KR102087647B1 - Display device production method - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a display device in which a predetermined display portion is formed on a resin substrate integrated with a support in advance, and then the resin substrate can be easily separated from the support and the display device can be obtained easily. do. The present invention forms a predetermined display portion 4 on the second resin layer in a state where the first resin layer 7 and the second resin layer 8 are laminated on the support 1, and then the first number It is a manufacturing method of the display apparatus characterized by obtaining the display apparatus provided with the display part on the resin base material which consists of a 2nd resin layer isolate | separating from the interface surface of a ground layer and a 2nd resin layer.

Description

Manufacturing method of display device {DISPLAY DEVICE PRODUCTION METHOD}

TECHNICAL FIELD This invention relates to the manufacturing method of a display apparatus. Specifically, It is related with the manufacturing method of the display apparatus in which the display part in a liquid crystal display device, an organic electroluminescence display, etc. was formed on the resin base material.

Display devices such as liquid crystal display devices and organic EL display devices are used for various display applications such as large displays such as televisions and small displays such as mobile phones, PCs, and smartphones. As an example of a display device, there is an organic EL display device. For example, in this organic EL display device, a thin film transistor (hereinafter referred to as TFT) is formed on a glass substrate serving as a supporting substrate, and an electrode, a light emitting layer, and an electrode are sequentially formed. Finally, it is produced by hermetically sealing with a glass substrate, a multilayer thin film, or the like separately.

Here, by replacing the glass substrate which is a support base material with the resin base material from the conventional glass substrate, thickness, light weight, and flexibleization can be implement | achieved, and the use of a display apparatus can further be expanded. However, since resin generally has inferior dimensional stability, transparency, heat resistance, moisture resistance, gas barrier property, etc. compared with glass, various examination is made in the research stage at this time.

For example, Patent Literature 1 relates to a polyimide useful as a plastic substrate for a flexible display and the invention by its precursor, and various diamines using tetracarboxylic acids including alicyclic structures such as cyclohexylphenyltetracarboxylic acid and the like. It has been reported that the polyimide reacted with is excellent in transparency. In addition, an attempt has been made to reduce the weight by using a flexible resin for the supporting substrate. For example, in Non-Patent Documents 1 and 2, an organic EL display device in which a polyimide having high transparency is applied to the supporting substrate is proposed. .

Thus, although it is known that resin films, such as polyimide, are useful for the plastic substrate for flexible displays, the manufacturing process of a display apparatus is already performed using a glass substrate, and most of the production facilities are designed on the assumption that a glass substrate is used. It is. Therefore, it is desirable to make it possible to produce a display device while effectively utilizing existing production equipment.

As a specific example of the examination, the manufacturing method of the display apparatus provided with the display part on the resin base material is completed by completing the manufacturing process of a predetermined display apparatus in the state which laminated | stacked the resin film on the glass substrate, and removing a glass substrate after that. It is known (refer patent document 2, nonpatent literature 3, nonpatent literature 4). And in these cases, it is necessary to separate a resin base material and glass, without damaging the display part (display part) formed on the resin base material.

That is, in the non-patent document 3, after forming a predetermined display part with respect to the resin base material apply | coated and fixed on the glass substrate, it irradiates a laser from the glass side by the method called EPLaR (Electronics on Plastic by Laser Release) process, and displays it. The resin substrate provided with was forcibly separated from the glass. However, this method not only requires an expensive laser device but also takes a long time for separation, and thus has a disadvantage of low productivity. Moreover, there exists a possibility that it may adversely affect the surface property of a resin base material and the display part mounted in it at the time of separation.

On the other hand, the method described in Non-Patent Document 4 is a method of improving the shortcomings of the EPLaR method. After applying and forming a release layer on a glass substrate, a polyimide resin is applied onto the release layer, and a manufacturing process of the organic EL display device is performed. It is a method of peeling a polyimide film layer from a peeling layer after completion. Here, the manufacturing method of the organic electroluminescence display of nonpatent literature 4 is shown to FIG. 1, FIG. In this method, after forming the peeling layer 2 on the glass substrate 1, the polyimide layer 3 is formed larger than the peeling layer 2, and the process of predetermined TFT and organic electroluminescent process is performed after that, After the TFT / organic EL panel portion (display portion) 4 is formed, the polyimide layer 3 and the TFT are cut along the cut line 5 inside the release layer 2 to the release layer 2. The organic EL panel portion (display portion) 4 is peeled off from the release layer 2. However, Non-Patent Document 4 has no specific description such as what kind to use for the release layer. For this reason, it is unclear how much force actually requires separation from the release layer, and what kind of state the surface properties of the separated polyimide layer 3 become. Moreover, since the area of a peeling layer needs to be made smaller than the area of a polyimide layer, there exists a restriction | limiting in the area which can be formed of an organic electroluminescence display, and there exists a subject to productivity. In order to prevent a fall of productivity, when the area of a peeling layer is enlarged, the area of the polyimide layer adhering to glass in the outer peripheral part of a peeling layer will become small, and there exists a problem that peeling occurs easily by the stress in a process.

Moreover, the method of patent document 2 forms a polyimide layer much larger than a peeling layer like the method of nonpatent literature 4, after forming the peeling layer which consists of parylene or a cyclic olefin copolymer on a glass substrate, It is a method of peeling a polyimide layer after creating an electronic device on it. The formation of TFTs required for display applications generally requires an annealing process of up to about 400 ° C, but in this method, the heat resistance temperature of the release layer is inferior to that of the polyimide. There is a problem that is limited to the heat resistance of the release layer. In addition, since the adhesion between the glass and the release layer and between the release layer and the polyimide layer is weak, it can not withstand the stress in the process and may cause peeling. In addition, the coefficient of thermal expansion of the release layer is larger than that of polyimide, and the difference in coefficient of thermal expansion due to the difference in resin type may be a cause of warpage.

Moreover, patent document 3 describes the manufacturing method of the semiconductor device which peels a support substrate from a resin film after forming a semiconductor element in the upper layer of the resin film formed through the peeling layer on the support substrate. In this patent document 3, polybenzoxazole is disclosed as a resin film. Generally polybenzoxazole is excellent in peelability with other materials compared with polyimide. Generally, in order to ensure good peelability with other materials, the heat treatment time in contact with the adherend is preferably short, but in the case of polyimide benzoxazole, the heterocycle and the aromatic ring have coplanar structures. The crystallinity tends to be high, and in order to complete the reaction and sufficiently lower the volatile matter concentration remaining in the film, a relatively long heat treatment time at a high temperature is required. By the way, in this patent document 3, it is unclear how much force separation from a peeling layer requires, but peeling of a peeling layer and a resin film is disclosed by being immersed in warm water. Moreover, since a crystallinity is high, a film tends to fall off and when a alicyclic structure which is a flexible structure is introduced in order to prevent this, there exists a problem that heat resistance falls. In addition, the thermal expansion also becomes difficult to be lowered due to the introduction of the alicyclic structure.

The methods described in these Patent Documents 2 to 3 and Non-Patent Documents 3 to 4 can all ensure the handleability and dimensional stability of the resin substrate by forming a display portion on the resin substrate fixed to the glass using glass as a support. There exists an advantage that a glass substrate can be used as it is in the current manufacturing line which manufactures display apparatuses, such as a display apparatus and an organic electroluminescence display. Therefore, if a predetermined display portion can be formed, it can be separated very easily, and if it can be prevented from affecting the resin substrate or the display portion, it can not only be a method having excellent mass productivity, but also the substitution from the glass substrate to the resin substrate can be further performed. Can be promoted.

Japanese Patent Publication No. 2008-231327 Japanese Patent Publication No. 2010-67957 Japanese Patent Publication No. 2009-21322

 S. An et. al., "2.8-inch WQVGA Flexible AMOLED Using High Performance Low Temperature Polysilicon TFT on Plastic Substrates", SID 2010 DIGEST, p706 (2010)  Oishi et. al., "Transparent PI for flexible display", IDW'11 FLX2 / FMC4-1  E.I. Haskal et. al. "Flexible OLED Displays Made with the EPLaR Process", Proc.Eurodisplay '07, pp.36-39 (2007)  Cheng-Chung Lee et. al. "A Novel Approach to Make Flexible Active Matrix Displays", SID10 Digest, pp. 810-813 (2010)

It is therefore an object of the present invention to provide a method in which a predetermined display portion is formed on a resin substrate integrated with a support in advance, and then the resin substrate can be easily separated from the support, thereby easily obtaining a display device.

MEANS TO SOLVE THE PROBLEM As a result of examining in order to solve the said subject, as a result, the predetermined | prescribed display part was formed on the 2nd resin layer in the state in which the 1st resin layer and the 2nd resin layer were laminated | stacked on the support body, and after that, the 1st resin layer and By separating at the boundary surface of a 2nd resin layer, the display apparatus provided with the display part on the resin base material which consists of a 2nd resin layer was found to be extremely simple, and the present invention was completed.

That is, the gist of the present invention is as follows.

(1) A predetermined display portion is formed on the second resin layer in a state where the first resin layer and the second resin layer are laminated on the support, and then separated from the interface between the first resin layer and the second resin layer, The display apparatus provided with the display part on the resin base material which consists of 2 resin layers is obtained, The manufacturing method of the display apparatus characterized by the above-mentioned.

(2) In (1), after laminating | stacking the laminated | multilayer film and support body which the 1st resin layer and the 2nd resin layer directly laminated | stacked the 1st resin layer surface of the said laminated | multilayer film, and one surface of the said support body through an adhesive layer, it laminated | stacked on the laminated film The predetermined display part is formed in the following, and after that, it isolate | separates from the interface surface of a 1st resin layer and a 2nd resin layer, and obtains the display apparatus provided with the display part on the resin base material which consists of a 2nd resin layer, The manufacture of the display apparatus characterized by the above-mentioned. Way.

(3) The method of manufacturing a display device according to (2), wherein the first resin layer and the second resin layer constituting the laminated film are each made of polyimide.

(4) In (1), after forming a 1st polyimide layer and a 2nd polyimide layer on a support body, a predetermined display part is further formed, and then the interface surface of a 1st polyimide layer and a 2nd polyimide layer The display apparatus provided with the display part on the polyimide base material which isolate | separates from the 2nd polyimide layer, and is obtained, The manufacturing method of the display apparatus characterized by the above-mentioned.

(5) In (4), after forming a predetermined display part, after removing a support body, it isolate | separates at the interface surface of a 1st polyimide layer and a 2nd polyimide layer, and obtains the display apparatus provided with a display part on the polyimide base material. The manufacturing method of the display apparatus characterized by the above-mentioned.

(6) In (4) or (5), formation of a 1st polyimide layer is performed by lamination of a polyimide film, and formation of a 2nd polyimide layer is applied to application | coating of the resin solution of a polyimide or a polyimide precursor. The manufacturing method of the display apparatus characterized by the above-mentioned.

(7) The display device according to (4) or (5), wherein the formation of the first polyimide layer and the second polyimide layer is performed by applying and heating a resin solution of a polyimide or polyimide precursor. Way.

(8) The method according to any one of (4) to (7), wherein a part of the second polyimide layer protrudes from the peripheral edge of the first polyimide layer, and the protrusion of the second polyimide layer is fixed to the support. The manufacturing method of the display device characterized by the above-mentioned.

(9) The display device according to any one of (4) to (7), wherein part of one layer of the first polyimide layer or the second polyimide layer is projected from the peripheral edge portion of the other layer. Method of preparation.

(10) The display device according to any one of (4) to (9), wherein the first resin layer and the second resin layer are separated after inserting a gap in the first resin layer along the outer periphery of the display portion. Method of preparation.

(11) The high temperature holding time of a 2nd polyimide layer is 60 minutes at the time of performing formation of the 2nd polyimide layer by apply | coating the resin solution of a polyimide or a polyimide precursor, after heating. It is less than, The manufacturing method of the display apparatus characterized by the above-mentioned.

(12) The method of manufacturing a display device according to any one of (1) to (11), wherein the support is a glass substrate.

(13) The method of manufacturing a display device according to any one of (1) to (12), wherein the thermal expansion coefficient of the first resin layer is 25 ppm / K or less.

(14) The method of manufacturing a display device according to any one of (1) to (13), wherein the thermal expansion coefficient of the second resin layer is 25 ppm / K or less.

(15) The method of manufacturing a display device according to any one of (1) to (14), wherein the second resin layer has a transmittance of 80% or more in a wavelength region of 440 nm to 780 nm.

(16) The display device according to any one of (1) to (15), wherein the display portion is formed through the gas barrier layer, and the difference in thermal expansion coefficient between the second resin layer and the gas barrier layer is 10 ppm / K or less. Manufacturing method.

(17) The method of manufacturing a display device according to any one of (1) to (16), wherein the display unit is a color filter layer.

(18) The method of manufacturing a display device according to any one of (1) to (17), wherein the peeling strength of the first resin layer and the second resin layer is 200 N / m or less.

(19) In any one of (1)-(18), at least one of a 1st resin layer or a 2nd resin layer consists of polyimide which has a structural unit represented by following General formula (1), It is characterized by the above-mentioned. Method of manufacturing the display device.

[In the formula, Ar ₁ represents a tetravalent organic group having an aromatic ring, and Ar ₂ is a divalent organic group represented by the following General Formula (2) or (3).

(Herein, R ₁ to R ₈ in General Formula (2) or General Formula (3) are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group or a fluorine substituted hydrocarbon group, In at least one of R ₁ to R ₄ in General Formula (2), and at least one of R ₁ to R ₈ in General Formula (3) is a fluorine atom or a fluorine substituted hydrocarbon group.]

(Effects of the Invention)

According to the present invention, the predetermined display portion can be formed while ensuring the handleability and the dimensional stability by allowing the first resin layer and the second resin layer to be laminated on the support. After formation of the display unit, a display device can be obtained very simply in that it can be easily separated using the interface of the first resin layer and the second resin layer without requiring laser irradiation or the like. In addition, it is possible to reuse the support in the manufacture of the display device, as well as not affecting the second resin layer or the display portion, which becomes the resin substrate after separation, and not damaging the support. It can contribute greatly.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram explaining the manufacturing method of the organic electroluminescence display in a prior art.
2 is a schematic diagram illustrating a manufacturing method of an organic EL display device in the prior art.
3 is a schematic diagram illustrating a method of manufacturing a display device according to the present invention.
4 is a schematic diagram illustrating a method of manufacturing a display device according to the present invention.
5 is a schematic diagram (partially enlarged view) illustrating a method for manufacturing a display device according to the present invention.
6 is a schematic view for explaining a method for manufacturing a display device according to the present invention.
7 is a schematic view for explaining a method for manufacturing a display device according to the present invention.
8 is a schematic diagram illustrating a method of manufacturing a display device according to the present invention.
9 is a schematic view for explaining a method for manufacturing a display device according to the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail, referring drawings, this invention is not limited to the following description.

In the manufacturing method of the display apparatus in this invention, a predetermined | prescribed display part is formed on a 2nd resin layer in the state in which the 1st resin layer and the 2nd resin layer were laminated | stacked on the support body, and after that, a 1st resin layer and 2nd It is characterized by obtaining the display apparatus provided with the display part on the resin base material which consists of 2nd resin layers isolate | separating from the interface of a resin layer. It is as demonstrated in detail below. In addition, although the case where both a 1st resin layer and a 2nd resin layer are formed from polyimide is demonstrated as a suitable example below, you may form at least one resin layer from resin other than polyimide.

In the manufacturing method of the display apparatus of this invention, what provided the 1st polyimide layer and the 2nd polyimide layer on the support body beforehand is used. And a predetermined | prescribed display part is formed in the 2nd polyimide layer side, and after that, it isolate | separates at the interface surface of a 1st polyimide layer and a 2nd polyimide layer, and a display part on the resin base material (polyimide base material) which consists of a 2nd polyimide layer A display device provided with the same can be manufactured.

More specifically, first, as shown in FIG. 3, the support body 1 used as a base in the manufacturing process of the display part in a liquid crystal display device, an organic electroluminescence display, etc. is prepared. The support 1 is not particularly limited as long as it has chemical strength and mechanical strength that can withstand thermal history, atmosphere, and the like in the manufacturing process of the display unit for forming various display devices. It is preferable to use a glass substrate. The glass substrate can use what is generally used in manufacture of an organic electroluminescence display, for example. However, in the display device manufactured by this invention, the support base material of a display part is a polyimide base material which consists of the 2nd polyimide layer 8. That is, the glass substrate referred to here plays a role of a base when forming the display portion on the polyimide substrate, and finally, even though the handleability and dimensional stability of the polyimide substrate are guaranteed in the manufacturing process of the display portion, It does not constitute a display device. In addition, the support body may perform surface treatment for controlling the peelability of the 1st polyimide layer 7 and the 2nd polyimide layer 8.

In this invention, although the 1st polyimide layer and the 2nd polyimide layer are formed on this support body 1, 1) the 1st polyimide layer and the 2nd polyimide layer are laminated | stacked previously, and the laminated poly is Method of laminating and forming a mid laminated film on a support (lamination method), 2) Resin of polyimide or polyimide precursor (henceforth "polyamic acid") is formed of 1st polyimide layer and 2nd polyimide layer. Method (coating method) performed by apply | coating a solution, 3) Laminating | stacking a polyimide film on a support body, forming a 1st polyimide layer and forming 2nd polyimide layer by application | coating of the resin solution of a polyimide or a polyimide precursor. Any method of performing (combination method) to perform by may be sufficient. In addition, the support body 1 and a 1st polyimide layer may be directly bonded and laminated here, or may be laminated | stacked through an adhesive layer as shown in FIG.

In addition, in this invention, you may form so that at least one part of any one of a 1st polyimide layer and a 2nd polyimide layer may protrude from the peripheral part of another layer. By forming a portion where the thickness of the polyimide layer is thinner on the outer periphery than the portion where the display portion is formed, stress generated during the process can be dispersed, and the support and the polyimide layer can be prevented from being peeled off during the process. Although the distance which protrudes is not specifically limited, It is preferable that it is more than the thickness which combined the 1st polyimide layer and the 2nd polyimide layer, and it is more preferable that it is 10 times or more of the thickness of the sum total.

Hereinafter, the above three methods will be described individually.

<Lamination method>

FIG. 3 shows a state in which a polyimide laminated film is attached to the support 1 with the adhesive layer 6 and the display portion is further laminated. Here, the polyimide laminated film is composed of the first polyimide layer 7 and the second polyimide layer 8, and the first polyimide layer 7 and the second polyimide layer 8 are directly laminated in advance. Structure. In order to obtain such a polyimide laminated | multilayer film, the resin solution of the polyamic acid used as the 2nd polyimide layer 8 is apply | coated on the polyimide film used as the 1st polyimide layer 7, and then The method of drying and imidating by heat processing (cast method) is mentioned. Moreover, as the adhesive layer 6, the adhesive film etc. which provided the adhesion layer on both surfaces of the support film besides resin adhesives, such as an epoxy resin and an acrylic resin, can be used. In addition, although the adhesive layer 6 is used in this FIG. 3, as shown in FIG. 7, you may adhere | attach the 1st polyimide layer 7 side directly to the support body 1 by means, such as a hot press.

Here, it is preferable that it is 3 micrometers or more and 50 micrometers or less about the thickness of the 2nd polyimide layer 8 which comprises a laminated | multilayer film. If the thickness of the second polyimide layer 8 is not more than 3 µm, it becomes difficult to secure the electrical insulation or the prevention of damage to the resin layer due to external factors when the resin substrate of the display device is formed. If it exceeds, there exists a possibility that the flexibility, transparency, etc. of a display apparatus may fall. Since the 1st polyimide layer 7 does not comprise a display apparatus directly, it is good that it is 10 micrometers or more in consideration of handling property etc. as laminated | multilayer film. The upper limit of the thickness is not particularly limited, but is preferably 100 μm or less in consideration of cost and the like.

As described above, the polyimide laminated film is moved to a process for forming a display portion which is laminated on the support 1 and continues in an integrated state with or without the adhesive layer 6 therebetween. Herein, the process for forming the display portion refers to, for example, a process process of a predetermined TFT / organic EL process in the case of an organic EL display device, and the TFT, an electrode, an organic EL element including a light emitting layer, and the like formed thereby. It corresponds to this display part. Here, the organic EL which color-displays by combining a color filter with the organic EL of white light emission is also proposed. This color filter is manufactured by separately bonding the TFT / organic EL process and then bonding to the TFT / organic EL side, but this color filter also corresponds to the display unit. In addition, in the case of a liquid crystal display device, it refers to the process process of a TFT process, and TFT formed by this, a drive circuit, a color filter, etc. correspond to a display part as needed. That is, the process of forming the display portion is various functional layers conventionally formed on a glass substrate, including various display devices such as electronic paper or MEMS display, in addition to an organic EL display device or a liquid crystal display device, and a predetermined image (video or The process of forming a component necessary for illuminating the image) is referred to, and the display portion is collectively included, including the component obtained thereby. By passing through this process, the display part 4 is laminated | stacked and formed in the 2nd polyimide layer 8 side integrated with the 1st polyimide layer 7. Then, when all the display part lamination processes are completed, it advances to the cutting process which cut | disconnects to predetermined size.

4 shows a cutting process. In this invention, a cutting process is not essential and is arbitrarily performed according to the form of the apparatus and process manufactured. Taking the manufacturing of the organic EL display device as an example, the cutting is completely performed along the cutting line 5 shown in FIG. 4 to the display portion (TFT / organic EL panel portion) 4 and the second polyimide layer 8. . At this time, as shown in FIG. 5 which shows the enlarged view of the cutting | disconnection area | region 9 shown in FIG. 4, the cutting line 10 reaches to the vicinity of the center of the 1st polyimide layer 7, along the outer periphery of a display part. If a gap is inserted in the resin layer, the second polyimide layer 8 can be reliably and easily separated at the interface with the first polyimide layer 7 without mechanically damaging the TFT / organic EL panel portion 4. Can be.

Here, in order to be able to isolate | separate 2nd polyimide layer 8 easily from the interface with the 1st polyimide layer 7, it is necessary to make it easy to peel off a polyimide interface. Although the means is not specifically limited, The use of the polyimide which has a specific chemical structure in at least one of a 1st or 2nd polyimide layer is mentioned.

Generally, a polyimide is obtained by superposing | polymerizing the acid anhydride and diamine which are raw materials normally, and are represented by following General formula (1).

In the formula, Ar ₁ represents a tetravalent organic group that is an acid anhydride residue, and Ar ₂ is a divalent organic group that is a diamine residue, but from the viewpoint of heat resistance, at least one of Ar ₁ and Ar ₂ is preferably an aromatic residue.

As a polyimide resin used suitably for the 1st polyimide layer or the 2nd polyimide layer in this invention, the polyimide which has the following repeating structural unit is mentioned, for example,

Especially preferably, it is a polyimide which has the following repeating structural unit.

Moreover, a fluorine-containing polyimide is mentioned other than these. Here, fluorine-containing polyimide refers to having a fluorine atom in the polyimide structure, and has a fluorine-containing group in at least one component of an acid anhydride and diamine which is a polyimide raw material. As such a fluorinated polyimide, for the example above general formula (1), and Ar ₁ is a tetravalent organic group in the formula, to the Ar _2, the general formula (2) or general formula (3) of the one represented by The thing represented by the divalent organic group shown is mentioned.

R ₁ to R ₈ in the general formula (2) or (3) are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group or a fluorine-substituted hydrocarbon group. In (2), at least one of R ₁ to R ₄ is a fluorine atom or a fluorine-substituted hydrocarbon group, and in general formula (3), at least one of R ₁ to R ₈ is a fluorine atom or a fluorine-substituted hydrocarbon group. .

Among these, suitable examples of R ₁ to R ₈ include -H, -CH ₃ , -OCH ₃ , -F, and -CF ₃ , but at least one substituent in formula (2) or formula (3) may be used. One of -F or -CF ₃ is preferable.

Moreover, as an example of Ar <_1> in General formula (1) at the time of forming a fluorine-containing polyimide, the following tetravalent acid anhydride residue is mentioned, for example.

Moreover, also when forming a fluorine polyimide, in consideration of the transparency of a polyimide or the separation of the other layers sex given below it is preferable as the specific diamine residue to give the Ar ₂ in the formula (1) Can be.

If such a fluorine-containing polyimide is used, good separation properties can be exhibited even at an interface with a polyimide having a structure other than the fluorine-containing polyimide (of course, both of the first and second polyimide layers are fluorinated polyimide. The separation property at the back interface is further improved). In addition, in such a fluorine-containing polyimide, when any one of the structural units represented by following General formula (4) or (5) has a ratio of 80 mol% or more, in addition to transparency and peelability, It is good to use it as a polyimide which forms a 2nd polyimide layer suitably from the point which is low and excellent in dimensional stability.

Here, when a polyimide is made into the polyimide by the structure of General formula (4) or (5), it will restrict | limit especially about the other polyimide which may be added in the ratio below 20 mol% in addition to the polyimide. General acid anhydrides and diamines can be used. Especially, as an acid anhydride used preferably, a pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 1, 4- cyclohexanedicarboxylic acid, 1,2,3 , 4-cyclobutanetetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like. In addition, as a diamine, 4,4'- diamino diphenyl sulfone, a trans-1, 4- diamino cyclohexane, 4,4'- diamino cyclohexyl methane, 2,2'-bis (4-amino cyclohexyl) -Hexafluoropropane, 2,2'-bis (trifluoromethyl) -4,4'-diaminobicyclohexane, etc. are mentioned.

Although various polyimide demonstrated above is obtained by imidating polyamic acid, the resin solution of polyamic acid can be obtained by making it react in an organic solvent using substantially equimolar diamine and acid dianhydride which are raw materials. More specifically, after dissolving diamine in organic polar solvents, such as N, N- dimethylacetamide, under nitrogen stream, it can obtain by adding tetracarboxylic dianhydride and making it react at room temperature for about 5 hours. As for the weight average molecular weight of the polyamic acid obtained from the viewpoint of the film thickness uniformity at the time of coating and the mechanical strength of the polyimide film obtained, 10,000-300,000 are preferable. Moreover, the preferable molecular weight range of a polyimide layer is also the same molecular weight range as a polyamic acid.

In the present invention, preferably, the second polyimide layer 8 is a polyimide having a structural unit represented by the formula (4) or (5), and the coefficient of thermal expansion is 25 ppm / K or less, advantageously 10 ppm /. It can be set as K or less polyimide layer, and is suitable as a polyimide base material which forms a display apparatus. Moreover, the polyimide which has these structural units shows the glass transition temperature (Tg) of 300 degreeC or more, and the transmittance | permeability in the wavelength range of 440 nm-780 nm shows 80% or more.

As described above, in order to be able to easily separate from each other at the interface of the first polyimide layer and the second polyimide layer by using a predetermined polyimide, at least one polyimide layer is preferably a fluorinated polyimide. It is good to form. By forming at least one polyimide layer from a fluorine-containing polyimide, the adhesive strength at the interface between the first polyimide layer and the second polyimide layer is 1N / m or more and 500N / m or less, more preferably 5N. Since it becomes / N or more and 300N / m or less, More preferably, it becomes 10N / m or more and 200N / m or less, and it has a detachment enough to peel easily with a human hand. The separated display device has no appearance defects such as wrinkles or fractures in the second polyimide layer serving as the polyimide substrate, and the separation surface of the second polyimide layer has a surface roughness (generally a surface obtained by a cast method). Since roughness Ra = 1 to about 80 nm) is maintained as it is, it does not adversely affect the visibility of the display device.

The present invention 1) after forming the predetermined display portion, and then in addition to the method of separating at the interface between the first polyimide layer and the second polyimide layer 2) after forming the predetermined display portion, first of the first polyimide layer side The method also removes a support body, isolate | separates at the interface surface of the 1st polyimide layer and the 2nd polyimide layer which remain after that, and also obtains the display apparatus provided with the display part on the polyimide base material (2nd polyimide layer). In the method of 2), the separation of the first polyimide layer 7 and the second polyimide layer 8 after the support 1 is removed has a shape of the second polyimide layer 8 and the display portion 4. It is preferable to separate the first polyimide layer 7 while fixing it to remain constant during separation. Thereby, the stress applied to the display part 4 can be made small, and even if the 2nd polyimide layer 8 is made thinner, the possibility of the damage of the device of the display part 4 can be reduced. The means for removing the support in the method of 2) is not particularly limited as long as no damage is caused to the display portion 4 or the second polyimide layer 8, but the following method may be used. That is, since the example using the adhesive layer 6 was shown in the said description by FIG. 3, this point is supplemented by the description place of the coating method by FIG. However, even in the lamination method, the adhesive layer 6 does not need to be essential as shown in FIG. 3 as long as the first polyimide layer 7 can be directly adhered to the support 1 by means such as hot pressing. The support 1 can be removed in the same way as the later described means.

Next, the application example in the apply | coating method of this invention is demonstrated.

<Application method>

FIG. 6 shows a state in which the first polyimide layer 7 and the second polyimide layer 8 are sequentially formed on the support 1 by a coating method, and then the display portion 4 is further laminated. In this method, first, the support body 1 is prepared, the resin solution of the polyamic acid used as the 1st polyimide layer 7 is apply | coated, dried by heat processing, and imidation is completed, and a 1st polyimide layer ( 7). Subsequently, the resin solution of the polyamic acid used as the 2nd polyimide layer 8 is apply | coated on the said 1st polyimide layer 7, drying and heat | fever imidation are completed by heat processing, and the 2nd polyimide layer 8 It is done. Thus, it can be set as the board | substrate with which the 1st polyimide layer 7 and the 2nd polyimide layer 8 were formed sequentially on the support body 1. As shown in FIG. And it is provided to the process after the display part formation process continued after that. Since the process after the display part formation process is the same as that of the said lamination method, it abbreviate | omits in detail and abbreviate | omits the removal of the support body 1 in the method of 2) mentioned above.

As described above, FIG. 6 illustrates a state in which the first polyimide layer 7, the second polyimide layer 8, and the display portion 4 are stacked on the support 1. Although the support body 1 may be removed from this state before the process of separating at the interface of the 1st polyimide layer 7 and the 2nd polyimide layer 8, as a method of removing the support body 1 here, As a 1st polyimide layer 7, the method of removing these with an etching liquid using the polyimide material which is easy to peel from the support body 1, or using metal foil, such as copper foil, or a metal substrate as the support body 1 is illustrated.

Moreover, you may apply methods other than a well-known as a method of removing the support body 1, too. That is, you may remove the support body 1 by using laser irradiation in the nonpatent literature 3, and the peeling layer in the nonpatent literature 4. When the support body 1 is removed by laser irradiation, the 1st polyimide layer can absorb a laser, and can prevent the bad influence of the laser to a 2nd polyimide layer and a display part. Even when the support layer 1 is removed using the release layer, the first polyimide layer functions as a stress relaxation layer against the stress generated during the peeling and prevents a decrease in yield due to damage to the display portion during peeling. have.

However, in Japanese Patent Publication No. 2007-512568, a yellow film such as polyimide is formed on glass, followed by forming a thin film electronic device on the yellow film, and then irradiating UV laser light to the bottom of the yellow film through glass. It discloses that it is possible to peel glass and a yellow film. However, it is also disclosed that it is necessary to form an absorbing / peeling layer such as amorphous silicon under the film in advance because, unlike the yellow film, the transparent plastic does not absorb UV laser light. On the other hand, Japanese Unexamined Patent Publication No. 2012-511173 discloses that it is necessary to use a laser within the range of 300 to 410 nm in order to peel the glass and the polyimide film by irradiation of UV laser light.

In this invention, when removing a support body from a 1st polyimide layer using a laser beam, it is preferable to use colored polyimide for a 1st polyimide layer. It is one of the preferable aspects of this invention to make a 1st polyimide layer into a colored polyimide, and to make a 2nd polyimide layer into a transparent polyimide.

In the coating method, the resin solution of the polyamic acid to be the first polyimide layer 7 is applied onto the support 1, and the heat treatment is performed. However, at this point, the first polyimide layer is imidized by sufficient heat treatment. It is preferable to facilitate separation of the 2 polyimide layer. Moreover, also in the coating method, it is preferable to use the polyimide which has a specific chemical structure in at least one of a 1st or 2nd polyimide layer similarly to what was described by the lamination method. The first polyimide layer and the second polyimide layer may be polyimide having the same chemical structure.

In the coating method, both the first polyimide layer and the second polyimide layer can be obtained by drying or drying and curing the resin solution after application by heat treatment, but in the present invention, the maximum heating temperature at the time of the temperature increase in the heat treatment (highest) It is preferable that the heating time (hereinafter referred to as high temperature holding time) in the high temperature heating temperature range from the temperature lower than 20 ° C to the highest achieved temperature is shorter in the range in which necessary characteristics are obtained. In the original application method, the purpose of maintaining the first and / or second polyimide layer in the high temperature heating temperature range is to provide the characteristics required for the original polyimide layer by completely removing the remaining solvent, promoting the orientation of the polyimide resin, and the like. To get it. However, when the high temperature holding time of a 2nd polyimide layer is long, peelability with a 1st polyimide layer will fall, or there exists a tendency for a transmittance | permeability to fall by coloring etc. Although the optimum high temperature holding time changes with heating type, polyimide thickness, and the kind of polyimide, it is preferable to set it as 0.5 to 60 minutes, and it is more preferable to set it as 0.5 to 30 minutes.

Next, the application example in the combination method of the film lamination and resin solution application of this invention is demonstrated.

<Combination>

FIG. 8 bonds the first polyimide layer 7 cut smaller than the support 1 onto the support 1 with the adhesive layer 6, and the second polyimide layer 8 and the display portion 4 thereon. The state which laminated | stacked is shown.

In this method, the support body 1 is prepared first, and the polyimide film used as the 1st polyimide layer 7 is bonded by the adhesive layer 6 on it. In this respect, the same method can be applied using the same polyimide film as the said lamination method.

Subsequently, the resin solution of the polyamic acid used as the 2nd polyimide layer 8 is apply | coated on the said 1st polyimide layer 7, dried by heat processing, complete | finishes imidization, and the 2nd polyimide layer 8 ). In this respect, the same method can be applied using the same resin solution as the said coating method. Thus, it can be set as the board | substrate with which the 1st polyimide layer 7 and the 2nd polyimide layer 8 were formed sequentially on the support body 1. As shown in FIG. And it is provided to the process after the display part formation process continued after that. The process after the display portion forming step is omitted in the same manner as described above.

In the combination method, after bonding the 1st polyimide layer 7 and the support body 1, the resin solution of the polyamic acid which gives the 2nd polyimide layer 8 is varnish-like on the 1st polyimide layer 7 Apply so that the whole surface is covered. The resin solution of the applied polyamic acid is dried by heat treatment and imidized to form the second polyimide layer 8, but as shown in Fig. 8, the second polyimide layer 8 is laminated in this state. The surface is larger than the first polyimide layer, and at least a part of the portion not in contact with the first polyimide layer 7 of the second polyimide layer 8 is in contact with the support 1. In other words, a part of the second polyimide layer 8 protrudes from the peripheral edge of the first polyimide layer 7 so that the protruding portion of the second polyimide layer 8 is fixed to the support 1. Also in this method, although the 2nd polyimide layer 8 and the 1st polyimide layer 7 are comprised easily to peel, the 2nd polyimide layer 8 and the support body 1 are the 2nd polyimide layer 8 Since it can be firmly adhered by the protrusion of), it is possible to increase the adhesiveness around the support to ensure more stability during the process. After the display section is formed, the display section 4 and the second poly may be cut along the cutting line 5 for cutting the display section 4 as shown in FIG. 9. When the mid layer 8 is cut and separated at the interface between the first polyimide layer 7 and the second polyimide layer 8, the display portion 4 is formed on the polyimide substrate composed of the second polyimide layer 8. A display device provided with the same can be obtained.

In the present invention, since the first polyimide layer is separated later, including when employing the above three methods and when employing other methods, the present invention does not contribute to the function of the display device. In consideration of the change in temperature, the characteristic until separation becomes an important factor, and from such a viewpoint, the thermal expansion coefficient of the first polyimide layer is preferably 25 ppm / K or less. Moreover, it is good that glass transition temperature Tg is 300 degreeC or more. As a specific example of such a 1st polyimide layer, the polyimide etc. which have a structural unit which consists of biphenyl tetracarboxylic dianhydride and phenylenediamine as a main component etc. are mentioned, for example. As a commercial item, UPILEX-S by UBE INDUSTRIES, LTD., KAPTON by DU PONT-TORAY CO., LTD. And XENOMAX by TOYOBO CO., LTD. Can be used, for example.

In the present invention, when the display portion is formed, barrier properties against oxygen, water vapor, etc. made of inorganic oxide films such as silicon oxide, aluminum oxide, silicon carbide, silicon oxide, silicon carbide, silicon nitride, silicon nitride oxide, and the like are provided. The gas barrier layer may be interposed. In order to reduce curvature etc. of the display device obtained at that time, it is preferable to make the difference of the thermal expansion coefficient of a 2nd polyimide layer and a gas barrier layer into 10 ppm / K or less.

The first polyimide layer 7 and the second polyimide layer 8 can be easily separated from the interface by a method other than using a polyimide having a specific chemical structure for the first or second polyimide layer. In order to achieve this, the surface state of the first polyimide layer 7 is changed by, for example, heat treatment of the first polyimide layer 7 to reduce the wettability of the surface, and then the second polyimide layer 8 The method of using the laminated | multilayer film which apply | coated) is mentioned. The appropriate temperature of this heat treatment varies depending on the type of the first polyimide layer 7, but the first polyimide layer 7 may be formed by KAPTON, UBE INDUSTRIES, LTD., UPILEX, etc. manufactured by DU PONT-TORAY CO., LTD. When making it a polyimide film, 300 degreeC or more and 500 degrees C or less are preferable.

In this invention, after forming a predetermined | prescribed display part, in the method of isolate | separating at the interface surface of a 1st polyimide layer and a 2nd polyimide layer, the product of the laminated body of the support body from which the 2nd polyimide layer was isolate | separated, and the 1st polyimide layer You may reuse the laminated body of a support body and a 1st polyimide layer by forming a 2nd polyimide layer again on the 1 polyimide layer side. When using repeatedly, after separating a 2nd polyimide layer, you may make it wash | clean the laminated body of a support body and a 1st polyimide layer. Moreover, you may make it apply | coat a 2nd polyimide layer, after heat-processing the laminated body of a support body and a 1st polyimide layer, making the wettability of the surface of a 1st polyimide layer small.

Moreover, as another method of using the laminated body of a support body and a 1st polyimide layer repeatedly, a 1st polyimide is again at the 1st polyimide layer side of the laminated body of the support body and 1st polyimide layer which separated the 2nd polyimide layer. A method of forming a layer and then forming a second polyimide layer may also be used.

In the present invention, the support removed from the first polyimide layer may be reused. Before reuse, the support may be cleaned, heat treated, or surface treated.

Example

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated further more concretely based on an Example. In addition, this invention is not limited to the content of the following Example.

In the following Examples, evaluation methods such as physical properties are shown.

[Transmittance (%)]

The average value of the light transmittance in 440 nm-780 nm was calculated | required for the polyimide film (50 mm x 50 mm) with a U4000 type spectrophotometer.

[Glass Transition Temperature (Tg)]

The glass transition temperature was raised at a rate of 10 ° C./min from room temperature to 400 ° C. while giving a vibration of 1 Hz using a 10 mm wide sample using a viscoelastic analyzer (RSA-II manufactured by Rheometric Scientific Inc.). It was calculated | required from the maximum of loss tangent (Tandelta).

[Coefficient of Thermal Expansion (CTE)]

The polyimide film of size 3mm x 15mm was subjected to a tensile test at a temperature range of 30 ° C to 260 ° C at a constant heating rate (20 ° C / min) while applying a load of 5.0 g with a thermomechanical analysis (TMA) device. The thermal expansion coefficient (x10 <^-6> / K) was measured from the elongation amount of the polyimide film with respect to temperature.

Example 1

Thickness after hardening the resin solution of the polyamic acid obtained from PDA (1, 4- phenylenediamine) and BPDA (3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride) on the glass base material as a support body Was applied so as to have a coating area of 20 µm and 300 mm x 380 mm, and the solvent (DMAc: N, N-dimethylacetamide) in the resin solution was removed by heating to dry at 130 deg. Next, it imidated by heat-processing from 160 degreeC to 360 degreeC at the temperature increase rate of about 1 degree-C / min, and formed the 1st polyimide layer (surface roughness Ra = 1.3 nm, Tg = 355 degreeC) of 20 micrometers in thickness.

PMDA (pyromellitic dianhydride), 6FDA (2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride) and TFMB (2,2'-bis) on this first polyimide layer 310 mm x so that the resin solution of the polyamic acid obtained from (trifluoromethyl) -4,4'- diaminobiphenyl) is larger than the application area of a 1st polyimide layer, and covers the 1st polyimide layer whole. It apply | coated so that the thickness after hardening might be 25 micrometers in the application area of 390 mm, and the solvent (DMAc: N, N- dimethylacetamide) in the resin solution was heated and removed at 130 degreeC. Subsequently, it imidated by heat-processing from 160 degreeC to 360 degreeC at the temperature increase rate of about 20 degreeC / min, and formed the 2nd polyimide layer of thickness 25micrometer. The high temperature holding time at this time was 1 minute. In addition, in the synthesis | combination of the said polyamic acid, the diamine component and the acid dianhydride component were made into substantially equimolar, and the ratio of PMDA / 6FDA was 85/15.

Thus, it was set as the laminated body by which the 1st and 2nd polyimide layer were laminated | stacked sequentially on glass, and the EL element which is a display part was formed in the 2nd polyimide layer side of this laminated body. Then, the incision is made in the 2nd polyimide layer so that a display part may be enclosed, the interface of a 1st polyimide layer and a 2nd polyimide layer is peeled-separated, and will have an EL element on the polyimide base material which consists of a 2nd polyimide layer. A display device was obtained. At this time, between the 1st polyimide layer and the 2nd polyimide layer, it was easy to isolate | separate by peeling a person, without using a means, such as laser peeling, without damaging the device of display parts, such as TFT and an electrode. Peeling strength of the 1st polyimide layer and the 2nd polyimide layer was 3.5 N / m. In addition, in the said Example, the linear expansion coefficient of the 1st polyimide layer was 12.0 ppm / K, and the linear expansion coefficient of the 2nd polyimide layer was 9.7 ppm / K. Moreover, the transmittance | permeability in the wavelength range of 440 nm-780 nm of a 2nd polyimide layer was 83.5%.

Example 2

Thickness after hardening the resin solution of the polyamic acid obtained from PDA (1, 4- phenylenediamine) and BPDA (3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride) on the glass base material as a support body Was applied so as to have a coating area of 20 µm and 310 mm x 390 mm, and the solvent (DMAc: N, N-dimethylacetamide) in the resin solution was removed by heating to dryness at 120 ° C. Next, it imidated by heat-processing from 130 degreeC to 360 degreeC at the temperature increase rate of about 1 degree-C / min, and formed the 1st polyimide layer (surface roughness Ra = 1.3 nm, Tg = 355 degreeC) of thickness 25micrometer.

PMDA (pyromellitic dianhydride), 6FDA (2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride) and TFMB (2,2'-bis) on this first polyimide layer The resin solution of the polyamic acid obtained from (trifluoromethyl) -4,4'-diaminobiphenyl) on the first polyimide layer at a coating area of 310 mm x 390 mm so that the thickness after curing was 5 m. It apply | coated and removed the solvent (DMAc: N, N-dimethylacetamide) in resin solution by heating at 130 degreeC. Next, it imidated by heat-processing from 160 degreeC to 360 degreeC at the temperature increase rate of about 20 degree-C / min, and formed the 2nd polyimide layer of thickness 5micrometer. In addition, in the synthesis | combination of the said polyamic acid, the diamine component and the acid dianhydride component were made into substantially equimolar, and ratio of PMDA / 6FDA was 60/40.

Thus, it was set as the laminated body by which the 1st and 2nd polyimide layer were laminated | stacked sequentially on glass, and the EL element which is a display part was formed in the 2nd polyimide layer side of this laminated body. After that, the incision is made in the thickness direction of the first polyimide layer and the second polyimide layer so as to surround the display unit, and the glass on the side of the first polyimide layer is peeled off to remove the first polyimide layer and the second polyimide layer. It peeled at the interface and obtained the display apparatus which has an EL element on the polyimide base material which consists of a 2nd polyimide layer. At this time, between the glass and the first polyimide layer, and between the first polyimide layer and the second polyimide layer, a person peels without using a means such as laser peeling without damaging the device of a display unit such as a TFT or an electrode. It could be easily separated. Peeling strength of the 1st polyimide layer and the 2nd polyimide layer was 4.0 N / m. In addition, in the said Example, the linear expansion coefficient of the 1st polyimide layer was 7.0 ppm / K, and the linear expansion coefficient of the 2nd polyimide layer was 20.4 ppm / K. Moreover, the transmittance | permeability in the wavelength range of 440 nm-780 nm of a 2nd polyimide layer was 86.7%.

(Example 3)

In Example 1, after removing the periphery of the remaining 2nd polyimide layer in order to reuse the laminated body of the support body and 1st polyimide layer which peeled and isolate | separated from the 2nd polyimide layer, it wash | cleaned with pure water and wash | cleaned with 100 degreeC and 200 degreeC 2 minutes of heat treatment were further performed at each of 300 degreeC and 360 degreeC.

The polyamic acid resin solution was apply | coated similarly to the 2nd polyimide layer of Example 1 on this 1st polyimide layer, heat-dried at 130 degreeC, and then the speed | rate of about 20 degreeC / min from 160 degreeC to 360 degreeC The temperature was raised to and maintained at 360 ° C. for 60 minutes to form a second polyimide layer having a thickness of 25 μm. The high temperature holding time at this time was 61 minutes.

Thus, the display apparatus was obtained by the procedure similar to Example 1 as a laminated body in which the 1st polyimide layer and the 2nd polyimide layer were laminated | stacked sequentially on the glass. In addition, the peeling strength of the 1st polyimide layer and the 2nd polyimide layer was 10.0 N / m, and it was easy to isolate | separate by a human hand. Moreover, the linear expansion coefficient of the 2nd polyimide layer was 9.3 ppm / K, and the transmittance | permeability in the 440 nm-780 nm wavelength range of the 2nd polyimide layer was 78.5%.

(Example 4)

17.70 g of m-TB (2,2'-dimethylbenzidine), 4.3 g of TPE-R (1,3-bis (4-aminophenoxy) benzene and PMDA (pyromellitic dianhydride) 17.20 on a glass substrate as a support g and BPDA (3,3 ', 4,4'-biphenyltetracarboxylic dianhydride) thickness after curing the resin solution of the polyamic acid obtained from 5.8g is 25㎛, coating area of 310mm x 390mm It was applied so as to remove the solvent (DMAc: N, N-dimethylacetamide) in the resin solution by heating to dryness at 120 ° C. Then, imidization by heat treatment at 130 ° C. to 160 ° C. at a temperature increase rate of about 15 ° C./min. To form a first polyimide layer (surface roughness Ra = 1.0 nm, Tg = 360 ° C.) having a thickness of 25 μm.

On this first polyimide layer, a polyamic acid resin solution was applied in the same manner as the second polyimide layer of Example 1 so as to have a coating area of 306 mm x 386 mm, heat-dried at 130 ° C, and then from 160 ° C. It heated up at the speed | rate of about 20 degree-C / min to 360 degreeC, hold | maintained at 360 degreeC for 30 minutes, and formed the 2nd polyimide layer of thickness 25micrometer. The high temperature holding time at this time was 31 minutes.

Thus, the display apparatus was obtained by the procedure similar to Example 2 as a laminated body in which the 1st polyimide layer and the 2nd polyimide layer were laminated | stacked sequentially on the glass. Peeling strength of the 1st polyimide layer and the 2nd polyimide layer was 110 N / m, and it was separable by a human hand. In addition, the linear expansion coefficient of the first polyimide layer was 20.0 ppm / K, and the linear expansion coefficient of the second polyimide layer was 9.5 ppm / K. Moreover, the transmittance | permeability in the wavelength range of 440 nm-780 nm of a 2nd polyimide layer was 80.5%.

(Example 5)

The thickness after hardening the resin solution of the polyamic acid obtained from PDA (1, 4- phenylenediamine) and BPDA (3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride) on copper foil is 20 micrometers It apply | coated so that it might become, and the solvent (DMAc: N, N- dimethylacetamide) in the resin solution was removed by heat-drying at 130 degreeC. Next, it imidated by heat-processing from 160 degreeC to 360 degreeC at the temperature increase rate of about 1 degree-C / min, and formed the 1st polyimide layer (surface roughness Ra = 1.3 nm, Tg = 355 degreeC) of thickness 20micrometer on copper foil. .

PMDA (pyromellitic dianhydride), 6FDA (2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride) and TFMB (2,2'-bis) on this first polyimide layer The resin solution of the polyamic acid obtained from (trifluoromethyl) -4,4'-diaminobiphenyl) was applied so as to have a thickness of 25 占 퐉 after curing, and the solvent in the resin solution (DMAc: N, N-dimethylacetate Amide) was removed by heating to dryness at 130 ° C. Subsequently, it imidated by heat-processing from 160 degreeC to 360 degreeC at the temperature increase rate of about 20 degreeC / min, and formed the 2nd polyimide layer of thickness 25micrometer. In addition, in the synthesis | combination of the said polyamic acid, the diamine component and the acid dianhydride component were made into about the same mole, and the ratio of PMDA / 6FDA was 85/15.

The copper foil part of the laminated body which consists of this copper foil / 1st polyimide layer / 2nd polyimide layer was removed by ferric chloride etching, and the laminated | multilayer film which consists of a 1st polyimide layer / 2nd polyimide layer was obtained.

This laminated | multilayer film was stuck on the glass substrate which is a support body with an epoxy resin adhesive, and the EL element which is a display part was formed in the 2nd polyimide layer side after that. Then, the interface of a 1st polyimide layer and a 2nd polyimide layer was isolate | separated by peeling, and the display apparatus which has an EL element on a polyimide base material was obtained. The 1st polyimide layer and the 2nd polyimide layer could be easily isolate | separated without damaging the device of display parts, such as TFT and an electrode. In addition, in the said Example, the linear expansion coefficient of the 1st polyimide layer was 12.0 ppm / K, and the linear expansion coefficient of the 2nd polyimide layer was 9.7 ppm / K. Moreover, the transmittance | permeability in the wavelength range of 440 nm-780 nm of a 2nd polyimide layer was 83.5%.

1: glass substrate 2: release layer
3: polyimide layer 4: display part (TFT / organic EL panel part)
5: cutting line 6: adhesive layer
7: first polyimide layer 8: second polyimide layer
9: cutting area 10: cutting surface

Claims (20)

After bonding the laminated film and the support body on which the first polyimide layer and the second polyimide layer are directly laminated, the first polyimide layer side of the laminated film and one side of the support body are bonded through an adhesive layer, The display part is formed, and after that, it isolate | separates at the interface surface of a 1st polyimide layer and a 2nd polyimide layer, and obtains the display apparatus provided with a display part on the resin base material which consists of a 2nd polyimide layer, The manufacture of the display apparatus characterized by the above-mentioned. Way. After forming a 1st polyimide layer and a 2nd polyimide layer on a support body, after forming a predetermined | prescribed display part further on a 2nd polyimide layer, after removing a support body, a 1st polyimide layer and a 2nd polyimide The display device provided with the display part on the polyimide base material which consists of a 2nd polyimide layer isolate | separates at the interface of a layer, The manufacturing method of the display device characterized by the above-mentioned. The method of claim 2,
Formation of a 1st polyimide layer is performed by lamination | stacking of a polyimide film, and formation of a 2nd polyimide layer is performed by application | coating of the resin solution of a polyimide or a polyimide precursor, The manufacturing method of the display apparatus characterized by the above-mentioned. The method of claim 2,
Formation of a 1st polyimide layer and a 2nd polyimide layer is performed by apply | coating and heating the resin solution of a polyimide or a polyimide precursor, The manufacturing method of the display apparatus characterized by the above-mentioned. After forming the first polyimide layer and the second polyimide layer on the support, a predetermined display portion is further formed on the second polyimide layer, and then the interface between the first polyimide layer and the second polyimide layer. In the manufacturing method of the display apparatus which isolate | separates and obtains the display apparatus provided with the display part on the polyimide base material which consists of a 2nd polyimide layer,
And a part of the second polyimide layer protrudes from the peripheral edge of the first polyimide layer, and the protrusion of the second polyimide layer is fixed to the support. After forming the first polyimide layer and the second polyimide layer on the support, a predetermined display portion is further formed on the second polyimide layer, and then the interface between the first polyimide layer and the second polyimide layer. In the manufacturing method of the display apparatus which isolate | separates and obtains the display apparatus provided with the display part on the polyimide base material which consists of a 2nd polyimide layer,
A part of one layer of a 1st polyimide layer or a 2nd polyimide layer is made to protrude from the peripheral edge part of another layer, The manufacturing method of the display apparatus characterized by the above-mentioned. After forming the first polyimide layer and the second polyimide layer on the support, a predetermined display portion is further formed on the second polyimide layer, and then the interface between the first polyimide layer and the second polyimide layer. In the manufacturing method of the display apparatus which isolate | separates and obtains the display apparatus provided with the display part on the polyimide base material which consists of a 2nd polyimide layer,
A first polyimide layer is formed along the outer periphery of the display unit, and then the first polyimide layer and the second polyimide layer are separated. The method of claim 3, wherein
The high temperature holding time of a 2nd polyimide layer is less than 60 minutes, when performing formation of a 2nd polyimide layer by apply | coating and heating a resin solution of a polyimide or polyimide precursor, The manufacturing method of the display apparatus characterized by the above-mentioned. The method of claim 4, wherein
The high temperature holding time of a 2nd polyimide layer is less than 60 minutes, when performing formation of a 2nd polyimide layer by apply | coating and heating a resin solution of a polyimide or polyimide precursor, The manufacturing method of the display apparatus characterized by the above-mentioned. The method according to claim 1 or 2,
The support body is a glass substrate, The manufacturing method of the display apparatus characterized by the above-mentioned. The method according to claim 1 or 2,
The thermal expansion coefficient of a 1st polyimide layer is 25 ppm / K or less, The manufacturing method of the display apparatus characterized by the above-mentioned. The method according to claim 1 or 2,
The thermal expansion coefficient of a 2nd polyimide layer is 25 ppm / K or less, The manufacturing method of the display apparatus characterized by the above-mentioned. The method according to claim 1 or 2,
The second polyimide layer has a transmittance of 80% or more in a wavelength region of 440 nm to 780 nm. The method according to claim 1 or 2,
A display portion is formed through a gas barrier layer, and the difference in thermal expansion coefficient between the second polyimide layer and the gas barrier layer is 10 ppm / K or less. The method according to claim 1 or 2,
The display unit is a color filter layer. The method according to claim 1 or 2,
The peeling strength of a 1st polyimide layer and a 2nd polyimide layer is 200 N / m or less, The manufacturing method of the display apparatus characterized by the above-mentioned. The method according to claim 1 or 2,
At least one of a 1st polyimide layer or a 2nd polyimide layer consists of polyimide which has a structural unit represented by following General formula (1), The manufacturing method of the display apparatus characterized by the above-mentioned.

[In the formula, Ar ₁ represents a tetravalent organic group having an aromatic ring, and Ar ₂ is a divalent organic group represented by the following General Formula (2) or (3).

(Herein, R ₁ to R ₈ in General Formula (2) or General Formula (3) are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group or a fluorine-substituted hydrocarbon group. , At least one of R ₁ to R ₄ in General Formula (2), and at least one of R ₁ to R ₈ in General Formula (3) is a fluorine atom or a fluorine-substituted hydrocarbon group.] The method of claim 17,
The polyimide which has a structural unit represented by the said General formula (1) is an acid anhydride residue, The manufacturing method of the display apparatus characterized by the above-mentioned. The method of claim 17,
The polyimide which has a structural unit represented by the said General formula (1) is an acid anhydride which is a raw material from the group which consists of a 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride and a pyromellitic dianhydride. And at least one acid anhydride selected. The method of claim 17,
As for the polyimide which has a structural unit represented by the said General formula (1), diamine which is a raw material is 1, 4- phenylenediamine, 2, 2'- dimethylbenzidine, and 1, 3-bis (4-amino phenoxy) benzene. At least one diamine selected from the group consisting of the manufacturing method of the display device.

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