminobenzimidamide, diaminobenzoic acid ester, diaminodiphenyl sulfide, 2,2 - bis(p-aminophenyl)propane, 2,2-bis(p-aminophenyl)hexafluoropropane, 1,5-diaminonaphthalene, diaminotoluene, diaminotrifluorotoluene, 1, 4-bis(p-aminophenoxy)benzene, 4,4'-bis(p-aminophenoxy)biphenyl, diaminoguanidine, 4,4'-bis(3-aminophenoxy) Phenyl)diphenylanthracene, 1,3-bis(anilino)hexafluoropropane, 1,4-bis(anilino)octafluorobutane, 1,5-bis(anilino)decafluoropentane, 1 , 7-bis(anilino)tetradecfluoroheptane, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6- Hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, cis-1, 4-diaminocyclohexane, trans-1,4-di Cyclohexane, 1,4-diaminocyclohexane isomer mixture, cis-cis-4,4'-diaminodicyclohexylmethane, cis-trans-4,4'-diaminodi Cyclohexylmethane, trans-trans-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane isomer mixture, cis-1,3-bis(aminoethyl) Cyclohexane, trans-1,3-bis(aminoethyl)cyclohexane, 1,3-bis(aminoethyl)cyclohexane isomer mixture, cis-trans-4,4'- Methylene bis(2-methylcyclohexylamine), trans-trans-4,4'-methylenebis(2-methylcyclohexylamine), 4,4'-methylenebis(2-methyl Cyclohexylamine) isomer mixture, cis-cis-4,4'-diaminodicyclohexylpropane, cis-trans-4,4'-diaminodicyclohexylpropane, 4,4' - Diamine-based dicyclohexylpropane, etc., but is not limited thereto.

Here, p-phenylenediamine, 4,4'-diaminodiphenyl ether, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane are particularly preferably used.

The solid content concentration of the polyimide precursor is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The polyamidoacid solution can be partially imidized by hydrazine.

The viscosity of the polyimine precursor solution of the present invention at 25 ° C is preferably from 1 to 150 Pa. s, more preferably 5~100Pa. s.

The solvent used for the polyimide precursor solution is not particularly limited as long as it is a solvent for dissolving the polyimide precursor, and examples thereof include a guanamine solvent, an ether solvent, and a water-soluble alcohol solvent.

Specific examples of the guanamine-based solvent include N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide ( DMAc) and so on.

Examples of the ether solvent include 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethoxyethanol, 2-isopropoxyethanol, and 2-butoxyethanol. , tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monoethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, polyethylene glycol, polypropylene glycol, Tetrahydrofuran, two Alkane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like.

Examples of the water-soluble alcohol-based solvent include methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-butane. Alcohol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol 1,2,6-hexanetriol, diacetone alcohol, and the like.

These solvents can be used by mixing two or more types. About these solvents As a separate solvent, N,N-dimethylacetamide and N-methyl-2-pyrrolidone are exemplified, and as a mixed solvent, N,N-dimethylacetonitrile is mentioned. The amine is combined with N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone with methanol, N-methyl-2-pyrrolidone and 2-methoxyethanol.

Hereinafter, a method of producing the polyimine-based resin layers A and B using a polyimide precursor solution will be described, but it is clear that the polymer other than the above-mentioned polyimine is used as the polyimine system. In the case of a resin, the polyimine-based resin layers A and B can also be produced by applying the following description.

When manufacturing the polyimine-based resin layers A and B, first, the "polyimine precursor solution A" for producing the polyimide-based resin layer A, and the polyimine-based resin are prepared. "Polyimide precursor solution B" of layer B (sometimes referred to as "polyimine solution A" and "polyimine solution B", respectively). Then, the polyimine solution A is applied onto the inorganic substrate, and after drying, the polyimide film B is applied onto the surface of the dried coating film and the inorganic substrate and dried. Then, the coating films are collectively thermally cured to be imidized. The term "drying" as used herein means reducing the amount of solvent in the polyimide precursor solution by means of heating or the like. In this case, it is preferred to remove the solvent until the solid content concentration in the coating film is 50% by mass or more and 90% by mass or less. By drying in this manner, the adhesion between the polyimide-based resin layer A and the polyimide-based resin layer B is ensured, and integration can be carried out. Any device may be used for drying, preferably a hot air dryer, or infrared heating, electromagnetic induction heating, or the like. The temperature range for drying is suitably 50 to 200 °C. Further, the term "thermosetting" as used herein refers to a step of converting a polyimide precursor to a polyimine. The temperature range for thermal hardening is suitably 300 to 450 °C. When the polyimine-based solution B is applied, the polyimide-based resin layer A is completely coated in its entirety, and the area of the polyimide-based resin layer B is large. The area of the polyimine-based resin layer A can be made into the above-mentioned layer structure.

In the polyimine precursor solution A, in order to obtain the above-mentioned adhesive strength of the polyimine-based resin layer A, for example, a higher-grade fatty acid such as stearic acid or palmitic acid or a release agent such as a guanamine or a metal salt may be blended. Among these, stearic acid is preferred. The more the amount of the release agent is, the smaller the adhesion strength of the polyimide film is. On the other hand, the smaller the amount of the release agent, the greater the adhesion strength of the polyimide film.

The amount of the release agent in the polyimide intermediate solution A is not particularly limited as long as the polyimide layer has a predetermined adhesive strength, and is usually added in preference to the mass of the polyimide. 0.01 to 2% by mass, more preferably 0.1 to 1% by mass. In the present specification, the term "polyimine" refers to the total mass of the polyimine in terms of polyimine contained in the polyimide precursor solution.

In the polyimine precursor solution A, in order to obtain the above-mentioned adhesive strength of the polyimine-based resin layer A, the following adhesion improving agent may be formulated. The effect on the adhesion strength caused by the formulation of the adhesion improving agent is the same as in the polyimide intermediate solution B.

In the polyimine precursor solution B, in order to obtain the above adhesive strength, an adhesion improving agent such as a decane coupling agent may be formulated in the solution as needed. The type of the decane coupling agent is not limited, and examples thereof include an amine type, an epoxy type, and an acrylic type, and an amine type is preferable. The more the amount of the adhesion improving agent is, the greater the adhesion strength of the polyimide film. On the other hand, the smaller the blending amount of the adhesion improving agent, the smaller the adhesive strength of the polyimide film.

The blending amount of the adhesion improving agent in the polyimide precursor solution B is preferably 0.05 to 0.5% by mass, more preferably 0.05 to 0.2% by mass, even more preferably 0.1% based on the mass of the polyimide. ~0.2% by mass.

In the polyimine precursor solution B, in order to obtain the above-mentioned adhesive strength of the polyimine-based resin layer B, the above-mentioned release agent may be blended. The effect on the adhesion strength caused by the formulation of the release agent is the same as in the polyamidene precursor solution A.

The coating of the polyimine precursor solutions A and B can be carried out continuously or monolithically.

The continuous coating can be carried out by a coater such as a die coater, a lip coater, a notch coater, a gravure coater, or a reverse roll coater.

Continuous coating can also be carried out by a coater such as a bar coater, a knife coater, or a spin coater.

Here, since the inorganic substrate is rigid, continuous coating is often accompanied by difficulty. Therefore, from the viewpoint of industrial production, monolithic coating is preferred.

The coating thickness of the polyimine-based resin layer A is preferably 0.5 to 10 μm, more preferably 1 to 5 μm, after thermosetting.

Moreover, as the coating thickness of the polyimine-based resin layer B, the thickness after heat curing is preferably 5 to 200 μm, more preferably 10 to 100 μm. The thickness of the polyimine-based resin layer B is the thickness of the entire polyimide-based film including the polyimide-based resin layer A, and is equivalent to the thickness of the outer edge portion 220.

As described above, in an electronic device using a polyimide film as a flexible substrate, a gas barrier layer is usually provided in order to prevent penetration of water vapor or the like into the OLED light-emitting layer or the like. In the laminate of the present invention, the gas barrier layer may be provided on a portion of the surface of the polyilylimine-based resin layer B in which the polyimide-based resin layer A is laminated (embedded). As the gas barrier layer, a film containing an inorganic oxide such as cerium oxide, aluminum oxide, cerium carbide, cerium oxycarbonate, cerium carbonitride, cerium nitride or cerium oxynitride may be used, and a coating containing cerium oxide is preferred. Examples of the method of forming the film include a sputtering method, a vacuum evaporation method, and a heat method. A known method such as a CVD (Chemical Vapor Deposition) method, a plasma CVD method, or a photo CVD method is preferably a sputtering method. The thickness of the gas barrier layer is preferably from 10 to 100 nm, more preferably from 20 to 50 nm.

As shown in Fig. 2 (A) and (B), the gas barrier layer 3 is provided at a position (region) in which the surface of the polyimide-based resin layer B overlaps with the position of the polyimide-based resin layer A in the vertical direction. The gas barrier layer 3 is not necessarily provided in the surface of the polyimide-based resin layer B (22) and overlaps with the polyimide-based resin layer A in the vertical direction as shown in Figs. 2(A) and (B). The whole may also be disposed in one part of the overlapping area. The region overlapping the polyimine-based resin layer A on the surface of the polyimide-based resin layer B in the vertical direction means a region indicated by reference numeral 211 in Fig. 1(B). When the gas barrier layer is formed beyond the overlap region 211, the outer edge portion 220 of the polyimide-based resin layer B located directly under the gas barrier layer beyond the overlap region cannot sufficiently receive the moisture absorption treatment described below. Therefore, it is difficult to peel the polyimide film from the inorganic substrate. Fig. 2(A) is a schematic view showing a layered body of an embodiment of the present invention in which the gas barrier layer 3 is formed on the surface of the polyimide-based resin layer B (22) of the laminate of Fig. 1(A). Figure). Fig. 2(B) is a schematic view showing the laminated body of Fig. 2(A) viewed from above in the figure. The same reference numerals as in Figs. 1(A) and (B) in Figs. 2(A) and (B) denote the same members and regions as those in Fig. 1.

By providing the gas barrier layer 3 in a part or the entirety of the repeating region 211, the area of the portion of the polyimide-based resin layer B exposed to the atmosphere can be 10 of the total area of the polyimide-based resin layer B. %the above. In other words, even if a gas barrier layer is provided on the surface of the polyimide-based resin layer B, a part of the polyimide-based resin layer B, particularly the outer edge portion 220, is exposed to the atmosphere, so that it can be treated by moisture absorption. And stripped. The area of the portion of the polyimine-based resin layer B exposed to the atmosphere refers to the surface obtained by subtracting the area of the surface of the gas barrier layer from the area of the surface of the polyimide-based resin layer B. The product is equivalent to the area of the oblique line region 220 in Fig. 2(B). The total area of the polyimine-based resin layer B is equivalent to the area of the region 22 (square shape) of the polyimide-based resin layer B in Fig. 2(B).

As described above, the single-layer portion (outer edge portion 220) of the polyimide-based resin layer B (22) which is in contact with the inorganic substrate is firmly adhered to the inorganic substrate, so that the polyimine-based film 2 can be ensured. Adhesion of inorganic substrates.

[Processing method of laminated body]

The laminate 100 of the present invention can easily peel the polyimide film 2 from the inorganic substrate by the treatment method shown below (the treatment method 1 or 2 for the laminate). The peeled polyimide-based film 2 is useful as a flexible substrate. In this case, by forming a member such as an electronic component on the surface of the polyimide film 2 of the laminate 100 in advance, the peeled polyimide film 2 can be made into a flexible device. When manufacturing a flexible device, it is preferable to form the gas barrier layer 3 on the surface of the polyimide film 2 before the formation of a member such as an electronic component.

(Processing method of laminated body 1)

First, the layered body 100 of the present invention is subjected to the following moisture absorption treatment. Then, the polyimide film 2 is peeled off. As a specific peeling method, a method of peeling off the hand from the end or a method of using a mechanical device such as a driving roller or a robot can be employed. After that, the polyimine-based resin layer B (22) portion that is in contact with the inorganic substrate 1 is cut and removed to obtain a polyimide film 2 as a flexible substrate. The portion of the polyimine-based resin layer B (22) that is in contact with the inorganic substrate 1 refers to a single-layer portion (outer edge portion 220) of the polyimide-based resin layer B (22).

In the method, for example, in the case of using the layered body 100 shown in FIGS. 1(A) and 1(B), first, after the moisture absorption treatment, as shown in FIG. 3(A), the polyimide film 2 is peeled off. . Then, by cutting and removing the single-layer portion (outer edge portion 220) of the polyimide-based resin layer B (22) as an excess portion, a flexible substrate as shown in FIG. 3(B) is obtained. Polyimine film 2 . 3(A) and 3(B) are schematic views (cross-sectional views) of a polyimine-based film for explaining a method of producing a flexible substrate by the method 1 for processing a laminate using the laminate of Fig. 1(A); . The same reference numerals as in Fig. 1 in Fig. 3 denote the same members and regions as those in Fig. 1.

In the method, for example, in the case of using the layered body 100 shown in FIGS. 2(A) and (B), first, after the moisture absorption treatment, as shown in FIG. 4(A), the polymerization having the gas barrier layer 3 is peeled off. Bismuth imide film 2. Then, by cutting and removing the single layer portion (outer edge portion 220) of the polyimide film B layer (22) as an excess portion, a flexible substrate as shown in FIG. 4(B) is obtained. Polyimide film 2 having gas barrier layer 3. 4(A) and 4(B) are schematic views (cross-sectional views) of a polyimine-based film for explaining a method of producing a flexible substrate by the method 1 for processing a laminate using the laminate of Fig. 2(A); . The same reference numerals as in Fig. 2 in Fig. 4 denote the same members and regions as those in Fig. 2.

In the present method, the outer edge portion 220 is preferably peeled off by moisture absorption treatment, and may be peeled off by, for example, irradiating the outer edge portion 220 with laser light, infrared light, ultraviolet light, glitter, or the like. Moreover, peeling can also be performed by immersing the laminated body 100 of this invention in water.

In the method 1 of the present invention, the polyimide-based film 2 obtained by forming a member (not shown) such as an electronic component on the surface of the polyimide film 2 of the laminate 100 is used as a flexible device. is useful.

(Processing method of laminated body 2)

First, a slit is formed in a predetermined portion of the polyimide film 2, and is divided into a portion to be peeled off in the polyimide film, and a polyimide-based resin layer B which is in contact with the inorganic substrate 1. Part of part (22). The predetermined portion of the polyimine-based film to be cut out is a portion where the polyimine-based resin layer A (21) is present directly below, as shown in Figs. 5(A) and 6(A). The slit 200 is formed along the outer periphery of the polyimine-based resin layer A (21). The slit forming method is not particularly limited as long as the slit 200 reaching the inorganic substrate 1 can be formed, and examples thereof include a method using a commercially available cutter or a method using irradiation with laser light. 5(A) and (B) are schematic views (cross-sectional views) of a polyimide film which is a method for producing a flexible substrate by the method 2 for processing a laminate using the laminate of Fig. 1(A); ). 6(A) and 6(B) are schematic views (cross-sectional views) of a polyimide film which is a method for producing a flexible substrate by the method 2 for processing a laminate using the laminate of Fig. 2(A); ).

The portion to be peeled off is a portion of the region to be peeled off later, specifically, a portion 250 corresponding to the polyimide film 2 which is peeled off as shown in Figs. 5(B) and 6(B), For example, when a member (not shown) such as an electronic component is formed on the surface of the polyimide film 2, a portion including a region where the member is formed is included. The portion of the polyimine-based resin layer B (22) that is in contact with the inorganic substrate 1 is also referred to as a single layer portion (outer edge portion 220) of the polyimide-based resin layer B (22).

In this method, after the slit 200 is divided, as shown in FIGS. 5(B) and 6(B), the peeling predetermined region portion 250 is peeled off to obtain a flexible substrate. The peeling-predetermined region portion 250 is in contact with the inorganic substrate 1 only by the polyimide-based resin layer A (21), and thus can be easily peeled off by division. As a specific peeling method, a method of peeling off the hand from the end or using a driving roller or a robot may be employed in the method. The method of mechanical means. In the method 2 of the present invention, the polyimide film 2 (250) obtained by forming a member (not shown) such as an electronic component on the surface of the polyimide film 2 of the laminate 100 is used as Flexible devices are useful.

In the method, the polyimine-based resin layer B (outer edge portion 220) remaining on the inorganic substrate (see FIGS. 5(B) and 6(B)) can be self-inorganized by the moisture absorption treatment described below. Peel off. In the present method, the outer edge portion 220 is preferably peeled off by moisture absorption treatment, and may be peeled off by, for example, irradiating the outer edge portion 220 with laser light, infrared light, ultraviolet light, glitter, or the like. Moreover, peeling can also be performed by immersing in water. The inorganic substrate on which the outer edge portion 220 has been peeled off can be reused.

(moisture absorption treatment)

In the present invention, the moisture absorbing treatment includes at least a moisture absorbing treatment step of maintaining the laminate in a high temperature and high humidity environment.

The moisture absorption condition is not particularly limited, and the moisture absorption temperature is preferably 70° C. or higher, more preferably 80° C. or higher, under conditions of a relative humidity of preferably 70% or more, more preferably 80% or more. Processing steps. Further, pressurized steam of more than 100 ° C may be used, but it is preferred to carry out the moisture absorption treatment step at 100 ° C or lower. The moisture absorption treatment time is preferably 1 hour or longer, more preferably 3 hours or longer, and still more preferably 5 hours or longer. The upper limit of the moisture absorption treatment time is not particularly limited as long as the release of the polyimide film 2 is carried out, and the moisture absorption treatment step is carried out usually for 20 hours or shorter, preferably 15 hours or shorter, more preferably 12 hours or shorter. .

In the moisture absorption treatment, it is preferred to perform dehumidification by decompression after the moisture absorption treatment step. By dehumidification, the polyimide film which is expanded in volume due to moisture absorption can be rapidly shrunk. Expanding and shrinking polyimine system by the moisture absorption and dehumidification operation The film generates stress so that the strength at the interface of the polyimide film which is in contact with the inorganic substrate having almost no volume change under moisture absorption and dehumidification is remarkably lowered. By this action, the polyimide film can be more easily peeled off. This moisture absorption and dehumidification can further improve the peelability by repeating twice or more. In the present invention, moisture absorption and dehumidification are usually carried out 1 to 3 times, whereby the polyimide film can be easily peeled off.

The pressure reduction condition is not particularly limited, and the pressure reduction is preferably 100 Torr or less, more preferably 50 Torr or less, still more preferably 10 Torr or less, and the temperature is preferably 70 ° C, more preferably 80 ° C or higher. deal with. Further, the temperature at the time of the pressure reduction treatment may be the same as or different from the moisture absorption treatment temperature, and is preferably the same. The reduced pressure treatment time is preferably 1 hour or longer, more preferably 3 hours or longer, and still more preferably 5 hours or longer. The upper limit of the pressure reduction treatment time is not particularly limited as long as the release of the polyimide film 2 is promoted, and the pressure reduction treatment step is usually carried out for 20 hours or shorter, preferably 15 hours or shorter, more preferably 12 hours or shorter. .

As a specific method of peeling off the polyimine-based film from the polyimine laminate which has been treated as described above, a method of peeling off the hand from the end portion or a method using a mechanical device such as a driving roller or a robot may be employed.

Further, the polyimide film of the present invention is preferably transparent. The light transmittance at 500 nm, which is an index of transparency, is preferably 70% or more, more preferably 80% or more.

As described above, the laminate of the present invention can easily obtain a polyimide film from a polyimide laminate by a simple step such as moisture absorption treatment, and thus can be suitably used for producing a flexible device or can be used. Flexible wiring board device.

Specifically, after a member such as an electronic component is formed on the surface of the polyimide film of the laminate of the present invention, the member having the above member is peeled off from the inorganic substrate. Amine film. Thereby, the polyimine-based film provided with the above member can be easily obtained as a flexible device or a flexible wiring board device.

A method of forming a member such as an electronic component can be a method known in the art of using an electronic device in which a polyimide film is used as a flexible substrate. The method of forming the gas barrier layer is the same as the above method.

[Examples]

Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to the examples.

[Reference Example 1]

Preparation of U imide AR manufactured by UNITIKA Co., Ltd. (a poly-imidazolium precursor solution obtained from 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine) The solvent was NMP, and the solid concentration was 18% by mass). The solution was coated on a surface of an alkali-free glass plate having a thickness of 0.7 mm by a bar coater so as to have a thickness of 30 μm after heat-hardening (referred to as a polyimine solution A-1). The film was dried at ° C for 10 minutes to form a polyimide film precursor film. Then, under a nitrogen gas stream, the temperature was raised from 100 ° C to 350 ° C for 2 hours, and then heat-treated at 350 ° C for 2 hours to thermally cure the polyimide precursor to be imidized. Thereby, a laminate L-1 having a glass substrate and a polyimide film layer having a thickness of 30 μm was obtained.

[Reference Example 2]

To the polyimine solution A-1, 0.006 mass% of an amine decane coupling agent (KBE903 manufactured by Shin-Etsu Silicones Co., Ltd.) was added to the mass of the polyimine and uniformly mixed to obtain a polyimine solution A- 2. In addition to using the polyimine solution A-2, A laminate L-2 having a glass substrate and a polyimide film layer having a thickness of 30 μm was obtained in the same manner as in Reference Example 1.

[Reference Example 3]

To the polyimine solution A-1, 0.06 mass% of the same decane coupling agent as in Reference Example 2 was added and uniformly mixed with respect to the mass of the polyimine to obtain a polyimine solution B-1. A laminate L-3 having a glass substrate and a polyimide film layer having a thickness of 30 μm was obtained in the same manner as in Reference Example 1 except that the polyimine solution B-1 was used.

[Reference Example 4]

To the polyimine solution A-1, 0.1% by mass of the same decane coupling agent as in Reference Example 2 was added to the mass of the polyimine and uniformly mixed to obtain a polyimine solution B-2. A laminate L-4 having a glass substrate and a polyimide film layer having a thickness of 30 μm was obtained in the same manner as in Reference Example 1 except that the polyimine solution B-2 was used.

[Reference Example 5]

Prepare U imide CR manufactured by UNITIKA Co., Ltd. (which is a polyaminic acid type obtained from 3,3',4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether. Polyimine precursor solution, the solvent is NMP, and the solid concentration is 18% by mass). The solution was coated on a surface of an alkali-free glass plate having a thickness of 0.7 mm by a thickness of 30 μm, and the solution was coated with a bar coater (referred to as a polyimine solution B-3). The film was dried at 130 ° C for 10 minutes to form a polyimide film precursor film. Then, under a nitrogen gas stream, the temperature was raised from 100 ° C to 350 ° C for 2 hours, and then heat-treated at 350 ° C for 2 hours to thermally cure the polyimide precursor to be imidized. Thereby obtaining a glass substrate with A laminate L-5 of a polyimide film layer having a thickness of 30 μm.

[Reference Example 6]

To the polyimine solution B-1, 0.8% by mass of stearic acid was added to the mass of the polyimine and uniformly mixed to obtain a polyimine solution A-3. A laminate L-6 having a glass substrate and a polyimide film layer having a thickness of 30 μm was obtained in the same manner as in Reference Example 5 except that the polyimine solution A-3 was used.

<Adhesion (before moisture absorption treatment) evaluation>

The adhesion strength between the layers of the glass substrate of the laminates L-1 to L-6 and the polyimide film layer was measured by a 180° peel test based on JIS K6854. Moreover, the slit is cut out at the end of the polyimide film of the laminate, and the adhesion at the interface is judged to be "good" in the case where the film cannot be easily peeled off from the glass substrate by hand. In the case of peeling, it is judged that the adhesion is "poor". The results are shown in Table 1. In addition, in Table 1, since it is difficult to specify an accurate adhesive strength in the case where the adhesive strength is 0.1 N/cm or less, it is referred to as "0.1 or less".

As shown in Table 1, the adhesion of the laminates L-3, L-4, and L-5 was good. On the other hand, the laminated bodies L-1, L-2, and L-6 have poor adhesion, that is, the peeling property is good.

<Removability (after moisture absorption treatment) evaluation-1>

The laminates L-3, L-4, and L-5 having good adhesion were treated under the conditions of a relative humidity of 95% and a temperature of 90 ° C for 10 hours to absorb the polyimide film. Thereafter, the pressure-reducing treatment was carried out for 10 hours under the same temperature and a reduced pressure of 5 Torr to dehumidify the moisture-absorbing polyimine. The adhesion strength between the layers of the obtained laminate was measured by a 180° peel test based on JIS K6854. Moreover, in the case where the end of the polyimide film cut out from the slit is easily pulled from the glass sheet by hand, it is judged that the peeling property at the interface is "good" and cannot be easily peeled off. In the case, it was judged that the peeling property was "poor". The results are shown in Table 2. In addition, in Table 2, since it is difficult to specify an accurate adhesive strength in the case where the adhesive strength is 0.1 N/cm or less, it is referred to as "0.1 or less".

<Evaluation of peelability (after moisture absorption treatment)-2>

The laminates L-3, L-4, and L-5 having good adhesion were treated under the conditions of a relative humidity of 80% and a temperature of 50 ° C for 3 hours to absorb the polyimide film. Thereafter, the pressure-reducing treatment was carried out for 10 hours under the same temperature and a reduced pressure of 5 Torr to dehumidify the moisture-absorbing polyimine. The adhesion strength between the layers of the obtained laminate was measured by a 180° peel test based on JIS K6854. Moreover, in the case where the end of the polyimide film cut out from the slit is easily pulled from the glass sheet by hand, it is judged that the peeling property at the interface is "good" and cannot be easily peeled off. In the case, it was judged that the peeling property was "poor". The results are shown in Table 3.

As shown in Table 2 and Table 3, the laminates L-3, L-4, and L-5 having good adhesion before the moisture absorption treatment can be formed into a laminate having good releasability by performing moisture absorption treatment.

[Example 1]

As shown in Fig. 1 (A) and (B), on the surface of the alkali-free glass plate 1 having a thickness of 0.7 mm, the thickness of the film after the heat curing was 3 μm, and the polycondensation was applied by a bar coater. The imine solution A-1 was used as a solution for forming a polyimine layer A (21), and dried at 130 ° C for 10 minutes to form a polyimide film of a polyimide precursor. Here, the area of the coated surface was set to be about 400 cm ² (20 cm × 20 cm). On the surface of the film, the polyimine solution B-1 was applied as a solution for forming a polyimine layer B (22) by a bar coater so that the thickness of the entire film after heat curing was 30 μm. The polyimine precursor film was formed by drying at 130 ° C for 10 minutes. Then, under a nitrogen gas stream, the temperature was raised from 100 ° C to 360 ° C for 2 hours, and then heat-treated at 360 ° C for 2 hours to thermally harden the polyimide precursor to iodide, thereby making the polyimide layer Integration of layers. Here, the area of the coated surface of the polyimine layer B (22) is about 576 cm ² (24 cm × 24 cm), and the outer peripheral region 210 of the polyimine layer A (21) in the surface of the glass plate, The outer edge portion 220 of the amine layer B (22) directly contacts the inorganic substrate 1 as a single layer with a width (W) of 2 cm. Then, as shown in FIGS. 2(A) and (B), a portion (area of about 400 cm ² ) of the surface of the obtained polyimide film 2 is obtained by sputtering to form a thickness of 30 nm. A gas barrier layer 3 formed of a ruthenium oxide film is obtained, thereby obtaining a laminate M-1. The formation region of the gas barrier layer 3 is the entire overlap region 211 (see FIG. 1(B)) of the polyimine layer A (21) on the surface of the polyimide layer B (22).

[Embodiment 2]

A layered product M-2 was obtained in the same manner as in Example 1 except that the polyimine solution A-1 was used as the polyimine solution A-2.

[Example 3]

The layered product M-3 was obtained in the same manner as in Example 1 except that the polyimine solution A-1 was used as the polyimine solution A-3.

[Example 4]

A layered product M-4 was obtained in the same manner as in Example 1 except that the polyimine solution B-1 was used as the polyimine solution B-2.

[Example 5]

A layered product M-5 was obtained in the same manner as in Example 1 except that the polyimine solution B-1 was used as the polyimine solution B-3.

[Embodiment 6]

The polyimine solution A-1 was set to the polyimine solution A-2, and the polyimine solution B-1 was set to the polyimine solution B-3, and the same as Example 1 The laminate M-6 was obtained in the same manner.

[Embodiment 7]

The polyimine solution A-1 was set to the polyimine solution A-3, and the polyimine solution B-1 was set to the polyimine solution B-3, and the same as Example 1 The laminate M-7 was obtained in the same manner.

[Embodiment 8]

The polyimine solution A-1 was set to the polyimine solution A-2, and the polyimine solution B-1 was set to the polyimine solution B-2, and the same as Example 1 The laminate M-8 was obtained in the same manner.

[Embodiment 9]

The area of the coated surface of the polyimide layer B was set to about 484 cm ² (22 cm × 22 cm), and the outer edge portion 220 of the polyimide layer B was directly formed as a single layer with a width (W) of 1 cm. Then, a layered body M-9 was obtained in the same manner as in Example 1 except for the above.

[Embodiment 10]

The area of the coated surface of the polyimide layer B was set to about 441 cm ² (21 cm × 21 cm), and the outer edge portion 220 of the polyimide layer B was made as a single layer with a width (W) of 0.5 cm directly to the glass substrate. A layered body M-10 was obtained in the same manner as in Example 1 except for the above.

[Comparative Example 1]

On the surface of the alkali-free glass plate having a thickness of 0.7 mm, the polyimide film A-1 was coated by a bar coater at a thickness of 30 μm, and dried at 130 ° C for 10 minutes. The polyimine precursor film is formed. Here, the area of the coated surface was set to be about 400 cm ² (20 cm × 20 cm). Then, under a nitrogen gas stream, after heating for 2 hours from 100 ° C to 360 ° C, heat treatment at 360 ° C for 2 hours, the polyimide precursor is thermally hardened and yttrium imidized, thereby forming a polyimine layer. A. The surface of the obtained polyimide layer A (having an area of about 400 cm ² ) was completely treated by a sputtering method to form a gas barrier layer formed of a cerium oxide film having a thickness of 30 nm, thereby obtaining a layered body N-1.

[Comparative Example 2]

Polyimine layer B-1 is used instead of polyimine solution A-1 to form polyimine layer B, and a gas barrier layer is formed on the surface of the polyimine layer B, and other comparisons are made. In the same manner as in Example 1, a layered body N-2 was obtained.

[Comparative Example 3]

Polyimine layer B is formed by using polyimine solution B-3 instead of polyimine solution A-1, and a gas barrier layer is formed on the surface of the polyimine layer B, and other comparisons are made. In the same manner as in Example 1, a layered body N-3 was obtained.

[Comparative Example 4]

The area of the coated surface of the polyimide layer B was set to about 400 cm ² (20 cm × 20 cm), and the polyimine layer B and the polyimide layer A were mostly overlapped, and the examples were The laminate N-4 was obtained in the same manner.

<Evaluation of adhesion and peelability>

With respect to the laminate obtained in the above Examples and Comparative Examples, the adhesion before the moisture absorption treatment and the peelability after the moisture absorption treatment were evaluated by the methods described above. In particular, the evaluation of the peeling property after the moisture absorption treatment was carried out in accordance with the method of "evaluation (after moisture absorption treatment)-1". The results are shown in Table 4.

As shown in Table 4, the laminate obtained in the examples had good adhesion before moisture absorption treatment and peelability after moisture absorption treatment. On the other hand, in the laminate obtained in the comparative example, one of the adhesion before the moisture absorption treatment and the peelability after the moisture absorption treatment was poor.

[Example 11]

In the layered product M-1 obtained in the first embodiment, the slit 200 is cut around the fourth region where the gas barrier layer 3 is formed (see FIGS. 2(A) and (B), and FIG. 6(A)). Further, it is divided into a portion of the outer edge portion 220 of the polyimide layer B (22) directly in contact with the glass substrate 1, and a region where the gas barrier layer 3 is formed. The end portion of the portion where the gas barrier layer 3 is formed is divided by the hand 拽, and as a result, the formation region of the gas barrier layer 3 can be easily peeled off from the glass substrate 1. Part of it. Then, the glass substrate (see FIG. 6(B)) in which the outer edge portion 220 of the polyimide layer B (22) remains is treated at a relative humidity of 95% and a temperature of 90 ° C for 10 hours. The polyimine layer B is made hygroscopic. Thereafter, the pressure-reducing treatment was carried out for 10 hours under reduced pressure of 5 Torr at the same temperature to dehumidify the moisture-absorbing polyimine, and as a result, the polyimide phase B was easily peeled off by hand. The same operation as in Example 1 was carried out using the glass substrate from which the polyimide layer B was peeled off, and as a result, the same laminate as in Example 1 was obtained.

[Embodiment 12]

The laminate M-12 was obtained in the same manner as in Example 1 except that the gas barrier layer was not formed. The slit 200 is cut around the overlapping region 211 (see FIG. 1(B)) of the laminate (see FIGS. 1(A) and (B), and FIG. 5(A)), and is divided into the glass substrate 1 directly. The outer edge portion 220 of the adjacent polyimide layer B (22) and the portion of the overlap region 211. The end portion of the overlapping region 211 is divided by the hand 拽, and as a result, the portion of the overlapping region 211 can be easily peeled off from the glass substrate 1. Then, the glass substrate (see FIG. 5(B)) in which the outer edge portion 220 of the polyimide layer B (22) remains is treated under the conditions of a relative humidity of 85% and a temperature of 80 ° C for 8 hours. The polyimine layer B is made hygroscopic. Thereafter, it was dried under normal pressure at 100 ° C for 2 hours to dehumidify the moisture-absorbing polyimide, and as a result, the polyimide layer B was easily peeled off by hand.

[Example 13]

The glass substrate (see FIG. 5(B)) in which the outer edge portion 220 of the polyimide layer B (22) was obtained in Example 12 was immersed in warm water of 30 ° C for 10 hours. Thereafter, it was dried under normal pressure at 100 ° C for 2 hours, and as a result, the polyimide layer B was easily peeled off by hand.

(industrial availability)

As described above, in the laminate of the present invention, the polyimide film can be easily adhered to the inorganic substrate, and the polyimide film can be easily peeled off from the inorganic substrate by, for example, moisture absorption treatment. A flexible substrate for an electronic device of a polyimide film is useful. In the laminate of the present invention, even when a gas barrier layer is formed on the surface of the polyimide film which constitutes the laminate, the adhesion before the moisture absorption treatment and the peelability after the moisture absorption treatment are also good. It is useful for producing a flexible device or a flexible wiring board in which a polyimine-based film as a flexible substrate is formed with a member such as an electronic component.

Claims (8)

A laminate comprising an inorganic substrate and a polyimide film formed on the inorganic substrate, and having the following characteristics: (1) the polyimide film comprises a polyimine resin layer A and The laminated film of the polyimine-based resin layer B, the polyimine-based resin layer A is in contact with the inorganic substrate, and the polyimine-based resin layer B formed on the surface of the polyimide-based resin layer A a part of the inorganic substrate is in contact with the inorganic substrate; (2) the adhesive strength of the polyimine-based resin layer A and the inorganic substrate is 2 N/cm or less; and (3) the adhesion of the polyimide-based resin layer B to the inorganic substrate When the strength exceeds 2 N/cm, the adhesion strength between the polyimide-based resin layer B and the inorganic substrate is 2 N/cm or less by moisture absorption treatment; (4) The polyamidene-based resin layers A and B are directly formed. On the surface of the above inorganic substrate. The laminate according to claim 1, wherein the inorganic substrate is a glass substrate. The laminate of the first or second aspect of the invention is characterized in that a gas barrier layer is formed on the surface of the polyamidene resin layer B. A method of treating a laminate, which is characterized in that the laminate is subjected to moisture absorption treatment according to any one of claims 1 to 3, and the polyimide film is peeled off from the inorganic substrate. The method for treating a laminate according to the fourth aspect of the invention, wherein the moisture absorption treatment is performed by dehumidifying under reduced pressure after maintaining the laminate at a temperature of 100 ° C or lower and a relative humidity of 70% or more. A method for producing a flexible device, which is characterized in that a flexible device is obtained by forming a surface of a polyimide film of a laminate according to any one of claims 1 to 3. After selecting one or more components from electronic components and wiring, borrow The laminate is subjected to moisture absorption treatment, and the polyimine-based film having the above member is peeled off from the inorganic substrate, and then the portion of the polyimide-based resin layer B that is in contact with the inorganic substrate is cut and removed. A method for producing a flexible device, which is characterized in that the surface of the polyimide film of the laminate according to any one of claims 1 to 3 is one selected from the group consisting of electronic components and wiring. In the above-mentioned member, a slit is formed in a predetermined portion of the polyimide film having the above-mentioned member, and a portion of the formation region of the member which is divided into a polyimide film and a polymerized layer which is in contact with the inorganic substrate The portion of the imide-based resin layer B, and then the portion of the formation region of the above-mentioned member in the polyimide film is peeled off to obtain a flexible device, and the polyiphthalide-based resin layer B remaining on the inorganic substrate is subjected to The moisture absorption treatment is performed, and it is peeled off from the inorganic substrate. The method for producing a flexible device according to claim 6 or 7, wherein the moisture absorption treatment is carried out under reduced pressure after maintaining the laminate at a temperature of 100 ° C or lower and a relative humidity of 70% or more. Dehumidification treatment.