Laminate, display device, and method for manufacturing a display device

Abstract

The purpose of the present invention is to provide a multilayer body which comprises a cured resin that has high liquid repellency after a UV ozone treatment, and which exhibits high durability if used in a display device.　In order to achieve the above-described purpose, a multilayer body according to the present invention is obtained by sequentially stacking a substrate, a patterned first electrode on the substrate and a cured resin, while having an opening in at least a part of the cured resin that is positioned on the first electrode; and this multilayer body is characterized in that the analysis of the cured resin by means of X-ray photoelectron spectroscopy (XPS) satisfies specific characteristics.

Description

Technical Field

[0001] The present invention relates to a laminate, a display device, and a method for manufacturing a display device.

Background Art

[0002] In display devices having a thin display, such as smartphones, tablet PCs, and televisions, many products for forming functional layers by printing methods typified by the inkjet method have been developed. For example, in the case of an organic electroluminescence (hereinafter, "organic EL") display device, after forming a partition pattern on a substrate, functional material solutions such as a light-emitting material, a hole transport material, and an electron transport material are dropped into the openings between the partitions using the inkjet method to form an organic EL display device having a functional layer.

[0003] Generally, an organic EL display device has a drive circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first electrode and second electrode. Among these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are generally used as materials for the planarization layer and the insulating layer. In particular, photosensitive resin compositions using polyimide resins and polybenzoxazole resins are preferably used because they have high heat resistance of the resin and few gas components generated from the cured product, and can provide a highly durable organic EL display device (Patent Document 1).

[0004] When forming a functional layer by the inkjet method, it is necessary to impart liquid repellency to the upper surface of the partition for the purpose of preventing color mixing of the inks injected into adjacent openings. Further, in order to prevent white spots in the organic EL display device, the openings between the partitions need to have good wettability with respect to the ink.

[0005] In order to achieve this, a method of performing fluorination treatment by plasma irradiation on the upper surface of the partition pattern on the substrate to exhibit liquid repellency has been studied (Patent Document 2).

[0006] In addition, methods for forming partitions using a photosensitive resin composition containing an alkali-soluble resin and a liquid-repellent compound have been investigated. For example, a resist composition containing a fluorinated acrylic polymer (Patent Document 3) and a photosensitive resin composition containing a polysiloxane having an alkyl fluoride group (Patent Document 4) have been investigated. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2002-91343 [Patent Document 2] Japanese Patent Publication No. 2002-207114 [Patent Document 3] Japanese Patent Publication No. 2012-220855 [Patent Document 4] International Publication No. 2019 / 159000 [Overview of the project] [Problems that the invention aims to solve]

[0008] The technology described in Patent Document 1 has a problem in that, because the upper surface of the formed partition wall does not have liquid-repellent properties, the functional material solution dropped by the inkjet method can penetrate the partition wall and mix into nearby pixels, causing luminescence defects.

[0009] The technology described in Patent Document 2 has a problem in that the fluorination treatment causes liquid-repellent components to adhere to the openings between the partitions, resulting in insufficient ink wettability of the openings.

[0010] The technologies described in Patent Documents 3 and 4 possess sufficient liquid repellency and allow for pattern formation as a photosensitive resin composition. However, the fluorine-based acrylic polymer in Patent Document 3 has poor UV-ozone resistance, resulting in insufficient liquid repellency on the upper surface of the partition after UV-ozone treatment.

[0011] The polysiloxane containing fluorine atoms described in Patent Document 4 exhibits excellent UV-ozone resistance and can impart sufficient liquid repellency to the upper surface of the partition after UV-ozone treatment. On the other hand, the cured product has high water absorption, which poses durability problems when used in the partitions of a display device.

[0012] Therefore, the present invention aims to provide a laminate that has high durability when used in a display device, comprising a resin cured product that has high liquid-repellent properties after UV ozone treatment. [Means for solving the problem]

[0013] To solve the above problems, the present invention has the following configuration.

[0014] In other words, the laminate of the present invention is A laminate comprising a substrate, a first electrode patterned on the substrate, and a cured resin in that order, wherein at least a portion of the cured resin on the first electrode is open, A laminate in which the analysis of the cured resin by X-ray photoelectron spectroscopy (XPS) satisfies characteristic (i) and characteristic (ii). (i) The concentration of F atoms in the resin cured product, as measured from at least a portion of the surface opposite to the interface where the first electrode and the resin cured product are in contact, is 8.1 atom% or more and 30.0 atom% or less, and the concentration of Si atoms is 1.0 atom% or more and 6.0 atom% or less. (ii) The concentration of F atoms in the resin curing product, measured perpendicular to the interface where the first electrode and the resin curing product are in contact, and in the direction from the substrate to the resin curing product, and within the range of 100 to 200 nm starting from the interface where the first electrode and the resin curing product are in contact, is 0.1 atom% or more and 8.0 atom% or less. [Effects of the Invention]

[0015] The present invention provides a laminate that has high durability when used in a display device, as it comprises a resin cured product with high liquid repellency after UV ozone treatment. [Brief explanation of the drawing]

[0016] [Figure 1] This is a schematic diagram of the laminate used for evaluation in the examples. [Figure 2] This is a schematic diagram of the partition wall pattern 12 used for evaluation in the embodiment. [Figure 3] This is a schematic diagram of the partition wall pattern 12 used for evaluation in the embodiment. [Figure 4] This is a schematic diagram of a cross-section of an example of a laminate. [Figure 5] This is a schematic diagram of a cross-section of another example of a laminate. [Figure 6] This is the C1s spectrum from the XPS analysis in Example 7. [Figure 7] This is the C1s spectrum from the XPS analysis in Comparative Example 5. [Figure 8] This is the C1s spectrum from the XPS analysis in Example 11. [Figure 9] This is the C1s spectrum from the XPS analysis in Example 12. [Figure 10] This is the C1s spectrum from the XPS analysis in Example 13. [Figure 11] This is the C1s spectrum from the XPS analysis in Example 14. [Figure 12] This is the C1s spectrum from the XPS analysis in Example 16. [Figure 13] This is the C1s spectrum from the XPS analysis in Example 17. [Modes for carrying out the invention]

[0017] Embodiments of the present invention will be described in detail. <Laminate> The laminate of the present invention is a laminate in which a substrate, a first electrode patterned on the substrate, and a resin cured product are laminated in that order, and at least a portion of the resin cured product on the first electrode is open. Analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS) reveals that the laminate satisfies characteristics (i) and (ii). (i) The concentration of F atoms in the resin cured product, measured from at least a portion of the surface opposite to the interface where the first electrode and the resin cured product are in contact, is 8.1 atom% or more and 30.0 atom% or less, and the concentration of Si atoms is 1.0 atom% or more and 6.0 atom% or less. (ii) The concentration of F atoms in the resin cured product, measured perpendicular to the interface where the first electrode and the resin cured product are in contact, and in the direction from the substrate to the resin cured product, and within the range of 100 to 200 nm starting from the interface where the first electrode and the resin cured product are in contact, is 0.1 atom% or more and 8.0 atom% or less.

[0018] The resin cured product comprising the laminate of the present invention has property (i) as a surface property and property (ii) within the resin cured product. Due to these compositional properties, the laminate of the present invention comprises a resin cured product with high liquid repellency after UV ozone treatment and exhibits excellent durability when used in a display device.

[0019] Next, we will explain the properties of the cured resin product obtained by X-ray photoelectron spectroscopy (XPS) (i).

[0020] The characteristic (i) is measured from at least a portion of the surface of the resin cured product opposite to the interface where the first electrode and the resin cured product are in contact. Preferably, the measurement is taken within a range of 100 μm from the edge of the opening in the resin cured product. By measuring within this range, the liquid repellency of the resin cured product surface to functional inks can be analyzed.

[0021] The first characteristic (i) is that the concentration of F atoms is 8.1 atom% or more and 30.0 atom% or less, more preferably 15.0 atom% or more and 26 atom% or less. A concentration of F atoms of 8.1 atom% or more results in excellent liquid repellency of the surface of the cured resin. On the other hand, a concentration of F atoms of 30 atom% or less suppresses the aggregation of F atoms, allowing for the production of a cured resin with fewer defects. The second characteristic (i) is that the concentration of Si atoms is 1.0 atom% or more and 6.0 atom% or less, more preferably 1.5 atom% or more and 4.5 atom% or less. A concentration of Si atoms of 1.0 atom% or more improves the UV-ozone resistance of the cured resin, allowing for good liquid repellency even after UV-ozone treatment. On the other hand, a concentration of Si atoms of 6.0 atom% or less suppresses the aggregation of Si atoms, allowing for the production of a cured resin with fewer defects.

[0022] As a method for the laminate of the present invention to satisfy characteristic (i), for example, a method of forming a resin cured product with a photosensitive resin composition containing a compound (a-1) having a fluorinated alkyl group with 7 to 21 fluorines and 5 to 12 carbon atoms, and a compound (a-2) having a siloxane structure. A siloxane structure refers to a structure in which silicon (Si) and oxygen (O) are alternately bonded. The present invention may contain two types of compounds: a compound (a-1) having a fluorinated alkyl group with 7 to 21 fluorines and 5 to 12 carbon atoms, and a compound (a-2) having a siloxane structure. Alternatively, as with polysiloxane (A) described later, a single compound may have both a fluorinated alkyl group with 7 to 21 fluorines and 5 to 12 carbon atoms and a siloxane structure.

[0023] One method for adjusting the concentration of the F atom in characteristic (i) to the above range is to adjust the content of compound (a-1) having fluoride alkyl groups with 7 to 21 fluorines and 5 to 12 carbon atoms in the photosensitive resin composition. Increasing the content can increase the concentration of the F atom in characteristic (i), and decreasing the content can decrease the concentration of the F atom in characteristic (i). Alternatively, one can adjust the concentration of the fluoride alkyl group in compound (a-1). Increasing the concentration of the fluoride alkyl group can increase the concentration of the F atom in characteristic (i), and decreasing the concentration of the fluoride alkyl group can decrease the concentration of the F atom in characteristic (i).

[0024] One method for adjusting the concentration of Si atoms in characteristic (i) to the above range is to adjust the content of compound (a-2) having a siloxane structure in the photosensitive resin composition. Increasing the content increases the concentration of Si atoms in characteristic (i), and decreasing the content decreases the concentration of Si atoms in characteristic (i). Another method is to adjust the concentration of the siloxane structure in compound (a-2). Increasing the concentration of the siloxane structure increases the concentration of Si atoms in characteristic (i), and decreasing the concentration of the siloxane structure decreases the concentration of Si atoms in characteristic (i).

[0025] The structure of compound (a-1) having 7 to 21 fluorines and 5 to 12 carbon atoms in a fluorinated alkyl group is not particularly limited. Examples include acrylic resins copolymerized from one or more selected from the group consisting of 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, and 2-(perfluorooctyl)ethyl (meth)acrylate, and polysiloxane (A) described later. From the viewpoint of UV ozone resistance, polysiloxane (A) described later is preferred.

[0026] The structure of the compound (a-2) having a siloxane structure is not particularly limited. Examples include alkyl-modified silicone, polyether-modified silicone, and polysiloxane (A) described later. From the viewpoint of uneven distribution on the surface of the cured resin, polyether-modified silicone and polysiloxane (A) described later are preferred. Furthermore, from the viewpoint of liquid repellency, polysiloxane (A) described later is more preferred.

[0027] Examples of commercially available polyether-modified silicones include KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-642 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH8400, SH8700, SF8410 (manufactured by Toray Dow Corning Co., Ltd.), and BYK-300, BYK-306, BYK-307, BYK-320, BYK-325, and BYK-330 (manufactured by Bic Chemie).

[0028] Characteristic (i) is preferably analyzed using an XPS instrument with a detector tilt of 45° relative to the sample surface. A 45° detector tilt allows for analysis of the region near the surface of the cured resin.

[0029] Next, we will explain the properties of the cured resin product obtained by X-ray photoelectron spectroscopy (XPS) (ii).

[0030] Characteristic (ii) is measured perpendicular to the interface between the first electrode and the cured resin, and in the direction from the substrate to the cured resin, within a range of 100 to 200 nm, starting from the interface between the first electrode and the cured resin. If the thickness of the cured resin is 200 nm or less, the measurement is taken at the median thickness of the cured resin. By having F atoms inside the cured resin, the water absorption of the cured resin is reduced, suppressing electrode corrosion, and thus improving the durability of the display device.

[0031] In characteristic (ii), the concentration of F atoms is 0.1 atom% or more and 8.0 atom% or less, preferably 4.0 atom% or more and 7.5 atom% or less. A concentration of F atoms of 0.1 atom% or more reduces the water absorption of the cured resin and suppresses electrode corrosion, thereby improving the durability of the display device. On the other hand, a concentration of F atoms of 8.0 atom% or less allows for both the durability of the display device and good mechanical properties of the cured resin.

[0032] One method for producing a laminate of the present invention that satisfies characteristic (ii) is to form a resin cured product using a photosensitive resin composition containing an alkali-soluble resin (b-1) having CF3 groups. CF3 groups have little tendency to be unevenly distributed on the surface of the resin cured product, and can retain F atoms within the resin cured product.

[0033] One method for adjusting the concentration of the F atom in property (ii) to the above range is to adjust the content of the alkali-soluble resin (b-1) having CF3 groups in the photosensitive resin composition. Increasing the content can increase the concentration of the F atom in property (ii), and decreasing the content can decrease the concentration of the F atom in property (ii). Another method is to adjust the concentration of the CF3 groups in the alkali-soluble resin (b-1). Increasing the concentration of CF3 groups can increase the concentration of the F atom in property (ii), and decreasing the concentration of CF3 groups can decrease the concentration of the F atom in property (ii). The alkali-soluble resin (b-1) having CF3 groups is not limited in terms of the main chain skeleton and side chain types of the polymer constituting the resin. Examples include, but are not limited to, polyimide resins, polybenzoxazole resins, polyamideimide resins, acrylic resins, novolac resins, polyhydroxystyrene resins, phenolic resins, and polysiloxane resins. From the viewpoint of heat resistance, the alkali-soluble resin (b-1) having CF3 groups preferably contains one or more selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors of any of these, and copolymers thereof. Because these alkali-soluble resins have high heat resistance, when used in a display device, the amount of outgassing at high temperatures of 200°C or higher after heat treatment is reduced, thereby improving the durability of the display device.

[0034] The characteristic (ii) can be obtained by excavating the cured material with Ar gas cluster ions (Ar-GCIB), exposing a region perpendicular to the interface between the first electrode and the cured material, in the direction from the substrate to the cured material, and in the range of 100 to 200 nm starting from the first electrode, and then performing X-ray photoelectron spectroscopy (XPS) analysis.

[0035] In the laminate of the present invention, the thickness of the resin curing material starting from the interface where the first electrode and the resin curing material meet is preferably 0.8 to 10 μm. If the thickness is 0.8 μm or more, the functional ink can be easily retained when a functional ink is applied to an open region of the resin curing material on the first electrode. Furthermore, from the viewpoint of facilitating processing by photolithography, etc., the thickness is preferably 10 μm or less.

[0036] In the laminate of the present invention, the method for forming a resin cured product having at least a portion of the first electrode open is not particularly limited. For example, it can be formed by using the method for manufacturing a resin cured product of a photosensitive resin composition described below. Another method is to form the resin cured product on the front surface of the substrate, then mask an arbitrary area with a photoresist, and then etch the opening.

[0037] The resin cured product comprising the laminate of the present invention is not particularly limited as long as it has the above-mentioned properties (i) and (ii) determined by analysis using XPS. A resin cured product having these properties can be formed by using, for example, the photosensitive resin composition described below, thereby achieving both properties (i) and (ii). Alternatively, a resin cured product having property (i) and a resin cured product having property (ii) may be formed by laminating them together.

[0038] The laminate of the present invention includes a substrate. As the substrate, materials such as metal, glass, and resin film can be appropriately selected as they are suitable for supporting the display device and transporting it in subsequent processes. If a glass substrate is used, soda-lime glass or alkali-free glass can be used, and the thickness should be sufficient to maintain mechanical strength. Regarding the glass material, alkali-free glass is preferred because it is better to have fewer ions eluted from the glass, but soda-lime glass coated with a barrier coating such as SiO2 is also commercially available and can be used. If a resin film is used, it is preferable to include a resin material selected from polyimide, polyamide, polybenzoxazole, polyamideimide, and poly(p-xylylene), and these resin materials may be included individually or in combination. For example, when forming a resin film with polyimide, it can also be formed by applying a solution containing polyamic acid (including partially imidized polyamic acid), which is a precursor of polyimide, or soluble polyimide, to the support substrate, firing it, and then peeling the polyimide resin film from the support substrate.

[0039] The laminate of the present invention includes a first electrode patterned on a substrate. The first electrode preferably contains ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), Ag, Al, etc. The patterning of the first electrode can be carried out by known methods. For example, one method is to form the first electrode over the entire surface of the substrate by sputtering, then mask an arbitrary area with photoresist, and then etch the openings.

[0040] The laminate of the present invention may further laminate a planarizing layer between the substrate and the first electrode patterned on the substrate. When the laminate of the present invention is used in a display device, a TFT (thin-film transistor) and wiring located on the side of the TFT and connected to the TFT are often provided on a substrate such as glass. If the first electrode follows the irregularities of the wiring, appearance defects such as uneven light emission will occur. Therefore, a planarizing layer is formed on the drive circuit so as to cover the irregularities, and the first electrode is further provided on the planarizing layer. The planarizing layer preferably contains a resin material selected from polyimide, polyamide, polybenzoxazole, polyamideimide, acrylic, cardo, and poly(p-xylylene), and may contain one of these resin materials or a combination of several types.

[0041] Figure 4 shows a schematic cross-sectional view of an example of the laminate of the present invention. A planarization layer 14, a patterned first electrode 8, and a resin cured product 16 are laminated on a substrate 13 in that order, with at least a portion of the resin cured product 16 on the patterned first electrode 8 being open. The properties (i) of the resin cured product by X-ray photoelectron spectroscopy (XPS) analysis are measured from the surface 17 opposite to the interface where the first electrode and the resin cured product are in contact. It is preferable that the XPS is measured in any range of 100 μm from the edge of the opening of the resin cured product 16. Furthermore, the properties (ii) are measured perpendicular to the interface 18 where the first electrode and the resin cured product are in contact, and in the direction from the substrate to the resin cured product, in a range of 100 nm 30 to another 100 nm starting from the interface where the first electrode and the resin cured product are in contact, that is, perpendicular to the interface where the first electrode and the resin cured product are in contact, and in the direction from the substrate to the resin cured product, in any range of 100 to 200 nm 19 starting from the interface where the first electrode and the resin cured product are in contact. In the opening of the first electrode patterned on the substrate, the first electrode is assumed to exist perpendicular to the interface between the first electrode and the resin curing material, and in the direction from the substrate to the resin curing material, within a range of 100 to 200 nm from the interface between the first electrode and the resin curing material. The measurement is taken at any point within the range of 100 to 200 nm from the height of the first electrode. If there is variation in the thickness of the first electrode, the first electrode with an average thickness at the opening edge of the patterned first electrode is assumed to exist.

[0042] In the analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS), the laminate of the present invention is as follows: The C1s spectrum [A] of the resin cured product, measured from at least a portion of the surface of the resin cured product opposite to the interface where the first electrode and the resin cured product are in contact, The C1s spectrum [B] of the resin cured product, measured perpendicular to the interface where the first electrode and the resin cured product are in contact, and in the direction from the substrate to the resin cured product, and starting from the interface where the first electrode and the resin cured product are in contact, is: It is preferable that the characteristics (iii) and (iv) are satisfied. (iii) The peak height of the peak originating from the CF2 group, which has a peak top in the bond energy range of 290–292 eV in the C1s spectrum [B], is higher than the peak height of the same peak in the C1s spectrum [A]. (iv) The peak height of the peak originating from the CF3 group, which has its peak top in the bond energy range of 292–294 eV in the C1s spectrum [A], is higher than the peak height of the same peak in the C1s spectrum [B].

[0043] The C1s spectrum [A] is the spectrum of the cured resin surface, measured from at least a portion of the surface opposite to the interface between the first electrode and the cured resin. On the other hand, the C1s spectrum [B] is the spectrum of the inside of the cured resin, measured perpendicular to the interface between the first electrode and the cured resin, in the direction from the substrate to the cured resin, and starting from the interface between the first electrode and the cured resin, in a range of 100 to 200 nm. If the thickness of the cured resin is 200 nm or less, the measurement is taken at the median thickness of the cured resin.

[0044] The resin cured product comprising the laminate of the present invention exhibits property (iii), thereby providing excellent liquid repellency on the surface of the resin cured product. Structures exhibiting peaks originating from CF2 groups with peak tops in the bond energy range of 290 to 292 eV include, for example, heptafluoropentyl groups, nonafluorohexyl groups, tridecafluorooctyl groups, heptadecafluorodecyl groups, and 5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl groups, which have the property of being unevenly distributed on the surface of the resin cured product and can impart good liquid repellency to the surface of the resin cured product.

[0045] The resin cured product comprising the laminate of the present invention exhibits characteristic (iv), thereby reducing the water absorption of the resin cured product and suppressing electrode corrosion, thus improving the durability of the display device. The CF3 group has little tendency to be unevenly distributed on the surface of the resin cured product, and can retain F atoms inside the resin cured product.

[0046] Characteristics (iii) and (iv) are preferably determined by comparing C1s spectra [A] and C1s spectra [B] measured with the same XPS apparatus. The C1s spectrum [A] is measured from at least a portion of the surface of the resin cured product opposite to the interface where the first electrode and the resin cured product are in contact. Subsequently, the resin cured product is excavated with Ar gas cluster ions (Ar-GCIB), and the C1s spectrum [B] can be measured after exposing a region perpendicular to the interface where the first electrode and the resin cured product are in contact, in the direction from the substrate to the cured product, and in the range of 100 to 200 nm starting from the interface between the first electrode and the resin cured product.

[0047] Figure 4 shows a schematic cross-sectional view of an example of the laminate of the present invention. A planarization layer 14, a patterned first electrode 8, and a resin cured product 16 are laminated on a substrate 13 in that order, with at least a portion of the resin cured product 16 on the first electrode 8 being open. In the analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS), the C1s spectrum [A] is measured from the surface 17 opposite to the interface where the first electrode and the resin cured product are in contact. It is preferable to measure within a range of 100 μm from the edge of the opening of the resin cured product 16. Furthermore, the C1s spectrum [B] is measured perpendicular to the interface 18 where the first electrode and the cured resin are in contact, and in the direction from the substrate to the cured resin, in a range of 100 nm 30 to 100 nm starting from the interface where the first electrode and the cured resin are in contact, that is, perpendicular to the interface where the first electrode and the cured resin are in contact, and in the direction from the substrate to the cured resin, and in a range of 100 to 200 nm 19 starting from the interface where the first electrode and the cured resin are in contact. At the opening of the patterned first electrode, the first electrode is assumed to exist perpendicular to the interface where the first electrode and the cured resin are in contact, and in the direction from the substrate to the cured resin, and in a range of 100 to 200 nm 19 starting from the interface where the first electrode and the cured resin are in contact, and the measurement is taken at a range of 100 to 200 nm 19 from the height of the first electrode. If there is variation in the thickness of the first electrode, it is assumed that the first electrode exists at the opening of the patterned first electrode with an average thickness at the opening edge.

[0048] As a method for forming the resin cured product comprising the laminate of the present invention, for example, a resin cured product satisfying properties (i) to (iv) can be formed by using the photosensitive resin composition described below. Alternatively, a resin cured product having properties (i) and (iii) may be laminated with a resin cured product having properties (ii) and (iv).

[0049] In the laminate of the present invention, it is preferable that the resin cured product contains a compound having an imide ring structure. The compound having an imide ring structure is preferably a structure derived from a polyimide resin or a residue thereof. Examples of polyimide resins include the polyimides described in alkali-soluble resin (B) below, polyamide-imides, their precursors, and copolymers thereof. By including a compound having an imide ring structure in the resin cured product, the amount of outgassing at high temperatures is reduced, and when the laminate is used in an organic EL display device, it is possible to obtain an organic EL display device with small pixel shrinkage and excellent durability.

[0050] In the laminate of the present invention, it is preferable that the cured resin product contains a compound having an indene structure. The compound having an indene structure is preferably a structure derived from a quinone diazide compound or a residue thereof. Examples of quinone diazide compounds include the quinone diazide compound (C-2) described later. By including a quinone diazide compound in the photosensitive resin composition described below, a positive-type photosensitive resin composition can be obtained.

[0051] In the laminate of the present invention, when the cured resin is a cured product of a positive-type photosensitive resin composition, the surface of the cured resin formed by the "half-exposure" described later does not have liquid-repellent properties and can have good ink-coating properties. That is, a cured resin with a liquid-repellent surface and a cured resin with a hydrophilic surface can be formed in a single photolithography.

[0052] In the laminate of the present invention, the resin cured product is a stepped resin cured product having a first stage with a thickness of 0.8 μm to 10.0 μm starting from the interface between the first electrode and the resin cured product, and a second stage with a thickness of 0.1 μm to 0.7 μm starting from the interface between the first electrode and the resin cured product. Furthermore, it is preferable that in analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS), the first stage of the resin cured product satisfies characteristic (i) and the second stage of the resin cured product satisfies characteristic (v). (v) The concentration of F atoms measured from at least a portion of the surface of the resin cured product opposite to the interface between the first electrode and the resin cured product is 0.1 atom% or more and 20.0 atom% or less, and the concentration of Si atoms is 0.1 atom% or more and 0.9 atom% or less, and the peak with the maximum peak height measured in the bond energy range of 290 to 295 eV in the C1s spectrum is a peak originating from a CF3 group with a peak top in the range of 292 to 294 eV.

[0053] The first stage, having a thickness of 0.8 μm to 10.0 μm starting from the interface between the first electrode and the cured resin, is a cured resin with a liquid-repellent surface having characteristic (i). If the thickness is 0.8 μm or more, the functional ink can be easily retained when a functional ink is applied to an open region of the cured resin on the first electrode. Furthermore, from the viewpoint of facilitating processing by photolithography, etc., a thickness of 10.0 μm or less is preferable.

[0054] The second stage, having a thickness of 0.1 μm to 0.7 μm starting from the interface between the first electrode and the cured resin, is a cured resin with a hydrophilic surface possessing characteristic (v). Characteristic (v) is a characteristic of the cured resin surface measured from at least a portion of the surface opposite to the interface where the first electrode and the cured resin contact in the second stage of the cured resin. By exhibiting characteristic (v), the cured resin has a hydrophilic surface, low water absorption, and a laminate with excellent durability when used in a display device. A thickness of 0.1 μm or more allows the cured resin to exhibit insulating properties. On the other hand, a thickness of 0.7 μm or less suppresses defects such as white spots in the functional layer when a functional ink is continuously inkjet coated from an open region on the cured resin on the first electrode to the second stage of the cured resin to form a functional layer.

[0055] In characteristic (v), the concentration of F atoms measured from at least a portion of the surface of the resin cured product opposite to the interface between the first electrode and the resin cured product is 0.1 atom% or more and 20.0 atom% or less, preferably 8.0 atom% or more and 18.0 atom% or less. A concentration of F atoms of 0.1 atom% or more results in a low water absorption rate of the resin cured product, improving its durability when used in a display device. On the other hand, a concentration of F atoms of 20.0 atom% suppresses the aggregation of F atoms. Furthermore, in characteristic (v), the peak with the maximum peak height measured in the binding energy range of 290 to 295 eV in the C1s spectrum measured from at least a portion of the surface opposite to the interface between the first electrode and the resin cured product is a peak originating from a CF3 group with a peak top in the range of 292 to 294 eV. The CF3 structure of fluorine allows for both the hydrophilicity of the resin cured product surface and the durability of the display device.

[0056] In characteristic (v), the concentration of Si atoms measured from the surface of the resin cured product opposite to the interface where the first electrode and the resin cured product are in contact is 0.1 atom% or more and 0.9 atom% or less, more preferably 0.1 atom% or more and 0.5 atom% or less. A Si atom concentration of 0.1 atom% or more improves adhesion to the electrode and improves the durability of the display device. A Si atom concentration of 0.9 atom% or less allows the surface of the resin cured product to exhibit good hydrophilicity.

[0057] It is preferable to measure characteristic (i) within a range of 100 μm from the edge of the opening of the first stage of the resin cured product. By measuring within this range, the liquid repellency of the surface of the first stage of the resin cured product to the functional ink can be analyzed. It is also preferable to measure characteristic (v) within a range of 100 μm from the edge of the opening of the second stage of the resin cured product. By measuring within this range, the hydrophilicity of the surface of the second stage of the resin cured product to the functional ink can be analyzed.

[0058] As a method for the laminate of the present invention to satisfy characteristic (v), for example, a method of forming a resin cured product with a photosensitive resin composition containing an alkali-soluble resin (b-1) having CF3 groups and an alkali-soluble resin (b-2) having a siloxane structure. The alkali-soluble resin (b-1) having CF3 groups may also have a siloxane structure. By including the alkali-soluble resin (b-1) having CF3 groups, the peak with the maximum peak height measured in the bond energy range of 290 to 295 eV in the C1s spectrum becomes a peak originating from the CF3 group with a peak top in the range of 292 to 294 eV. The CF3 group has little tendency to be unevenly distributed on the surface of the resin cured product and can retain F atoms inside the resin cured product.

[0059] One method for adjusting the concentration of F atoms in characteristic (v) to the above range is to adjust the content of the alkali-soluble resin (b-1) having CF3 groups in the photosensitive resin composition. Increasing the content can increase the concentration of F atoms in characteristic (v), and decreasing the content can decrease the concentration of F atoms in characteristic (v). Alternatively, one can adjust the concentration of CF3 groups in the alkali-soluble resin (b-1). Increasing the concentration of CF3 groups can increase the concentration of F atoms in characteristic (v), and decreasing the concentration of CF3 groups can decrease the concentration of F atoms in characteristic (v).

[0060] One method for adjusting the concentration of Si atoms in characteristic (v) to the above range is to adjust the content of the alkali-soluble resin (b-2) having a siloxane structure in the photosensitive resin composition. Increasing the content increases the concentration of Si atoms in characteristic (v), and decreasing the content decreases the concentration of Si atoms in characteristic (v). Another method is to adjust the concentration of the siloxane structure in the alkali-soluble resin (b-2). Increasing the concentration of the siloxane structure increases the concentration of Si atoms in characteristic (v), and decreasing the concentration of the siloxane structure decreases the concentration of Si atoms in characteristic (v).

[0061] Characteristic (v) is preferably analyzed using an XPS instrument with a detector tilt of 45° relative to the sample surface. A 45° detector tilt allows for analysis of the region near the surface of the cured resin.

[0062] A laminate comprising a stepped resin cured product having the first and second stages can be formed, for example, from resin cured products having at least characteristic (i), characteristic (ii), and characteristic (v). Such a laminate can be formed, for example, by using a photosensitive resin composition described below. Specifically, when a positive-type photosensitive resin composition is used, a first stage having characteristic (i) can be formed in the unexposed area, a second stage having characteristic (v) can be formed in the "half-exposed area" described later, and the inside of the resin cured product can exhibit characteristic (ii). Alternatively, a resin cured product having characteristic (i) and a resin cured product having characteristic (v) may be laminated together. When two types of resin cured products are laminated, at least one type of resin cured product has characteristic (ii). From the viewpoint of the durability of the display device, it is more preferable that both types of resin cured products have characteristic (ii).

[0063] As an example of a laminate comprising a stepped resin cured material having the first and second stages, there is a laminate as shown in Figure 2 or Figure 3, in which a first electrode 8 patterned on a substrate and a resin cured material are stacked in that order, and the resin cured material comprises a first stage 9 that defines the area to be inkjet coated, and a second stage 10 that defines two or more areas arranged within the first stage. A functional layer 11, which is continuously arranged on the first electrode 8 patterned on the substrate and the second stage 10 of the resin cured material, can be formed by an inkjet coating method.

[0064] A laminate comprising a stepped resin cured product having the first and second stages described above can be formed using a photosensitive resin composition. Specifically, a photosensitive resin dried product obtained from a positive-type photosensitive resin composition is prepared on a first electrode 8 patterned on a substrate, and an unexposed area, a half-exposed area, and an exposed area are formed in a subsequent exposure process. Subsequently, a development process and a heat treatment process are performed to form the first stage 9 of the resin cured product in the unexposed area and the second stage 10 of the resin cured product in the half-exposed area, while the exposed area exposes the first electrode 8 patterned on the substrate. Alternatively, as shown in Figure 3, the second stage 10 of the resin cured product and the first stage 9 of the resin cured product may be laminated on the first electrode 8 patterned on the substrate in that order.

[0065] Figure 5 shows a schematic cross-sectional view of another example of the laminate of the present invention. A planarization layer 14, a patterned first electrode 8, and a resin curing product are laminated on a substrate 13 in that order, with at least a portion of the resin curing product being open on the first electrode 8, and having a first stage 9 and a second stage 10 of the resin curing product. The properties (i) of the resin curing product, determined by X-ray photoelectron spectroscopy (XPS), are measured from the surface 20 opposite to the interface where the first electrode of the first stage of the resin curing product contacts the resin curing product. The properties (v) are measured from the surface 21 opposite to the interface where the first electrode of the second stage of the resin curing product contacts the resin curing product. Characteristics (ii) are measured perpendicular to the interface 18 where the first electrode and the resin cured product are in contact, and in the direction from the substrate to the resin cured product, in a range of 100 nm 30 to another 100 nm starting from the interface where the first electrode and the resin cured product are in contact, that is, perpendicular to the interface where the first electrode and the resin cured product are in contact, and in the direction from the substrate to the resin cured product, and in any of the ranges 19 from 100 to 200 nm starting from the interface where the first electrode and the resin cured product are in contact. In the opening of the patterned first electrode, the first electrode is assumed to exist perpendicular to the interface where the first electrode and the resin cured product are in contact, and in the direction from the substrate to the resin cured product, and is measured in any of the ranges 19 from 100 to 200 nm starting from the height of the first electrode. If there is variation in the thickness of the first electrode, it is assumed that the first electrode has an average thickness at the opening edge in the opening of the patterned first electrode. Next, a functional layer 11, which is continuously arranged on the first electrode 8 patterned on the substrate and the second stage 10 of the cured resin, can be formed by an inkjet coating method.

[0066] In the laminate of the present invention, the cured resin product is not particularly limited as long as it has the above-described properties. As a method for forming a cured resin product that satisfies properties (i) to (v), for example, a method of forming a cured resin product using a photosensitive resin composition containing a compound having 7 to 21 fluorine atoms and 5 to 12 carbon atoms in a fluoride alkyl group (a-1), a compound having a siloxane structure (a-2), an alkali-soluble resin having a CF3 group (b-1), and an alkali-soluble resin having a siloxane structure (b-2).

[0067] From the viewpoint of UV-ozone resistance and liquid repellency of the cured resin, preferred structures for the compound having 7 to 21 fluorine groups and 5 to 12 carbon atoms (a-1) and the compound having a siloxane structure (a-2) include the siloxane (A) described later. Furthermore, from the viewpoint of heat resistance, preferred structures for the alkali-soluble resin having a CF3 group (b-1) and the alkali-soluble resin having a siloxane structure (b-2) include the alkali-soluble resin (B) described later.

[0068] Let's explain polysiloxane (A).

[0069] By including polysiloxane (A) in the photosensitive resin composition, high liquid repellency can be imparted to the surface of the cured resin. Furthermore, the polysiloxane in the main chain has high UV-ozone resistance, making it easier to impart high liquid repellency to the surface of the cured resin after UV-ozone treatment.

[0070] Polysiloxane (A) has a repeating unit structure represented by formula (1) and / or formula (2).

[0071] [ka]

[0072] R in the repeating unit structure shown in equation (1) and / or equation (2) fThe alkyl fluoride is a fluoride alkyl group having 7 to 21 fluorines and 5 to 12 carbon atoms. More preferably, it is a fluoride alkyl group having 9 to 13 fluorines and 6 to 8 carbon atoms. By using an alkyl fluoride with 7 or more fluorines and 5 or more carbon atoms, the cured resin product is more likely to satisfy characteristic (i), and the upper surface of the cured resin product can exhibit better liquid repellency. Furthermore, by using an alkyl fluoride with 21 or fewer fluorines and 12 or more carbon atoms, good compatibility with alkali-soluble resins, as described later, is more easily obtained. In addition, to reduce the burden on the environment, alkyl fluoride with 13 or fewer fluorines and 8 or fewer carbon atoms is more preferable.

[0073] R f The alkyl fluoride is preferably composed of a CF2 group. Having a CF2 group in the alkyl fluoride makes it easier for the cured resin to satisfy property (iii), and the upper surface of the cured resin can exhibit better liquid repellency. Specific examples of alkyl fluoride having a CF2 group include heptafluoropentyl group, nonafluorohexyl group, tridecafluorooctyl group, heptadecafluorodecyl group, and 5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl group. From the viewpoint of liquid repellency and environmental impact, nonafluorohexyl group and tridecafluorooctyl group, which have 9 to 13 fluorines and 6 to 8 carbon atoms, are preferred.

[0074] The polysiloxane (A) preferably contains 5 to 30 mol% of the total repeating unit structure represented by formula (1) and the repeating unit structure represented by formula (2) in 100 mol% of the total repeating unit structure of the polysiloxane (A). More preferably, it is 10 to 25 mol%. By containing 5 mol% or more of the repeating unit structure represented by formula (1) and / or the structure represented by formula (2), the cured resin product is more likely to satisfy property (i) and exhibit better liquid repellency. Furthermore, by having 30 mol% or less, aggregation of alkyl fluoride can be reduced.

[0075] Furthermore, it is preferable that polysiloxane (A) has a repeating unit structure of (I) and (II). (I) Repeating unit structure shown by equation (3) and / or repeating unit structure shown by equation (4) (II) Repeating unit structure shown by equation (5) and / or repeating unit structure shown by equation (6)

[0076] [ka]

[0077] R 1 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. 2 R is an aryl group having 6 to 15 carbon atoms. 3 R is a single bond or an alkylene group with 1 to 4 carbon atoms, and Y is 1 or 2. 4 * indicates an organic group with 2 to 20 carbon atoms that contains an acidic group. * indicates a covalent bond.

[0078] The polysiloxane (A) preferably has a repeating unit structure represented by formula (3) and / or formula (4). Since the repeating unit structure represented by formula (3) and / or formula (4) has an aryl group, the steric hindrance of the aryl group suppresses the aggregation of the aforementioned alkyl fluoride, making it easier to obtain a cured product with fewer defects.

[0079] In the repeating unit structure shown in equation (3) and / or equation (4), R 2 This refers to an aryl group having 6 to 15 carbon atoms. Specific examples include the phenyl group, 4-methylphenyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, 4-t-butylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-phenylethyl group, 4-hydroxybenzyl group, and the structure shown in formula (7).

[0080] [ka]

[0081] Here, * represents a covalent bond directly connecting to R 3 When R 3 is a single bond, it represents a covalent bond directly connecting to the silicon atom. a is an integer from 1 to 3. From the perspective of chemical resistance, a is preferably 1 to 2, and more preferably a is 1. When these specific examples are shown in a general formula, the following structures can be cited.

[0082]

Chemical formula

[0083] In the repeating unit structure represented by formula (3) and / or the repeating unit structure represented by formula (4), at least one of R 2 is preferably a 1-naphthyl group, a 2-naphthyl group, or a structure represented by formula (7) from the perspectives of the effect of suppressing aggregation of the alkyl fluoride group and the control of polymerizability. Also, from the perspective of controlling polymerizability, Y in the repeating unit structure represented by formula (4) is more preferably 1.

[0084] In the repeating unit structure represented by formula (3) and / or the repeating unit structure represented by formula (4), R 3 is a single bond or an alkylene group having 1 to 4 carbon atoms. Specific examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a t-butylene group, and the like.

[0085] In 100 mol% of the total repeating unit structure of polysiloxane (A), it is preferable to contain 20 to 70 mol% in total of the repeating unit structure represented by formula (3) and the repeating unit structure represented by formula (4). More preferably, it is 30 to 60 mol%. By containing 20 mol% or more in total of the repeating unit structure represented by formula (3) and the repeating unit structure represented by formula (4), it is likely to exhibit a good effect of suppressing aggregation of the alkyl fluoride group. Also, from the perspective of controlling polymerizability, 70 mol% or less is preferable.

[0086] Polysiloxane (A) has a repeating unit structure represented by formula (5) and / or formula (6). The repeating unit structure represented by formula (5) and / or formula (6) has an organic group having 2 to 20 carbon atoms that contains an acidic group, which improves solubility in alkaline developers and reduces residue at the openings. In addition, it is easier to suppress the aggregation of the aforementioned alkyl fluoride, making it easier to obtain a cured product with fewer defects.

[0087] The C2-C20 organic group containing an acidic group is preferably an organic group containing at least one acidic group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, and a sulfonic acid group, and more preferably has the structure represented by formula (8) or formula (9).

[0088] [ka]

[0089] R 15 * indicates a single bond or an alkylene group with 1 to 10 carbon atoms. * indicates a covalent bond.

[0090] From the perspective of residue at the opening, R 4 It is more preferable that the group has a carboxyl group. Furthermore, it is even more preferable that the group is a dicarboxyl group obtained by hydrolysis of a carboxylic acid anhydride group. Specific examples of organic groups with 2 to 20 carbon atoms that contain an acidic group include 2-hydroxyethyl group, 3-hydroxypropyl group, bis(2-hydroxyethyl)-3-aminopropyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, and the structures (α) and (β) shown below. As for structures having a carboxyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, structure (α), and structure (β) are preferred, with structure (α) and structure (β) being more preferred.

[0091] [ka]

[0092] Here, * indicates a covalent bond directly connected to the silicon atom.

[0093] It is preferable that the total amount of the repeating unit structure represented by formula (5) and the repeating unit structure represented by formula (6) is 1 to 40 mol% of the total repeating unit structure of polysiloxane (A). More preferably, it is 5 to 30 mol%. By including 1 mol% or more of the total repeating unit structure represented by formula (5) and the repeating unit structure represented by formula (6), better ink wettability and compatibility of the opening can be obtained. Furthermore, by having 40 mol% or less, better liquid repellency can be obtained.

[0094] Polysiloxane (A) may have a repeating unit structure represented by formula (10) and / or formula (11).

[0095] [ka]

[0096] R 1 A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R 5 R f , R 2 -R 3 -, R 4 This shows organic groups with 1 to 10 carbon atoms other than those listed above.

[0097] R 5 R f , R 2 -R 3 -, R 4 Any organic group with 1 to 10 carbon atoms other than those specified is not particularly limited. 5Specific examples include hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and cyclohexyl groups; amino group-containing groups such as 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl, and N-β-(aminoethyl)-γ-aminopropyl; cyano group-containing groups such as β-cyanoethyl; glycidoxymethyl, α-glycidoxyethyl, α-glycidoxypropyl, β-glycidoxypropyl, γ-glycidoxypropyl, α-glycidoxybutyl, and β-glycidoxybutyl. Examples include epoxy group-containing groups such as chloropropylmethyl group, γ-glycidoxybutyl group, σ-glycidoxybutyl group, (3,4-epoxycyclohexyl)methyl group, 3-(3,4-epoxycyclohexyl)propyl group, and 4-(3,4-epoxycyclohexyl)butyl group; chloro group-containing groups such as 3-chloropropylmethyl group; fluoro group-containing groups such as 2,2,2-trifluoroethyl group and 3,3,3-trifluoropropyl group; α,β-unsaturated ester group-containing groups such as γ-acryloylpropyl group and γ-methacryloylpropyl group; and vinyl group-containing groups such as vinyl group and styryl group.

[0098] In equations (1), (3), (5), and (10), R 1 The group is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 acyl group, or a C6-C15 aryl group. From the viewpoint of controlling polymerizability, a hydrogen atom and a C1-C6 alkyl group are preferred. Specific examples of C1-C6 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. Of these, a hydrogen atom, methyl, and ethyl groups are more preferred from the viewpoint of controlling polymerizability.

[0099] In the photosensitive resin composition of the present invention, it is preferable that the content of polysiloxane (A) is 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of alkali-soluble resin (B). More preferably, it is 0.2 parts by mass or more and 5 parts by mass or less. When the content of polysiloxane (A) is 0.1 parts by mass or more, the cured resin product is more likely to satisfy characteristic (i), and better liquid repellency is more easily obtained. Furthermore, when it is 10 parts by mass or less, the aggregation of the aforementioned alkyl fluoride is more easily suppressed.

[0100] (A) Polysiloxanes can be obtained by hydrolysis and polycondensation of alkoxysilanes represented by the following general formulas (12), (13), (14), and (15) in a solvent. (A) Polysiloxanes obtained in this manner are preferred.

[0101] [ka]

[0102] R f These are alkyl fluorides with 7 to 21 fluorine atoms and 5 to 12 carbon atoms, R 1 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. 2 R is an aryl group having 6 to 15 carbon atoms. 3 R is a single bond or an alkylene group with 1 to 4 carbon atoms, and Y is 1 or 2. 4 R is an organic group with 2 to 20 carbon atoms that contains an acidic group. 5 It is an organic group with 1 to 10 carbon atoms.

[0103] The hydrolysis reaction is preferably carried out in a solvent by adding an acid catalyst and water to the alkoxysilane represented by general formulas (12), (13), (14), and (15), and then reacting at room temperature to 110°C for 1 to 180 minutes. By carrying out the hydrolysis reaction under these conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 40 to 105°C.

[0104] Furthermore, after obtaining a silanol compound by hydrolysis, it is preferable to heat the reaction solution at a temperature above 50°C and below the boiling point of the solvent for 1 to 100 hours to carry out a condensation reaction. In addition, it is possible to add an acid or base catalyst or reheat the mixture in order to increase the degree of polymerization of the siloxane compound obtained by the condensation reaction.

[0105] Various conditions in the hydrolysis reaction can be appropriately set, taking into consideration the reaction scale, size, and shape of the reaction vessel. For example, by setting the acid concentration, reaction temperature, and reaction time, a polysiloxane of the desired degree of polymerization can be obtained.

[0106] Deionized water is preferred for use in the hydrolysis reaction. The amount of water can be selected arbitrarily, but it is preferable to use 1.0 to 4.0 moles per mole of alkoxysilane compound.

[0107] The solvents used in the hydrolysis reaction include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, propylene glycol, benzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 4-isopropylbenzyl alcohol, 1-phenylethyl alcohol, 2-phenyl-2-propanol, 2-ethylbenzyl alcohol Alcohol-based solvents such as dipropyl alcohol, 3-ethylbenzyl alcohol, and 4-ethylbenzyl alcohol; ether-based solvents such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; γ-butyrolactone, δ-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-propyl acetate Examples include ester solvents such as ethyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetoacetate, and cyclohexanol acetate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyrate, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropylene urea; and aromatic hydrocarbons such as toluene and xylene.

[0108] Acid catalysts used in hydrolysis reactions include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphate, polycarboxylic acid or its anhydride, and ion exchange resins. Acidic aqueous solutions using formic acid, acetic acid, or phosphoric acid are particularly preferred.

[0109] The preferred content of the acid catalyst is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, per 100 parts by mass of the total alkoxysilane compound used in the hydrolysis reaction. Furthermore, the acid catalyst content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. Here, the total amount of alkoxysilane compound refers to the amount including all of the alkoxysilane compound, its hydrolysates, and their condensates, and the same applies hereinafter. By using 0.05 parts by mass or more of acid catalyst, hydrolysis proceeds smoothly, and by using 10 parts by mass or less, the hydrolysis reaction can be easily controlled.

[0110] Furthermore, from the viewpoint of storage stability of the composition, it is preferable that the polysiloxane solution after hydrolysis and partial condensation does not contain the catalyst, and the catalyst can be removed as needed. There are no particular restrictions on the removal method, but water washing and / or treatment with an ion exchange resin are preferred in terms of ease of operation and removal efficiency. Water washing is a method in which the polysiloxane solution is diluted with a suitable hydrophobic solvent, and the organic layer obtained by washing it several times with water is concentrated using an evaporator or the like. Treatment with an ion exchange resin is a method in which the polysiloxane solution is brought into contact with a suitable ion exchange resin.

[0111] (A) The weight-average molecular weight (Mw) of the polysiloxane is not particularly limited, but is preferably 500 or more, more preferably 1,500 or more, in terms of polystyrene as measured by gel per emission chromatography (GPC). It is also preferably 20,000 or less, and even more preferably 10,000 or less.

[0112] Next, we will explain alkali-soluble resin (B).

[0113] In this invention, an alkali-soluble resin refers to a resin having a dissolution rate of 50 nm / min or more, as defined below. More specifically, it refers to a resin in which a solution of a resin dissolved in γ-butyrolactone is coated onto a silicon wafer, pre-baked at 120°C for 4 minutes to form a pre-baked film with a thickness of 10 μm ± 0.5 μm, the pre-baked film is immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ± 1°C for 1 minute, and then rinsed with pure water, and the dissolution rate determined from the thickness reduction is 50 nm / min or more.

[0114] The alkali-soluble resin (B) preferably has alkali-soluble groups in its structural units and / or at the ends of its main chain in order to impart alkali solubility. An alkali-soluble group refers to a functional group that increases solubility in an alkaline solution by interacting with or reacting with an alkali. Preferred alkali-soluble groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups.

[0115] The alkali-soluble resin (B) is not limited in terms of the type of main chain skeleton and side chains of the polymer constituting the resin, as long as it has the aforementioned alkali-soluble group structure. Examples include, but are not limited to, polyimide resins, polybenzoxazole resins, polyamide-imide resins, acrylic resins, novolac resins, polyhydroxystyrene resins, phenolic resins, and polysiloxane resins.

[0116] Furthermore, it is preferable that the alkali-soluble resin (B) has CF3 groups. Having CF3 groups makes it easier for the cured resin to satisfy properties (ii) and (iv), reduces the water absorption of the cured resin and suppresses electrode corrosion, thereby further improving the durability of the display device. CF3 groups have little tendency to be unevenly distributed on the surface of the cured resin and can retain F atoms inside the cured resin. In addition, having CF3 groups contributes to the concentration of F atoms and the C1s spectrum in property (v) of the cured resin. Since CF3 groups do not exhibit liquid repellency, it is easier to achieve both the hydrophilicity of the cured resin surface and the durability of the display device.

[0117] The alkali-soluble resin (B) preferably has a siloxane structure. Having a siloxane structure contributes to the concentration of Si atoms in the properties (v) of the cured resin. Furthermore, it improves adhesion to the electrodes and can further improve the durability of the display device.

[0118] The alkali-soluble resin (B) included in the photosensitive resin composition preferably has an imide ring structure. More preferably, it contains one or more selected from the group consisting of polyimide, polyamide-imide, their precursors, and copolymers thereof. These alkali-soluble resins may be used individually or in combination of multiple alkali-soluble resins. Having an imide ring structure reduces outgassing at high temperatures, and when the laminate is used in an organic EL display device, pixel shrinkage is reduced, resulting in an organic EL display device with superior durability. Furthermore, polybenzoxazole and / or its precursors may be included as a resin with high heat resistance.

[0119] Polyimides can be obtained, for example, by reacting tetracarboxylic acids or tetracarboxylic dianhydrides, tetracarboxylic diester dichlorides, etc., with diamines or diisocyanate compounds, trimethylsilylated diamines, etc. Polyimides have tetracarboxylic acid residues and diamine residues. Alternatively, polyimides can be obtained by dehydrating and cyclizing polyamic acid, one of the polyimide precursors obtained by reacting tetracarboxylic dianhydrides with diamines, by heat treatment. During this heat treatment, a solvent that forms an azeotrope with water, such as m-xylene, can also be added. Alternatively, they can be obtained by dehydrating and cyclizing by chemical heat treatment with a dehydration condensation agent such as a carboxylic acid anhydride or dicyclohexylcarbodiimide, or a base such as triethylamine, as a cyclization catalyst. Or, they can be obtained by adding a weakly acidic carboxylic acid compound and dehydrating and cyclizing by heat treatment at a low temperature of 100°C or less.

[0120] Polybenzoxazoles can be obtained, for example, by reacting a bisaminophenol compound with a dicarboxylic acid, a dicarboxylic acid chloride, or a dicarboxylic acid active ester. Polybenzoxazoles have dicarboxylic acid residues and bisaminophenol residues. Alternatively, polybenzoxazoles can be obtained by dehydrating and cyclizing a polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid, through heat treatment. Or, they can be obtained by dehydrating and cyclizing through chemical treatment with the addition of phosphoric anhydride, a base, a carbodiimide compound, etc.

[0121] Examples of polyimide precursors include polyamic acid, polyamic acid esters, polyamic acid amides, and polyisoimides. For example, polyamic acid can be obtained by reacting tetracarboxylic acid or tetracarboxylic dianhydride, tetracarboxylic diester dichloride, etc., with diamine or diisocyanate compounds, or trimethylsilylated diamines. Polyimides can be obtained, for example, by dehydrating and cyclizing the polyamic acid obtained by the above method through heating or chemical treatment with acids or bases.

[0122] Examples of polybenzoxazole precursors include polyhydroxyamides. For example, polyhydroxyamides can be obtained by reacting bisaminophenol with dicarboxylic acids, dicarboxylic acid chlorides, or dicarboxylic acid active esters. Polybenzoxazoles can be obtained, for example, by dehydrating and cyclizing the polyhydroxyamide obtained by the above method through heating or chemical treatment with phosphoric anhydride, a base, or a carbodiimide compound.

[0123] Polyamide-imide precursors can be obtained, for example, by reacting tricarboxylic acids, corresponding tricarboxylic acid anhydrides, or tricarboxylic acid anhydride halides with diamines or diisocyanates. Polyamide-imides can be obtained, for example, by dehydrating and cyclizing the precursors obtained by the above methods through heating or chemical treatment with acids or bases.

[0124] Copolymers of polyimides, polybenzoxazoles, polyamideimides, or their precursors may be obtained through block copolymerization, random copolymerization, alternating copolymerization, graft copolymerization, or a combination thereof. For example, block copolymers can be obtained by reacting polyhydroxyamide with tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, or tetracarboxylic diester dichloride. Furthermore, dehydration and ring closure can be achieved by heating or chemical treatment with acids or bases.

[0125] Polyimides, polybenzoxazoles, or polyamideimides, their precursors, and copolymers thereof preferably have CF3 groups in the carboxylic acid component residues and / or diamine component residues, and more preferably have the structure shown in formula (16). The structure shown in formula (16) has excellent compatibility with the aforementioned polysiloxane (A), so it is possible to suppress the aggregation of polysiloxane (A) and obtain a cured product with fewer defects. Furthermore, the CF3 groups in the structure shown in (16) reduce the water absorption of the cured product of the photosensitive resin composition, which can further improve the durability of the display device. In addition, since the CF3 groups do not impart liquid repellency, a cured product with a hydrophilic surface can be formed by "half exposure" as described later.

[0126] [ka]

[0127] * indicates a covalent bond.

[0128] From the viewpoint of compatibility with the aforementioned polysiloxane (A) and the water absorption of the cured resin, it is more preferable that polyimides, polybenzoxazoles, or polyamideimides, any of these precursors, and copolymers thereof have the structure shown in formula (16) in the carboxylic acid component residues and diamine component residues.

[0129] The alkali-soluble resin (B) preferably has structural units represented by any of formulas (17) to (20), and more preferably has structural units represented by formula (20). It may contain two or more resins having these structural units, or two or more structural units may be copolymerized. The resin of alkali-soluble resin (B) preferably contains 3 to 1000 structural units represented by any of formulas (17) to (20) in its molecule, and more preferably contains 20 to 200.

[0130] [ka]

[0131] In formulas (17) to (20), R 6 and R 9 R is a tetravalent organic group. 7 , R 8 and R 11 R is a divalent organic group. 10 R is a trivalent organic group. 12 R is a 2-6 valent organic group. 13 R represents a 2- to 12-valent organic group. 14 represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms. p represents an integer from 0 to 2, q represents an integer from 0 to 10, and n represents an integer from 0 to 2.

[0132] R 6 ~R 13 Preferably, all of these have aromatic rings and / or aliphatic rings.

[0133] R in equations (17) to (20) 6 , R 8 , R 10 , R 12 (COOR 14 ) n (OH) p Substructures containing can be obtained, for example, by using the corresponding carboxylic acid components. That is, for example, R 6 is a tetracarboxylic acid, R 8 is a dicarboxylic acid, R 10 is a tricarboxylic acid, R 12This can be obtained by using di-, tri-, or tetra-carboxylic acids. 6 , R 8 , R 10 , R 12 (COOR 14 ) n (OH) p Examples of carboxylic acid components used to obtain the product include, as examples of dicarboxylic acids, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc.; as examples of tricarboxylic acids, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc.; as examples of tetracarboxylic acids, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxy Examples include aromatic tetracarboxylic acids such as phenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, and 3,4,9,10-perylenetetracarboxylic acid, as well as aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Of these, in formula (18), one or two carboxyl groups of the tricarboxylic acid and tetracarboxylic acid are COOR 14These correspond to the base. These acidic components can be used as is, or as acid anhydrides, active esters, etc. Furthermore, two or more of these acidic components may be used in combination.

[0134] As mentioned above, the alkali-soluble resin (B) preferably has a structure represented by formula (16) in the residue of the carboxylic acid component. Therefore, as examples of the carboxylic acid component, bis(carboxyphenyl)hexafluoropropane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane are preferred.

[0135] R in equations (17) to (20) 7 , R 9 , R 11 , R 13 (OH) q Substructures containing these components can be obtained, for example, by using the corresponding diamine components. 7 , R 9 , R 11 , R 13 (OH) qExamples of diamine components used to obtain the product include hydroxyl group-containing diamines such as bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, and bis(3-amino-4-hydroxyphenyl)fluorene, and 3-sulfonic acid-4,4' - Diamines containing sulfonic acid such as diaminodiphenyl ether, diamines containing thiol groups such as dimercaptophenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl Aromatic diamines such as phenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, as well as compounds in which some of the hydrogen atoms of these aromatic rings are substituted with C1-C10 alkyl groups, trifluoromethyl groups, halogen atoms, etc., alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine, 1,Examples of siloxane-based diamines include 3-bis(3-aminopropyl)tetramethyldisiloxane. These diamines can be used as is, or as corresponding diisocyanate compounds or trimethylsilylated diamines. Alternatively, two or more of these diamine components may be used in combination. For applications requiring heat resistance, it is preferable to use aromatic diamines in an amount of 50 mol or more of the total diamine composition.

[0136] As mentioned above, the alkali-soluble resin (B) preferably has a structure represented by formula (16) in the residue of the diamine component; therefore, bis(3-amino-4-hydroxyphenyl)hexafluoropropane is preferred as an example of the diamine component.

[0137] Furthermore, from the viewpoint of adhesion to the electrode, the alkali-soluble resin (B) preferably has a siloxane-based diamine such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane as its diamine component. This contributes to the concentration of Si atoms in the properties (v) of the cured resin.

[0138] R in equations (17) to (20) 6 ~R 13 This resin may contain phenolic hydroxyl groups, sulfonic acid groups, thiol groups, etc., in its skeleton. By using a resin that has an appropriate amount of phenolic hydroxyl groups, sulfonic acid groups, or thiol groups, a positive-type photosensitive resin composition with appropriate alkali solubility can be obtained.

[0139] Furthermore, in order to improve the storage stability of the photosensitive resin composition, it is preferable to encapsulate the main chain ends of the alkali-soluble resin (B) with known end-captive agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. The introduction rate of monoamines used as end-captive agents is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, and particularly preferably 50 mol% or less, relative to the total amine components. The introduction rate of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, or monoactive ester compounds used as end-captive agents is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 100 mol% or less, and particularly preferably 90 mol% or less, relative to the diamine components. Multiple different end groups may be introduced by reacting multiple end-captive agents.

[0140] In a resin having structural units represented by any of formulas (17) to (19), the number of repeating structural units is preferably 3 to 200. Furthermore, in a resin having structural units represented by formula (20), the number of repeating structural units is preferably 10 to 1000. Within this range, thick cured resin products can be easily formed.

[0141] The alkali-soluble resin (B) may consist solely of structural units represented by any of formulas (17) to (20), or it may be a copolymer or mixture of structural units with other structural units. In this case, it is preferable that the structural units represented by any of formulas (17) to (20) constitute 10% by mass or more of the total resin, and more preferably 30% by mass or more. The type and amount of structural units used in copolymerization or mixing can be selected within a range that does not impair the mechanical properties of the resin cured product obtained by the final heat treatment.

[0142] The photosensitive resin composition preferably contains a photosensitive agent (C). By including the photosensitive agent (C), the openings in the resin cured material on the first electrode in the laminate of the present invention can be formed by photolithography.

[0143] The photosensitive agent (C) may be a negative type that hardens with light, or a positive type that becomes solubilized with light. The photosensitive agent (C) may preferably contain a polymerizable unsaturated compound and a photopolymerization initiator (C-1), or a quinone diazide compound (C-2). In this invention, the polymerizable unsaturated compound and the photopolymerization initiator (C-1) may simply be referred to as (C-1). The inclusion of a quinone diazide compound (C-2) is preferable because it allows for the formation of a stepped resin cured product in a single photolithography step by "half-exposure" as described later. Therefore, it is preferable that the photosensitive agent (C) in the photosensitive resin composition contains a quinone diazide compound.

[0144] Examples of polymerizable unsaturated compounds in (C-1) include known compounds having unsaturated double bond functional groups such as vinyl groups, allyl groups, acryloyl groups, and methacryloyl groups, and / or unsaturated triple bond functional groups such as propargyl groups. Among these, conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred in terms of polymerizability. Furthermore, the number of functional groups contained is preferably 1 to 4 from the viewpoint of stability, and they do not have to be the same group. In addition, the compounds referred to here are preferably those with a molecular weight of 30 to 800. If the molecular weight is in the range of 30 to 800, the compatibility with the polymer and reactive diluent is good. Specifically, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecanediacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N, Examples include N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, and N-vinylcaprolactam. These are used individually or in combination of two or more.

[0145] In the present invention, the content of polymerizable unsaturated compound in (C-1) is not particularly limited, but from the viewpoint of improving alkali solubility, it is preferably 5 parts by mass or more, and from the viewpoint of good pattern formation, it is preferably 50 parts by mass or less, per 100 parts by mass of alkali-soluble resin (B).

[0146] In (C-1), the photopolymerization initiator refers to a substance that initiates polymerization primarily by generating radicals when irradiated with light in the ultraviolet to visible light range. From the viewpoint of being able to use a general-purpose light source and rapid curing, known photopolymerization initiators selected from acetophenone derivatives, benzophenone derivatives, benzoin ether derivatives, and xanthone derivatives are preferred. Examples of preferred photopolymerization initiators include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, isobutylbenzoin ether, benzoin methyl ether, thioxanthone, isopropylthioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.

[0147] The content of the photopolymerization initiator in (C-1) is not particularly limited, but it is preferably 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of alkali-soluble resin (B). Within this range, it is easier to ensure the interaction with the resin necessary for good pattern formation and transmittance necessary to obtain appropriate sensitivity.

[0148] Known quinone diazide compounds (C-2) include those in which the sulfonic acid of quinone diazide is ester-bonded to a polyhydroxy compound, those in which the sulfonic acid of quinone diazide is sulfonamide-bonded to a polyamino compound, and those in which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded to a polyhydroxypolyamino compound. Not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds are to be substituted with quinone diazide, but it is preferable that on average 40 mol% or more of the total functional groups are substituted with quinone diazide. In the present invention, the mol% of functional groups substituted with quinone diazide is referred to as the quinone diazide substitution rate. By using such quinone diazide compounds, a positive-type photosensitive resin composition that is sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays, can be obtained.

[0149] The polyhydroxy compounds used here have two or more, preferably three or more, phenolic hydroxyl groups in their molecule. Examples of polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethi Role-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML- Examples of such materials include, but are not limited to, BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolac resins.

[0150] Examples of polyamino compounds include, but are not limited to, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0151] Examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0152] Examples of quinone diazide sulfonic acids include, but are not limited to, 1,2-naphthoquinone diazide-4-sulfonic acid and 1,2-naphthoquinone diazide-5-sulfonic acid.

[0153] In this invention, a quinone diazide compound (C-2) is preferably one in which quinone diazidesulfonic acid is bonded to a polyhydroxy compound. By using such a quinone diazide compound, it is possible to obtain high sensitivity and higher resolution by being exposed to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of mercury lamps, which are common ultraviolet rays.

[0154] More preferred quinone diazide compounds (C-2) include those represented by formula (21) or formula (22).

[0155] [ka]

[0156] In formulas (21) and (22), Q independently represents a hydrogen atom, a group represented by structural formula (23), or a group represented by structural formula (24).

[0157] [ka]

[0158] It is even more preferable from the viewpoint of sensitivity that Q in formulas (21) and (22) is independently represented by a hydrogen atom or the group represented by structural formula (21).

[0159] The quinone diazide substitution ratio can be calculated as follows: for polyhydroxy compounds, "(moles of quinone diazidesulfonic acid ester groups) / (moles of hydroxyl groups before esterification of the polyhydroxy compound) × 100"; for polyamino compounds, "(moles of quinone diazidesulfonic acid amide groups) / (moles of amino groups before amidation of the polyamino compound) × 100"; and for polyhydroxypolyamino compounds, "{(moles of quinone diazidesulfonic acid ester groups) + (moles of quinone diazidesulfonic acid amide groups)} / {(moles of hydroxyl groups before esterification of the polyhydroxypolyamino compound) + (moles of amino groups before amidation of the polyhydroxypolyamino compound)} × 100".

[0160] In this invention, two or more quinone diazide compounds can be used. In this case, the quinone diazide substitution rate can be determined by summing the values ​​obtained by multiplying the quinone diazide substitution rate of each quinone diazide compound by its ratio to the total quinone diazide compounds, as shown in the formula below. Σ((Quinone diazide substitution rate of a certain quinone diazide compound) × (Ratio of a certain quinone diazide compound to all quinone diazide compounds)) Furthermore, the quinone diazide substitution rate of quinone diazide compounds in a photosensitive resin composition can be determined by removing the resin components of the photosensitive resin composition by reprecipitation or other methods, separating the constituent components by column preparation or other methods, and identifying their chemical structures by NMR or IR.

[0161] The method for producing quinone diazide compounds is not particularly limited, but they can be obtained by reacting quinone diazidesulfonic acid halide (preferably quinone diazidesulfonic acid chloride) with a polyhydroxy compound in a solvent such as acetone, dioxane, or tetrahydrofuran in the presence of an inorganic base such as sodium carbonate, sodium bicarbonate, sodium hydroxide, or potassium hydroxide, or an organic base such as trimethylamine, triethylamine, tripropylamine, diisopropylamine, tributylamine, pyrrolidine, piperidine, piperazine, morpholine, pyridine, or dicyclohexylamine, according to conventional methods.

[0162] The content of the quinone diazide compound (C-2) is not particularly limited, but the content of the quinone diazide compound (C-2) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, per 100 parts by mass of alkali-soluble resin (B). Furthermore, it is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less. By setting the content of the quinone diazide compound within this range, photosensitivity can be obtained without inhibiting liquid repellency.

[0163] When used as a positive-type photosensitive resin composition containing a quinone diazide compound (C-2) as the photosensitive agent (C), it is preferable that the alkali-soluble resin (B) contains a phenolic resin and / or a polyhydroxystyrene resin. Alternatively, two or more of these phenolic resins and / or polyhydroxystyrene resins may be used in combination. By including a quinone diazide compound (C-2) and a phenolic resin and / or polyhydroxystyrene resin, the amount of thickness reduction of the dried photosensitive resin in the development process described later can be reduced, which has the effect of making it easier to retain the polysiloxane (A) on the surface of the cured resin, and thus better liquid repellency can be obtained.

[0164] Phenolic resins include novolac phenolic resins and resol phenolic resins, and are obtained by polycondensation of various phenolic compounds, either individually or in mixtures thereof, using aldehyde compounds such as formalin, by known methods.

[0165] Examples of phenol compounds that constitute novolac phenol resin and resol phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebisp-cresol Examples of aldehyde compounds include resol, resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, and β-naphthol, which can be used individually or in mixtures of several. Examples of aldehyde compounds include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde, which can be used individually or in mixtures of several.

[0166] As the polyhydroxystyrene resin, it is also possible to use a homopolymer of vinylphenol or a copolymer with styrene.

[0167] The preferred weight-average molecular weight of phenolic resins and polyhydroxystyrene resins is 2,000 to 20,000, preferably 3,000 to 10,000, in polystyrene equivalent as determined by GPC (gel permeation chromatography). Within this range, a resin composition with high concentration and low viscosity can be obtained.

[0168] When the photosensitive resin composition is used as a positive-type photosensitive resin composition containing a quinone diazide compound (C-2) as the photosensitive agent (C), from the viewpoint of liquid repellency, it is preferable that the composition contains 20 parts by mass or more, and more preferably 30 parts by mass or more, of phenol resin and / or polyhydroxystyrene resin per 100 parts by mass of alkali-soluble resin (B). Furthermore, from the viewpoint of outgassing, it is preferable that the amount be 50 parts by mass or less, and more preferably 40 parts by mass or less.

[0169] The photosensitive resin composition preferably contains an organic solvent (D). Examples of organic solvents (D) include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, alcohols, and various other known organic solvents.

[0170] More specifically, for example, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, or tetrahydrofuran, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as "PGMEA"), acetates such as 3-methoxybutyl acetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 3-methoxy-3-methyl-1-butyl acetate, methyl ethyl acetate Ketones such as cyclohexanone, 2-heptanone or 3-heptanone, alkyl lactates such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyethyl acetate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Examples include esters such as cete, 3-methyl-3-methoxybutylpropionate, ethyl acetate, propyl acetate, butyl acetate, γ-butyrolactone, aromatic hydrocarbons such as toluene or xylene, amides such as N-methylpyrrolidone, N,N-dimethylformamide, or N,N-dimethylacetamide, or alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, or diacetone alcohol.

[0171] The amount of the organic solvent (D) used is not particularly limited as it can be changed depending on the required thickness and the coating method adopted, but it is preferably 100 to 2000 parts by mass, and particularly preferably 150 to 900 parts by mass, per 100 parts by mass of the solid content (other components excluding the organic solvent (D)) of the photosensitive resin composition.

[0172] The photosensitive resin composition may further contain a thermal crosslinking agent. A thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups in its molecule, including methylol groups, alkoxymethyl groups, epoxy groups, oxetanyl groups, and other known thermal crosslinking agents. The thermal crosslinking agent can crosslink the alkali-soluble resin (B) or other components, thereby improving the durability of the cured resin product.

[0173] Preferred examples of compounds having at least two alkoxymethyl groups or methylol groups include, for example, HMOM-TPPHBA, HMOM-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC® MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (trade names, manufactured by Sanwa Chemical Co., Ltd.), each of which is available from the respective companies.

[0174] Compounds having epoxy or oxetanyl groups include VG3101L (trade name, manufactured by Printec Co., Ltd.), "Tepic" (registered trademark) S, "Tepic" G, "Tepic" P (all trade names, manufactured by Nissan Chemical Industries, Ltd.), "Epiclon" N660, "Epiclon" N695, HP7200 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), "Denacol" EX-321L (trade name, manufactured by Nagase ChemteX Corporation), NC6000, EPPN502H, NC3000 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) Examples of compounds with two or more oxetanyl groups include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (all product names, manufactured by Toagosei Co., Ltd.), "Etanacol" (registered trademark) OXBP, and "Etanacol" OXTP (both product names, manufactured by Ube Industries, Ltd.), all of which are available from their respective companies.

[0175] Preferably, the thermal crosslinking agent has a phenolic hydroxyl group in one molecule, and has a methylol group and / or alkoxymethyl group at both ortho positions of the phenolic hydroxyl group. The presence of the methylol group and / or alkoxymethyl group adjacent to the phenolic hydroxyl group can further enhance the durability of the cured resin. Examples of alkoxymethyl groups include, but are not limited to, methoxymethyl, ethoxymethyl, propoxymethyl, and butoxymethyl groups.

[0176] The content of the thermal crosslinking agent is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of the total amount of alkali-soluble resin (B). Furthermore, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less. By setting the content of the thermal crosslinking agent to 5 parts by mass or more, the heat resistance of the cured resin is improved, and by setting it to 50 parts by mass or less, a decrease in the elongation of the cured resin can be prevented.

[0177] A method for producing a photosensitive resin composition will be described. For example, it can be obtained by dissolving the polysiloxane (A) to the photosensitive agent (C) and other components in an organic solvent (D). Dissolution methods include stirring and heating. When heating, the heating temperature should preferably be set within a range that does not impair the performance of the resin composition, and is usually between 20°C and 80°C. Furthermore, the order in which each component is dissolved is not particularly limited; for example, compounds with lower solubility can be dissolved sequentially.

[0178] The resulting photosensitive resin composition is preferably filtered using a filtration filter to remove dirt and particles. The pore size of the filter can be, for example, 1 μm, 0.5 μm, 0.2 μm, 0.1 μm, or 0.05 μm, but is not limited to these. The material of the filtration filter can be polypropylene (PP), polyethylene (PE), nylon (NY), or polytetrafluoroethylene (PTFE), but it is preferable to use polyethylene or nylon for filtration.

[0179] Next, a method for producing a cured resin product of a photosensitive resin composition will be described. A cured resin product is obtained by applying the photosensitive resin composition and drying it. Furthermore, by performing the following steps (1) to (4) in this order, a cured resin product in which at least a portion of the first electrode is open can be formed. (1) A step of applying a photosensitive resin composition onto a substrate having a first electrode to form a photosensitive resin dried product. (2) Exposing the photosensitive resin dried product to light (3) Process of developing the exposed photosensitive resin dry product (4) A process of forming a cured resin by heat treatment of the developed photosensitive resin dry product. First, we will explain the process of (1) applying a photosensitive resin composition to a substrate having a first electrode to form a photosensitive resin dried product.

[0180] Methods for coating a photosensitive resin composition onto a substrate having a first electrode include spin coating, slit coating, dip coating, spray coating, and printing. Prior to coating, the substrate to be coated with the photosensitive resin composition may be pre-treated with the adhesion improver described above. For example, a method of treating the substrate surface is used in which the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate at a concentration of 0.5 to 20% by mass. Methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0181] Next, for example, the coated photosensitive resin can be subjected to vacuum drying as needed, and then a dried photosensitive resin can be obtained by heat treatment using a hot plate, oven, infrared, etc., at a temperature of 50°C to 180°C for 1 minute to several hours.

[0182] Next, (2) the process of exposing the photosensitive resin dried product to light will be described.

[0183] A chemical beam is irradiated onto a photosensitive resin dry product through a photomask having a desired pattern. Chemical beams used for exposure include ultraviolet light, visible light, electron beams, and X-rays, but in this invention, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. After irradiation with the chemical beam, post-exposure baking may be performed. Post-exposure baking can be expected to improve resolution after development or increase the tolerance range of development conditions. Post-exposure baking can be performed using an oven, hot plate, infrared light, flash annealing device, or laser annealing device. The post-exposure baking temperature is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to several hours. When the post-exposure baking time is within the above range, the reaction proceeds well, and the development time may be shortened. At this time, a grid-shaped photomask can be used to obtain a grid-shaped cured product.

[0184] In this invention, "half exposure" may be used. "Half exposure" refers to a process that ensures that a certain amount of the underlying layer of the photosensitive resin dry material remains exposed when development is complete. In other words, it refers to a process that exposes the material so that the lower layer of the photosensitive resin dry material is not exposed to light. For example, when forming the resin cured product shown in Figure 5 using a positive-type photosensitive resin dry material, the area that will become the first stage 9 of the thicker resin cured product is left unexposed, and the area that will become the second stage 10 of the thinner resin cured product is exposed using "half exposure" with a chemical dose that does not expose the lower layer of the photosensitive resin dry material to light, and then the product is formed by developing and heat-treating. Furthermore, the thickness of the photosensitive resin dry material remaining after development is complete can be adjusted by adjusting the chemical dose irradiated onto the photosensitive resin dry material. Specifically, if the photosensitive resin dry material is of the positive type, increasing the chemical dose will reduce the thickness of the photosensitive resin dry material remaining after development is complete. On the other hand, if the photosensitive resin dry product is of the negative type, increasing the chemical dose will increase the thickness of the photosensitive resin dry product remaining after development is complete. The chemical dose may be adjusted by irradiating the product with chemical rays through a photomask having two or more areas with different transmittances.

[0185] When the photosensitive resin dried product formed from the photosensitive resin composition of the present invention is of the positive type, the surface of the cured product formed by half-exposure does not exhibit liquid repellency and can have good ink coating properties. In other words, both a cured product with a liquid-repellent surface and a cured product with a hydrophilic surface can be formed in a single photolithography.

[0186] Next, we will explain the process of developing (3) the photosensitive resin that has been exposed to light.

[0187] In the developing process for developing the exposed photosensitive resin dry product, the exposed photosensitive resin dry product is developed using a developer solution to remove areas other than the exposed parts. Preferred developers are aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide (TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added to these alkaline aqueous solutions, either individually or in combination. Possible development methods include spraying, paddle development, immersion, and ultrasonic development.

[0188] Next, it is preferable to rinse the pattern formed by development with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0189] Next, we will explain the process of forming a cured resin by heat-treating the developed photosensitive resin dried product.

[0190] A cured product is obtained by a heat treatment process of the developed and dried photosensitive resin. In this invention, the cured product of the photosensitive resin composition can be suitably used as a partition in an organic EL display device. Since residual solvents and components with low heat resistance can be removed by the heat treatment, heat resistance and chemical resistance can be improved. Furthermore, by including a crosslinking agent, a thermal crosslinking reaction can be promoted by the heat treatment, further improving heat resistance and chemical resistance. This heat treatment is carried out by selecting a temperature and raising it in stages, or by selecting a temperature range and continuously raising the temperature for 5 minutes to 5 hours. One example is a method of heat treatment at 150°C and 250°C for 30 minutes each. Alternatively, one example is a method of linearly raising the temperature from room temperature to 300°C over 2 hours. In this invention, the heat treatment conditions are preferably 180°C or higher, more preferably 200°C or higher, and even more preferably 230°C or higher. Furthermore, the heat treatment conditions are preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower. <Display device> The display device of the present invention comprises the laminate of the present invention. Specific examples of the display device include LCDs, organic ELs, and the like.

[0191] The resin cured product comprising the laminate of the present invention has high liquid repellency on the surface of the cured product after UV ozone treatment, and is therefore suitably used in a display device in which a functional layer is formed by inkjet application of a functional ink into an open area of ​​the resin cured product on the first electrode. For example, it can be used as an organic EL display device by forming an organic EL light-emitting layer containing at least one selected from organic EL light-emitting material, hole injection material, and hole transport material.

[0192] The resin cured material comprising the laminate of the present invention has F atoms inside the resin cured material, which reduces the water absorption of the resin cured material and suppresses electrode corrosion, thereby enabling the production of a display device with minimal pixel shrinkage and excellent durability.

[0193] The resin cured product comprising the laminate of the present invention exhibits low outgassing at high temperatures, making it preferable to use it in an organic EL display device that includes at least one material selected from the group consisting of organic EL light-emitting materials, hole injection materials, and hole transport materials in its functional layer. This allows for the creation of an organic EL display device with minimal pixel shrinkage and excellent durability.

[0194] An organic EL display device has a drive circuit, a planarization layer, a first electrode, a partition wall, an organic EL light-emitting layer, and a second electrode on a substrate. Taking an active-matrix type display device as an example, it has a TFT and wiring located on the side of the TFT and connected to the TFT on a substrate such as glass or a resin film, a planarization layer covering the irregularities, and a display element further provided on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer.

[0195] <Method for manufacturing a display device> A first aspect of the method for manufacturing the display device of the present invention comprises steps (5) and (6) in this order. (5) A step in which a functional layer is formed by applying a functional ink onto the first electrode using an inkjet printer in the laminate of the present invention. (6) A step of forming a second electrode on the functional layer.

[0196] (5) In step (5), a functional ink is applied to the first electrode of the laminate of the present invention by inkjet to form a functional layer. For example, in the case of an organic EL display device, an organic EL light-emitting layer can be formed by dropping a composition containing at least one selected from the group consisting of organic EL light-emitting material, hole injection material, and hole transport material into the pixel as a functional ink and drying it. For drying, it is preferable to heat it at 150°C to 250°C for 0.5 to 120 minutes using a hot plate or oven.

[0197] (6) In step (6), a second electrode is formed on the functional layer. It is preferable that the second electrode is formed so as to cover the entire partition wall and the functional layer. Methods for forming the second electrode include sputtering and vapor deposition. It is preferable that the second electrode is formed with no breaks in the wire and with a uniform layer thickness.

[0198] When the laminate of the present invention comprises a resin cured product having the first and second stages described above, a second aspect of the method for manufacturing the display device of the present invention comprises steps (7) and (8) in this order. (7) A step in which a functional layer is formed in the laminate of the present invention by applying a functional ink on the first electrode and the second layer of the cured resin by inkjet. (8) A step of forming a second electrode on the functional layer.

[0199] (7) In step (7), a functional ink is applied by inkjet on the first electrode of the laminate of the present invention and on the second layer of the cured resin to form a functional layer. For example, in the case of an organic EL display device, an organic EL light-emitting layer can be formed by dropping a composition containing at least one selected from the group consisting of organic EL light-emitting material, hole injection material, and hole transport material into the pixels as a functional ink and drying it. For drying, it is preferable to heat at 150°C to 250°C for 0.5 to 120 minutes using a hot plate or oven.

[0200] For example, as shown in Figure 2, a laminate is formed by stacking a patterned first electrode 8 on a substrate and a cured resin in that order, with the cured resin forming a first stage 9 that defines the area to be inkjet coated and a second stage 10 that defines two or more pixel areas arranged within the area to be inkjet coated. This laminate can be suitably used in a method for manufacturing a display device in which a functional layer 11 is formed by inkjet coating on the first electrode 8 patterned on the substrate and the second stage 10 of the cured resin.

[0201] (8) In step (8), a second electrode is formed on the functional layer. It is preferable that the second electrode is formed so as to cover the entire partition wall and the functional layer. Methods for forming the second electrode include sputtering and vapor deposition. It is preferable that the second electrode is formed with no breaks in the wire and with a uniform layer thickness. [Examples]

[0202] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0203] <Partition wall pattern used in the example> Partition pattern 4: A partition pattern that exposes the first electrode patterned on the substrate through an opening in the cured resin, wherein the opening has a width of 70 μm and a length of 260 μm, and the opening is located in the center of the cured resin. Partition pattern 5: A partition pattern that exposes the first electrode patterned on the substrate through an opening in the cured resin, the opening having a width of 70 μm and a length of 260 μm, and the cured resin is arranged with a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction. Partition pattern 12: A partition pattern as shown in Figure 2 or Figure 3, in which a second stage 10 of resin cured material with a width a of 205 μm and a first stage 9 of resin cured material with a width b of 85 μm are arranged so as to expose the first electrode 8 which is patterned on a substrate with a width of 70 μm and a length of 260 μm. First, we will explain the measurement and evaluation methods.

[0204] (1) Average molecular weight measurement The molecular weights of the polysiloxane (P-1) synthesized in Synthesis Example 1, the acrylic liquid repellent (Ac-1) synthesized in Synthesis Example 2, the alkali-soluble resin (d1) synthesized in Synthesis Example 8, and the alkali-soluble resin (Ac-2) synthesized in Synthesis Example 9 were measured using a GPC (gel permeation chromatography) instrument (Waters 2690-996; manufactured by Waters Japan Ltd.) with tetrahydrofuran as the developing solvent, and the weight-average molecular weight (Mw) was calculated in polystyrene equivalent.

[0205] Furthermore, the molecular weights of the alkali-soluble resins (b1) to (b3) synthesized in synthesis examples 4 to 6 were measured using the GPC apparatus described above, with N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as the developing solvent, and the number-average molecular weight (Mn) was calculated in terms of polystyrene.

[0206] (2) Evaluation of liquid repellency To measure the contact angle, a laminate having partition pattern 4 as shown in Figure 1 was formed using the method described later, and 3 μL of PGMEA was dropped onto the resin cured product of partition pattern 4 to measure the contact angle. The measurement was performed using a contact angle measuring device (DMs-401; manufactured by Kyowa Interface Science Co., Ltd.) in accordance with JIS-R3257:1999, by the static drop method at 23°C.

[0207] The measurement results of the PGMEA contact angle on the cured material were judged as follows, with A being excellent, B good, C acceptable, and D unacceptable. A: Contact angle of 45° or more B: Contact angle between 35° and less than 45° C: Contact angle between 25° and less than 35° D: Contact angle is less than 25°.

[0208] (3) Evaluation of UV ozone resistance The laminates whose liquid repellency was evaluated as described in (2) above were subjected to UV ozone treatment under the following conditions. Subsequently, 3 μL of PGMEA was dropped onto the resin-cured material of partition wall pattern 4 and the contact angle was measured. For the measurement, a contact angle measuring device (DMs-401; manufactured by Kyowa Interface Science Co., Ltd.) was used, and the measurement was performed by the static drop method at 23°C in accordance with JIS-R3257.

[0209] Compared with the evaluation results of the above-mentioned (2) liquid repellency, if the change in the contact angle is 10% or less, it is rated as A (qualified); if the change in the contact angle is more than 10%, it is rated as B (unqualified).

[0210] · UV ozone conditions Equipment: PL16 (manufactured by SEN LIGHTS Corp.) Illuminance: 15 mW / cm2 Irradiation distance: 75 mm Irradiation time: 120 sec (4) Analysis of the cured resin by X-ray photoelectron spectroscopy (XPS) The analysis method of the cured resin by X-ray photoelectron spectroscopy (XPS) is shown.

[0211] <Preparation of the cured product for X-ray photoelectron spectroscopy (XPS) analysis> A laminate with the partition pattern 4 in FIG. 1 formed by the method described below was prepared, and XPS analysis was performed at any location within a range of 100 μm from the edge of the opening of the cured resin in the partition pattern 4.

[0212] <Analysis method of the cured resin by X-ray photoelectron spectroscopy (XPS)> (4-1) XPS analysis of the surface of the cured resin, measurement methods for characteristics (i) and (v) Analysis by X-ray photoelectron spectroscopy (XPS) was performed on the surface of the cured resin of the partition pattern 4 or the partition pattern 12 in FIG. 1 under the measurement conditions described below. The measurement conditions and data processing conditions are described below.

[0213] · Measurement conditions Equipment: Quantera SXM (manufactured by PHI) Excitation X-ray: monochromatic Al K 1,2 line (1486.6 eV) X-ray diameter: 200 μm Photoelectron detection angle: 45° (tilt of the detector with respect to the sample surface) · Data processing conditions Smoothing: 9-point smoothing The main peak of the horizontal axis correction C1s (CHx, C-C, C=C) was set to 284.6 eV.

[0214] (4-2) Measurement method of characteristic (ii) of XPS analysis inside the cured resin For the cured resin of the partition pattern 4 in Fig. 1, perpendicular to the interface where the patterned first electrode 8 and the cured resin of the partition pattern 4 are in contact, and in the direction from the alkali-free glass substrate 1 to the partition pattern 4, Ar gas cluster ions (Ar-GCIB) were performed so that any range from 100 to 200 nm was exposed starting from the interface where the patterned first electrode 8 and the cured resin of the partition pattern 4 are in contact. Thereafter, X-ray photoelectron spectroscopy (XPS) analysis was performed at the location where Ar-GCIB was performed. The measurement conditions and data processing are described below.

[0215] ·Measurement conditions Apparatus: K-Alpha (manufactured by Thermo Fisher Scientific) Excitation X-ray: monochromatic Al K 1,2 line (1486.6 eV) X-ray diameter: 400 μm Photoelectron escape angle: 90° (tilt of the detector with respect to the sample surface) Ion etching conditions: Ar gas cluster ions (Ar-GCIB) Etching rate: 3.5 nm / min ·Data processing Smoothing: 11-point smoothing The main peak of the horizontal axis correction C1s (CHx, C-C) was set to 284.6 eV.

[0216] (4-3) Measurement method of characteristics (iii) and (iv) of XPS comparison between the surface and inside of the cured resin Analysis by X-ray photoelectron spectroscopy (XPS) was performed on the surface of the cured resin of the partition pattern 4 in FIG. 1 under the measurement conditions described below. Subsequently, with respect to the cured resin of the partition pattern 4, perpendicular to the interface where the patterned first electrode 8 and the cured resin of the partition pattern 4 are in contact, and in the direction from the non-alkali glass substrate 1 to the partition pattern 4, Ar gas cluster ions (Ar-GCIB) were applied so that any range from 100 to 200 nm starting from the interface where the patterned first electrode 8 and the cured resin of the partition pattern 4 are in contact was exposed. Thereafter, X-ray photoelectron spectroscopy (XPS) analysis was performed at the location where Ar-GCIB was applied. The measurement conditions and data processing are described below.

[0217] · Measurement conditions Device: K-Alpha (manufactured by Thermo Fisher Scientific) Excitation X-ray: monochromatic Al K 1,2 line (1486.6 eV) X-ray diameter: 400 μm Photoelectron escape angle: 90° (tilt of the detector with respect to the sample surface) Ion etching conditions: Ar gas cluster ions (Ar-GCIB) Etching rate: 3.5 nm / min · Data processing Smoothing: 11-point smoothing Horizontal axis correction: The C1s main peak (CHx, C-C) was set to 284.6 eV. (5) Evaluation of durability The laminate shown in Figure 1, in which partition pattern 5 or partition pattern 12 was formed using a cured photosensitive resin composition, was subjected to UV ozone treatment under the conditions described in (3) UV ozone resistance evaluation. Subsequently, in the case of partition pattern 5, as a hole injection layer, an ink of compound (HT-1) with methyl benzoate as the solvent was dropped onto the first electrode 8 patterned on the substrate surrounded by the cured resin using an inkjet device (ULVAC Litlex142), and then fired at 200°C to form the hole injection layer. Next, as a hole transport layer, compound (HT-2) with 4-methoxytoluene as the solvent was dropped into the region surrounded by the cured resin using an inkjet device, and then fired at 190°C to form the hole transport layer. Furthermore, as a light-emitting layer, a mixture of compound (GH-1) and compound (GD-1) with 4-methoxytoluene as the solvent was dropped into the region surrounded by the cured resin using an inkjet device, and then fired at 130°C to form a light-emitting layer. In the case of partition pattern 12, as a hole injection layer, an ink of compound (HT-1) with methyl benzoate as the solvent was continuously dropped onto the first electrode 8 patterned on the substrate in the region sandwiched between the first stages of cured resin and onto the second stage 10 of cured resin using an inkjet device (ULVAC Litlex142), and then fired at 200°C to form a hole injection layer. Next, as a hole transport layer, compound (HT-2) with 4-methoxytoluene as the solvent was dropped into the same region using an inkjet device, and then fired at 190°C to form a hole transport layer. Furthermore, as a light-emitting layer, a mixture of compound (GH-1) and compound (GD-1) with 4-methoxytoluene as the solvent was dropped onto the same area using an inkjet device, and then fired at 130°C to form the light-emitting layer.

[0218] Subsequently, as electron transport materials, compound (ET-1) and compound (LiQ) were sequentially layered in a volume ratio of 1:1 by vacuum deposition to form an organic EL layer 6. Next, after depositing compound (LiQ) at a density of 2 nm, Mg and Ag were deposited at a density of 10:1 at a density of 10 nm to form the second electrode 7. Finally, a cap-shaped glass plate was sealed by bonding it with an epoxy resin adhesive under a low-humidity nitrogen atmosphere, and a 5 mm square organic EL display device was fabricated on a single substrate.

[0219] [ka]

[0220] The organic EL display device fabricated using the method described above has a voltage of 10 mA / cm². 2 The device was then driven by DC current to induce light emission, and the initial light-emitting area was observed. Furthermore, it was held at 80°C for 500 hours, and then again at 10 mA / cm². 2 The device was then driven by DC to produce light, and it was checked for any change in the light-emitting area. Durability was then judged as follows, with A being excellent, B good, C acceptable, and D unacceptable. A: No change in luminescent area. B: The luminescent area changes from 90% to 99%. C: The luminescent area changes from 80% to 89%. D: The luminescent area changes to 79% or less. (6) Composition analysis of cured resin products This document describes methods for analyzing the components contained in cured resin products, but any method capable of compositional analysis is acceptable and is not limited to the methods described.

[0221] <Preparation of cured resin for compositional analysis> The photosensitive resin composition was applied onto an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited), and baked on a hot plate at 120°C for 3 minutes. Thereafter, development was carried out using 2.38 mass% TMAH aqueous solution with the above-mentioned ACT-8 developing apparatus. After rinsing with distilled water, it was spin-dried. Subsequently, the dried photosensitive resin after development was heated from 5°C / min to 250°C in a nitrogen atmosphere (oxygen concentration: 100 ppm or less) using a high-temperature inert gas oven (INH-9CD-S; manufactured by Kouyou Thermo System Co., Ltd.), and a thermosetting process of heat-treating at 250°C for 1 hour was performed to produce a resin cured product of the varnish. The thickness of the resin cured product was about 2.0 μm. <Composition analysis by FT-IR> For the obtained resin cured product, using an infrared microscope Nicolet iN10 (manufactured by Thermo Fisher SCIENTIFIC), for the range of wavenumber 4000~650 cm -1 the detector used was MCT, the resolution was 8 cm -1 and the IR spectrum was obtained by the measurement mode of single reflection ATR method (Ge, 45°) with 64 accumulations.

[0222] <Composition analysis by thermal decomposition GC / MS> For the obtained resin cured product, using a multi-shot pyrolyzer PY-3030D (manufactured by Frontier Lab), pyrolysis was carried out under the condition of a heating temperature of 600°C, and using a gas chromatograph mass spectrometer JMS-Q1050GC (manufactured by JEOL Ltd.), the GC column used was a stainless steel capillary column (inner diameter 0.25 mm × 30 m, stationary phase; 5% phenylpolydimethylsiloxane), the GC temperature was raised from 40°C (held for 3 minutes) to 320°C at a rate of 20°C / min, the injection port temperature was 300°C, the column flow rate was 1.5 mL / min, the ionization method was EI (electron ionization) method, the mass number range was m / z10~800, and the analysis was carried out with a scan rate of 0.5 sec / scan.

[0223] The abbreviations of the components used in the examples are shown below.

[0224] <Alkoxysilyl> MTMS: Methyltrimethoxysilane NapTMS: 1-Naphthyltrimethoxysilane TMSSucA: 3-Trimethoxysilylpropyl succinic anhydride TfTMS: Tridecafluorooctyltrimethoxysilane <Crosslinking agent> HMOM-TPHAP: (Compound shown in the following chemical formula, manufactured by Honshu Chemical Industry Co., Ltd.)

[0225]

Chem.

[0226] VG3101L: “Tekmoa” (registered trademark) VG3101L (Compound shown in the following chemical formula, manufactured by Printec Co., Ltd.).

[0227]

Chem.

[0228] <Organic solvent> PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether MAK: 2-Heptanone IPA: Isopropyl alcohol The compounds used in the examples and comparative examples are shown below.

[0229] Synthesis Example 1 Synthesis of polysiloxane (P-1) In a 500 mL three-necked flask, 39.80 g (0.17 mol) of TfTMS, 62.09 g (0.50 mol) of NapTMS, 13.12 g (0.10 mol) of TMSSucA, 15.66 g (0.23 mol) of MTMS, 131.05 g of MAK, and 14.56 g of IPA were charged. A phosphoric acid solution, prepared by mixing 27.90 g of water and 1.31 g of phosphoric acid (1.0 mass%) relative to the charged monomers, was added while stirring at 40°C. The flask was then immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 130°C over 15 minutes. Ten minutes after the start of heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 1 hour (internal temperature 100-125°C) to obtain polysiloxane (P-1). During the heating and stirring process, nitrogen was flowed at a rate of 0.07 l / min. The weight-average molecular weight was determined using GPC and found to be 3000.

[0230] Synthesis Example 2: Synthesis of Acrylic Liquid Repellent (Ac-1) 100 g of cyclohexanone was added to a glass reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas inlet, and the temperature was raised to 110°C under a nitrogen gas atmosphere. The temperature of the cyclohexanone was maintained at 110°C, and a monomer mixture consisting of 44 g (0.65 mol) of N,N-dimethylacrylamide, 30 g (0.10 mol) of 2-(perfluorohexyl)ethyl methacrylate, 21 g (0.22 mol) of glycidyl methacrylate, and 5 g (0.03 mol) of 3-phenoxybenzyl acrylate was added dropwise at a constant rate over 2 hours using a dropping funnel to prepare each monomer solution. After the addition was complete, the monomer solutions were raised to 115°C and reacted for 2 hours to obtain an acrylic liquid repellent (Ac-1). The weight-average molecular weight was determined using GPC, and the result was 5500.

[0231] Synthesis Example 3: Synthesis of Hydroxyl Group-Containing Diamine Compounds 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and the mixture was cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise. After the addition was complete, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off and vacuum-dried at 50°C.

[0232] 30 g of solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve. 2 g of 5% palladium-carbon was added. Hydrogen was introduced using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After the reaction was complete, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

[0233] [ka]

[0234] Synthesis Example 4: Synthesis of alkali-soluble resin (b1) Under a stream of dry nitrogen, 88.8 g (0.20 mol) of 2,2-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride was dissolved in 500 g of NMP. 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added along with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, followed by 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol was added as a terminal encapsulant along with 50 g of NMP, and the mixture was reacted at 50°C for 2 hours. Afterward, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethylacetal diluted with 100 g of NMP was added. The mixture was then stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature, and then added to 5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyimide precursor, alkali-soluble resin (b1). The number-average molecular weight of alkali-soluble resin (b1) was 12,000.

[0235] Synthesis Example 5: Synthesis of alkali-soluble resin (b2) Under a stream of dry nitrogen, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride was dissolved in 500 g of NMP. 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added along with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, followed by 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol was added as a terminal encapsulant along with 50 g of NMP, and the mixture was reacted at 50°C for 2 hours. Then, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal diluted with 100 g of NMP was added. After addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature, and then added to 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyimide precursor, alkali-soluble resin (b2). The number-average molecular weight of alkali-soluble resin (b2) was 11,000.

[0236] Synthesis Example 6: Synthesis of alkali-soluble resin (b3) Under a stream of dry nitrogen, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was dissolved in 500 g of NMP. To this, 44.85 g (0.16 mol) of bis(3-amino-4-hydroxyphenyl) sulfone and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added along with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, followed by a reaction at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol was added as a terminal encapsulant along with 50 g of NMP, and the mixture was reacted at 50°C for 2 hours. After that, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal diluted with 100 g of NMP was added. After the addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature, and then added to 5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyimide precursor, alkali-soluble resin (b3). The number-average molecular weight of alkali-soluble resin (b3) was 11,000.

[0237] Synthesis Example 7: Synthesis of quinone diazide compound (C2) Under a stream of dry nitrogen, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 33.58 g (0.125 mol) of 4-naphthoquinone diazidosulfonylic acid chloride were dissolved in 450 g of 1,4-dioxane and allowed to rise to room temperature. To this, 12.65 g (0.125 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, ensuring that the reaction system temperature did not exceed 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain the naphthoquinone diazide compound (c2). The quinone diazide substitution rate of this naphthoquinone diazide compound was 83%.

[0238] [ka]

[0239] Synthesis Example 8: Synthesis of alkali-soluble resin (d1) Under a stream of dry nitrogen, 108.0 g (1.00 mol) of m-cresol, 75.5 g (0.93 mol) of 37% by mass formaldehyde aqueous solution, 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone were charged. The mixture was then immersed in an oil bath, and the polycondensation reaction was carried out for 4 hours under reflux of the reaction solution. Subsequently, the temperature of the oil bath was raised over 3 hours, and then the pressure in the flask was reduced to 4.0 kPa to 6.7 kPa to remove volatile components. The dissolved resin was then cooled to room temperature to obtain an alkali-soluble resin (d1), which is a novolac-type phenolic resin. The weight-average molecular weight was 3,500 from GPC.

[0240] Synthesis Example 9: Synthesis of alkali-soluble resin (Ac-2) 100g of isopropyl alcohol was placed in a 1000cc four-necked flask. This was kept in an oil bath at 80°C, nitrogen sealed, and stirred. 30g of methyl methacrylate, 40g of styrene, 30g of methacrylic acid, and 2g of NN-azobisisobutyronitrile were mixed and added dropwise over 30 minutes using a dropping funnel. After continuing the reaction for 4 hours, 1g of hydroquinone monomethyl ether was added, and the mixture was returned to room temperature to complete polymerization. Next, 100g of isopropyl alcohol was added, and while maintaining the temperature at 75°C, 40g of glycidyl methacrylate and 3g of triethylbenzylammonium chloride were added and reacted for 3 hours to obtain a copolymer solution. Subsequently, the copolymer solution was cooled to room temperature, and then added to 5L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80°C for 24 hours to obtain the target acrylic resin, alkali-soluble resin (Ac-2). The weight-average molecular weight of this alkali-soluble resin (Ac-2) was 10,000.

[0241] Examples 1-6 and 15, Comparative Examples 1-4 and 8 Figure 1 shows a schematic diagram of the laminate used for evaluation.

[0242] A 10 nm transparent conductive ITO film was formed on the entire surface of an alkali-free glass plate 1 by sputtering, and etched onto a substrate as a patterned first electrode 8. An auxiliary electrode 3 was also formed simultaneously to allow for the extraction of the second electrode. The resulting substrate was ultrasonically cleaned for 10 minutes with "Semicoclean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.), then washed with ultrapure water, dried, and prepared as an evaluation intermediate.

[0243] Next, under a yellow light, the components were mixed according to the proportions shown in Table 1 and thoroughly stirred at room temperature to dissolve. The resulting solution was then filtered through a 0.45 μm pore size filter to obtain photosensitive resin compositions W1 to W12.

[0244] [Table 1]

[0245] Next, the obtained photosensitive resin compositions W1 to W12 were applied to the evaluation intermediate by spin coating, and pre-baked on a hot plate at 120°C for 2 minutes to form a photosensitive resin dry product with a thickness of approximately 2 μm. Then, the product was exposed to the full wavelength of a mercury lamp at an exposure dose of 120 mJ / cm² through a photomask having a predetermined pattern. 2 After irradiation with ultraviolet light (equivalent to h-ray), the material was developed with a 2.38 mass% TMAH aqueous solution for 60 seconds, rinsed with water, and two uncured pieces were prepared, one with partition pattern 4 and the other with partition pattern 5. Next, the material was cured by heating in a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C under a nitrogen atmosphere for 1 hour to form laminate A with partition pattern 4 or partition pattern 5.

[0246] Using laminate A with partition pattern 4 formed on it, (2) liquid repellency was evaluated, followed by (3) UV ozone resistance. The results are shown in Table 2. Furthermore, using laminate A with a second partition pattern 4 formed on it, (4-1) XPS analysis of the resin cured surface was performed, followed by (4-2) XPS analysis of the inside of the resin cured material. The elemental concentrations (atom%) of F and Si atoms obtained are shown in Table 2.

[0247] Next, using laminate A with partition wall pattern 5 formed on it, (5) durability was evaluated, and the results are shown in Table 2.

[0248] [Table 2]

[0249] Example 7 A laminate A was prepared by forming the partition wall pattern 4 described in Example 1 using the photosensitive resin composition W3, and (4-3) an evaluation of the XPS comparison between the surface and interior of the cured resin was performed. The cured resin of the photosensitive resin composition W3 will be referred to as cured resin W3. The C1s spectrum 22 of the surface of the obtained cured resin W3 and the C1s spectrum 23 of the interior of the cured resin W3 are shown in Figure 6.

[0250] The peak height of the peak originating from CF2 groups with a peak top in the bond energy range of 290-292 eV was higher in the C1s spectrum 22 on the surface of the cured resin W3. On the other hand, the peak height of the peak originating from CF3 groups with a peak top in the bond energy range of 292-294 eV was higher in the C1s spectrum 23 inside the cured resin W3. Furthermore, the cured resin W3 exhibited high liquid repellency after UV ozone treatment and showed high durability when used in display devices.

[0251] Comparative Example 5 A substrate was prepared using the photosensitive resin composition W10 to form the partition pattern 4 described in Example 1, and (4-3) an XPS comparison of the surface and interior of the cured resin was performed. The cured resin of the photosensitive resin composition W10 will be referred to as cured resin W10. The C1s spectrum 24 of the surface of the obtained cured resin W10 and the C1s spectrum 25 of the interior of the cured resin W10 are shown in Figure 7. In the comparison of the C1s spectrum 24 of the surface of the cured resin W10 and the C1s spectrum 25 of the interior of the cured resin W10, the peak height of the peak originating from CF2 groups and the peak height of the peak originating from CF3 groups were similar. In addition, the cured resin W10 showed poor evaluation of liquid repellency.

[0252] Example 8, Comparative Examples 6 and 7 Using the method described in <Composition Analysis by FT-IR>, the IR spectra of the resin cured products formed from the photosensitive resin compositions W3 (Example 8), W7 (Comparative Example 6), and W8 (Comparative Example 7) were measured. From the IR spectra of the resin cured products of the photosensitive resin compositions W3 and W7, peaks derived from the stretching vibration of the carbonyl group in the imide ring structure were obtained at 1775 - 1780 cm -1 and 1720 - 1725 cm -1 On the other hand, no spectrum indicating the presence of the imide ring structure was observed from the IR spectrum of the resin cured product of the photosensitive resin composition W8.

[0253] Using the method described in <Composition Analysis by Pyrolysis GC / MS>, the pyrolyzates of the resin cured products of the photosensitive resin compositions W3, W7, and W8 were analyzed. As a result, peaks attributed to the imide ring structure (840 - 850 seconds) were obtained from the resin cured products of the photosensitive resin compositions W3 and W7. On the other hand, no peak attributed to the imide ring structure was observed from the cured product of the photosensitive resin composition W8.

[0254] The evaluation result of (5) durability of the photosensitive resin composition W3 used in Example 8 was Example 3, with no change in the emission area and the judgment being A.

[0255] The evaluation result of (5) durability of the photosensitive resin composition W7 used in Comparative Example 6 was Comparative Example 1. Since the emission area decreased to 83%, the judgment was C. Although the presence of the imide ring structure was confirmed from the resin cured product of the photosensitive resin composition W7, it is presumed that the emission area decreased because the fluorine atom was 0 atom% in the XPS analysis inside the (4-2) resin cured product of Comparative Example 1.

[0256] The evaluation result of (5) durability of the photosensitive resin composition W8 used in Comparative Example 7 was Comparative Example 2. Since the emission area decreased to 60%, the judgment was D.

[0257] Thus, it was confirmed that using a resin cured product containing a compound having an imide ring structure as a partition wall allows the performance as a light-emitting element to be maintained even after durability testing under accelerated conditions, resulting in a highly durable organic EL display device.

[0258] Examples 9, 10 The thermal decomposition products of the cured resins of photosensitive resin compositions W3 (Example 9) and W6 (Example 10) were analyzed using the method described in <Compositional Analysis by Pyrolysis GC / MS> above. As a result of the analysis, a peak attributed to indene (450-455 seconds) was obtained from the cured resin of photosensitive resin composition W3. On the other hand, no peak attributed to indene was observed from the cured resin of photosensitive resin composition W6.

[0259] Next, photosensitive resin compositions W3 and W6 were applied to the substrate by spin coating and pre-baked on a 120°C hot plate for 2 minutes to form a photosensitive resin dry product with a thickness of approximately 2 μm. Subsequently, half of the area of ​​the photosensitive resin dry product was subjected to "half exposure," in which ultraviolet light was irradiated with the full wavelength of a mercury lamp so that the thickness after development would be 0.5 μm. For the remaining half of the area, the photosensitive resin dry product of W3, which has positive-type photosensitivity, was left unexposed so that its thickness would not decrease during the development process. On the other hand, W6, which has negative-type photosensitivity, was exposed to an exposure dose of 120 mJ / cm² to prevent thickness reduction during the development process. 2 The material was irradiated with ultraviolet light (equivalent to the h-ray). Next, it was developed with a 2.38 mass% TMAH aqueous solution for 60 seconds, followed by rinsing with water to prepare an intermediate with a photosensitive resin coating. Then, the obtained intermediate with the photosensitive resin coating was heated in a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C under a nitrogen atmosphere for 1 hour to cure it and prepare laminate B with cured resin.

[0260] Regarding the contact angle of PGMEA measured on the surface of the cured resin product of photosensitive resin composition W3, the unexposed area was 46° and the partially exposed area was 5° or less. Thus, it was confirmed that the surface of the cured resin product prepared by partially exposing a photosensitive resin composition containing an indene-containing compound exhibits hydrophilicity. In other words, it is possible to form both a hydrophobic and a hydrophilic cured resin product with a single photolithography. On the other hand, regarding the contact angle of PGMEA measured on the surface of the cured resin product of photosensitive resin composition W6, the exposed area was 46° and the partially exposed area was 40°, confirming hydrophobicity in both areas.

[0261] Example 11 Figure 1 shows a schematic diagram of the laminate used for evaluation.

[0262] A 10 nm transparent conductive ITO film was formed on the entire surface of an alkali-free glass plate 1 by sputtering, and etched onto a substrate as a patterned first electrode 8. An auxiliary electrode 3 was also formed simultaneously to allow for the extraction of the second electrode. The resulting substrate was ultrasonically cleaned for 10 minutes with "Semicoclean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.), then washed with ultrapure water, dried, and prepared as an evaluation intermediate.

[0263] Furthermore, the obtained photosensitive resin composition W3 was applied to the evaluation intermediate by spin coating and pre-baked on a hot plate at 120°C for 2 minutes to form a photosensitive resin dry product with a thickness of approximately 2 μm. Next, exposure was performed at the full wavelength of a mercury lamp at a dose of 120 mJ / cm² through a photomask having areas with adjusted transmittance to allow for a predetermined pattern and half exposure. 2 After irradiation with ultraviolet light (equivalent to h-ray), the substrate was developed with a 2.38 mass% TMAH aqueous solution for 60 seconds, rinsed with water, and an uncured partition wall pattern 12 was formed. Next, the substrate with the partition wall pattern 12 was heated in a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C for 1 hour under a nitrogen atmosphere to cure it and obtain a laminate A with the partition wall pattern 12 formed. The formed partition wall pattern 12 had a first layer thickness of 1.8 μm and a second layer thickness of 0.5 μm.

[0264] (4-1) XPS analysis was performed on the surface of the resin cured product W3 (second stage) formed with half exposure and the resin cured product W3 (first stage) formed with no exposure, and the elemental concentrations (atom%) of F and Si atoms obtained are shown in Table 3. Also, the C1s spectrum 26 of the surface of the resin cured product W3 (second stage) formed with half exposure is shown in Figure 8. In addition, (5) the durability evaluation results are shown in Table 3.

[0265] XPS analysis of the surface of the resin cured product W3 (second stage) formed by half exposure showed results that satisfied characteristic (v). The surface of the resin cured product W3 (second stage) formed by half exposure was hydrophilic, and in the evaluation of durability (5), as shown in Figure 2, the functional ink 11 could be continuously dropped onto the first electrode 8 patterned on the substrate and onto the second stage 10 of the resin cured product without any white spots.

[0266] [Table 3]

[0267] Example 12 The evaluation was the same as in Example 11, except that the photosensitive resin composition was changed to W5. For the resin cured product W5 (second stage) formed by half exposure and the resin cured product W5 (first stage) formed by no exposure, (4-1) XPS analysis was performed on the surface of the resin cured product, and the elemental concentrations (atom%) of F atoms and Si atoms obtained are shown in Table 3. The C1s spectrum 27 of the surface of the resin cured product W5 (second stage) formed by half exposure is shown in Figure 9. Also, (5) the durability evaluation results are shown in Table 3.

[0268] XPS analysis of the surface of the resin cured product W5 (second stage) formed by half exposure yielded results that satisfied characteristic (v). The surface of the resin cured product W5 (second stage) formed by half exposure was hydrophilic, and in the evaluation of durability (5), as shown in Figure 2, the functional ink 11 could be continuously dropped onto the first electrode 8 patterned on the substrate and onto the second stage 10 of the resin cured product without any white spots.

[0269] Compared to Example 11, we surmise that the durability test was poor because the concentration of fluorine atoms in the resin cured product (second stage) formed by half-exposure was lower.

[0270] Example 13 The evaluation was the same as in Example 11, except that the method for creating the partition wall pattern 12 was changed as follows.

[0271] A photosensitive resin composition W10 was applied to an evaluation intermediate by spin coating, and pre-baked on a hot plate at 120°C for 2 minutes to form a photosensitive resin dry product with a thickness of approximately 0.6 μm. Next, exposure was performed at the full wavelength of a mercury lamp at a dose of 60 mJ / cm² through a photomask having a predetermined pattern. 2 After irradiation with ultraviolet light (equivalent to the h-line), the material was developed with a 2.38% by mass TMAH aqueous solution for 50 seconds and rinsed with water. Next, it was cured by heating in a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C under a nitrogen atmosphere for 1 hour, forming a second stage 10 of the cured resin on the first electrode as shown in Figure 3. Next, the photosensitive resin composition W3 was applied by spin coating and pre-baked on a hot plate at 120°C for 2 minutes to form a photosensitive resin dry product with a thickness of approximately 2.0 μm. Next, exposure at 120 mJ / cm² was applied to the full wavelength of a mercury lamp through a photomask having a predetermined pattern. 2 After irradiation with ultraviolet light (equivalent to h-ray), the material was developed in a 2.38 mass% TMAH aqueous solution for 60 seconds and rinsed with water. Next, it was cured by heating in a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C under a nitrogen atmosphere for 1 hour, forming the first layer 9 of the resin curing material on the first electrode and the second layer 10 of the resin curing material, and two laminates A with partition wall patterns 12 were created as shown in Figure 3.

[0272] The formed partition pattern 12 had a first layer thickness of 1.8 μm and a second layer thickness of 0.5 μm.

[0273] For the cured resin product W10 (second stage) and cured resin product W3 (first stage), XPS analysis was performed on the surface of the cured resin product in the second stage (4-1), and the elemental concentrations (atom%) of F and Si atoms obtained are shown in Table 3. Also, the C1s spectrum 28 of the surface of the cured resin product W10 (second stage) is shown in Figure 10. Furthermore, the results of the durability evaluation (5) are shown in Table 3.

[0274] The XPS analysis results of the resin cured product W10 (second stage) surface satisfied characteristic (v). The resin cured product W10 (second stage) surface was hydrophilic, and in the evaluation of (5) durability, as shown in Figure 3, the functional ink 11 could be continuously dropped onto the first electrode 8 patterned on the substrate and onto the second stage 9 of the resin cured product without any whitening.

[0275] Example 14 The evaluation was carried out in the same manner as in Example 13, except that the photosensitive resin composition was changed to the type listed in Table 3. XPS analysis was performed on the surface of the resin cured product in the first and second stages (4-1), and the elemental concentrations (atom%) of F and Si atoms obtained are shown in Table 3. In addition, the C1s spectrum 29 of the surface of the resin cured product W10 in the second stage is shown in Figure 11. Furthermore, the results of the durability evaluation (5) are shown in Table 3. The XPS analysis results of the resin cured product W10 (second stage) surface satisfied characteristic (v). The resin cured product W10 (second stage) surface was hydrophilic, and in the evaluation of (5) durability, as shown in Figure 3, the functional ink 11 could be continuously dropped onto the first electrode 8 patterned on the substrate and onto the second stage 9 of the resin cured product without any whitening.

[0276] Compared to Example 13, Example 14 showed a reduction in the luminescent area in the durability evaluation of the display device. It is presumed that the reduction in the luminescent area was due to the fact that the concentration of F atoms in the photosensitive resin composition W8 used in the first stage was 0 atom%, as analyzed inside the cured resin by XPS in Comparative Example 2.

[0277] Example 16 The evaluation was the same as in Example 11, except that the photosensitive resin composition was changed to W11. For the resin cured product W11 (second stage) formed by half exposure and the resin cured product W11 (first stage) formed by no exposure, (4-1) XPS analysis was performed on the surface of the resin cured product, and the elemental concentrations (atom%) of F atoms and Si atoms obtained are shown in Table 3. The C1s spectrum 31 of the surface of the resin cured product W5 (second stage) formed by half exposure is shown in Figure 12. Also, (5) the durability evaluation results are shown in Table 3.

[0278] XPS analysis of the surface of the resin cured product W11 (second stage) formed by half exposure showed results that satisfied characteristic (v). The surface of the resin cured product W11 (second stage) formed by half exposure was hydrophilic, and in the evaluation of durability (5), as shown in Figure 2, the functional ink 11 could be continuously dropped onto the first electrode 8 patterned on the substrate and onto the second stage 10 of the resin cured product without any white spots.

[0279] Example 17 The evaluation was carried out in the same manner as in Example 13, except that the photosensitive resin composition was changed to the type listed in Table 3. XPS analysis was performed on the surface of the resin cured product in the first and second stages (4-1), and the elemental concentrations (atom%) of F and Si atoms obtained are shown in Table 3. Also, the C1s spectrum 32 of the surface of the resin cured product W10 in the second stage is shown in Figure 13. Furthermore, the results of the durability evaluation (5) are shown in Table 3. The XPS analysis results of the resin cured product W10 (second stage) surface satisfied characteristic (v). The resin cured product W10 (second stage) surface was hydrophilic, and in the evaluation of (5) durability, as shown in Figure 3, the functional ink 11 could be continuously dropped onto the first electrode 8 patterned on the substrate and onto the second stage 9 of the resin cured product without any whitening.

[0280] Compared to Example 13, Example 17 showed a reduction in the luminescent area in the durability evaluation of the display device. It is presumed that the reduction in the luminescent area was due to the fact that the concentration of F atoms in the photosensitive resin composition W12 used in the first stage was 0 atom%, as analyzed inside the cured resin by XPS in Comparative Example 8. [Explanation of symbols]

[0281] 1. Alkali-free glass substrate 3 Auxiliary electrode 4 partition patterns 5 partition patterns 6 Organic EL layer 7 Second electrode 8. First electrode patterned on the substrate 9. First stage of the cured resin 10. Second stage of the cured resin 11 Functional Layers 12 partition patterns 13 circuit boards 14 Planarization layer 16 Cured resin 17 The surface opposite to the interface where the first electrode and the cured resin come into contact. 18 Interface where the first electrode and the cured resin product come into contact 19 Perpendicular to the interface where the first electrode and the cured resin are in contact, and in the direction from the substrate to the cured resin, and in a range of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. 20 The surface opposite to the interface where the first electrode of the first stage of the cured resin and the cured resin come into contact. 21 The surface opposite to the interface where the first electrode of the second stage of the cured resin and the cured resin come into contact. 22 C1s spectrum of the surface of resin cured product W3 23 C1s spectrum inside resin cured product W3 24 C1s spectrum of the surface of resin cured product W10 25 C1s spectrum inside resin cured product W10 26 C1s spectrum of the surface of resin cured product W3 (second stage) formed by half exposure 27 C1s spectrum of the surface of resin cured product W5 (second stage) formed by half exposure 28 C1s spectrum of the surface of the second stage resin cured product W10 29 C1s spectrum of the surface of the second stage resin cured product W10 30 Perpendicular to the interface where the first electrode and the cured resin contact, and in the direction from the substrate to the cured resin, starting from the interface where the first electrode and the cured resin contact, 100 nm 31 C1s spectrum of the surface of resin cured product W5 (second stage) formed by half exposure. 32 C1s spectrum of the surface of the second stage resin cured product W10

Claims

1. A laminate comprising a substrate, a first electrode patterned on the substrate, and a cured resin in that order, wherein at least a portion of the cured resin on the first electrode is open, The resin cured product is a stepped resin cured product having a first stage with a thickness of 0.8 μm to 10.0 μm starting from the interface where the first electrode and the resin cured product are in contact, and a second stage with a thickness of 0.1 μm to 0.7 μm starting from the interface where the first electrode and the resin cured product are in contact. The first stage of the cured resin product is obtained by curing a photosensitive resin composition containing a compound (a-1) having 7 to 21 fluorine atoms and 5 to 12 carbon atoms of an alkyl fluoride and a compound (a-2) having a siloxane structure, or a photosensitive resin composition containing a compound having 7 to 21 fluorine atoms and 5 to 12 carbon atoms of an alkyl fluoride and a siloxane structure. The second stage of the resin cured product is obtained by curing a photosensitive resin composition containing an alkali-soluble resin (b-1) having CF3 groups and an alkali-soluble resin (b-2) having a siloxane structure. or The first and second stages of the cured resin product are obtained by curing a photosensitive resin composition that includes a compound (a-1) having 7 to 21 fluorine atoms and 5 to 12 carbon atoms in a fluorinated alkyl group and a compound (a-2) having a siloxane structure, or a compound having 7 to 21 fluorine atoms and 5 to 12 carbon atoms in a fluorinated alkyl group and a siloxane structure, and further includes an alkali-soluble resin (b-1) having a CF3 group and an alkali-soluble resin (b-2) having a siloxane structure. In analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS), the laminate is such that the first stage of the resin cured product satisfies characteristic (i), and the second stage of the resin cured product satisfies characteristics (ii) and (v). (i) The concentration of F atoms in the resin cured product, as measured from at least a portion of the surface opposite to the interface where the first electrode and the resin cured product are in contact, is 8.1 atom% or more and 30.0 atom% or less, and the concentration of Si atoms is 1.0 atom% or more and 6.0 atom% or less. (ii) The concentration of F atoms in the resin cured product, measured perpendicular to the interface where the first electrode and the resin cured product are in contact, and in the direction from the substrate to the resin cured product, in a range of 100 to 200 nm starting from the interface where the first electrode and the resin cured product are in contact, is 0.1 atom% or more and 8.0 atom% or less. (v) The concentration of F atoms measured from at least a portion of the surface opposite to the interface between the first electrode and the resin cured product is 0.1 atom% or more and 20.0 atom% or less, and the concentration of Si atoms is 0.1 atom% or more and 0.9 atom% or less, and the peak with the maximum peak height measured in the bond energy range of 290 to 295 eV in the C1s spectrum is a peak originating from a CF3 group with a peak top in the range of 292 to 294 eV.

2. The laminate according to claim 1, wherein the concentration of F atoms in the above characteristic (ii) is 4.0 atom% or more and 7.5 atom% or less.

3. In the analysis of the cured resin product by X-ray photoelectron spectroscopy (XPS), The C1s spectrum [A] of the resin cured product, measured from at least a portion of the surface opposite to the interface where the first electrode and the resin cured product are in contact, The C1s spectrum [B] of the resin cured product, measured perpendicular to the interface where the first electrode and the resin cured product are in contact, and in the direction from the substrate to the resin cured product, and starting from the interface where the first electrode and the resin cured product are in contact, is measured in a range of 100 to 200 nm. A laminate according to claim 1 or 2 that satisfies characteristic (iii) and characteristic (iv). (iii) CF with a peak top in the binding energy range of 290–292 eV in the C1s spectrum [B] ２ The peak height in the C1s spectrum [A] is higher than the peak height of the peak originating from the group. (iv) CF with a peak top in the binding energy range of 292–294 eV in the C1s spectrum [A] ３ The peak height in the C1s spectrum [B] is higher than the peak height of the peak originating from the group.

4. The laminate according to any one of claims 1 to 3, wherein the cured resin product comprises a compound having an imide ring structure.

5. The laminate according to any one of claims 1 to 4, wherein the cured resin product comprises a compound having an indene structure.

6. The laminate according to claim 1, wherein the concentration of F atoms in characteristic (v) is 8.0 atom% or more and 18.0 atom% or less.

7. A display device comprising a laminate according to any one of claims 1 to 6.

8. A method for manufacturing a display device, comprising steps (5) and (6) in this order. (5) A step in which a functional layer is formed by applying a functional ink onto the first electrode using an inkjet printer in the laminate according to any one of claims 1 to 6. (6) Step of forming a second electrode on the functional layer.

9. A method for manufacturing a display device, comprising steps (7) and (8) in this order. (7) A step in which a functional layer is formed in the laminate according to claim 1 or 6 by applying a functional ink on the first electrode and the second layer of the cured resin by inkjet. (8) Step of forming a second electrode on the functional layer.

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