JP6259028B2 - Flexible device substrate, flexible device, and method of manufacturing flexible device substrate - Google Patents

Description

The present invention is a flexible device substrate suitably used in flexible devices, its Re method of manufacturing a substrate for a flexible device and the flexible device using.

  Currently, glass substrates are mainly used as substrates for devices such as solar cell modules and flat panel displays, but resin substrates are being studied to reduce weight and thickness. The resin substrate under consideration is a heat treatment step of 400 ° C. or higher required in a device manufacturing process using a silicon-based semiconductor, and a temperature of 300 ° C. or higher required in a device manufacturing step using a metal oxide semiconductor. Resistant to the heat treatment process is required, and in order to suppress the dimensional difference during the heat treatment process caused by the difference in thermal expansion coefficient between the resin substrate and the silicon-based semiconductor or metal oxide semiconductor, the resin substrate and the inorganic substrate The process which peels a resin substrate from an inorganic substrate after device manufacture is required.

  In general, a polyimide having a thermal expansion coefficient close to that of a silicon-based semiconductor and having a heat resistance of 400 ° C. or higher is low in thermal expansion by molecular orientation, and thus does not have adhesion to an inorganic substrate. For this reason, forming an inorganic layer for resin adhesion, such as a silicon nitride layer and an amorphous silicon layer, on the surface of an inorganic substrate has been performed. In this case, in order to peel off the resin substrate from the inorganic substrate, as in Patent Document 1, polyimide is decomposed by laser after device manufacture, or as in Patent Document 2, hydrogen from a hydrogenated amorphous silicon layer is used. The peeling method etc. which peel the resin substrate from an inorganic substrate by generation | occurrence | production are taken.

  On the other hand, in the field of an interlayer insulating film (passivation film) and a surface protection film (overcoat film) of a semiconductor element, a resin composition containing polyimide, a silane coupling agent, and a solvent is known (Patent Literature). 3).

  In the field of surface protection films and interlayer insulating films of various electronic components such as semiconductor devices, a specific diamine and a specific carboxylic acid and / or derivative thereof are dissolved as a solute in an organic solvent, and are made of silicone oil. A polyimide precursor solution containing a specific amount of a surfactant is known (see Patent Document 4).

  Further, a photosensitive resin composition containing an alkali-soluble resin, a photoacid generator, a fatty acid alcohol compound, and an organosilicon compound is known as a surface protective film or an interlayer insulating film in a semiconductor device (see Patent Document 5). .

  Further, a positive photosensitive resin composition that is a polybenzoxazole-based heat-resistant polymer that can be applied as a surface protective film, an interlayer insulating film, or the like of electronic components such as semiconductor elements is known (see Patent Document 6).

  There is also known a flexible light-receiving element that includes a flexible transparent plastic substrate, an electrode layer, and a semiconductor layer, and the substrate is formed of a polyimide film containing polyimide as a main component (patent) Reference 7).

Special table 2012-511173 gazette International Publication No. 2009/037797 Pamphlet JP 2009-102505 A JP 2001-139808 A JP 2008-216569 A JP 2004-170611 A Japanese Unexamined Patent Publication No. 64-774

  However, in the peeling methods described in Patent Document 1 and Patent Document 2, defects derived from an adhesive layer (such as an inorganic layer for resin adhesion) may occur during these peeling processes. In addition, the resin substrate may be defective by the laser. As a result, the durability and mechanical strength of the resin substrate are lowered, and the film thickness variation tends to increase.

  And in the flexible device manufactured using the resin substrate formed in this way, there is a possibility that device malfunction, for example, fluctuation or variation in threshold voltage of the thin film transistor may occur. For these reasons, the yield of device manufacturing is reduced, which is a major obstacle in terms of cost reduction and productivity improvement.

  Moreover, in the resin substrate produced with the resin composition of patent document 3 and patent document 4, it cannot be said that coexistence of the adhesiveness with respect to an inorganic substrate and peelability is necessarily enough, and needs further improvement. .

  Moreover, in patent document 5, patent document 6, and patent document 7, it does not mention peelability other than the adhesiveness with respect to an inorganic substrate. Patent Document 5 forms a surface protective film or an interlayer insulating layer of a semiconductor device from a resin composition. In the examples, only sensitivity and adhesiveness experiments are conducted. In Patent Document 5, an inorganic substrate is used. On the other hand, a resin composition having a composition for achieving both adhesion and peelability is not envisaged.

  In Patent Document 6, a silane coupling agent is added to improve the adhesion of the positive photosensitive resin composition to the substrate, but peeling from the substrate is not assumed. Similarly, Patent Document 6 does not assume a resin composition having a composition for achieving both adhesiveness and peelability for an inorganic substrate.

  Patent Document 7 describes a substrate made of a polyimide film. However, it does not assume that the substrate made of a polyimide film is peeled off from the inorganic substrate, and has both adhesion and peelability to the inorganic substrate. The polyimide film which consists of a composition for making it do is not assumed.

  In any of the patent documents, there is no disclosure of a composition that can reduce variations in film thickness in a flexible device substrate mainly composed of polyimide. As shown in a comparative example to be described later, conventionally, a variation in the film thickness of a flexible device substrate mainly composed of polyimide has been likely to be large. Also, none of the patent documents discloses a flexible device substrate mainly composed of polyimide or a flexible device including a polyimide resin layer that exhibits good in-plane uniformity in property evaluation such as electrical properties. .

The present invention has been made in view of the foregoing, the thickness variation is small, the device malfunction hardly occurs flexible device substrate when constituting a device, its Re for a flexible device and the flexible device using An object is to provide a method for manufacturing a substrate .

  The substrate for a flexible device of the present invention is represented by (α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a chemical structure represented by the following general formula (1) and / or the following general formula (2). (Γ) a chemical structure represented by the following general formula (3), a compound having one or more of the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, (δ) an amide group, amino A compound having a chemical structure represented by the following general formula (4) having at least one functional group selected from the group consisting of a group, a carbamate group, a carboxyl group, an aryl group, an acid anhydride group and a polymerizable cyclic ether group It is characterized by containing.

Alternatively, the substrate for a flexible device of the present invention includes (α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a compound having a chemical structure represented by the following general formula (1), (γ) Selected from the group consisting of the chemical structure represented by formula (3), a compound having one or more of the group consisting of hydroxyl group, carboxyl group and sulfo group, (δ) carbamate group, carboxyl group, amide group and aryl group A compound having a chemical structure represented by the following general formula (4) having at least one kind of functional group, or (α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, and (β) an intramolecular as a nonpolar site Represented by the following general formula (2) having a C—F group bond of 3 to 100 and having a polyether group, hydroxyl group, carboxyl group or sulfo group of 1 to 100 in the molecule as a polar moiety. (Γ) a chemical structure represented by the following general formula (3), a compound having one or more of the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, (δ) an amide group, an amino group A compound having a chemical structure represented by the following general formula (4) having at least one functional group selected from the group consisting of a carbamate group, a carboxyl group, an aryl group, an acid anhydride group and a polymerizable cyclic ether group, It is characterized by containing.

  The flexible device of the present invention is represented by (α) polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a chemical structure represented by the following general formula (1) and / or the following general formula (2). A compound having a chemical structure, (γ) a chemical structure represented by the following general formula (3), a compound having one or more members selected from the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, (δ) an amide group, an amino group, Contains a compound having a chemical structure represented by the following general formula (4) having at least one functional group selected from the group consisting of a carbamate group, a carboxyl group, an aryl group, an acid anhydride group and a polymerizable cyclic ether group And a polyimide resin layer.

Alternatively, the flexible device of the present invention includes (α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a compound having a chemical structure represented by the following general formula (1), (γ) the following general formula ( 3) at least one compound selected from the group consisting of a chemical structure represented by 3), a compound having one or more of the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, and (δ) a carbamate group, a carboxyl group, an amide group and an aryl group. A compound having a chemical structure represented by the following general formula (4) having various functional groups, or (α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, and (β) 3 as a nonpolar site in the molecule. It is represented by the following general formula (2) having a C—F group bond of 100 or less and having a polyether group, hydroxyl group, carboxyl group or sulfo group of 1 to 100 in the molecule as a polar site. A compound having a chemical structure, (γ) a chemical structure represented by the following general formula (3), a compound having one or more members selected from the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, (δ) an amide group, an amino group, A compound having a chemical structure represented by the following general formula (4) having at least one functional group selected from the group consisting of a carbamate group, a carboxyl group, an aryl group, an acid anhydride group and a polymerizable cyclic ether group; It contains the polyimide resin layer to contain.

The manufacturing method of the substrate for flexible devices of the present invention comprises the steps of forming the substrate for flexible devices of the present invention described above on the substrate and the step of peeling the substrate for flexible devices from the substrate. Features.

According to the present invention, the thickness variation is small, malfunction hardly occurs flexible device substrate device when configuring the device, to provide a method for manufacturing a substrate for a flexible device and the flexible device using the Re their it can.

It is a cross-sectional schematic diagram which shows the manufacturing process of the flexible display which uses the resin composition which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the manufacturing process of the flexible display which uses the resin composition which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the manufacturing process of the flexible display which uses the resin composition which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the manufacturing process of the flexible display which uses the resin composition which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the manufacturing process of the flexible display which uses the resin composition which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the manufacturing process of the flexible display which uses the resin composition which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the manufacturing process of the flexible display which uses the resin composition which concerns on this Embodiment. It is a conceptual diagram which shows the change of adhesiveness when the additive which raises adhesiveness is added to a polyimide. The result of m / z = 78.7-79.3 of TOF-SIMS in Example 27, Comparative Example 5, and Comparative Example 7 is shown. The result of m / z = 58.4-59.5 of TOF-SIMS in Example 27, Comparative Example 5, and Comparative Example 7 is shown. The result of m / z = 44.5-45.5 of TOF-SIMS in Example 27, Comparative Example 5, and Comparative Example 7 is shown.

  As a result of intensive studies to solve the above problems, the present inventors have controlled the 180 ° peel strength between the polyimide resin layer and the inorganic substrate, thereby allowing the adhesion and peeling between the polyimide resin layer and the inorganic substrate. The polyimide resin layer formed using a resin composition containing a specific surfactant and a polyimide containing a specific alkoxysilane compound or a polyimide precursor is superior to an inorganic substrate. It has been found that it exhibits adhesion and easy peelability, and the present invention has been made based on this finding.

  The polyimide resin layer in the present invention has flexibility, for example, a thin film shape, and is used for flexible devices such as flexible memories, sensors, and RF-IDs. Typically used for flexible displays.

  In order to form a thin film-like polyimide resin layer in this way and further appropriately form each functional layer constituting the device on the polyimide resin layer, the polyimide resin layer is first formed on a rigid substrate, It is necessary to form each functional layer that constitutes the device on the polyimide resin layer in order with the polyimide resin layer in close contact with the rigid substrate, and then peel off the completed flexible device from the rigid substrate. The

  The advantage of the polyimide resin layer is that it has good heat resistance against the curing step (including the drying step) applied to the device formation process. For this reason, even if a curing process is performed on the polyimide resin layer in the device formation process, no defects occur in the polyimide resin layer.

  In the device formation process using the polyimide resin layer, it is important that the polyimide resin layer has appropriate adhesion and peelability with respect to the inorganic substrate which is a rigid substrate as described above.

  FIG. 8 is a conceptual diagram showing a change in adhesion when an additive for increasing adhesion is added to polyimide.

  (1) shown in FIG. 8 shows the adhesiveness to the inorganic substrate when the additive for improving the adhesion is added to the polyimide in the state where the additive for improving the peelability is not added.

  In the case of (1), it can be seen that the adhesion is rapidly increased by adding a small amount of an additive for increasing the adhesion. For this reason, in the state (1), the adhesion cannot be controlled, and the 180 ° peel strength between the polyimide resin layer and the inorganic substrate cannot be appropriately controlled.

  On the other hand, (2) shown in FIG. 8 shows the adhesiveness with the inorganic substrate when the additive for improving the adhesiveness is added to the polyimide in the state where the additive for improving the peelability is added.

  In (2), it can be seen that the adhesion gradually increases as an additive for increasing the adhesion is added. According to the case (2), the 180 ° peel strength between the polyimide resin layer and the inorganic substrate can be appropriately controlled, and good adhesion and peelability can be obtained. The present invention has been made based on the concept (2) shown in FIG.

  Hereinafter, an embodiment of the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Laminated body>
The laminate according to the present embodiment includes an inorganic substrate, and (a) a polyimide resin layer containing polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher provided on the surface of the inorganic substrate, The 180 ° peel strength between the polyimide resin layer and the inorganic substrate is 0.004 to 0.250 N / cm.

  Here, “180 ° peel strength” is a test method for evaluating the peel strength of a laminated film or adhesive tape bonded by an adhesive layer, as defined in Japanese Industrial Standard (JIS Handbook Adhesion, K-6854). Yes, here, the adhesion to the polyimide resin layer formed on the surface of the inorganic substrate is shown.

  In the laminate of the present embodiment, the heat resistance adhesion between the polyimide resin layer (polyimide film) and the inorganic substrate is sufficient because the 180 ° peel strength between the polyimide resin layer and the inorganic substrate is 0.004 N / cm or more. It will be a thing. The 180 ° peel strength is more preferably 0.010 N / cm or more, and further preferably 0.015 N / cm or more. On the other hand, when the 180 ° peel strength is 0.250 N / cm or less, the peelability of the polyimide resin layer from the inorganic substrate can be controlled. The 180 ° peel strength is more preferably 0.075 N / cm or less, and further preferably 0.050 N / cm or less.

  The 180 ° peel strength is controlled by, for example, (b) a silicone-based surfactant or a fluorine-based surfactant, and (c) an amino group, a carbamate group, a carboxyl group, an aryl group, an acid anhydride group, as described later. In the case of further containing an alkoxysilane compound having at least one functional group selected from the group consisting of an amide group and a polymerizable cyclic ether group, it can be carried out by adjusting these types and amounts.

  In the laminated body of the present embodiment, the thickness of the polyimide resin layer is preferably 5 μm to 200 μm. In particular, the thickness is preferably 10 μm to 30 μm. If it is 5 μm or more, the resin layer has excellent mechanical strength, and if it is 200 μm or less, the resin layer has excellent flexibility and lightness. The thickness of the inorganic substrate is preferably 0.2 mm to 5 mm.

<Resin composition>
The resin composition of the present embodiment includes (a) a polyimide precursor having a 5% thermal decomposition temperature of 350 ° C. or higher or a polyimide precursor having a 5% thermal decomposition temperature of 350 ° C. or higher, and (b) a silicone-based surface activity. And (c) at least one functional group selected from the group consisting of an amino group, a carbamate group, a carboxyl group, an aryl group, an acid anhydride group, an amide group, and a polymerizable cyclic ether group. And having an alkoxysilane compound.

  According to such a configuration, first, a polyimide resin layer made of polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, or formed by polyimidizing a polyimide precursor has a 5% thermal decomposition temperature of 350 ° C. or higher. Therefore, it is possible to form a polyimide resin layer that can withstand a heat treatment step, for example, exceeding 300 ° C., which is necessary for manufacturing a flexible display.

  Here, the thermal decomposition temperature refers to a thermal decomposition temperature obtained by TG / DTA measurement. The 5% thermal decomposition temperature is a TG / DTA measurement. When held at 40 ° C. for 1 hour in a nitrogen atmosphere and then heated at a rate of 10 ° C./minute, the weight change due to thermal decomposition is 5%. It means the temperature when the temperature is reached.

  Moreover, the film thickness uniformity at the time of coating a varnish-like composition on an inorganic substrate improves by adding a silicone type surfactant or a fluorine-type surfactant. In the manufacture of flexible devices, the good uniformity of film thickness has the advantage that a polyimide resin layer can be stably formed on an inorganic substrate and appearance abnormality is unlikely to occur during heat treatment.

  An alkoxysilane compound having at least one functional group selected from the group consisting of an amino group, a carbamate group, a carboxyl group, an aryl group, an acid anhydride group, an amide group and a polymerizable cyclic ether group is a functional group of the compound. Due to the direct bond between the group and the polymer and the intermolecular interaction, it is difficult to volatilize when the resin composition is heated. In addition, since the alkoxysilane compound is effectively taken into the polyimide resin layer by heat treatment during imidization / orientation, the polyimide resin layer is held at a desired thickness with respect to the inorganic substrate. And exhibit heat-resistant adhesion (initial adhesion and long-term adhesion) exceeding 300 ° C. in an inert atmosphere.

  On the other hand, alkoxysilane compounds that do not have these functional groups volatilize except for compounds that adhere to and bind to the surface of the inorganic substrate during the heating process before imidization, and are not effectively retained in the composition. The polyimide resin layer in close contact with the substrate becomes thin and has poor heat resistant adhesion.

  The heat-resistant adhesion includes initial adhesion when handling the laminate and long-term adhesion during heat treatment during device formation. The initial adhesion means that a polyimide precursor resin composition that becomes a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher is coated on an inorganic substrate by imidization, and then polyimide is formed by heat treatment to form a polyimide resin layer. Refers to the adhesion between the polyimide resin layer immediately after the heating and the inorganic substrate under a high temperature condition, or a polyimide resin composition having a 5% thermal decomposition temperature of 350 ° C. or higher is coated on the inorganic substrate, and then heat treatment The adhesion between the polyimide resin layer immediately after removing the solvent and the inorganic substrate under high-temperature conditions refers to adhesion at 300 ° C. or higher. On the other hand, long-term adhesion refers to heat treatment of a laminate comprising an inorganic substrate and a polyimide resin layer for a long time under a higher temperature condition, specifically, for example, at 300 to 500 ° C. for 6 minutes to 5 hours. Refers to adhesion after application. In the production of flexible devices, good initial adhesion and long-term adhesion have the advantage of suppressing appearance abnormalities such as peeling and swelling during heat treatment.

  On the other hand, as a result of the surface active effect of the added silicone-based surfactant or fluorine-based surfactant, the easy release property of the polyimide resin layer with respect to the inorganic substrate is manifested by the heat treatment. As a result, the polyimide resin layer does not peel off from the inorganic substrate by heat treatment during device formation, and the device can be formed well, and the polyimide resin layer can be easily peeled off from the inorganic substrate after forming the device, resulting in a good flexible device. It is done.

Here, easy peelability means that a polyimide resin layer can be easily peeled from an inorganic substrate. The excellent easy peelability has an advantage that the inorganic substrate can be easily peeled from the polyimide resin layer in the manufacture of the flexible device. In this embodiment mode, the polyimide resin layer can be peeled cleanly from the inorganic substrate, and a polyimide resin layer having a flat surface without any defects on the peeled surface can be obtained.
Hereinafter, each component of the resin composition according to the present embodiment will be described in detail.

(A) Polyimide or polyimide precursor The polyimide or polyimide precursor according to the present embodiment is obtained by reacting tetracarboxylic dianhydride and diamine. In addition, a polyimide precursor means what becomes a polyimide by imidation, and does not mean only a polyamic acid, The thing which a part of polyamic acid imidated and polyamic acid ester are also included. Among these, polyamic acid is preferable from the viewpoints of solubility in a solvent to be used and heat resistance after polyimide formation.

  From the viewpoint of heat resistance and mechanical strength, polyimide or polyimide precursor is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′. -Biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 1,2,5,6- The group consisting of naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′-oxydiphthalic dianhydride, and 4,4′-oxydiphthalic dianhydride At least one selected from the group consisting of 80 mol% or more of all tetracarboxylic dianhydrides, and p-phenylenediamine, m-phenylenediamine, benzidine, 4,4 ′-(or 3 4'-, 3,3'-, 2,4 '-) diamino-diphenyl ether, 5-amino-2- (p-amino-phenyl) benzoxazole, 6-amino-2- (p-amino-phenyl) At least one selected from the group consisting of benzoxazole and 5-amino-2- (m-amino-phenyl) benzoxazole 6-amino-2- (m-amino-phenyl) benzoxazole It is preferable that it is a polyimide or polyamic acid obtained by making it react as 80 mol% or more.

  From the viewpoint of transparency and heat resistance, the polyimide or polyimide precursor consists of a fluorine-containing aromatic acid dianhydride, an alicyclic acid dianhydride, and a sulfur-containing acid dianhydride as a tetracarboxylic dianhydride. It is a polyimide or polyamic acid obtained by reacting at least one selected from the group consisting of fluorine group-containing aromatic diamine, alicyclic diamine, and sulfur-containing diamine as at least one selected from the group, or diamine. It is preferable.

  Fluorine group-containing aromatic dianhydrides include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 2,2-bis (4- (3,4-dicarboxyphenoxy). Phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, and 2,2'-bis (trifluoromethyl)- 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride and the like.

  Examples of alicyclic acid dianhydrides include bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, etc. Can be mentioned.

  Examples of the sulfur-containing dianhydride include bis (3,4-dicarboxyphenyl) sulfone dianhydride.

  Fluorine group-containing aromatic diamines include 1,1,1,3,3,3-hexafluoro-2,2-bis (4-amino-phenyl) propane and 2,2′-bis (trifluoromethyl) benzidine 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2′-bis (3-amino-2,4-dihydroxyphenyl) hexafluoropropane, 2,2′-bis (4 -Amino-3,5-dihydroxyphenyl) hexafluoropropane, 2,2-bis [4- (3-amino-phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2, Examples include 2-bis [4- (4-amino-phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane.

  Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylpropane, and 2,3-diaminobicyclo [2.2. 1] heptane, 2,5-diaminobicyclo [2.2.1] heptane, 2,6-diaminobicyclo [2.2.1] heptane, 2,7-diaminobicyclo [2.2.1] heptane, 2 , 5-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,3-bis (aminomethyl) -bicyclo [2.2.1] heptane and the like.

  As the sulfur-containing diamine, 4,4 ′-(or 3,4′-, 3,3′-, 2,4 ′-) diamino-diphenylsulfone, 4,4 ′-(or 3,4′-, 3 , 3 ′-, 2,4 ′-) diamino-diphenyl sulfide, 4,4′-di (4-amino-phenoxy) phenyl sulfone, 4,4′-di (3-amino-phenoxy) phenyl sulfone, 3, 3′-diamino-diphenylsulfone, 3,3′-dimethyl-4,4′-diamino-biphenyl-6,6′-disulfone, bis (3-amino-phenyl) sulfide, bis (4-amino-phenyl) sulfide Bis (3-amino-phenyl) sulfoxide, bis (4-amino-phenyl) sulfoxide, bis (3-amino-phenyl) sulfone, bis (4-amino-phenyl) sulfone, etc. It is.

  Other tetracarboxylic dianhydrides that can be used include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2 , 2 ′, 3,3′-benzophenone tetracarboxylic dianhydride and the like. These tetracarboxylic dianhydrides may be used alone or in admixture of two or more.

  Furthermore, as a tetracarboxylic dianhydride, other conventionally known tetracarboxylic dianhydrides can be used within a range where the effects of the present embodiment are exhibited.

  Examples of other tetracarboxylic dianhydrides include 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride and 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride. 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 2,2-bis (4- (4-amino-phenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo- 5-isobenzofurancarboxylic acid-1,4-phenylene ester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid Anhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic acid dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Examples of other diamines that can be used include the following.
3,3′-dimethyl-4,4′-diamino-biphenyl, 2,2′-dimethyl-4,4′-diamino-biphenyl, 3,3′-diethyl-4,4′-diamino-biphenyl, 2, 2'-diethyl-4,4'-diamino-biphenyl, 1,4-cyclohexyldiamine, p-xylylenediamine, m-xylylenediamine, 1,5-diamino-naphthalene, 3,3'-dimethoxybenzidine, 4 , 4 '-(or 3,4'-, 3,3'-, 2,4'-) diamino-diphenylmethane, 4,4 '-(or 3,4'-, 3,3'-, 2,4 '-) Diamino-diphenyl ether, 4,4'-benzophenone diamine, 3,3'-benzophenone diamine, 4,4'-bis (4-amino-7phenoxy) biphenyl, 1,4-bis (4-amino-phenoxy) ) Benzene, 1,3-bi (4-amino-phenoxy) benzene, 2,2-bis [4- (4-amino-phenoxy) phenyl] propane, 3,3-dimethyl-4,4′-diamino-diphenylmethane, 3,3 ′, 5 5'-tetramethyl-4,4'-diamino-diphenylmethane, 2,2'-bis (4-amino-phenyl) propane, 5,5'-methylene-bis- (anthranilic acid), 3,5-diamino- Aromatic diamines such as benzoic acid and 3,3′-dihydroxy-4,4′-diamino-biphenyl

  2,6-diamino-pyridine, 2,4-diamino-pyridine, 2,4-diamino-s-triazine, 2,7-diamino-benzofuran, 2,7-diamino-carbazole, 3,7-diamino-phenothiazine, Heterocyclic diamines such as 2,5-diamino-1,3,4-thiadiazole and 2,4-diamino-6-phenyl-s-triazine

  Trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,2-dimethylpropylenediamine, 1,4-cyclohexanediamine 3,3′-diamino-biphenyl-4,4′-diol, 3,3′-diamino-biphenyl -4,4'-diol, 4,3'-diamino-biphenyl-3,4'-diol, 4,4'-diamino-biphenyl-3,3 ', 5,5'-tetraol, 3,3' -Diamino-biphenyl-4,4 ', 5,5'-tetraol, 3,3'-diamino-benzophenone, 4,4'-diamino-benzophenone, 3,3'-diamino-diphenyl ether, 4,4'- Diamino-diphenyl ether, 1,3-bis (3-amino-phenoxy) benzene, 1,4-bis (4-amino-phenoxy) ben , Bis (3- (3-amino-phenoxy) phenyl) ether, bis (4- (4-amino-phenoxy) phenyl) ether, 1,3-bis (3- (3-amino-phenoxy) phenoxy) benzene 1,4-bis (4- (4-amino-phenoxy) phenoxy) benzene, bis (3- (3- (3-amino-phenoxy) phenoxy) phenyl) ether, bis (4- (4- (4- (4- Amino-phenoxy) phenoxy) phenyl) ether, 1,3-bis (3- (3- (3-amino-phenoxy) phenoxy) phenoxy) benzene, 1,4-bis (4- (4- (4-amino- Phenoxy) phenoxy) phenoxy) benzene, 4,4′-bis (3-amino-phenoxy) biphenyl, 4,4′-bis (4-amino-phenoxy) biphenyl 2,2-bis [4- (3-amino-phenoxy) phenyl] propane, 2,2-bis [4- (4-amino-phenoxy) phenyl] propane, 2,2-bis [4- (3- Diamines such as amino-phenoxy) phenyl] butane

α, ω-bis (2-amino-ethyl) polydimethylsiloxane, α, ω-bis (3-amino-propyl) polydimethylsiloxane, α, ω-bis (4-amino-butyl) polydimethylsiloxane, α, Silicone diamines such as ω-bis (4-amino-phenyl) polydimethylsiloxane and α, ω-bis (3-amino-propyl) polydiphenylsiloxane These diamines may be used alone or in combination of two or more. May be used.

  Next, a method for producing a polyimide precursor will be described. As a method for producing a polyimide precursor according to the present embodiment, all methods capable of producing a polyimide precursor, including known methods, can be applied. Among these, it is preferable to perform the reaction in an organic solvent.

  As a solvent used in such a reaction, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 1,3 -Dioxane, 1,4-dioxane, dimethyl sulfoxide, benzene, toluene, xylene, mesitylene, phenol, cresol, ethyl benzoate and butyl benzoate. These may be used alone or in combination of two or more.

  As the solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and γ-butyrolactone are preferable, and N-methyl-2-pyrrolidone is particularly preferable.

  As a density | concentration of the reaction raw material in this reaction, it is 2 mass%-80 mass% normally, Preferably it is 5 mass%-30 mass%.

  The molar ratio of tetracarboxylic dianhydride to be reacted and diamine is in the range of 0.8 to 1.2. Within this range, the molecular weight can be increased, and the elongation and the like are excellent. The molar ratio is preferably 0.9 to 1.1, more preferably 0.92 to 1.07.

  The weight average molecular weight of the polyimide precursor is preferably 1000 or more and 1000000 or less. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The weight average molecular weight is more preferably from 10,000 to 500,000, and most preferably from 20,000 to 300,000. When the weight average molecular weight is 1,000 or more and 1,000,000 or less, the strength and elongation of the resin layer obtained using the resin composition is improved, and the mechanical properties are excellent. Furthermore, it can be applied without bleeding at a desired film thickness during processing such as coating.

  The polyimide precursor is obtained by the following method. First, polyamic acid is produced by subjecting the reaction raw material to a polycondensation reaction from room temperature to 80 ° C.

  Moreover, the terminal of the polymer main chain of the polyimide precursor can be end-capped with an end-capping agent made of a monoamine derivative or a carboxylic acid derivative. By sealing the terminal of the polymer main chain of polyimide, the storage stability derived from the terminal functional group is excellent.

  Examples of the end capping agent comprising a monoamine derivative include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, and 3,5-xylidine. , O-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, p-nitroaniline, m-nitroaniline, o-amino- Phenol, p-amino-phenol, m-amino-phenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o-amino-benzaldehyde, p-amino-benzaldehyde, m-amino-benzaldehyde, o-amino-benzonitrile, p- Mino-benzonitrile, m-amino-benzonitrile, 2-amino-biphenyl, 3-amino-biphenyl, 4-amino-biphenyl, 2-amino-phenylphenyl ether, 3-amino-phenylphenyl ether, 4-amino- Phenylphenyl ether, 2-amino-benzophenone, 3-amino-benzophenone, 4-amino-benzophenone, 2-amino-phenylphenyl sulfide, 3-amino-phenylphenyl sulfide, 4-amino-phenylphenyl sulfide, 2-amino- Phenylphenylsulfone, 3-amino-phenylphenylsulfone, 4-amino-phenylphenylsulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 5-amino-1-naphthol, 2-amino-1- Phthol, 4-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-amino-anthracene, 2- Aromatic monoamines such as amino-anthracene and 9-amino-anthracene are exemplified. Of these, aniline derivatives are preferably used. These may be used alone or in combination of two or more.

  Examples of the terminal blocking agent made of a carboxylic acid derivative mainly include carboxylic anhydride derivatives.

  Examples of the carboxylic anhydride derivative include phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-di Carboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride, 3,4-biphenyl dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalene Dicarboxylic anhydride, 1,2-anthracenedica Bon acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, and, 1,9-anthracene dicarboxylic acid aromatic dicarboxylic acid anhydride anhydrides and the like. Of these aromatic dicarboxylic acid anhydrides, phthalic anhydride is preferably used. These may be used alone or in combination of two or more.

  The obtained polyimide precursor solution may be used as it is without removing the solvent, and may further be used as a resin composition according to the present embodiment by blending necessary solvents, additives and the like.

(B) Silicone-based surfactant or fluorine-based surfactant The silicone-based surfactant according to the present embodiment is not particularly limited as long as it has a siloxane structure as a nonpolar site. A silicone surfactant having 2 to 1000 Si—O bonds in the molecule and 1 to 100 polyether groups, hydroxyl groups, carboxyl groups, or sulfo groups in the molecule as polar sites. Is preferred.

  In order to express the difference in polarity from polyimide or polyimide precursor, the number of Si—O bonds in one molecule which is a nonpolar site is preferably 2 or more. From the viewpoint of uniform film formation with polyimide or polyimide precursor, the number of Si—O bonds in one molecule which is a nonpolar site is preferably 1000 or less, more preferably 500 or less, and even more preferably 100 or less. is there.

  From the viewpoint of affinity with an inorganic substrate, the number of polyether groups, hydroxyl groups, carboxyl groups, or sulfo groups in one molecule, which is a polar site, is preferably 1 or more. From the viewpoint of heat resistance, the number of polyether groups, hydroxyl groups, carboxyl groups, or sulfo groups in one molecule that are polar sites is preferably 100 or less, more preferably 70 or less, and even more preferably 50 or less.

  The maximum value of the molecular weight of the silicone-based surfactant to be added is that the silicone-based surfactant gathers at the interface between the polyimide resin layer and the inorganic substrate due to the solvent drying of the varnish and the heating in the curing process. The size is adjusted so as to obtain good peelability from the inorganic substrate. Therefore, the molecular weight of the silicone surfactant is preferably 20000 or less, and more preferably 5000 or less. The minimum molecular weight of the silicone surfactant to be added is that the silicone surfactant does not volatilize and remains in the polyimide resin layer due to solvent drying of the varnish and heating in the curing process. The size is adjusted so as to obtain good peelability from the substrate. Therefore, the molecular weight of the silicone surfactant is preferably 50 or more, and more preferably 100 or more.

  Further, the fluorosurfactant according to the present embodiment is not particularly limited as long as it has a C—F group binding structure as a nonpolar site, but it is 3 or more and 100 or less in the molecule as a nonpolar site. A fluorosurfactant having a C—F group bond and having 1 to 100 polyether groups, hydroxyl groups, carboxyl groups, or sulfo groups in the molecule as polar sites.

  In order to express the difference in polarity from polyimide or polyimide precursor, the number of C—F bonds in one molecule which is a nonpolar site is preferably 3 or more. From the viewpoint of uniform film formation with polyimide or polyimide precursor, the number of C—F bonds in one molecule which is a nonpolar site is preferably 100 or less, more preferably 70 or less, and even more preferably 50 or less. is there.

  From the viewpoint of affinity with an inorganic substrate, the number of polyether groups, hydroxyl groups, carboxyl groups, or sulfo groups in one molecule, which is a polar site, is preferably 1 or more. From the viewpoint of heat resistance, the number of polyether groups, hydroxyl groups, carboxyl groups, or sulfo groups in one molecule that are polar sites is preferably 100 or less, more preferably 70 or less, and even more preferably 50 or less.

  The maximum value of the molecular weight of the fluorosurfactant to be added is that the fluorosurfactant gathers at the interface between the polyimide resin layer and the inorganic substrate due to the solvent drying of the varnish and the heating in the curing process. The size is adjusted so as to obtain good peelability from the substrate. Therefore, the molecular weight of the fluorosurfactant is preferably 10,000 or less, and more preferably 5000 or less. The minimum molecular weight of the fluorosurfactant to be added is that the fluorosurfactant does not volatilize and remains in the polyimide resin layer by heating in the solvent drying and curing process of the varnish, and the polyimide resin layer inorganic substrate Is adjusted to such a size that good peelability can be obtained. Therefore, the molecular weight of the fluorosurfactant is preferably 50 or more, and more preferably 100 or more.

  Examples of silicone surfactants include polyoxyethylene (POE) -modified organopolysiloxane, polyoxyethylene / polyoxypropylene (POE / POP) -modified organopolysiloxane, POE sorbitan-modified organopolysiloxane, and POE glyceryl-modified organopolysiloxane. And organopolysiloxane modified with a hydrophilic group.

  Specific examples include DBE-712, DBE-821 (manufactured by Amax Co.), KF-6015, KF-6016, KF-6017, KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.), ABIL-EM97 (manufactured by Goldschmidt) Polyflow KL-100, Polyflow KL-401, Polyflow KL-402, Polyflow KL-700 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

  Fluorosurfactants include anionic fluorosurfactants such as perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkylethylene oxide adducts, and perfluoroalkyls. Nonionic fluorine-based surfactants such as amine oxide, perfluoroalkyl polyoxyethylene ethanol, perfluoroalkyl alkoxylate, and fluorinated alkyl ester can be exemplified.

  As specific examples, LE-604, LE-605, LINC-151-EPA (manufactured by Kyoeisha Chemical Co., Ltd.), MegaFac (registered trademark) F171, 172, 173 (manufactured by DIC), Florard (registered trademark) FC430, FC431 ( Sumitomo 3M Co., Ltd.), Asahi Guard AG (registered trademark) 710, Surflon (registered trademark) S-382, SC-101, 102, 103, 104, 105 (Asahi Glass Co., Ltd.) and the like.

  The addition amount of the component (b) added to the resin composition of the present embodiment is 0.001 mass relative to 100 mass parts of the polyimide or polyimide precursor from the viewpoint of peelability of the polyimide resin layer from the glass substrate. Part or more is preferable, and more preferably 0.01 part by weight or more. On the other hand, from the viewpoint of the adhesion of the polyimide resin layer to the glass substrate and the heat resistance of the polyimide, the addition amount is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. When the addition amount is 10 parts by mass or less, contamination of the device due to generation of outgas can be prevented in the device manufacturing process.

  The amount of component (b) added in the present embodiment can be measured by liquid chromatography mass spectrometry (LC-MS).

(C) Alkoxysilane Compound The alkoxysilane compound according to the present embodiment is at least one selected from the group consisting of an amino group, a carbamate group, a carboxyl group, an aryl group, an acid anhydride group, an amide group, and a polymerizable cyclic ether group. It is not particularly limited as long as it is an alkoxysilane compound having a kind of functional group. By having these functional groups, compatibility with polyamic acid or polyimide is improved, polyimide by reaction with aromatic stacking, intermolecular interaction of imide, amino group or acid anhydride group in polyamic acid or polyimide Adhesion of the resin layer to the glass substrate is improved.

  The alkoxysilane compound according to the present embodiment has at least one functional group selected from the group of carbamate group, carboxyl group, amide group and aryl group, so that the release property of the polyimide resin layer from the glass substrate is good. From the viewpoint of becoming.

The alkoxysilane compound according to the present embodiment is specifically a silane compound represented by the following general formula (I).
R ¹ R ² _a Si (R ³ ) _3-a (I)
{In the formula, R ¹ is an amino group, carbamate group, carboxyl group, aryl group, acid anhydride group, amide group in a linear, branched, or cyclic organic group having 1 to 20 carbon atoms. And an organic group having at least one functional group selected from the group of polymerizable cyclic ether groups, and R ² has a carbon atom number containing a photopolymerizable unsaturated double bond group or a polymerizable cyclic ether bond group 2-20 groups, aryl groups having 6-20 carbon atoms, alkylaryl groups having 2-20 carbon atoms, mercapto groups, or alkyls having 1-20 carbon atoms that may be substituted with amino groups Group, a cycloalkyl group having 5 to 20 carbon atoms, or a group having 4 to 20 carbon atoms including a carboxyl group or a dicarboxylic anhydride group, and R ³ represents a methoxy group, an ethoxy group, a propoxy group, Iso At least one monovalent organic group selected from the group consisting of propoxy group, a hydroxyl group, or a chlorine (Cl), and a is an integer of 0 or 1. }

Here, the alkoxysilane compound having an amino group is an alkoxysilane compound having an amino group in a linear, branched or cyclic organic group having 1 to 20 carbon atoms in R ¹ . For example, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N- 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Aminopropylmethyldimethoxysilane, 3-aminopropyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like.

The alkoxysilane compound having a carbamate group is an alkoxysilane compound having a carbamate group in a linear, branched, or cyclic organic group having 1 to 20 carbon atoms of R ¹ . Examples include (3-trimethoxysilylpropyl) -t-butyl carbamate and (3-triethoxysilylpropyl) -t-butyl carbamate.

The alkoxysilane compound having an acid anhydride group is an alkoxysilane compound having a dicarboxylic anhydride group in a linear, branched, or cyclic organic group having 1 to 20 carbon atoms in R ^1. is there.

Preferred organic group as R ^1, for example, succinic anhydride groups ^(R 1 -1), cyclohexane dicarboxylic acid anhydride group ^(R 1 -2), 4- methyl - cyclohexane dicarboxylic anhydride group ^{(R 1} - 3), 5-methyl - cyclohexane dicarboxylic anhydride group ^(R 1 -4), bicycloheptane dicarboxylic acid anhydride group ^(R 1 -5), 7- oxa - bicycloheptane dicarboxylic acid anhydride group ^(R 1 -6 ), and include phthalic anhydride group ^(R 1 -7) is.

The alkoxysilane compound having a carboxyl group is an alkoxysilane compound containing a carboxyl group in a linear, branched or cyclic organic group having 1 to 20 carbon atoms in R ¹ .

Preferred organic group as R ^1, for example, succinic acid, or a half ester group ^(R 1 -8), cyclohexane dicarboxylic acid, or its half ester groups ^(R 1 -9), 4- methyl - cyclohexanedicarboxylic acid, or its half ester groups ^(R 1 -10), 5-methyl - cyclohexane dicarboxylic acid, or its half ester groups ^(R 1 -11), bicycloheptane dicarboxylic acid, or its half ester groups ^{(R 1} -12), 7-oxa - bicycloheptane dicarboxylic acid or half ester group ^(R 1 -13 thereof), phthalic acid, or half ester group ^(R 1 -14) thereof.

The alkoxysilane compound having an aryl group, number of carbon atoms of R ¹ is 1 to 20 linear, branched, or in the cyclic organic group, an aromatic ring having 6 to 20 carbon atoms 1 It is an alkoxysilane compound having two or more. For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl An example is the hydrochloride of trimethoxysilane.

The alkoxysilane compound having an amide group is an alkoxysilane in which R ¹ in the general formula (I) has an amide group in a linear, branched, or cyclic organic group having 1 to 20 carbon atoms. A compound.

  The alkoxysilane compound having an amide group is a reaction of an alkoxysilane compound having an amino group with a carboxylic acid, an acid chloride, a dicarboxylic acid anhydride, or a tetracarboxylic acid anhydride, or a carboxyl group, an acid chloride group, or an acid anhydride. It is obtained by a reaction between an alkoxysilane compound having a physical group and an amine.

  Among these, from the viewpoint of the ease of reaction and the purity of the obtained reaction product, an amino group-containing alkoxysilane compound and a dicarboxylic acid anhydride or a tetracarboxylic acid anhydride are obtained, or an acid anhydride group is obtained. It is preferable that it is an alkoxysilane compound which has an amide group obtained by reaction with the alkoxysilane compound which has and an amine.

  When reacting an alkoxysilane compound having an amino group with an acid anhydride, examples of the alkoxysilane compound having an amino group include the compounds described above. Examples of the dicarboxylic acid anhydride include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, 5-methyl-cyclohexane dicarboxylic acid anhydride, bicycloheptane dicarboxylic acid anhydride, 7-oxabicyclo Heptanedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) succinic anhydride, (3-tri And polybasic acid anhydrides such as ethoxysilylpropyl) succinic anhydride. Examples of tetracarboxylic acid anhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 1,2,5,6-naphthalenetetracarboxylic acid And dianhydrides, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′-oxydiphthalic dianhydride, and 4,4′-oxydiphthalic dianhydride. These may be used alone or in combination of two or more.

  When the alkoxysilane compound having an acid anhydride group is reacted with an amine, examples of the alkoxysilane compound having an acid anhydride group include the compounds described above. Examples of the amine include ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, t-butylamine, pentylamine, hexylamine, 2-ethylhexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecyl. Amine, tetradecylamine, hexadecylamine, 1-aminooctadecane, aniline, benzylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, 2-aminotoluene, 3-aminotoluene 4-aminotoluene, 2,4-dimethylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, , 4-dimethylaniline, 3,5-dimethylaniline, 2,4,5-trimethylaniline, 2,4,6-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,5,6 -Tetramethylaniline, 2,3,4,6-tetramethylaniline, 2-ethyl-3-hexylaniline, 2-ethyl-4-hexylaniline, 2-ethyl-5-hexylaniline, 2-ethyl-6- Hexylaniline, 3-ethyl-4-hexylaniline, 3-ethyl-5-hexylaniline, 3-ethyl-2-hexylaniline, 4-ethyl-2-hexylaniline, 5-ethyl-2-hexylaniline, 6- Ethyl-2-hexylaniline, 4-ethyl-3-hexylaniline, 5-ethyl-3-hexylaniline, 1,2-phenylenediamine, , 3-phenylenediamine, 1,4-phenylenediamine, 2-aminobenzylamine, 3-aminobenzylamine, 4-aminobenzylamine, 2- (4-aminophenyl) ethylamine, 2- (3-aminophenyl) ethylamine 2- (2-aminophenyl) ethylamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 2,3- Dimethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-dimethyl-m-phenylenediamine 2,6-dimethyl-m-phenylenediamine, 4,5-dimethyl-m-phenylene Diamine, 3,4-dimethyl-o-phenylenediamine, 3,5-dimethyl-o-phenylenediamine, 3,6-dimethyl-o-phenylenediamine, 1,3-diamino-2,4,6-trimethylbenzene, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetramethyl-1,3-phenylenediamine, 3,4,5,6-tetramethyl-1,2, -Phenylenediamine, 2,4-diamino-3,5-diethyltoluene, 2,3-diamino-4,5-diethyltoluene, 2,4-diamino-4,6-diethyltoluene, 2,3-diamino-5 , 6-diethyltoluene, 2,4-diamino-3,6-diethyltoluene, 2,5-diamino-3,4-diethyltoluene, 2,5-diamino-3,6-diethyltoluene 2,5-diamino-4,6-diethyltoluene, 2,3-diamino-4,5-diethyltoluene, 2,3-diamino-4,6-diethyltoluene, 2,3-diamino-4,5,6 -Triethyltoluene, 2,4-diamino-3,5,6-triethyltoluene, 2,5-diamino-3,4,6-triethyltoluene, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2 -Methoxy-3-methylaniline, 2-methoxy-4-methylaniline, 2-methoxy-5-methylaniline, 2-methoxy-6-methylaniline, 3-methoxy-2-methylaniline, 3-methoxy-4- Methylaniline, 3-methoxy-5-methylaniline, 3-methoxy-6-methylaniline, 4-methoxy-2-methylaniline, 4-methoxy -3-methylaniline, 2-ethoxyaniline, 3-ethoxyaniline, 4-ethoxyaniline, 4-methoxy-5-methylaniline, 4-methoxy-6-methylaniline, 2-methoxy-3-ethylaniline, 2- Methoxy-4-ethylaniline, 2-methoxy-5-ethylaniline, 2-methoxy-6-ethylaniline, 3-methoxy-2-ethylaniline, 3-methoxy-4-ethylaniline, 3-methoxy-5-ethyl Aniline, 3-methoxy-6-ethylaniline, 4-methoxy-2-ethylaniline, 4-methoxy-3-ethylaniline, 2-methoxy-3,4,5-trimethylaniline, 3-methoxy-2,4 Examples include 5-trimethylaniline and 4-methoxy-2,3,5-trimethylaniline. These may be used alone or in combination of two or more.

The alkoxysilane compound having a polymerizable cyclic ether group is a linear, branched, or cyclic organic group having 1 to 20 carbon atoms in R ¹ , such as a glycidyl group or an epoxycyclohexyl group, It is an alkoxysilane compound having a reactive cyclic ether group. For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4- Epoxycyclohexyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) triethoxysilane, 2- (3,4-epoxycyclohexyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldiethoxysilane Can be mentioned.

  Specific examples of alkoxysilane compounds that can be added in combination with the above include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, diethyldimethoxysilane, diethyl Diethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, octadecyltrimethoxysilane , Octadecyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Toxisilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, tri-i-propylchlorosilane, etc. Can be mentioned. These may be used alone or in combination of two or more.

  From the viewpoint of the adhesion of the polyimide resin layer from the glass substrate, the amount of component (c) added to the resin composition of the present embodiment is 0.001 mass relative to 100 mass parts of the polyimide or polyimide precursor. Part or more is preferable, and more preferably 0.01 part by weight or more. On the other hand, from the viewpoint of the peelability of the polyimide resin layer from the glass substrate and the heat resistance of the polyimide, the addition amount is preferably 9 parts by mass or less, more preferably 5 parts by mass or less.

  The amount of component (c) added in the present embodiment can be measured by liquid chromatography mass spectrometry (LC-MS).

(D) Solvent The resin composition of the present embodiment may be dissolved in a solvent to take the form of a varnish-like resin composition. As the solvent used here, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, pyrubin Examples thereof include methyl acid, ethyl pyruvate, methyl-3-methoxypropionate and the like, and may be used alone or in combination.

  Among these, aprotic polar solvents are more preferable, and specific examples include N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone. Particularly preferred is N-methyl-2-pyrrolidone (NMP).

  The usage-amount of such a solvent changes with film thicknesses obtained, and is used in 10 mass parts-10000 mass parts with respect to 100 mass parts of polyimides or a polyimide precursor.

  The resin composition and polyimide resin layer of the present embodiment may contain other components than those described above, but the other additive components do not affect the 180 ° peel strength between the polyimide resin and the inorganic substrate. The amount is adjusted so that both good adhesion and releasability can be achieved.

  Next, the laminated body of this Embodiment is demonstrated. The laminated body of the present embodiment is a varnish-like polyimide precursor composition which is converted to a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher by imidization treatment on an inorganic substrate and subjected to heat treatment. By a method of forming a polyimide resin layer by polyimidizing a polyimide precursor, or by applying a polyimide composition having a 5% thermal decomposition temperature of 350 ° C. or more on an inorganic substrate and performing a heat treatment to remove the solvent can get.

  Here, as an inorganic substrate, it is preferable that it is transparent from the point which aligns at a device formation process, and a glass substrate is especially preferable. As glass substrates, alkali-free glass substrates, soda-lime glass substrates, quartz glass substrates, etc. are used, but alkali-free glass substrates are used in many semiconductor manufacturing processes, and alkali-free glass substrates as inorganic substrates. Is preferred.

  Moreover, as an inorganic substrate, in order to control adhesiveness with a polyimide composition film | membrane and peelability, what processed the coupling agent on the surface of an inorganic substrate previously is included.

  Moreover, the method of manufacturing the laminated body of this Embodiment becomes possible by developing the resin composition of this Embodiment on an inorganic substrate by a well-known method, and heat-processing.

  Examples of the spreading method include known coating methods such as spin coating, slit coating, and blade coating. In addition, the heat treatment is performed on the inorganic substrate after the resin composition is developed, and heat treatment is performed at a temperature of 300 ° C. or lower for 1 to 300 minutes mainly for the purpose of solvent removal, and further at a temperature of 300 ° C. to 550 ° C. in an inert atmosphere such as nitrogen. Heat treatment for 1 minute to 300 minutes to polyimidize the polyimide precursor.

  The laminate of the present embodiment exhibits excellent heat resistance, dimensional stability, and heat adhesion to an inorganic substrate by heat-treating the resin composition of the present embodiment. It can be applied as a substrate. In particular, a laminate exceeding 300 ° C. in an inert atmosphere such as a thermal aging step or an excimer laser step when forming a low-temperature polysilicon thin semiconductor or oxide semiconductor, more specifically, a laminate at 300 ° C. to 500 ° C. Thus, the polyimide resin layer does not peel off and a device can be formed satisfactorily. After device formation, devices can be easily formed from laminates by cutting and peeling the polyimide resin layer and glass interface, removing the resin adhesive layer of the laminate with a laser, or heat-treating in the air. The prepared polyimide resin layer can be peeled off. The “resin adhesive layer” is an inorganic layer or an organic layer provided on the surface of an inorganic substrate for resin adhesion. In the present embodiment, the resin adhesive layer may or may not be provided.

  According to this embodiment, the polyimide resin layer can be peeled cleanly from the inorganic substrate, and the polyimide resin layer can be formed without any defects on the release surface.

  Next, the case where the resin composition according to the present embodiment is used for manufacturing a low-temperature polysilicon, oxide semiconductor TFT drive type organic EL flexible display will be described.

  1-7 is a cross-sectional schematic diagram which shows the manufacturing process of the flexible display which uses the resin composition which concerns on this Embodiment.

  First, as shown in FIG. 1A, for example, a first substrate 11 made of an alkali-free glass substrate is prepared. Next, as shown in FIG. 1B, a polyimide precursor resin composition that becomes a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher is applied to the surface of the first substrate 11 by the imidization treatment of the present embodiment described above. Then, the first polyimide resin layer 12 is formed by a method of forming a polyimide by heat treatment or a method of applying a polyimide resin composition having a 5% thermal decomposition temperature of 350 ° C. or higher and then removing the solvent by heat treatment. To do.

  Next, as shown in FIG. 2, a first barrier layer 101 is formed on the first polyimide resin layer 12 of the first substrate 11.

  Further, as shown in FIG. 2, a semiconductor layer 102, a gate insulating film 103, a gate electrode 104, an interlayer insulating film 105, a contact hole 106, and source / drain electrodes 107a and 107b are sequentially formed on the first barrier layer 101. A thin film transistor (TFT) 108 is formed.

  Here, the semiconductor layer 102 is formed of polysilicon. The semiconductor layer 102 is formed by first forming amorphous silicon, crystallizing it, and changing it to polysilicon. Such crystallization methods include, for example, RTA (Rapid Thermal Annealing), SPC (Solid Phase Crystallization), ELA (Excimer Laser Crystallization), MIC (Metal Induced Crystallization), MI (Metal Induced Crystallization), and MI (Metal Induced Crystallization). Lateral Solidification).

  Next, a display element is formed on the TFT 108. As shown in FIG. 3, first, a planarization layer 109 is formed on the source / drain electrodes 107a and 107b. Next, in order to form an organic light emitting device (OLED) on the TFT 108, first, a contact hole 110 is formed in one electrode 107b of the source / drain electrodes 107a and 107b and is electrically connected to the first electrode 111. To do. The 1st electrode 111 functions as one electrode among the electrodes with which an organic light emitting element is equipped later.

  Next, as illustrated in FIG. 4, a pixel definition film 112 patterned with an insulating material is formed on the first electrode 111 so that at least a part of the first electrode 111 is exposed. Next, an intermediate layer 113 including a light emitting layer is formed on the exposed portion of the first electrode 111. A second electrode 114 facing the first electrode 111 is formed around the intermediate layer 113. Thereby, an organic light emitting device (OLED) (210 in FIG. 6) is obtained.

  Next, the above organic light emitting device is sealed. The sealing member 201 shown in FIG. 5 is manufactured separately, and the sealing member 201 is coupled to the upper portion of the organic light emitting device, and then the second substrate 202 of the sealing member 201 is separated.

  As shown in FIG. 5, the sealing member 201 has a second polyimide resin layer 203 formed on one main surface of a second substrate 202 made of an alkali-free glass substrate, for example, and further on the surface of the second polyimide resin layer 203. The second barrier layer 204 is formed. Here, the second polyimide resin layer 203 can be formed using the resin composition of the present embodiment. Next, as shown in FIG. 6, after the sealing member 201 is disposed on the organic light emitting element 210, these are bonded.

  Finally, heat treatment is performed at 300 ° C. to 350 ° C. in an air atmosphere in the state shown in FIG. 6 in the presence of oxygen. Accordingly, the first substrate 11 in contact with the first polyimide resin layer 12 can be peeled off, and the second substrate 202 in contact with the second polyimide resin layer 203 can be peeled off. As a result, a flexible display 100 as shown in FIG. 7 is obtained.

  In the manufacturing method of the flexible display 100 described above, the following effects can be obtained by using the resin composition of the present embodiment.

  First, the first polyimide resin layer 12 formed by polyimidizing the polyimide precursor has a 5% thermal decomposition temperature of 350 ° C. or higher. Has heat resistance to withstand. Specifically, the semiconductor layer 102 can withstand a process such as polysilicon formation.

  An alkoxysilane compound having at least one functional group selected from the group consisting of an amino group, a carbamate group, a carboxyl group, an aryl group, an acid anhydride group, an amide group and a polymerizable cyclic ether group does not have these groups. Compared to alkoxysilane compounds, it interacts with polyimide and is less likely to volatilize when the resin composition is heated, and is effectively incorporated into the polyimide resin layer during imidization / orientation at 400 ° C. or higher. On the other hand, the polyimide resin layer is maintained at a desired thickness, and exhibits good heat-resistant adhesion (long-term adhesion) during long-time heat treatment. As a result, when the RTA, SPC, MIC, MIL, SLS or the like is employed to form an amorphous silicon layer and crystallize the amorphous silicon layer when forming the semiconductor layer 102, the first substrate 11 and The temperature of the laminate composed of the first polyimide resin layer 12 reaches 350 ° C. to 500 ° C. and is left for 6 minutes to 5 hours until the formation of polysilicon is completed. However, since the first polyimide resin layer 12 is excellent in long-term adhesion by using the resin composition of the present embodiment, the first polyimide resin layer 12 becomes the first substrate 11 during the polysiliconization. It is possible to suppress the occurrence of problems such as peeling from the surface.

  Further, since the alkoxysilane compound is introduced into the polyimide by heat treatment when forming the polyimide, for example, it exhibits heat-resistant adhesion (initial adhesion) exceeding 400 ° C. in an inert atmosphere. Thereby, in the manufacture of the flexible display 100, there is an effect of suppressing the appearance abnormality.

  In addition, the resin composition and the polyimide resin layer of the present embodiment have a silicone surfactant or a fluorosurfactant. Thereby, the peelability with respect to an inorganic substrate can be improved.

  Thus, in this Embodiment, while adding a silicone surfactant or a fluorine-type surfactant to a polyimide or a polyimide precursor, and adding the alkoxysilane compound which has a predetermined functional group, a polyimide resin layer It is possible to form a resin composition having good adhesion and peelability to an inorganic substrate and a laminate using the resin composition.

  In the above description, the polysilicon semiconductor driven flexible display has been described as an example. However, the flexible device manufacturing method according to the present embodiment is also applied to a metal oxide semiconductor driven flexible device such as IGZO. can do.

  Moreover, the glass substrate which peeled the polyimide resin layer with the method of this Embodiment can peel all the polyimide resin layers from the glass substrate by the easy peelability of a polyimide. Therefore, it is possible to recycle the used glass substrate by passing the glass substrate surface through an easy glass substrate cleaning process using oxygen plasma, acid, or alkali solution.

  Next, as a result of intensive studies, the inventors have made a flexible device substrate containing polyimide and a specific compound, thereby reducing variations in film thickness, and further, the flexible device substrate. It has been found that when a device is used, a good operation response is shown, and the present invention has been made based on this finding.

  The flexible device substrate in the present invention has flexibility, for example, a thin film shape, and is used for flexible devices such as flexible memories, sensors, and RF-IDs. Typically used for flexible displays.

  In order to obtain stable device operation using such a thin film substrate for flexible devices, it is important that the surface of the flexible device substrate that forms the functional layers of the device has high flatness. For this purpose, the film thickness variation of the flexible device substrate must be reduced. Of course, the flexible device substrate is required to have good flexibility, and in order to obtain good flexibility, the thickness together with the composition of the flexible device substrate is also an important factor. The

  The flexible device substrate having flexibility is, for example, carried in a roll-to-roll process and used for a device formation process. Therefore, in general, the flexible device substrate is marketed in the state of a flexible device including each functional layer of the device, but the flexible device substrate may be marketed alone.

  Hereinafter, an embodiment of the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Flexible device substrate>
The substrate for a flexible device of the present embodiment includes (α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a chemical structure represented by the following general formula (1) and / or the following general formula (2). (Γ) a compound having a chemical structure represented by the following general formula (3), a compound having one or more of the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, (δ) The compound which has a chemical structure represented by Formula (4) is contained.

  Here, the nonpolar site | part of the silicone type surfactant represented by General formula (1) is shown below.

  Moreover, the nonpolar site | part of the fluorine-type surfactant represented by General formula (2) is shown below.

  In the following, one embodiment of the polar part of the silicone-based and fluorine-based surfactant represented by the general formula (3) is shown.

  Moreover, the hydrolysis condensate group of the trifunctional alkoxysilane represented by General formula (4) below is shown.

Hereinafter, each material which comprises the board | substrate for flexible devices of this Embodiment is demonstrated.
<Polyimide>
The polyimide used in the present embodiment has a 5% thermal decomposition temperature of 350 ° C. or higher. Such a polyimide is typically obtained by imidizing a polyimide precursor obtained by reacting tetracarboxylic dianhydride and diamine by heat treatment or the like.

  The polyimide precursor used here is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, in terms of heat resistance and mechanical strength. 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 1,2,5 From 6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride At least one selected from the group consisting of 80 mol% or more of all tetracarboxylic dianhydrides, and p-phenylenediamine, m-phenylenediamine, benzidine, 4,4 ′-(or 3 4'-, 3,3'-, 2,4 '-) diamino-diphenyl ether, 5-amino-2- (p-amino-phenyl) benzoxazole, 6-amino-2- (p-amino-phenyl) At least one selected from the group consisting of benzoxazole and 5-amino-2- (m-amino-phenyl) benzoxazole 6-amino-2- (m-amino-phenyl) benzoxazole It is preferable that it is a polyimide or polyamic acid obtained by making it react as 80 mol% or more.

  From the viewpoint of transparency and heat resistance, the polyimide or polyimide precursor consists of a fluorine-containing aromatic acid dianhydride, an alicyclic acid dianhydride, and a sulfur-containing acid dianhydride as a tetracarboxylic dianhydride. It is a polyimide or polyamic acid obtained by reacting at least one selected from the group consisting of fluorine group-containing aromatic diamine, alicyclic diamine, and sulfur-containing diamine as at least one selected from the group, or diamine. It is preferable.

  Fluorine group-containing aromatic dianhydrides include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 2,2-bis (4- (3,4-dicarboxyphenoxy). Phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, and 2,2'-bis (trifluoromethyl)- 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride and the like.

  Examples of alicyclic acid dianhydrides include bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, etc. Can be mentioned.

  Examples of the sulfur-containing dianhydride include bis (3,4-dicarboxyphenyl) sulfone dianhydride.

  Fluorine group-containing aromatic diamines include 1,1,1,3,3,3-hexafluoro-2,2-bis (4-amino-phenyl) propane and 2,2′-bis (trifluoromethyl) benzidine 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2′-bis (3-amino-2,4-dihydroxyphenyl) hexafluoropropane, 2,2′-bis (4 -Amino-3,5-dihydroxyphenyl) hexafluoropropane, 2,2-bis [4- (3-amino-phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2, Examples include 2-bis [4- (4-amino-phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane.

  Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylpropane, and 2,3-diaminobicyclo [2.2. 1] heptane, 2,5-diaminobicyclo [2.2.1] heptane, 2,6-diaminobicyclo [2.2.1] heptane, 2,7-diaminobicyclo [2.2.1] heptane, 2 , 5-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,3-bis (aminomethyl) -bicyclo [2.2.1] heptane and the like.

  As the sulfur-containing diamine, 4,4 ′-(or 3,4′-, 3,3′-, 2,4 ′-) diamino-diphenylsulfone, 4,4 ′-(or 3,4′-, 3 , 3 ′-, 2,4 ′-) diamino-diphenyl sulfide, 4,4′-di (4-amino-phenoxy) phenyl sulfone, 4,4′-di (3-amino-phenoxy) phenyl sulfone, 3, 3′-diamino-diphenylsulfone, 3,3′-dimethyl-4,4′-diamino-biphenyl-6,6′-disulfone, bis (3-amino-phenyl) sulfide, bis (4-amino-phenyl) sulfide Bis (3-amino-phenyl) sulfoxide, bis (4-amino-phenyl) sulfoxide, bis (3-amino-phenyl) sulfone, bis (4-amino-phenyl) sulfone, etc. It is.

  Other tetracarboxylic dianhydrides that can be used include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2 , 2 ′, 3,3′-benzophenone tetracarboxylic dianhydride and the like. These tetracarboxylic dianhydrides may be used alone or in admixture of two or more.

  Furthermore, as a tetracarboxylic dianhydride, other conventionally known tetracarboxylic dianhydrides can be used within a range where the effects of the present embodiment are exhibited.

  Examples of other tetracarboxylic dianhydrides include 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride and 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride. 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 2,2-bis (4- (4-amino-phenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo- 5-isobenzofurancarboxylic acid-1,4-phenylene ester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid Anhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic acid dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Examples of other diamines that can be used include the following.
3,3′-dimethyl-4,4′-diamino-biphenyl, 2,2′-dimethyl-4,4′-diamino-biphenyl, 3,3′-diethyl-4,4′-diamino-biphenyl, 2, 2'-diethyl-4,4'-diamino-biphenyl, 1,4-cyclohexyldiamine, p-xylylenediamine, m-xylylenediamine, 1,5-diamino-naphthalene, 3,3'-dimethoxybenzidine, 4 , 4 '-(or 3,4'-, 3,3'-, 2,4'-) diamino-diphenylmethane, 4,4 '-(or 3,4'-, 3,3'-, 2,4 '-) Diamino-diphenyl ether, 4,4'-benzophenone diamine, 3,3'-benzophenone diamine, 4,4'-bis (4-amino-7phenoxy) biphenyl, 1,4-bis (4-amino-phenoxy) ) Benzene, 1,3-bi (4-amino-phenoxy) benzene, 2,2-bis [4- (4-amino-phenoxy) phenyl] propane, 3,3-dimethyl-4,4′-diamino-diphenylmethane, 3,3 ′, 5 5'-tetramethyl-4,4'-diamino-diphenylmethane, 2,2'-bis (4-amino-phenyl) propane, 5,5'-methylene-bis- (anthranilic acid), 3,5-diamino- Aromatic diamines such as benzoic acid and 3,3′-dihydroxy-4,4′-diamino-biphenyl

  2,6-diamino-pyridine, 2,4-diamino-pyridine, 2,4-diamino-s-triazine, 2,7-diamino-benzofuran, 2,7-diamino-carbazole, 3,7-diamino-phenothiazine, Heterocyclic diamines such as 2,5-diamino-1,3,4-thiadiazole and 2,4-diamino-6-phenyl-s-triazine

  Trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,2-dimethylpropylenediamine, 1,4-cyclohexanediamine 3,3′-diamino-biphenyl-4,4′-diol, 3,3′-diamino-biphenyl -4,4'-diol, 4,3'-diamino-biphenyl-3,4'-diol, 4,4'-diamino-biphenyl-3,3 ', 5,5'-tetraol, 3,3' -Diamino-biphenyl-4,4 ', 5,5'-tetraol, 3,3'-diamino-benzophenone, 4,4'-diamino-benzophenone, 3,3'-diamino-diphenyl ether, 4,4'- Diamino-diphenyl ether, 1,3-bis (3-amino-phenoxy) benzene, 1,4-bis (4-amino-phenoxy) ben , Bis (3- (3-amino-phenoxy) phenyl) ether, bis (4- (4-amino-phenoxy) phenyl) ether, 1,3-bis (3- (3-amino-phenoxy) phenoxy) benzene 1,4-bis (4- (4-amino-phenoxy) phenoxy) benzene, bis (3- (3- (3-amino-phenoxy) phenoxy) phenyl) ether, bis (4- (4- (4- (4- Amino-phenoxy) phenoxy) phenyl) ether, 1,3-bis (3- (3- (3-amino-phenoxy) phenoxy) phenoxy) benzene, 1,4-bis (4- (4- (4-amino- Phenoxy) phenoxy) phenoxy) benzene, 4,4′-bis (3-amino-phenoxy) biphenyl, 4,4′-bis (4-amino-phenoxy) biphenyl 2,2-bis [4- (3-amino-phenoxy) phenyl] propane, 2,2-bis [4- (4-amino-phenoxy) phenyl] propane, 2,2-bis [4- (3- Diamines such as amino-phenoxy) phenyl] butane

  α, ω-bis (2-amino-ethyl) polydimethylsiloxane, α, ω-bis (3-amino-propyl) polydimethylsiloxane, α, ω-bis (4-amino-butyl) polydimethylsiloxane, α, Silicone diamines such as ω-bis (4-amino-phenyl) polydimethylsiloxane and α, ω-bis (3-amino-propyl) polydiphenylsiloxane

  These diamines may be used alone or in combination of two or more. As a method for producing the polyimide precursor, all methods that can produce a polyimide precursor, including known methods, can be applied. Among these, it is preferable to perform the reaction in an organic solvent.

  As a solvent used in such a reaction, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 1,3 -Dioxane, 1,4-dioxane, dimethyl sulfoxide, benzene, toluene, xylene, mesitylene, phenol, cresol, ethyl benzoate and butyl benzoate. These may be used alone or in combination of two or more.

  As the solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and γ-butyrolactone are preferable, and N-methyl-2-pyrrolidone is particularly preferable.

  As a density | concentration of the reaction raw material in this reaction, it is 2 mass%-80 mass% normally, Preferably it is 5 mass%-30 mass%.

  The molar ratio of tetracarboxylic dianhydride to be reacted and diamine is in the range of 0.8 to 1.2. Within this range, the molecular weight can be increased, and the elongation and the like are excellent. The molar ratio is preferably 0.9 to 1.1, more preferably 0.92 to 1.07.

  The weight average molecular weight of the polyimide precursor is preferably 1000 or more and 1000000 or less. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The weight average molecular weight is more preferably from 10,000 to 500,000, and most preferably from 20,000 to 300,000. When the weight average molecular weight is 1,000 or more and 1,000,000 or less, the strength and elongation of the resin layer obtained using the resin composition is improved, and the mechanical properties are excellent. Furthermore, it can be applied without bleeding at a desired film thickness during processing such as coating.

  The polyimide precursor is obtained by the following method. First, polyamic acid is produced by subjecting the reaction raw material to a polycondensation reaction from room temperature to 80 ° C.

  Moreover, the terminal of the polymer main chain of the polyimide precursor can be end-capped with an end-capping agent made of a monoamine derivative or a carboxylic acid derivative. By sealing the terminal of the polymer main chain of polyimide, the storage stability derived from the terminal functional group is excellent.

  Examples of the end capping agent comprising a monoamine derivative include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, and 3,5-xylidine. , O-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, p-nitroaniline, m-nitroaniline, o-amino- Phenol, p-amino-phenol, m-amino-phenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o-amino-benzaldehyde, p-amino-benzaldehyde, m-amino-benzaldehyde, o-amino-benzonitrile, p- Mino-benzonitrile, m-amino-benzonitrile, 2-amino-biphenyl, 3-amino-biphenyl, 4-amino-biphenyl, 2-amino-phenylphenyl ether, 3-amino-phenylphenyl ether, 4-amino- Phenylphenyl ether, 2-amino-benzophenone, 3-amino-benzophenone, 4-amino-benzophenone, 2-amino-phenylphenyl sulfide, 3-amino-phenylphenyl sulfide, 4-amino-phenylphenyl sulfide, 2-amino- Phenylphenylsulfone, 3-amino-phenylphenylsulfone, 4-amino-phenylphenylsulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 5-amino-1-naphthol, 2-amino-1- Phthol, 4-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-amino-anthracene, 2- Aromatic monoamines such as amino-anthracene and 9-amino-anthracene are exemplified. Of these, aniline derivatives are preferably used. These may be used alone or in combination of two or more.

  Examples of the terminal blocking agent made of a carboxylic acid derivative mainly include carboxylic anhydride derivatives.

  Examples of the carboxylic anhydride derivative include phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-di Carboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride, 3,4-biphenyl dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalene Dicarboxylic anhydride, 1,2-anthracenedica Bon acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, and, 1,9-anthracene dicarboxylic acid aromatic dicarboxylic acid anhydride anhydrides and the like. Of these aromatic dicarboxylic acid anhydrides, phthalic anhydride is preferably used. These may be used alone or in combination of two or more.

  The obtained polyimide precursor solution may be used as it is without removing the solvent, and may further be used as a resin composition according to the present embodiment by blending necessary solvents, additives and the like. Then, as will be described later, this resin composition is applied to the surface of the inorganic substrate, subjected to a predetermined heat treatment or the like to form a polyimide resin layer, and peeled off from the inorganic substrate, thereby forming a flexible resin composed of the polyimide resin layer. A device substrate can be obtained. This flexible device substrate includes a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher in a state where a predetermined heat treatment is performed on the polyimide or the polyimide precursor.

<Compound having a chemical structure represented by the general formula (1)>
The compound having the chemical structure represented by the general formula (1) is a compound derived from a bifunctional silicone compound. Examples of this compound include silicone oils typified by dimethylsiloxane and modified products thereof, or silicone surfactants having a hydrophilic group bonded to dimethylsiloxane. This compound should just have the structure of General formula (1) in the molecule | numerator, and the said hydrophilic group may couple | bond with the side chain or the terminal.

  In order to contain this compound in a flexible device substrate, it is convenient to dissolve this compound in a solvent together with the polyimide precursor and remove the solvent by heating.

  As long as it has the chemical structure of the general formula (1), this compound may be reacted and decomposed by heat in the flexible device substrate. When this compound is contained, surface tension can be controlled and the surface roughness of the substrate for flexible devices can be reduced.

<Compound having a chemical structure represented by the general formula (2)>
The compound having the chemical structure represented by the general formula (2) is a compound derived from a fluorinated hydrocarbon. A typical example of this compound is a fluorosurfactant, specifically, an anionic fluorosurfactant such as perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl sulfonate, Nonionic fluorinated surfactants such as perfluoroalkylethylene oxide adducts, perfluoroalkylamine oxides, perfluoroalkyl polyoxyethylene ethanol, perfluoroalkyl alkoxylates, fluorinated alkyl esters and the like can be mentioned. As the compound represented by the general formula (2), it is only necessary to have a structure derived from a fluorinated hydrocarbon. Therefore, the above fluorosurfactant itself may be used, or the fluorosurfactant. Those obtained by removing the hydrophilic group may be used.

  In order to contain this compound in a flexible device substrate, it is convenient to dissolve this compound in a solvent together with the polyimide precursor and remove the solvent by heating.

  As long as it has the chemical structure of the general formula (2), this compound may react and decompose by heat in the flexible device substrate. When this compound is contained, surface tension can be controlled and the surface roughness of the substrate for flexible devices can be reduced.

<Chemical structure represented by general formula (3), compound having one or more of the group consisting of a hydroxyl group, a carboxyl group and a sulfo group>
The compound having one or more chemical groups represented by the general formula (3), a hydroxyl group, a carboxyl group, and a sulfo group is a compound derived from a surfactant. Typical examples of this compound are silicone-based and fluorine-based surfactants. Examples of this compound include silicone-based surfactants having a hydrophilic group bonded to dimethylsiloxane, perfluoroalkyl carboxylates, perfluoroalkyls. Anionic fluorosurfactants such as phosphate esters and perfluoroalkyl sulfonates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl amine oxides, perfluoroalkyl polyoxyethylene ethanol, perfluoroalkyl alkoxylates, fluorine Nonionic fluorine-based surfactants such as alkylated alkyl esters. As the compound represented by the general formula (3), it is only necessary to have a hydrophilic group of a surfactant. Therefore, the above-mentioned silicone-based and fluorine-based surfactants themselves may be used, or these interfaces may be used. You may use what removed the hydrophobic group from the activator.

  In order to contain this compound in a flexible device substrate, it is convenient to dissolve this compound in a solvent together with the polyimide precursor and remove the solvent by heating.

  As long as it has the chemical structure of the general formula (3), this compound may react and decompose by heat in the flexible device substrate. When this compound is contained, surface tension can be controlled and the surface roughness of the substrate for flexible devices can be reduced.

<Compound having a chemical structure represented by the general formula (4)>
The compound having the chemical structure represented by the general formula (4) is a compound derived from a trifunctional silicone compound. Examples of this compound include hydrolysis condensates of trifunctional alkoxysilanes. Trifunctional alkoxysilanes used to obtain this compound include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl). ) -3-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc. Is mentioned. In order to contain this compound in a substrate for a flexible device, the compound is dissolved in a solvent together with the polyimide precursor, and the solvent is removed by heating, like the compound represented by the general formula (1). Convenient.

  If it has the chemical structure of the general formula (4), this compound may react and decompose by heat in the substrate for flexible devices. When this compound is included, the film thickness dispersion | variation of the board | substrate for flexible devices can be made small. The reason for this is not clear, but it is presumed that a compound derived from a trifunctional silicone compound segregates on the surface by heating and the surface tension is reduced, thereby exhibiting the above effect.

  The addition amount of the (β) component contained in the flexible device substrate of the present embodiment is 0.0001 to 9 parts by mass with respect to 100 parts by mass of the polyimide (α) from the viewpoint of film thickness uniformity and flexibility. It is preferable that it is a mass part, More preferably, it is 0.001 mass part-5 mass parts. Moreover, the addition amount of the (γ) component contained in the flexible device substrate of the present embodiment is 0.0001 parts by mass with respect to 100 parts by mass of the polyimide (α) from the viewpoint of film thickness uniformity and flexibility. It is preferable that it is -10 mass parts, More preferably, it is 0.0001 mass part-5 mass parts.

<Flexible device>
Although the kind of flexible device of this Embodiment is not specifically limited, A typical thing is an organic EL flexible display. Hereinafter, the case where it is used for manufacturing a low temperature polysilicon, oxide semiconductor TFT driving type organic EL flexible display will be described.

  1-7 is a cross-sectional schematic diagram which shows the manufacturing process of the flexible display which uses the resin composition which concerns on this Embodiment.

  First, as shown in FIG. 1A, for example, a first substrate 11 made of an alkali-free glass substrate is prepared. Next, as shown in FIG. 1B, on the surface of the first substrate 11, a polyimide precursor resin composition that becomes a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher by the imidization treatment of the present embodiment described above. The first polyimide resin layer 12 is then applied by a method of applying a polyimide by heat treatment or by applying a polyimide resin composition having a 5% thermal decomposition temperature of 350 ° C. or higher and then removing the solvent by heat treatment. Form.

  Next, as shown in FIG. 2, a first barrier layer 101 is formed on the first polyimide resin layer 12 of the first substrate 11.

  Further, as shown in FIG. 2, a semiconductor layer 102, a gate insulating film 103, a gate electrode 104, an interlayer insulating film 105, a contact hole 106, and source / drain electrodes 107a and 107b are sequentially formed on the first barrier layer 101. A thin film transistor (TFT) 108 is formed.

  Here, the semiconductor layer 102 is formed of polysilicon. The semiconductor layer 102 is formed by first forming amorphous silicon, crystallizing it, and changing it to polysilicon. Such crystallization methods include, for example, RTA (Rapid Thermal Annealing), SPC (Solid Phase Crystallization), ELA (Excimer Laser Crystallization), MIC (Metal Induced Crystallization), MI (Metal Induced Crystallization), and MI (Metal Induced Crystallization). Lateral Solidification).

  Next, a display element is formed on the TFT 108. As shown in FIG. 3, first, a planarization layer 109 is formed on the source / drain electrodes 107a and 107b. Next, in order to form an organic light emitting device (OLED) on the TFT 108, first, a contact hole 110 is formed in one electrode 107b of the source / drain electrodes 107a and 107b and is electrically connected to the first electrode 111. To do. The 1st electrode 111 functions as one electrode among the electrodes with which an organic light emitting element is equipped later.

  Next, as shown in FIG. 4, a pixel definition film 112 patterned with an insulating material is formed on the first electrode 111 so as to expose at least a part thereof. Next, an intermediate layer 113 including a light emitting layer is formed on the exposed portion of the first electrode 111. A second electrode 114 facing the first electrode 111 is formed around the intermediate layer 113. Thereby, an organic light emitting device (OLED) (210 in FIG. 6) is obtained.

  Next, the above organic light emitting device is sealed. The sealing member 201 shown in FIG. 5 is manufactured separately, and the sealing member 201 is coupled to the upper portion of the organic light emitting device, and then the second substrate 202 of the sealing member 201 is separated.

  As shown in FIG. 5, the sealing member 201 has a second polyimide resin layer 203 formed on one main surface of a second substrate 202 made of an alkali-free glass substrate, for example, and further on the surface of the second polyimide resin layer 203. The second barrier layer 204 is formed. Here, the second polyimide resin layer 203 can be formed using the resin composition of the present embodiment. Next, as shown in FIG. 6, after the sealing member 201 is disposed on the organic light emitting element 210, these are bonded.

  Finally, heat treatment is performed at 300 ° C. to 350 ° C. in an air atmosphere in the state shown in FIG. 6 in the presence of oxygen. Thereby, while peeling the 1st board | substrate 11 from the 1st polyimide resin layer 12, the 2nd board | substrate 202 from the 2nd polyimide resin layer 203 can be peeled. As a result, a flexible display 100 as shown in FIG. 7 is obtained.

  Each of the first polyimide resin layer 12 and the second polyimide resin layer 203 corresponds to a flexible device substrate. The flexible device substrate is a thin film-like insulating substrate having flexibility.

  A substrate generally refers to a base material or a support member that can form a functional layer on the surface thereof, but a flexible plate-like material that is bonded to the surface of a device and has a covering function or a protective function. Including.

  The flexible device according to the present embodiment includes (α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a chemical structure represented by the above general formula (1) and / or the above general formula (2). ) A compound having a chemical structure represented by (γ), (γ) a compound having one or more of the group consisting of a chemical structure represented by the above general formula (3), a hydroxyl group, a carboxyl group, and a sulfo group, (δ) It can be set as the structure containing the polyimide resin layer containing the compound which has a chemical structure represented by said General formula (4), and the polyimide resin layer does not need to comprise the board | substrate.

  In the above configuration, the polyimide resin layer may be a layer present in the flexible device as well as a layer appearing on the surface of the flexible device.

  The flexible device substrate according to the present embodiment described above has the following effects. That is, in this embodiment, the film thickness variation of the flexible device substrate can be reduced. The film thickness can be measured, for example, with an optical film thickness meter.

  The thickness of the flexible device substrate of the present embodiment is preferably 5 μm to 200 μm. In particular, the thickness is preferably 10 μm to 30 μm. If it is 5 μm or more, it is excellent in mechanical strength, and if it is 200 μm or less, it is excellent in flexibility and lightness.

  In the present embodiment, the film thickness variation of the substrate can be suppressed to 50 nm or less (film thickness variation with respect to a width of 10 cm) with respect to the above-described thin thickness dimension.

  In addition, a flexible device manufactured using the flexible device substrate of the present embodiment or a flexible device having a flexible polyimide resin layer exhibits good in-plane uniformity in property evaluation such as electrical properties. Can do. This is because the film thickness variation of the substrate for flexible devices is small and the flatness of the substrate surface is high, so that each layer constituting the device, which is formed on the substrate surface, can be uniformly formed in the plane.

  Although the reason is not clear, it is possible to improve the flexibility of the flexible device substrate, and it is possible to manufacture a flexible device that is not easily damaged even when the flexible device is greatly bent and has excellent durability.

  Hereinafter, the present embodiment will be described in detail according to examples. However, this embodiment is not limited to the following examples.

[Synthesis Example 1]
(Synthesis of polyamic acid varnish P-1)
A nitrogen inlet tube was attached to a 500 ml three-necked separable flask. In an oil bath at 30 ° C. under nitrogen, 270.0 g of N-methyl-2-pyrrolidone (NMP) and 21.94 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) were added, and uniform. Until dispersed. Further, 8.06 g of p-phenylenediamine (PPD) was added little by little and then heated at 80 ° C. for 4 hours to obtain a polyamic acid varnish P-1. The weight average molecular weight was 270,000.

[Synthesis Example 2]
(Synthesis of polyamic acid varnish P-2)
A nitrogen inlet tube was attached to a 500 ml three-necked separable flask. Under an oil bath at 30 ° C. under nitrogen, 270.0 g of N-methyl-2-pyrrolidone (NMP) and 22.14 g of 4,4′-oxydiphthalic dianhydride (ODPA) were added and stirred until uniformly dispersed. Further, 22.86 g of 2,2′-bis (trifluoromethyl) benzidine (TFMB) was added little by little and then heated at 80 ° C. for 4 hours to obtain a polyamic acid varnish P-2. The weight average molecular weight was 200,000.

[Synthesis Example 3]
(Synthesis of polyimide varnish P-3)
A 500 ml three-necked separable flask was equipped with a nitrogen inlet tube and a Dean Stark apparatus. In an oil bath at 30 ° C. under nitrogen, 185.0 g of N-methyl-2-pyrrolidone (NMP), 100.0 g of toluene, and 7.38 g of 4,4′-oxydiphthalic dianhydride (ODPA) are added and uniformly dispersed. Stir until Further, 7.62 g of 2,2′-bis (trifluoromethyl) benzidine (TFMB) was added little by little and then heated at 120 ° C. for 4 hours. Thereafter, 100.0 g of N-methyl-2-pyrrolidone (NMP) was added, and toluene was removed by heating at 120 ° C. in an oil bath to obtain a polyimide varnish P-3. The weight average molecular weight was 150,000.

[Synthesis Example 4]
(Synthesis of polyamic acid varnish P-4)
A nitrogen inlet tube was attached to a 500 ml three-necked separable flask. Under an oil bath at 30 ° C. under nitrogen, 255.0 g of N-methyl-2-pyrrolidone (NMP) and 16.84 g of 4,4′-oxydiphthalic dianhydride (ODPA) were added and stirred until evenly dispersed. Further, 28.16 g of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (HF-BAPP) was added little by little, and then heated at 80 ° C. for 4 hours to obtain a polyamic acid varnish. P-4 was obtained. The weight average molecular weight was 180,000.

[Synthesis Example 5]
(Synthesis of polyamic acid varnish P-5)
A nitrogen inlet tube was attached to a 500 ml three-necked separable flask. In an oil bath at 30 ° C. under nitrogen, 255.0 g of N-methyl-2-pyrrolidone (NMP) and 26.15 g of 2,2-bis (3,4-anhydrodicarboxyphenyl) -hexafluoropropane (6FDA) And stirred until evenly dispersed. Furthermore, 18.85 g of 2,2′-bis (trifluoromethyl) benzidine (TFMB) was added little by little and then heated at 80 ° C. for 4 hours to obtain a polyamic acid varnish P-5. The weight average molecular weight was 170,000.

[Synthesis Example 6]
(Synthesis of polyamic acid varnish P-6)
A nitrogen inlet tube was attached to a 500 ml three-necked separable flask. Under an oil bath at 30 ° C. under nitrogen, 255.0 g of N-methyl-2-pyrrolidone (NMP) and 18.53 g of cyclohexanetetracarboxylic dianhydride (PMDA-HH) were added and stirred until evenly dispersed. Further, after 31.42 g of 2,2′-bis (trifluoromethyl) benzidine (TFMB) was added little by little, the mixture was heated at 80 ° C. for 4 hours to obtain polyamic acid varnish P-6. The weight average molecular weight was 190,000.

[Examples 1 to 26 and Comparative Examples 1 to 4]
(Preparation of polyamic acid and polyimide composition)
Various components were prepared and mixed as shown in Table 1 and Table 2. This was pressure-filtered with a PTFE filter having a pore size of 2.5 microns to obtain varnish-like compositions of Examples 1 to 26 and Comparative Examples 1 to 4.

  Here, the used (B) silicone compound or fluorine compound and (C) alkoxysilane compound are as follows. The alkoxysilane compound included in Comparative Example 4 is methyltrimethoxysilane, and is selected from the group consisting of an amide group, an amino group, a carbamate group, a carboxyl group, an aryl group, an acid anhydride group, and a polymerizable cyclic ether group. This does not correspond to an alkoxysilane compound having at least one functional group.

(B) Silicone compound or fluorine compound A-1 DBE-712 (manufactured by Amax Co.)
A-2 DBE-821 (manufactured by Amax Co.)
A-3 Polyflow KL-100 (manufactured by Kyoeisha Chemical Co., Ltd.)
A-4 Polyflow KL-401 (manufactured by Kyoeisha Chemical Co., Ltd.)
A-5 Polyflow KL-402 (manufactured by Kyoeisha Chemical Co., Ltd.)
A-6 Polyflow KL700 (manufactured by Kyoeisha Chemical Co., Ltd.)
A-7 LE-604 (manufactured by Kyoeisha Chemical Co., Ltd.)
A-8 LE-605 (manufactured by Kyoeisha Chemical Co., Ltd.)
A-9 LINC-151-EPA (manufactured by Kyoeisha Chemical Co., Ltd.)

(C) Alkoxysilane compound S-1 3- (triethoxysilylpropyl) succinic anhydride (manufactured by GELEST)
S-2 3-Glycidoxypropyltrimethoxysilane (manufactured by GELEST)
S-3 3-aminopropyltriethoxysilane (manufactured by GELEST)
S-4 1: 1 reaction product of 3-aminopropyltriethoxysilane and phthalic anhydride S-5 1: 1 reaction product of 3-aminopropyltrimethoxysilane and phthalic anhydride S-6 (3-triethoxy Silylpropyl) -t-butylcarbamate (manufactured by GELEST)
S-7 1: 1 reaction product of 3-aminopropyltriethoxysilane and phenyl isocyanate S-8 1,3 of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 3-aminopropyltriethoxysilane : 2 reactant S-9 Methyltrimethoxysilane (manufactured by GELEST)

[Film formation of polyimide composition]
After curing the varnish-like compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 4 on a 10 cm square non-alkali glass substrate whose surface was cleaned by an alkali cleaning method and a plasma cleaning method. The film was coated so that the film thickness was 20 μm. These coating films were cured under any of the following curing conditions to form a 20 μm thick polyimide resin layer on the alkali-free glass substrate. The curing conditions applied to Examples 1 to 26 and Comparative Examples 1 to 4 are shown in Tables 3 and 4.
Cure conditions for varnish-like composition (all conducted under nitrogen atmosphere)
A: 140 ° C. × 1 hr + 250 ° C. × 1 hr + 350 ° C. × 1 hr
B: 140 ° C. × 1 hr + 450 ° C. × 1 hr
C: 140 ° C. × 1 hr + 500 ° C. × 1 hr

  As a result of TG / DTA measurement of the polyimide resin layers obtained in Examples 1 to 26 and Comparative Examples 1 to 4, the 5% thermal decomposition temperature was higher than 400 ° C.

[Evaluation of composition]
About the polyimide resin layer made from the varnish-like composition obtained in Examples 1-26 and Comparative Examples 1-4, the following items were evaluated and the results are shown in Tables 3 and 4.

1. Adhesion of the cured polyimide resin layer (in Tables 3 and 4, referred to as post-cure adhesion)
In the polyimide resin layer having a thickness of 20 μm after curing of the varnish-like compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 4, the adhesion between the alkali-free glass substrate and the polyimide resin layer was achieved. About the property, the state of the coating film was confirmed visually by the following criteria.
A: A uniform film was formed on the glass substrate after curing.
X: After curing, there are one or more places where the polyimide resin layer is partially floated or peeled off on the glass substrate.

2. Long-term adhesion of polyimide resin layer after inorganic film formation (in Tables 3 and 4, referred to as long-term adhesion)
The varnish-like compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 4 were formed on a non-alkali glass substrate, and after curing, on a polyimide resin layer having a thickness of 20 μm, the thickness was 50 nm using a vacuum deposition apparatus. A silicon dioxide film was deposited so that About the adhesiveness of the alkali free glass substrate and polyimide resin layer after heating this sample in 350 degreeC x 4 hr and nitrogen atmosphere, the state of the coating film was confirmed visually on the following references | standards.
A: After curing, a uniform polyimide resin layer was formed on the glass substrate.
X: After curing, there are one or more places where the polyimide resin layer is partially floated or peeled off on the glass substrate.

3. Light transmittance evaluation (in Tables 3 and 4, described as transparency)
A varnish-like composition obtained in Examples 1 to 26 and Comparative Examples 1 to 4 was coated on a glass substrate, and a polyimide resin layer having a thickness of 20 μm after curing was applied to a spectrophotometer UV-1600PC (manufactured by Shimadzu Corporation). Was used to measure the light transmittance of 800 nm to 300 nm, and the light transmittance of 550 nm was confirmed. At this time, an alkali-free glass substrate without a coating film was placed in the reference portion.

4. 180 ° peel strength evaluation (referred to as 180 ° peel strength in Tables 3 and 4)
A varnish-like composition obtained in Examples 1 to 26 and Comparative Examples 1 to 4 was coated on a glass substrate, and after curing, a 20 μm thick polyimide resin layer was cut into a length of 10 mm and a width of 10 mm, and a width of 10 mm. The width of 1.0 mm at the center of was masked with tape. After that, the humidity is adjusted for 24 hours or more in an environment of temperature 23 ± 2 ° C. and humidity 50 ± 5% RH, and in that environment, a 1.0 mm wide polyimide resin layer masked with tape is peeled from the glass substrate at an angle of 180 °. The stress was measured at a peeling rate of 50 mm / min.

5. Evaluation of releasability of polyimide resin layer from glass substrate (referred to as releasability in Tables 3 and 4)
In the polyimide resin layer having a thickness of 20 μm after curing (curing conditions: A, B, C) formed on a 20 cm square glass substrate of the varnish-like compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 4, The polyimide resin layer was cut into 2 cm portions from the ends of the four sides with a cutter knife to prepare a polyimide resin layer sample having a square cut of 16 cm on one side. The sample was peeled from the glass substrate by attaching a polyimide tape to the end of the sample and pulling up the polyimide tape. At that time, the ease of peeling was determined according to the following criteria.
A: The polyimide resin layer adhered to the glass substrate can be easily peeled off.
○: The polyimide resin layer in close contact with the glass substrate is in close contact, and there is a catch at the time of peeling, but the polyimide resin layer can be peeled off without tearing.
X: The polyimide resin layer is not adhered to the glass substrate, or the polyimide resin layer is adhered and does not peel off, and the film is torn.

  As can be seen from Table 3 and Table 4, (a) polyimide or polyimide precursor, (b) silicone surfactant or fluorine surfactant, (c) amino group, carbamate group, carboxyl group, aryl group And an alkoxysilane compound having at least one functional group selected from the group consisting of an acid anhydride group, an amide group, and a polymerizable cyclic ether group, In comparison, the release property of the polyimide resin layer formed on the inorganic substrate was improved while maintaining the film adhesion and long-term adhesion of the resin composition to the inorganic substrate after curing (Example 1 to Example 26).

  In addition, by selecting an alkoxysilane compound in which the component (c) has at least one functional group selected from the group consisting of a carbamate group, a carboxyl group, an amide group, and an aryl group, the polyimide resin layer is peeled from the inorganic substrate. The property became better.

  From these results, it can be seen that the resin compositions according to Examples 1 to 26 can be suitably used as a substrate for a flexible device, and the laminate can be suitably used as a substrate for manufacturing a flexible device.

[Example 27]
(A) P-1 shown in Synthesis Example 1 as a polyamic acid, (B) DBE-712 (manufactured by AMAX Co.) as a silicone compound, (C) 3-aminopropyltriethoxysilane and phthalic anhydride as an alkoxysilane compound (D) N-methyl-2-pyrrolidone (NMP) as a solvent was prepared and mixed at a mass ratio of 10.0: 0.05: 0.05: 89.90. This was pressure filtered with a PTFE filter having a pore size of 2.5 microns to obtain a varnish-like composition.

  A varnish-like composition was applied on a non-alkali glass substrate whose surface was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. The obtained coating film was cured under conditions of 140 ° C. × 1 hr + 250 ° C. × 1 hr + 350 ° C. × 1 hr.

[Example 28]
(A) P-1 shown in Synthesis Example 1 as a polyamic acid, (B) LE-605 (manufactured by Kyoeisha Chemical Co., Ltd.) as a fluorine compound, (C) 3-aminopropyltriethoxysilane and phthalic anhydride as an alkoxysilane compound And (D) N-methyl-2-pyrrolidone (NMP) as a solvent was prepared and mixed at a mass ratio of 10.0: 0.09: 0.01: 89.90. This was pressure filtered with a PTFE filter having a pore size of 2.5 microns to obtain a varnish-like composition.

  A varnish-like composition was applied on a non-alkali glass substrate whose surface was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. The obtained coating film was cured under conditions of 140 ° C. × 1 hr + 250 ° C. × 1 hr + 350 ° C. × 1 hr.

[Comparative Example 5]
(A) P-1 shown in Synthesis Example 1 as a polyamic acid, (B) DBE-712 (manufactured by Amax Co.) as a silicone compound, (D) N-methyl-2-pyrrolidone (NMP) as a solvent, 10. Prepared and mixed at a mass ratio of 0: 0.05: 89.95. This was pressure filtered with a PTFE filter having a pore size of 2.5 microns to obtain a varnish-like composition.

  A varnish-like composition was applied on a non-alkali glass substrate whose surface was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. The obtained coating film was cured under conditions of 140 ° C. × 1 hr + 250 ° C. × 1 hr + 350 ° C. × 1 hr.

[Comparative Example 6]
(A) P-1 shown in Synthesis Example 1 as a polyamic acid, (B) LE-605 (manufactured by Kyoeisha Chemical Co., Ltd.) as the fluorine compound, (D) N-methyl-2-pyrrolidone (NMP) as the solvent, 10 Prepared and mixed in a ratio of 0.0: 0.09: 89.91. This was pressure filtered with a PTFE filter having a pore size of 2.5 microns to obtain a varnish-like composition.

  A varnish-like composition was applied on a non-alkali glass substrate whose surface was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. The obtained coating film was cured under conditions of 140 ° C. × 1 hr + 250 ° C. × 1 hr + 350 ° C. × 1 hr.

[Comparative Example 7]
(A) P-1 shown in Synthesis Example 1 as polyamic acid, (C) 1: 1 reaction product of 3-aminopropyltriethoxysilane and phthalic anhydride as alkoxysilane compound, (D) N-methyl as solvent -2-pyrrolidone (NMP) was prepared and mixed at a mass ratio of 10.0: 0.05: 89.95. This was pressure filtered with a PTFE filter having a pore size of 2.5 microns to obtain a varnish-like composition.

  A varnish-like composition was applied on a non-alkali glass substrate whose surface was cleaned by an alkali cleaning method and a plasma cleaning method using a bar coater so that the film thickness after curing was 20 μm. The obtained coating film was cured under conditions of 140 ° C. × 1 hr + 250 ° C. × 1 hr + 350 ° C. × 1 hr.

[Structural analysis of composition (substrate for flexible device)]
In Examples 27 and 28 and Comparative Examples 5 to 7, the structural analysis of the flexible device substrate made of the composition coated and cured on the alkali-free glass substrate was performed using TOF-SIMS. The measurement conditions for TOF-SIMS are shown below.

[Analysis method (TOF-SIMS)]
Each sample was cut into 5 mm squares, set so that the measurement surface was on top, and subjected to TOF-SIMS measurement. First, in order to remove surface contamination, sputter cleaning was performed under the following conditions. The sputtering time was set until the Si intensity became constant.

<Sputter cleaning conditions>
(Measurement condition)
Equipment used: nanoTOF (manufactured by ULVAC-PHI)
Primary ion: Bi ₃ ⁺⁺
Acceleration voltage: 30 kV
Ion current: about 0.47 nA (as DC)
Analysis area: 200 μm × 200 μm
Analysis time: 6 sec
Detection ion: Positive ion Neutralization: Use electron gun (use + Ar monomer if necessary)

(Sputtering conditions)
Sputter ion: Ar ₂₅₀₀ ⁺
Acceleration voltage: 20 kV
Ion current: about 5 nA
Sputtering area: 600 μm × 600 μm
Sputtering time: 30 sec
Neutralization: Uses an electron gun

After removing the surface contamination, the measurement was performed under the following measurement conditions.
<Analysis conditions>
(Measurement condition)
Equipment used: nanoTOF (manufactured by ULVAC-PHI)
Primary ion: Bi ₃ ⁺⁺
Acceleration voltage: 30 kV
Ion current: about 0.47 nA (as DC)
Analysis area: 200 μm × 200 μm
Analysis time: 15 min
Detection ion: Positive ion Neutralization: Use electron gun (use + Ar monomer if necessary)

In FIG. 9, the result of m / z = 78.7-79.3 of TOF-SIMS in Example 27, Comparative Example 5, and Comparative Example 7 is shown. The vertical axis represents Total Counts (0.0005 amu). In Example 27 and Comparative Example 7, a peak (SiO ₃ H ₃ ) characteristic of an alkoxysilane compound could be detected between m / z = 78.98 and 79.00.

The obtained analysis results were judged according to the following criteria. A result is shown in Table 5. (circle): (C) It has a peak characteristic to an alkoxysilane compound.
X: (C) There is no peak characteristic of an alkoxysilane compound.

In FIG. 10, the result of m / z = 58.4-59.5 of TOF-SIMS in Example 27, Comparative Example 5, and Comparative Example 7 is shown. The vertical axis represents Total Counts (0.0009 amu). Although not described, the right end of the horizontal axis in FIG. 10 indicates 59.5. Moreover, in FIG. 11, the result of m / z = 44.5-45.5 of TOF-SIMS in Example 27, Comparative Example 5, and Comparative Example 7 is shown. The vertical axis represents Total Counts (0.0008 amu). Although not shown, the left end of the horizontal axis in FIG. 11 indicates 44.5, and the right end indicates 45.5. In Example 27 and Comparative Example 5, a characteristic peak (SiOCH ₃ ) (around m / z = 59.99 shown in FIG. 10) in the silicone part of the surfactant and a characteristic peak (C ₂ H ₅ O) (around m / z = 45.03 shown in FIG. 11) could be detected.
The obtained analysis results were judged according to the following criteria. The results are shown in Table 5.
(Circle): (B) It has a characteristic peak in surfactant.
X: (B) It does not have a characteristic peak in surfactant.

[Evaluation as a substrate for flexible devices]
The film thicknesses of the flexible device substrates (in the form of films having flexibility) obtained in Examples 27 and 28 and Comparative Examples 5 to 6 were measured with an optical film thickness meter, and judged according to the following criteria. The results are shown in Table 5.
○: Within 10 cm width, film thickness variation is 50 nm or less ×: Over 10 cm width, film thickness variation is greater than 50 nm −: Impossible to measure

[Example 29]
The laminated body obtained in Example 27 was used as a substrate for manufacturing a flexible device, and a first barrier layer was formed on the laminated body. Further, on the first barrier layer, a semiconductor layer, a gate insulating film, a gate electrode, an interlayer insulating film, a contact hole, and a source / drain electrode were sequentially formed to form a thin film transistor (TFT). Thereafter, the TFT device was peeled from the alkali-free glass substrate to obtain a flexible TFT device. The current-voltage characteristics of the obtained flexible TFT device were evaluated and confirmed to exhibit good in-plane uniformity.

[Example 30]
Using the laminate obtained in Example 28 as a substrate for manufacturing a flexible device, a first barrier layer was formed on the laminate. Further, on the first barrier layer, a semiconductor layer, a gate insulating film, a gate electrode, an interlayer insulating film, a contact hole, and a source / drain electrode were sequentially formed to form a thin film transistor (TFT). Thereafter, the TFT device was peeled from the alkali-free glass substrate to obtain a flexible TFT device. The current-voltage characteristics of the obtained flexible TFT device were evaluated and confirmed to exhibit good in-plane uniformity.

  In addition, this invention is not limited to the said embodiment, It can change and implement variously. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited to this, and can be appropriately changed within a range in which the effects of the present invention are exhibited.

  In the above embodiment, the example in which the resin composition of the present embodiment is used for a substrate of a flexible display has been described. However, the present invention is not limited to this. The present invention can also be applied to other flexible devices such as solar cell substrates, flexible wiring boards, and flexible memories.

  The present invention can be used, for example, in the production of flexible devices, particularly as a substrate, and can be suitably used, for example, in the production of flexible displays and solar cells.

  This application is based on Japanese Patent Application No. 2012-246473 filed on November 8, 2012. All this content is included here.

11 First substrate 12 First polyimide resin layer 100 Flexible display 101 First barrier layer 102 Semiconductor layer 103 Gate insulating film 104 Gate electrode 105 Interlayer insulating film 106 Contact holes 107a and 107b Drain electrode 109 Planarizing layer 110 Contact hole 111 First Electrode 112 Pixel definition film 113 Intermediate layer 114 Second electrode 201 Sealing member 202 Second substrate 203 Second polyimide resin layer 204 Second barrier layer 210 Organic light emitting device

Claims (10)

(Α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a compound having a chemical structure represented by the following general formula (1) and / or a chemical structure represented by the following general formula (2): γ) a chemical structure represented by the following general formula (3), a compound having one or more of the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, (δ) an amide group, an amino group, a carbamate group, a carboxyl group, an aryl A flexible material comprising a compound having a chemical structure represented by the following general formula (4) having at least one functional group selected from the group consisting of a group, an acid anhydride group and a polymerizable cyclic ether group Device substrate.

  The flexible device substrate according to claim 1, wherein the thickness is 10 μm to 30 μm. (Α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a compound having a chemical structure represented by the following general formula (1), (γ) a chemical structure represented by the following general formula (3), A compound having at least one selected from the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, (δ) the following general formula having at least one functional group selected from the group consisting of a carbamate group, a carboxyl group, an amide group and an aryl group (4) a compound having a chemical structure represented by:
(Α) Polyimide having a 5% pyrolysis temperature of 350 ° C. or higher, (β) 3 to 100 C—F group bonds in the molecule as nonpolar sites, and 1 to 100 in the molecules as polar sites A compound having a chemical structure represented by the following general formula (2) having a polyether group, a hydroxyl group, a carboxyl group or a sulfo group, (γ) a chemical structure represented by the following general formula (3), a hydroxyl group, a carboxyl group, and At least one selected from the group consisting of a compound having at least one member selected from the group consisting of a sulfo group, (δ) an amide group, an amino group, a carbamate group, a carboxyl group, an aryl group, an acid anhydride group, and a polymerizable cyclic ether group. A flexible device substrate comprising: a compound having a chemical structure represented by the following general formula (4) having a functional group of a species.

  A flexible device, wherein a semiconductor device is formed on the flexible device substrate according to any one of claims 1 to 3.   The flexible device according to claim 4, wherein the semiconductor device is a thin film transistor.   6. The flexible device according to claim 4, wherein the flexible device is a polysilicon semiconductor or metal oxide semiconductor driven flexible display. (Α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a compound having a chemical structure represented by the following general formula (1) and / or a chemical structure represented by the following general formula (2): γ) a chemical structure represented by the following general formula (3), a compound having one or more of the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, (δ) an amide group, an amino group, a carbamate group, a carboxyl group, an aryl A polyimide resin layer containing a compound having a chemical structure represented by the following general formula (4) having at least one functional group selected from the group consisting of a group, an acid anhydride group and a polymerizable cyclic ether group A flexible device characterized by

  The flexible device according to claim 7, wherein the polyimide resin layer has a thickness of 10 μm to 30 μm. (Α) a polyimide having a 5% thermal decomposition temperature of 350 ° C. or higher, (β) a compound having a chemical structure represented by the following general formula (1), (γ) a chemical structure represented by the following general formula (3), A compound having at least one selected from the group consisting of a hydroxyl group, a carboxyl group and a sulfo group, (δ) the following general formula having at least one functional group selected from the group consisting of a carbamate group, a carboxyl group, an amide group and an aryl group (4) a compound having a chemical structure represented by:
(Α) Polyimide having a 5% pyrolysis temperature of 350 ° C. or higher, (β) 3 to 100 C—F group bonds in the molecule as nonpolar sites, and 1 to 100 in the molecules as polar sites A compound having a chemical structure represented by the following general formula (2) having a polyether group, a hydroxyl group, a carboxyl group or a sulfo group, (γ) a chemical structure represented by the following general formula (3), a hydroxyl group, a carboxyl group, and At least one selected from the group consisting of a compound having at least one member selected from the group consisting of a sulfo group, (δ) an amide group, an amino group, a carbamate group, a carboxyl group, an aryl group, an acid anhydride group, and a polymerizable cyclic ether group. A flexible device comprising a polyimide resin layer containing a compound having a chemical structure represented by the following general formula (4) having a kind of functional group.

Forming a flexible device substrate according to any one of claims 1 to 3 on the substrate;
Peeling the flexible device substrate from the substrate;
The manufacturing method of the board | substrate for flexible devices characterized by comprising.

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