CN116745118A

CN116745118A - Laminate, display device, and method for manufacturing display device

Info

Publication number: CN116745118A
Application number: CN202280008462.0A
Authority: CN
Inventors: 有本真治; 立松结花; 龟本聪; 三好一登
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2021-02-24
Filing date: 2022-02-10
Publication date: 2023-09-12
Also published as: JPWO2022181351A1; TW202243910A; WO2022181351A1; KR20230148808A

Abstract

The purpose of the present invention is to obtain a laminate which has a resin cured product that has high liquid repellency after UV ozone treatment and has high durability when used in a display device. In order to achieve the above object, the laminate of the present invention is a laminate comprising a substrate, a 1 st electrode patterned on the substrate, and a resin cured product sequentially laminated, wherein at least a part of the resin cured product located on the 1 st electrode is opened, wherein the analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS) satisfies specific characteristics.

Description

Laminate, display device, and method for manufacturing display device

Technical Field

The invention relates to a laminate, a display device, and a method for manufacturing the display device.

Background

In display devices having a thin display such as a smart phone, a tablet PC, and a television, a large number of products have been developed in which a functional layer is formed by a printing method typified by an inkjet method. For example, in the case of an organic electroluminescence (hereinafter, "organic EL") display device, there is known a method of forming a barrier rib pattern on a substrate, and then, dropping a functional material solution such as a light-emitting material, a hole-transporting material, or an electron-transporting material into an opening between barrier ribs by inkjet, thereby forming an organic EL display device having a functional layer.

In general, an organic EL display device includes a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and emits light by applying a voltage between the first electrode and the second electrode that face each other. Among these, as a material for a planarizing layer and a material for an insulating layer, a photosensitive resin composition which can be patterned by ultraviolet irradiation is generally used. Among them, a photosensitive resin composition using a polyimide resin or a polybenzoxazole resin is suitably used in that it has high heat resistance and generates a small amount of gas components from a cured film, and thus can provide an organic EL display device having high durability (patent document 1).

When forming the functional layer by the inkjet method, it is necessary to impart liquid repellency to the upper surface of the partition wall in order to prevent color mixing or the like of ink injected into the adjacent opening. In addition, in order to prevent white spots in the organic EL display device, the openings between the barrier ribs need to have good wettability with respect to ink.

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

In addition, a method of forming a partition wall from a photosensitive resin composition containing an alkali-soluble resin and a compound having liquid repellency has been studied. For example, a resist composition containing a fluorinated acrylic polymer (patent document 3) and a photosensitive resin composition containing a polysiloxane having a fluorinated alkyl group (patent document 4) have been studied.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2002-91343

Patent document 2: japanese patent laid-open No. 2002-207114

Patent document 3: japanese patent application laid-open No. 2012-220855

Patent document 4: international publication No. 2019/159700.

Disclosure of Invention

Problems to be solved by the invention

In the technique of patent document 1, the upper surface of the partition wall formed does not have liquid repellency, and therefore there is a problem in that a functional material solution dropped by an inkjet method passes over the partition wall and is mixed into the pixels in the vicinity thereof, and light emission failure occurs.

In the technique of patent document 2, a liquid repellent component is also attached to the openings between the partition walls by the fluorination treatment, and there is a problem that the wettability of the ink in the openings becomes insufficient.

The techniques of patent document 3 and patent document 4 have sufficient liquid repellency, and can be used as a photosensitive resin composition to form a pattern. However, the fluorine-based acrylic polymer of patent document 3 has poor UV ozone resistance, and the liquid repellency of the upper surface of the partition wall after UV ozone treatment is insufficient.

The polysiloxane having fluorine atoms of patent document 4 is excellent in UV ozone resistance, and can impart sufficient liquid repellency to the upper surface of the partition wall after UV ozone treatment. On the other hand, the cured product has high water absorption and has a problem in durability when used for the partition wall of a display device.

Accordingly, an object of the present invention is to obtain a laminate which has a cured resin having high liquid repellency after UV ozone treatment and which has high durability when used in a display device.

Means for solving the problems

In order to solve the above problems, the present invention has the following configuration.

That is, the laminate of the present invention is a laminate comprising a substrate, a patterned 1 st electrode on the substrate, and a resin cured product sequentially laminated, wherein at least a part of the resin cured product located on the 1 st electrode is opened,

analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS) satisfies the characteristics (i) and (ii).

(i) The concentration of F atoms of the resin cured product measured from at least a part of a surface opposite to the interface between the 1 st electrode and the resin cured product is 8.1atom% or more and 30.0atom% or less, and the concentration of Si atoms is 1.0atom% or more and 6.0atom% or less;

(ii) The concentration of F atoms in the resin cured product measured at any position within a range of 100-200 nm starting from the interface between the 1 st electrode and the resin cured product in a direction perpendicular to the interface between the 1 st electrode and the resin cured product and in which the substrate faces the resin cured product is 0.1 to 8.0 atom%.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a laminate having a cured resin having high liquid repellency after UV ozone treatment and having high durability when used in a display device can be obtained.

Drawings

FIG. 1 is a schematic view of a laminate used for evaluation of examples.

Fig. 2 is a schematic view of the partition wall pattern 12 used for evaluation in the example.

Fig. 3 is a schematic view of the partition wall pattern 12 used for evaluation in the example.

Fig. 4 is a schematic cross-sectional view of an example of the laminate.

Fig. 5 is a schematic cross-sectional view of another example of the laminate.

FIG. 6 is a C1s spectrum of XPS analysis of example 7.

FIG. 7 is a C1s spectrum of XPS analysis of comparative example 5.

FIG. 8 is a C1s spectrum of XPS analysis of example 11.

FIG. 9 is a C1s spectrum of XPS analysis of example 12.

FIG. 10 is a C1s spectrum of XPS analysis of example 13.

FIG. 11 is a C1s spectrum of XPS analysis of example 14.

FIG. 12 is a C1s spectrum of XPS analysis of example 16.

FIG. 13 is a C1s spectrum of XPS analysis of example 17.

Detailed Description

Specific embodiments of the present invention will be described in detail.

< laminate >

The laminate of the present invention is a laminate comprising a substrate, a patterned 1 st electrode on the substrate, and a resin cured product sequentially laminated, wherein at least a part of the resin cured product on the 1 st electrode is opened,

(ii) The concentration of F atoms in the resin cured product measured from any one of the interfaces between the 1 st electrode and the resin cured product in the range of 100 to 200nm as a starting point in the direction perpendicular to the interface between the 1 st electrode and the resin cured product and toward the resin cured product from the substrate is 0.1 to 8.0 atom%.

The resin cured product provided in the laminate of the present invention has the characteristic (i) as a surface characteristic and the characteristic (ii) inside the resin cured product. With such composition characteristics, the laminate of the present invention has a cured resin product having high liquid repellency after UV ozone treatment, and is excellent in durability when used in a display device.

Next, characteristics (i) of a resin cured product obtained by X-ray photoelectron spectroscopy (XPS) will be described.

The characteristic (i) is measured from at least a part of a surface of the resin cured product on the opposite side of the interface between the 1 st electrode and the resin cured product. It is preferable that the measurement is carried out at any position within a range of 100 μm from the end of the opening of the cured resin. By measuring this range, the liquid repellency of the surface of the resin cured product to the functional ink can be analyzed.

As one of the characteristics (i), the concentration of F atoms is 8.1atom% or more and 30.0atom% or less, more preferably 15.0atom% or more and 26atom% or less. When the concentration of the F atom is 8.1atom% or more, the liquid repellency of the surface of the resin cured product is excellent. On the other hand, by setting the concentration of the F atoms to 30atom% or less, aggregation of the F atoms can be suppressed, and a resin cured product with few defects can be obtained. Further, as the second characteristic (i), the concentration of Si atoms is 1.0atom% or more and 6.0atom% or less, more preferably 1.5atom% or more and 4.5atom% or less. By setting the Si atom concentration to 1.0atom% or more, the UV ozone resistance of the resin cured product is improved, and good liquid repellency can be obtained even after UV ozone treatment. On the other hand, by setting the concentration of Si atoms to 6.0atom% or less, aggregation of Si atoms can be suppressed, and a resin cured product with few defects can be obtained.

The laminate of the present invention is produced by a method of forming a resin cured product from a photosensitive resin composition containing a compound (a-1) having a fluoroalkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms and a compound (a-2) having a siloxane structure, as a method of satisfying the characteristic (i). The siloxane structure refers to a structure in which silicon (Si) and oxygen (O) are alternately bonded. The silicone composition may contain both the compound (a-1) having a fluoroalkyl group having 7 to 21 carbon atoms and a fluoroalkyl group having 5 to 12 carbon atoms and the compound (a-2) having a siloxane structure, or may contain a fluoroalkyl group having 7 to 21 carbon atoms and a fluoroalkyl group having 5 to 12 carbon atoms and a siloxane structure in one compound as in the case of the polysiloxane (A) described later.

As a method for adjusting the concentration of the F atom in the characteristic (i) within the above range, there is a method for adjusting the content of the compound (a-1) having a fluoroalkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms in the photosensitive resin composition. If the content is increased, the concentration of the F atom of the property (i) can be increased; if the content is reduced, the concentration of the F atoms of the characteristic (i) can be reduced. In addition, there is a method of adjusting the concentration of the fluoroalkyl group of the compound (a-1). If the concentration of fluoroalkyl groups is increased, the concentration of F atoms of the characteristic (i) can be increased; if the concentration of fluoroalkyl groups is reduced, the concentration of F atoms of the characteristic (i) can be reduced.

As a method for adjusting the concentration of Si atoms of the property (i) within the above range, there is a method of adjusting the content of the compound (a-2) having a siloxane structure in the photosensitive resin composition. If the content is increased, the concentration of Si atoms of the characteristic (i) can be increased; if the content is reduced, the concentration of Si atoms of the characteristic (i) can be reduced. In addition, there is a method of adjusting the concentration of the siloxane structure of the compound (a-2). If the concentration of the siloxane structure is increased, the concentration of Si atoms of the characteristic (i) can be increased; if the concentration of the siloxane structure is reduced, the concentration of Si atoms of the characteristic (i) can be reduced.

The structure of the compound (a-1) having a fluoroalkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms is not particularly limited. For example, there may be mentioned an acrylic resin obtained by copolymerizing at least one selected from the group consisting of 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate and 2- (perfluorooctyl) ethyl (meth) acrylate, and a polysiloxane (a) described later. From the viewpoint of UV ozone resistance, the polysiloxane (a) described later is preferable.

The structure of the compound (a-2) having a siloxane structure is not particularly limited. Examples thereof include alkyl-modified silicone, polyether-modified silicone, and polysiloxane (a) described later. From the viewpoint of biasing the surface of the resin cured product, polyether-modified silicone and polysiloxane (a) described later are preferable. Further, from the viewpoint of liquid repellency, a polysiloxane (a) described later is more preferable.

Examples of the polyether-modified silicone include KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-642 (made by Xinyue chemical Co., ltd.), SH8400, SH8700, SF8410 (made by Tourethrin Co., ltd.), BYK-300, BYK-306, BYK-307, BYK-320, BYK-325, and BYK-330 (made by BYK-Chemie Co.).

The characteristic (i) is preferably analyzed by an XPS device in which the detector is tilted at 45 DEG with respect to the sample surface. By setting the inclination angle of the detector to 45 °, the area near the surface of the resin cured product can be analyzed.

Next, characteristics (ii) of a resin cured product obtained by X-ray photoelectron spectroscopy (XPS) will be described.

Regarding the characteristic (ii), the characteristic (ii) was measured at any position in the range of 100 to 200nm from the interface between the 1 st electrode and the resin cured product, in the direction perpendicular to the interface between the 1 st electrode and the resin cured product and toward the resin cured product from the substrate. When the thickness of the resin cured product is 200nm or less, the measurement is performed as a central value of the thickness of the resin cured product. By providing the resin cured product with an F atom, the water absorption of the resin cured product is reduced, and corrosion of the electrode is suppressed, so that the durability of the display device can be improved.

In the characteristic (ii), the concentration of the F atom is 0.1atom% or more and 8.0atom% or less, more preferably 4.0atom% or more and 7.5atom% or less. When the concentration of the F atom is 0.1atom% or more, the water absorption of the resin cured product is reduced, and corrosion of the electrode is suppressed, so that the durability of the display device can be improved. On the other hand, by setting the concentration of the F atom to 8.0atom% or less, durability of the display device and good mechanical properties of the resin cured product can be achieved.

As a method for satisfying the characteristic (ii) of the laminate of the present invention, for example, a method comprising the step of having CF ₃ A method for forming a resin cured product from the photosensitive resin composition of the base alkali-soluble resin (b-1). CF (compact flash) ₃ The radical bias is small in the nature of the surface of the resin cured product, and can cause the F atoms to stay in the inside of the resin cured product.

The concentration of F atoms as a catalyst for imparting the property (ii) is within the above rangeFor example, the photosensitive resin composition has CF therein ₃ A method of adjusting the content of the base alkali-soluble resin (b-1). If the content is increased, the concentration of the F atom of the property (ii) can be increased; if the content is reduced, the concentration of the F atoms in the characteristic (ii) can be reduced. In addition, CF is provided for the alkali-soluble resin (b-1) ₃ And (3) a method for adjusting the concentration of the radicals. If CF is increased ₃ The concentration of radicals can then increase the concentration of F atoms of characteristic (ii); if CF is reduced ₃ The concentration of radicals can then be reduced by the concentration of F atoms of the character (ii). For having CF ₃ The type of the main chain skeleton and the side chain of the polymer constituting the base alkali-soluble resin (b-1) is not limited. Examples thereof 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, has CF ₃ The base-soluble resin (b-1) preferably contains one or more selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, a precursor of any of them, and copolymers thereof. Since these alkali-soluble resins have high heat resistance, when used in a display device, the amount of outgas at a high temperature of 200 ℃ or higher after heat treatment is reduced, and the durability of the display device can be improved.

The characteristic (ii) can be obtained by excavating the cured product with an Ar gas cluster ion beam (Ar-GCIB), exposing any one of the areas ranging from 100 to 200nm from the 1 st electrode in a direction perpendicular to the interface between the 1 st electrode and the cured product and toward the cured product from the substrate, and then performing X-ray photoelectron spectroscopy (XPS) analysis.

In the laminate of the present invention, the thickness of the resin cured product starting from the interface between the 1 st electrode and the resin cured product is 0.8 to 10. Mu.m. When the thickness is 0.8 μm or more, the functional ink can be easily left when the functional ink is applied to the region where at least a part of the resin cured product on the 1 st electrode is opened. In addition, the thickness is preferably 10 μm or less from the viewpoint of easiness of processing by photolithography or the like.

The method for forming the resin cured product in which at least a part of the 1 st electrode is opened is not particularly limited in the laminate of the present invention. For example, the resin composition can be formed by a method for producing a resin cured product using the photosensitive resin composition described below. As another method, there is a method of forming a resin cured product on the front surface of a substrate, masking an arbitrary region with a photoresist, and etching an opening.

The resin cured product provided in the laminate of the present invention is not particularly limited as long as it has the above-mentioned properties (i) and (ii) obtained by analysis using XPS. The resin cured product having such characteristics can be formed into a resin cured product having both the characteristics (i) and (ii) by using, for example, a photosensitive resin composition described below. The resin cured product having the characteristic (i) and the resin cured product having the characteristic (ii) may be laminated.

The laminate of the present invention comprises a substrate. As the substrate, a substrate preferable for supporting the display device and transporting the display device in the subsequent steps, such as a metal, glass, and a resin film, can be appropriately selected. In the case of a glass substrate, soda lime glass, alkali-free glass, or the like may be used, and the thickness may be any thickness sufficient to maintain mechanical strength. As for the material of the glass, alkali-free glass is preferable because the smaller the amount of ions eluted from the glass, but SiO is also commercially available ₂ Soda lime glass of an equal barrier coating, therefore, the soda lime glass can be used. In the case of the resin film, the resin film containing a resin material selected from polyimide, polyamide, polybenzoxazole, polyamideimide and poly (p-xylene) is preferable, and these resin materials may be contained alone or in combination of plural kinds. For example, when forming a resin film from polyimide, the resin film may be formed by applying a solution containing polyamic acid (including a part of imidized polyamic acid) or soluble polyimide, which is a polyimide precursor, on a support substrate and baking the solution, and then peeling the polyimide resin film from the support substrate.

The laminate of the present invention includes a patterned 1 st electrode on a substrate. The 1 st electrode preferably contains ITO (indium tin oxide), IZO (indium zinc oxide), znO (zinc oxide), ag, al, or the like. In addition, patterning of the 1 st electrode may be performed by a known method. For example, a method of forming the 1 st electrode on the entire surface of the substrate by sputtering, masking an arbitrary region with a photoresist, and etching an opening is given.

The laminate of the present invention may further comprise a planarizing layer between the substrate and the 1 st electrode patterned on the substrate. In the case of using the laminate of the present invention for a display device, a TFT (thin film transistor) and a wiring which is located at a side portion of the TFT and connected to the TFT are often provided on a substrate such as glass. When the 1 st electrode follows the irregularities of the wiring, an appearance defect such as uneven light emission occurs. Therefore, a planarizing layer is formed on the driving circuit so as to cover the irregularities, and the 1 st electrode is further provided on the planarizing layer. The planarizing layer preferably contains a resin material selected from the group consisting of polyimide, polyamide, polybenzoxazole, polyamideimide, acrylic, cardo, and poly (p-xylene), and these resin materials may be contained alone or in combination.

Fig. 4 is a schematic cross-sectional view of an example of the laminate of the present invention. The planarizing layer 14, the patterned 1 st electrode 8, and the resin cured product 16 are sequentially laminated on the substrate 13, and at least a part of the resin cured product 16 located on the patterned 1 st electrode 8 is opened. The characteristic (i) of the resin cured product obtained by X-ray photoelectron spectroscopy (XPS) analysis was measured from the surface 17 on the opposite side of the interface between the 1 st electrode and the resin cured product. XPS is preferably measured from any place within a range of 100 μm from the end of the opening of the resin cured product 16. Further, the characteristic (ii) is measured at any position in the range of 100nm from 100nm30 to 100nm (i.e., in the range of 19 from 100 to 200nm from the interface between the 1 st electrode and the resin cured product in the direction perpendicular to the interface between the 1 st electrode and the resin cured product and from the substrate toward the resin cured product) in the direction perpendicular to the interface between the 1 st electrode and the resin cured product and from the substrate toward the resin cured product. The opening of the 1 st electrode patterned on the substrate is measured at any position in the range of 100 to 200nm from the height of the 1 st electrode, as a portion where the 1 st electrode is present, such as a portion 19 in the range of 100 to 200nm starting from the interface of the 1 st electrode and the resin cured product in the direction perpendicular to the interface of the 1 st electrode and the resin cured product and facing the resin cured product from the substrate. When there is a variation in the thickness of the 1 st electrode, the opening of the patterned 1 st electrode is configured to have a 1 st electrode having an average thickness at the end of the opening.

In the laminate of the present invention, it is preferable that the C1s spectrum [ A ] and the C1s spectrum [ B ] satisfy the characteristic (iii) and the characteristic (iv) in the analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS),

the C1s spectrum [ A ] is a C1s spectrum of the resin cured product measured from at least a part of a surface of the resin cured product on the opposite side of the interface between the 1 st electrode and the resin cured product,

the C1s spectrum [ B ] is a C1s spectrum of the resin cured product measured from any one of the interfaces between the 1 st electrode and the resin cured product as a starting point in a range of 100 to 200nm in a direction perpendicular to the interface between the 1 st electrode and the resin cured product and toward the resin cured product from the substrate,

(iii) And C1s spectrum [ B]From CF having peaks in the range of bond energy 290-292 eV ₂ C1s Spectrum [ A ] peak height of group peak]Is higher than the peak height of the die,

(iv) With C1s spectrum [ A]From CF having peaks in the bond energy range of 292-294 eV ₃ C1s Spectrum [ B ] peak height of group peak]Is higher.

The C1s spectrum [ a ] is a spectrum of a cured product surface measured from at least a part of a surface of the cured product on the opposite side of the interface between the 1 st electrode and the cured product. On the other hand, the C1s spectrum [ B ] is a C1s spectrum inside the cured product measured at any one of the positions ranging from 100 to 200nm starting from the interface between the 1 st electrode and the resin cured product in the direction perpendicular to the interface between the 1 st electrode and the resin cured product and directed from the substrate toward the resin cured product. When the thickness of the resin cured product is 200nm or less, the measurement is performed as a central value of the thickness of the resin cured product.

By making the resin cured product provided in the laminate of the present invention exhibit the property (iii), the liquid repellency of the surface of the resin cured product is excellent. For those from CF that exhibit peaks in the range of bond energy 290-292 eV ₂ The peak structure of the group includes, for example, heptafluoropentyl group, nonafluorohexyl group, tridecylfluorooctyl group, heptadecafluorodecyl group, 5,5,6,6,7,7,7-heptafluoro-4, 4-bis (trifluoromethyl) heptyl group, and the like, and has a property of being biased to the surface of the resin cured product, and can impart good liquid repellency to the surface of the resin cured product.

The resin cured product provided in the laminate of the present invention exhibits the characteristic (iv), whereby the water absorption of the resin cured product is reduced, and corrosion of the electrode is suppressed, so that the durability of the display device can be improved. CF (compact flash) ₃ The groups are biased to have small properties on the surface of the cured resin, and thus the F atoms can stay in the cured resin.

The characteristics (iii) and (iv) are preferably obtained by comparing the C1s spectrum [ A ] and the C1s spectrum [ B ] measured by the same XPS apparatus. The C1s spectrum [ A ] is measured from at least a part of the surface of the resin cured product on the opposite side of the interface between the 1 st electrode and the resin cured product. Then, the resin cured product was excavated by an Ar gas cluster ion beam (Ar-GCIB), and the C1s spectrum [ B ] was measured by exposing any one of the areas in the range of 100 to 200nm from the interface between the 1 st electrode and the resin cured product as the starting point in the direction from the substrate toward the cured product, perpendicular to the interface between the 1 st electrode and the resin cured product.

Fig. 4 is a schematic cross-sectional view of an example of the laminate of the present invention. The planarizing layer 14, the patterned 1 st electrode 8, and the resin cured product 16 are sequentially stacked on the substrate 13, and at least a part of the resin cured product 16 located on the 1 st electrode 8 is opened. In the analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS), the C1s spectrum [ a ] was measured from the surface 17 on the opposite side of the interface between the 1 st electrode and the resin cured product. The measurement is preferably performed at any position within a range of 100 μm from the end of the opening of the resin cured product 16. The C1s spectrum [ B ] is measured at any position from 100nm30 to 100nm in the direction perpendicular to the interface 18 between the 1 st electrode and the resin cured product and facing the resin cured product from the substrate, and from 100 to 200nm in the range from the interface between the 1 st electrode and the resin cured product (i.e., in the range from 100 to 200nm in the direction perpendicular to the interface between the 1 st electrode and the resin cured product and facing the resin cured product from the substrate, and from the interface between the 1 st electrode and the resin cured product, as the starting point, 19). The opening of the patterned 1 st electrode was measured at any one of the regions 19 ranging from 100 to 200nm from the height of the 1 st electrode as a portion where the 1 st electrode is present, such as a region 19 ranging from 100 to 200nm from the interface of the 1 st electrode and the resin cured product in a direction perpendicular to the interface of the 1 st electrode and the resin cured product and facing the substrate toward the resin cured product. When there is a variation in the thickness of the 1 st electrode, the opening of the patterned 1 st electrode is configured to have a 1 st electrode having an average thickness at the end of the opening.

As a method of forming the resin cured product provided in the laminate of the present invention, for example, a resin cured product satisfying the characteristics (i) to (iv) can be formed by using a photosensitive resin composition described below. The resin cured product having the characteristics (i) and (iii) and the resin cured product having the characteristics (ii) and (iv) may be laminated.

In the laminate of the present invention, the resin cured product preferably contains a compound having an imide ring structure. The compound having an imide ring structure is preferably derived from the structure of a polyimide resin or a residue thereof. Examples of the polyimide resin include polyimide, polyamideimide, a precursor thereof, and a copolymer thereof described in the alkali-soluble resin (B) described below. When the resin cured product is made to contain a compound having an imide ring structure, the amount of outgas at high temperature is small, and when the laminate is used in an organic EL display device, an organic EL display device with small pixel shrinkage and excellent durability can be obtained.

In the laminate of the present invention, the resin cured product preferably contains a compound having an indene structure. The compound having an indene structure preferably derives from the structure of a quinone diazide compound or a residue thereof. Examples of the quinone diazide compound include a quinone diazide compound (C-2) described below. The positive photosensitive resin composition can be obtained by incorporating a quinone diazide compound into the photosensitive resin composition described below.

In the laminate of the present invention, when the resin cured product is a cured product of a positive photosensitive resin composition, the surface of the resin cured product formed by "half exposure" described later is free from liquid repellency, and can have good ink coatability. That is, a resin cured product having a liquid repellent surface and a resin cured product having a lyophilic surface can be formed by one-time photolithography.

In the laminate of the present invention, it is preferable that the resin cured product has a 1 st order having a thickness of 0.8 μm to 10.0 μm starting from the interface between the 1 st electrode and the resin cured product, and a 2 nd order having a step shape of 0.1 μm to 0.7 μm starting from the interface between the 1 st electrode and the resin cured product, and further, in the analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS), the 1 st order of the resin cured product satisfies the characteristic (i) and the 2 nd order of the resin cured product satisfies the characteristic (v).

(v) A concentration of F atoms measured from at least a part of a surface of the resin cured product on the opposite side of the interface between the 1 st electrode and the resin cured product is 0.1 to 20.0atom%, a concentration of Si atoms is 0.1 to 0.9atom%, and a peak having a maximum peak height measured in a range of 290 to 295eV in a C1s spectrum is CF having a peak top in a range of 292 to 294eV ₃ Peaks of the groups.

The 1 st order of the resin cured product having a thickness of 0.8 μm to 10.0 μm starting from the interface between the 1 st electrode and the resin cured product is a resin cured product having a liquid repellent surface of the characteristic (i). When the thickness is 0.8 μm or more, the functional ink can be easily left when the functional ink is applied to the region where at least a part of the resin cured product on the 1 st electrode is opened. In addition, the thickness is preferably 10.0 μm or less from the viewpoint of easiness of processing by photolithography or the like.

The 2 nd step of the resin cured product having a thickness of 0.1 μm to 0.7 μm starting from the interface between the 1 st electrode and the resin cured product is a resin cured product having a hydrophilic surface with a characteristic (v). The characteristic (v) is a characteristic of the cured product surface measured from at least a part of the surface on the opposite side of the interface with the 1 st electrode and the resin cured product in the 2 nd stage of the resin cured product. By providing the resin cured product with the characteristic (v), a laminate having a lyophilic surface, a low water absorption and excellent durability when used in a display device can be obtained. By setting the thickness to 0.1 μm or more, the resin cured product can be made insulating. On the other hand, when the functional ink is continuously applied to the 2 nd step of the resin cured product from the region where at least a part of the resin cured product located on the 1 st electrode is opened by setting the thickness to 0.7 μm or less, the occurrence of white spots in the functional layer can be suppressed.

In the characteristic (v), the concentration of the F atoms measured from at least a portion of the surface of the resin cured product on the opposite side of the interface between the 1 st electrode and the resin cured product is 0.1atom% or more and 20.0atom% or less, preferably 8.0atom% or more and 18.0atom% or less. When the concentration of the F atom is 0.1atom% or more, the water absorption rate of the resin cured product is low, and the durability when used in a display device can be improved. On the other hand, by setting the concentration of the F atoms to 20.0atom% or less, aggregation of the F atoms can be suppressed. Further, regarding the characteristic (v), the peak having the largest peak height, which is measured in the range of 290 to 295eV in the bond energy in the C1s spectrum measured from at least a part of the surface on the opposite side of the interface with the 1 st electrode and the resin cured product, is a CF derived from the resin composition having a peak top in the range of 292 to 294eV ₃ Peaks of the groups. By making the fluorine structure CF ₃ The group can give consideration to both the lyophilic property of the surface of the cured resin and the durability of the display device.

In the characteristic (v), the concentration of Si atoms measured from the surface of the resin cured product on the opposite side of the interface between the 1 st electrode and the resin cured product is 0.1atom% or more and 0.9atom% or less, and more preferably 0.1atom% or more and 0.5atom% or less. By setting the Si atom concentration to 0.1atom% or more, the adhesion to the electrode is improved, and the durability of the display device can be improved. When the concentration of Si atoms is 0.9atom% or less, the surface of the resin cured product can exhibit good lyophilic properties.

The characteristic (i) is preferably measured from any position within a range of 100 μm from the end of the 1 st-order opening of the resin cured product. By measuring this range, the liquid repellency of the functional ink to the 1 st-order surface of the resin cured product can be analyzed. The characteristic (v) is preferably measured from any position within a range of 100 μm from the end of the opening of the 2 nd step of the resin cured product. By measuring this range, the hydrophilicity of the 2 nd-order surface of the resin cured product with respect to the functional ink can be analyzed.

As a method for satisfying the characteristic (v) of the laminate of the present invention, for example, a laminate having CF is used ₃ A method for forming a resin cured product from a photosensitive resin composition of the alkali-soluble resin (b-1) having a group and the alkali-soluble resin (b-2) having a siloxane structure. With CF (CF) ₃ The alkali-soluble resin (b-1) of the group may also have a siloxane structure. By inclusion of a film having CF ₃ The alkali-soluble resin (b-1) having a group having a peak with a maximum peak height measured in the range of 290 to 295eV in the C1s spectrum becomes a resin having a peak top in the range of 292 to 294eV and is derived from CF ₃ Peaks of the groups. CF (compact flash) ₃ The groups are small in the nature of the surface of the cured resin, and the F atoms can stay in the cured resin.

As a method for adjusting the F atom concentration of the characteristic (v) within the above-mentioned range, there is a method for producing a photosensitive resin composition having CF ₃ A method of adjusting the content of the alkali-soluble resin (b-1) of the group. When the content is increased, the concentration of the F atom of the characteristic (v) can be increased; when the content is reduced, the concentration of the F atoms of the characteristic (v) can be reduced. In addition, there areCF possessed by alkali-soluble resin (b-1) ₃ And (3) a method for adjusting the concentration of the group. Improving CF ₃ The concentration of the group can increase the concentration of the F atom of the property (v); reducing CF ₃ The concentration of the group can reduce the concentration of the F atom of the characteristic (v).

As a method for adjusting the concentration of Si atoms of the characteristic (v) within the above range, there is a method for adjusting the content of the alkali-soluble resin (b-2) having a siloxane structure in the photosensitive resin composition. When the content is increased, the concentration of Si atoms of the characteristic (v) can be increased; when the content is reduced, the concentration of Si atoms of the characteristic (v) can be reduced. In addition, there is also a method of adjusting the concentration of the siloxane structure of the alkali-soluble resin (b-2). When the concentration of the siloxane structure is increased, the concentration of Si atoms of the characteristic (v) can be increased; when the concentration of the siloxane structure is reduced, the concentration of Si atoms of the characteristic (v) can be reduced.

The characteristic (v) is preferably analyzed by an XPS device in which the detector is tilted at 45℃to the sample surface. By setting the inclination angle of the detector to 45 °, the area near the surface of the resin cured product can be analyzed.

The laminate including the resin cured product having the step shapes of the 1 st and 2 nd steps may be formed of, for example, a resin cured product having at least the characteristics (i), the characteristics (ii), and the characteristics (v). The laminate can be formed by using, for example, a photosensitive resin composition described below. Specifically, when the positive photosensitive resin composition is used, the 1 st order having the characteristic (i) can be formed in the unexposed portion, the 2 nd order having the characteristic (v) can be formed by the "half-exposed portion" described later, and the characteristic (ii) can be displayed in the cured resin. The resin cured product having the characteristic (i) and the resin cured product having the characteristic (v) may be laminated. When two resin cured products are laminated, at least one resin cured product has the characteristic (ii). From the viewpoint of durability of the display device, it is more preferable that both resin cured products have the characteristic (ii).

As a laminate including a resin cured product having the step shapes of the 1 st step and the 2 nd step, for example, as shown in fig. 2 or 3, a patterned 1 st electrode 8 and a resin cured product are laminated in this order on a substrate, and the resin cured product includes a laminate including a 1 st step 9 defining an inkjet coating region and a 2 nd step 10 defining 2 or more regions arranged in the region. The functional layer 11 continuously disposed on the patterned 1 st electrode 8 and the 2 nd step 10 of the resin cured product on the substrate can be formed by an inkjet coating method.

The laminate having the resin cured product having the step shapes of the 1 st and the 2 nd steps can be formed by using a photosensitive resin composition. Specifically, a photosensitive resin dried product obtained from a positive photosensitive resin composition is produced on the 1 st electrode 8 patterned on the substrate, and an unexposed portion, a half-exposed portion, and an exposed portion are formed in the subsequent exposure step. Next, when the development step and the heat treatment step are performed, the 1 st step 9 of the resin cured product is formed in the unexposed portion, the 2 nd step 10 of the resin cured product is formed in the half-exposed portion, and the 1 st electrode 8 patterned on the substrate is exposed in the exposed portion. As shown in fig. 3, the 2 nd step 10 of the cured resin and the 1 st step 9 of the cured resin may be sequentially stacked on the 1 st electrode 8 patterned on the substrate.

Fig. 5 is a schematic cross-sectional view of another example of the laminate of the present invention. A planarizing layer 14, a patterned 1 st electrode 8, and a resin cured product are sequentially laminated on a substrate 13, and the resin cured product is opened at least in a part of the 1 st electrode 8, and has a 1 st step 9 of the resin cured product and a 2 nd step 10 of the resin cured product. The characteristic (i) of the resin cured product obtained by analysis by X-ray photoelectron spectroscopy (XPS) was measured from the surface 20 of the resin cured product on the opposite side of the 1 st-order interface between the 1 st electrode and the resin cured product. The characteristic (v) was measured from the surface 21 of the resin cured product on the opposite side of the interface between the 1 st electrode and the resin cured product in the 2 nd stage. Regarding the characteristic (ii), measurement was carried out at any one of the positions ranging from 100nm30 to 100nm (i.e., ranging from 100 to 200nm from the interface between the 1 st electrode and the resin cured product in the direction perpendicular to the interface between the 1 st electrode and the resin cured product and from the substrate toward the resin cured product 19) starting from the interface between the 1 st electrode and the resin cured product in the direction perpendicular to the interface between the 1 st electrode and the resin cured product and from the substrate toward the resin cured product 18. The opening of the patterned 1 st electrode was measured at any one of the ranges 19 from 100 to 200nm from the height of the 1 st electrode as a portion where the 1 st electrode is present, such as a range 19 from 100 to 200nm from the interface of the 1 st electrode and the resin cured product in a direction perpendicular to the interface of the 1 st electrode and the resin cured product and from the substrate toward the resin cured product. When there is a variation in the thickness of the 1 st electrode, the opening of the patterned 1 st electrode is configured to have a 1 st electrode having an average thickness at the end of the opening. Next, the functional layer 11 continuously disposed on the patterned 1 st electrode 8 and the 2 nd step 10 of the resin cured product on the substrate may be formed by an inkjet coating method.

The laminate of the present invention is not particularly limited as long as the resin cured product has the above-described characteristics. Examples of the method for forming the cured resin product satisfying the characteristics (i) to (v) include a method comprising reacting a compound (a-1) containing a fluoroalkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms, a compound (a-2) having a siloxane structure, and a method comprising reacting a compound (a-2) having a CF ₃ A method for forming a resin cured product from a photosensitive resin composition of the alkali-soluble resin (b-1) having a group and the alkali-soluble resin (b-2) having a siloxane structure.

Preferred structures of the compound (a-1) having a fluoroalkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms and the compound (a-2) having a siloxane structure are the siloxane (A) described below from the viewpoint of UV ozone resistance and liquid repellency of the resin cured product. In addition, from the viewpoint of heat resistance, the material has CF ₃ Preferred structures of the alkali-soluble resin (B-1) of the group and the alkali-soluble resin (B-2) having a siloxane structure include alkali-soluble resins (B) described later.

Polysiloxane (a) will be described.

By containing the polysiloxane (a) in the photosensitive resin composition, high liquid repellency can be imparted to the upper surface of the resin cured product. Furthermore, the polysiloxane having a main chain has high resistance to UV ozone, and can easily impart high liquid repellency to the upper surface of the resin cured product after UV ozone treatment.

The polysiloxane (A) has a repeating unit structure represented by formula (1) and/or a repeating unit structure represented by formula (2).

[ chemical formula 1]

R in the repeating unit structure represented by the formula (1) and/or the repeating unit structure represented by the formula (2) ^f Is a fluoroalkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms. More preferably a fluoroalkyl group having 9 to 13 fluorine atoms and 6 to 8 carbon atoms. By using a fluoroalkyl group having 7 or more fluorine atoms and 5 or more carbon atoms, the cured resin product can easily satisfy the characteristic (i), and the upper surface of the cured resin product can exhibit more excellent liquid repellency. In addition, the fluorinated alkyl group having 21 or less fluorine atoms and 12 or more carbon atoms can easily provide good compatibility with an alkali-soluble resin to be described later. Further, in order to reduce the load on the environment, a fluoroalkyl group having 13 or less fluorine atoms and 8 or less carbon atoms is more preferable.

R ^f The fluoroalkyl group of (2) preferably has CF ₂ A group. By imparting CF to fluoroalkyl ₂ The group makes it easy for the cured resin to satisfy the property (iii), and the upper surface of the cured resin can exhibit more excellent liquid repellency. As a liquid crystal display having CF ₂ Specific examples of the fluoroalkyl group of the group include heptafluoropentyl group, nonafluorohexyl group, tridecafluorooctyl group, heptadecafluorodecyl group, 5,5,6,6,7,7,7-heptafluoro-4, 4-bis (trifluoromethyl) heptyl group, and the like. From the viewpoints of liquid repellency and environmental load, preferred are a nine-fluorohexyl group and a tridecyl group each having 9 to 13 fluorine atoms and 6 to 8 carbon atoms.

The polysiloxane (a) preferably contains 5 to 30 mol% in total of the repeating unit structure represented by the formula (1) and the repeating unit structure represented by the formula (2) in 100 mol% of the total repeating unit structure of the polysiloxane (a). More preferably 10 to 25 mol%. By containing 5 mol% or more of the repeating unit structure represented by the formula (1) and/or the structure represented by the formula (2), the resin cured product can easily satisfy the characteristic (i), and can exhibit more excellent liquid repellency. In addition, the amount of the fluorinated alkyl group is 30 mol% or less, whereby aggregation of the fluorinated alkyl group can be reduced.

Further, the polysiloxane (A) preferably has the repeating unit structure of (I) and (II).

(I) The repeating unit structure represented by the formula (3) and/or the repeating unit structure represented by the formula (4)

(II) the repeating unit structure represented by the formula (5) and/or the repeating unit structure represented by the formula (6)

[ chemical formula ]

R ¹ 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. R is R ² Is aryl with 6-15 carbon atoms, R ³ Is a single bond or an alkylene group having 1 to 4 carbon atoms, and Y is 1 or 2.R is R ⁴ Is an organic group having 2 to 20 carbon atoms and containing an acidic group. * Representing a covalent bond.

The polysiloxane (a) preferably has (I) a repeating unit structure represented by formula (3) and/or (ii) a repeating unit structure represented by formula (4). The repeating unit structure represented by the formula (3) and/or the repeating unit structure represented by the formula (4) has an aryl group and suppresses aggregation of the fluoroalkyl group by steric hindrance of the aryl group, whereby a cured product having few defects can be easily obtained.

In the repeating unit structure represented by the formula (3) and/or the repeating unit structure represented by the formula (4), R ² Specific examples of the aryl group include a phenyl group, a 4-methylphenyl group, a 4-hydroxyphenyl group, a 4-methoxyphenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, a 2-phenylethyl group, a 4-hydroxybenzyl group, and a structure represented by the formula (7).

[ chemical formula 3]

Here, represent and R ³ A directly linked covalent bond. R is R ³ In the case of a single bond, a covalent bond directly bonded to a silicon atom is represented. a is an integer of 1 to 3. From the viewpoint of chemical resistance, a is preferably 1 to 2, and more preferably a is 1. The following structures are examples of the general formulae.

[ chemical formula 4]

In the repeating unit structure represented by the formula (3) and/or the repeating unit structure represented by the formula (4), R is from the viewpoint of the effect of suppressing aggregation of fluoroalkyl groups and controlling polymerizability ² At least one of (2) is preferably 1-naphthyl, 2-naphthyl or a structure represented by the formula (7). Further, from the viewpoint of controlling polymerizability, Y in the repeating unit structure represented by formula (4) is more preferably 1.

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

The total of 100 mol% of the repeating unit structures of the polysiloxane (a) preferably contains 20 to 70 mol% of the repeating unit structure represented by the formula (3) and the repeating unit structure represented by the formula (4). More preferably 30 to 60 mol%. By including the repeating unit structure represented by the formula (3) and the repeating unit structure represented by the formula (4) in a total of 20 mol% or more, a favorable effect of suppressing the aggregation of fluoroalkyl groups is easily exhibited. From the viewpoint of controlling the polymerizability, it is preferably 70 mol% or less.

The polysiloxane (A) has a repeating unit structure represented by formula (II) and/or a repeating unit structure represented by formula (6). The repeating unit structure represented by the formula (5) and/or the repeating unit structure represented by the formula (6) has an organic group having 2 to 20 carbon atoms containing an acidic group, so that the solubility in an alkaline developer is easily improved, and residues at the opening can be reduced. In addition, aggregation of the fluoroalkyl groups is easily suppressed, and a cured product having few defects is easily obtained.

The organic group having 2 to 20 carbon atoms containing an acidic group is preferably an organic group having 2 to 20 carbon atoms containing at least one acidic group selected from the group consisting of a carboxyl group, a carboxylic anhydride group, a hydroxyl group and a sulfonic acid group, and more preferably a structure represented by the formula (8) or the formula (9).

[ chemical formula 5]

R ¹⁵ Is a single bond or an alkylene group having 1 to 10 carbon atoms. * Representing a covalent bond.

From the viewpoint of residues in the opening, R ⁴ More preferably having a carboxyl group. Further, a dicarboxylic group obtained by hydrolyzing a carboxylic anhydride group is more preferable. Specific examples of the organic group having 2 to 20 carbon atoms including an acidic group include 2-hydroxyethyl, 3-hydroxypropyl, bis (2-hydroxyethyl) -3-aminopropyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, and the following structures (. Alpha.) and (. Beta.). The structure having a carboxyl group is preferably carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, structure (α) and structure (β), and more preferably structure (α) and structure (β).

[ chemical formula 6]

Here, a covalent bond directly to a silicon atom is represented.

The total repeating unit structure of the polysiloxane (a) is preferably 100 mol% and contains 1 to 40 mol% in total of the repeating unit structure represented by the formula (5) and the repeating unit structure represented by the formula (6). More preferably 5 to 30 mol%. By including the repeating unit structure represented by the formula (5) and the repeating unit structure represented by the formula (6) in a total of 1 mol% or more, it is possible to exhibit more excellent ink wettability and compatibility at the opening. Further, by setting the content to 40 mol% or less, better liquid repellency can be obtained.

The polysiloxane (a) may have a repeating unit structure represented by the formula (10) and/or a repeating unit structure represented by the formula (11).

[ chemical formula 7]

R ¹ Is hydrogen atom, alkyl group with 1-6 carbon atoms, acyl group with 1-6 carbon atoms or aryl group with 6-15 carbon atoms, R ⁵ R represents ^f 、R ² -R ³ -、R ⁴ Other than organic groups having 1 to 10 carbon atoms.

R ⁵ As long as R ^f 、R ² -R ³ -、R ⁴ The other organic groups having 1 to 10 carbon atoms are not particularly limited. As R ⁵ Specific examples of (a) include hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and cyclohexyl; amino groups such as 3-aminopropyl, N- (2-aminoethyl) -3-aminopropyl, N- β - (aminoethyl) - γ -aminopropyl, and the like; cyano-containing groups such as beta-cyanoethyl; epoxy group-containing groups such as glycidoxymethyl, α -glycidoxyethyl, α -glycidoxypropyl, β -glycidoxypropyl, γ -glycidoxypropyl, α -glycidoxybutyl, β -glycidoxybutyl, γ -glycidoxybutyl, σ -glycidoxybutyl, (3, 4-epoxycyclohexyl) methyl, 3- (3, 4-epoxycyclohexyl) propyl, 4- (3, 4-epoxycyclohexyl) butyl and the like; chloro groups such as 3-chloropropylmethyl; fluorine-containing groups such as 2, 2-trifluoroethyl and 3, 3-trifluoropropyl; alpha, beta-unsaturated ester group-containing groups such as gamma-acryloylpropyl and gamma-methacryloylpropyl; vinyl-containing groups such as vinyl and styryl; etc.

A formula (1),(3) In (5) and (10), R ¹ The alkyl group having 1 to 6 carbon atoms, the acyl group having 1 to 6 carbon atoms, or the aryl group having 6 to 15 carbon atoms is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, from the viewpoint of controlling polymerizability, and specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. Among them, from the viewpoint of controlling polymerizability, a hydrogen atom, a methyl group, and an ethyl group are more preferable.

In the photosensitive resin composition of the present invention, the content of the polysiloxane (a) is preferably 0.1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the alkali-soluble resin (B). More preferably from 0.2 to 5 parts by mass. By setting the content of the polysiloxane (a) to 0.1 part by mass or more, the resin cured product becomes easy to satisfy the property (i), and further excellent liquid repellency is easy to be obtained. In addition, the amount of the fluorinated alkyl group is 10 parts by mass or less, whereby aggregation of the fluorinated alkyl group is easily suppressed.

(A) The polysiloxane can be obtained by hydrolyzing and polycondensing an alkoxysilane represented by the following general formulae (12), (13), (14) and (15) in a solvent. The polysiloxane (A) is preferably a polysiloxane thus obtained.

[ chemical formula 8]

R ^f Is fluoroalkyl having 7 to 21 fluorine atoms and 5 to 12 carbon atoms, R ¹ 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. R is R ² Is aryl with 6-15 carbon atoms, R ³ Is a single bond or an alkylene group having 1 to 4 carbon atoms, and Y is 1 or 2.R is R ⁴ Is an organic group having 2 to 20 carbon atoms and containing an acidic group. R is R ⁵ Is an organic group having 1 to 10 carbon atoms.

The hydrolysis reaction is preferably carried out by adding an acid catalyst and water to the alkoxysilanes represented by general formulae (12), (13), (14) and (15) in a solvent, and then reacting at room temperature to 110℃for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, the rapid reaction can be suppressed. The reaction temperature is more preferably 40 to 105 ℃.

It is preferable that the silanol compound is obtained by hydrolysis, and then the reaction solution is heated at 50 ℃ or higher and at most the boiling point of the solvent for 1 to 100 hours to carry out condensation reaction. In order to increase the polymerization degree of the siloxane compound obtained by the condensation reaction, an acid or base catalyst may be added or reheating may be performed.

The conditions in the hydrolysis reaction may be appropriately set in consideration of the scale of the reaction, the size and shape of the reaction vessel, and the like. For example, by setting the acid concentration, the reaction temperature, the reaction time, and the like, a polysiloxane of a target polymerization degree can be obtained.

As the water used in the hydrolysis reaction, ion-exchanged water is preferable. The amount of water may be arbitrarily selected, but is preferably used in the range of 1.0 to 4.0 moles relative to 1 mole of the alkoxysilane compound.

Examples of the solvent used in the hydrolysis reaction include alcohol solvents such as 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-methyl benzyl alcohol, 3-methyl benzyl alcohol, 4-isopropyl benzyl alcohol, 1-phenyl ethyl alcohol, 2-phenyl-2-propanol, 2-ethyl benzyl alcohol, 3-ethyl benzyl alcohol, and 4-ethyl benzyl alcohol; ether 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, dipropylene glycol dimethyl ether, and the like; ester solvents such as gamma-butyrolactone, delta-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl 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-dimethylacetamide, N-dimethylisobutyramide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and N, N-dimethylpropyleneurea; aromatic hydrocarbons such as toluene and xylene; etc.

Examples of the acid catalyst used in the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acid or an anhydride thereof, and ion exchange resins. Particular preference is given to using acidic aqueous solutions of formic acid, acetic acid or phosphoric acid.

The content of the acid catalyst is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total alkoxysilane compounds used in the hydrolysis reaction. The content of the acid catalyst is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. The total amount of the alkoxysilane compound herein means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate, and the same applies hereinafter. The hydrolysis proceeds smoothly by making the amount of the acid catalyst 0.05 parts by mass or more; in addition, the control of the hydrolysis reaction is facilitated by setting the amount of the acid catalyst to 10 parts by mass or less.

In addition, from the viewpoint of the storage stability of the composition, it is preferable that the above-mentioned catalyst is not contained in the polysiloxane solution after hydrolysis and partial condensation, and the catalyst may be removed if necessary. The method of removal is not particularly limited, but water washing and/or treatment with an ion exchange resin are preferable in terms of easiness of handling and removability. The water washing is a method in which the polysiloxane solution is diluted with an appropriate hydrophobic solvent, and then washed with water several times, and the organic layer thus obtained is concentrated with an evaporator or the like. The treatment of the ion exchange resin is a method of contacting the polysiloxane solution with a suitable ion exchange resin.

(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, as measured by Gel Permeation Chromatography (GPC) and converted to polystyrene. Further, it is preferably 20,000 or less, and more preferably 10,000 or less.

Next, the alkali-soluble resin (B) will be described.

The alkali-soluble resin in the present invention means a resin having a dissolution rate of 50 nm/min or more as defined below. Specifically, the following resins are meant: a solution of gamma-butyrolactone in which a resin is dissolved is applied to a silicon wafer, prebaked at 120 ℃ for 4 minutes to form a prebaked film having a thickness of 10 [ mu ] m + -0.5 [ mu ] m, the prebaked film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 + -1 ℃ for 1 minute, and then the resin having a dissolution rate of 50 nm/min or more, which is obtained by a reduction in thickness when rinsing with pure water, is obtained.

In the alkali-soluble resin (B), it is preferable to have alkali-soluble groups in the structural units of the resin and/or at the terminal of the main chain thereof in order to impart alkali-solubility. An alkali-soluble group refers to a functional group that increases solubility in an alkaline solution by interaction or reaction with an alkali. Preferable alkali-soluble groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, thiol groups, and the like.

The alkali-soluble resin (B) is not limited as long as it has the above-mentioned alkali-soluble group structure, and the type of the main chain skeleton and side chain of the polymer constituting the resin is not limited. Examples thereof include, but are not limited to, polyimide resins, polybenzoxazole resins, polyamideimide resins, acrylic resins, novolac resins, polyhydroxystyrene resins, phenolic resins, and polysiloxane resins.

In addition, the alkali-soluble resin (B) preferably has CF ₃ A group. By having CF ₃ The group makes it easy for the resin cured product to satisfy the characteristics (ii) and (iv), and the water absorption of the resin cured product is reduced to suppress corrosion of the electrode, so that the durability of the display device can be further improved. CF (compact flash) ₃ The group is less likely to be located on the surface of the cured resin, and the F atom can be retained in the cured resin. In addition, by having CF ₃ The group contributes to the concentration of F atoms and the C1s spectrum in the characteristic (v) of the resin cured product. From the following componentsIn CF ₃ The group does not exhibit liquid repellency, and therefore can easily combine the lyophilic property of the surface of the resin cured product with the durability of the display device.

The alkali-soluble resin (B) preferably has a siloxane structure. The concentration of Si atoms in the characteristic (v) of the resin cured product is facilitated by having a siloxane structure. In addition, the adhesiveness to the electrode is improved, and the durability of the display device can be further improved.

The alkali-soluble resin (B) contained in the photosensitive resin composition preferably has an imide ring structure. More preferably, the resin composition contains at least one selected from the group consisting of polyimide, polyamideimide, a precursor thereof, and a copolymer thereof. These alkali-soluble resins may be used alone, or a combination of plural alkali-soluble resins may be used. By having the imide ring structure, when the laminate is used in an organic EL display device, the amount of outgas at high temperature is small, and the organic EL display device having small pixel shrinkage and more excellent durability can be obtained. Furthermore, as the resin having high heat resistance, polybenzoxazole and/or a precursor thereof may be contained.

The polyimide can be obtained by reacting, for example, a tetracarboxylic acid, a tetracarboxylic dianhydride, a tetracarboxylic acid diester diacid chloride, or the like with a diamine, a diisocyanate compound, a trimethylsilylated diamine, or the like. The polyimide has a tetracarboxylic acid residue and a diamine residue. The polyimide can be obtained, for example, as follows: the polyamide acid, which is one of polyimide precursors obtained by reacting tetracarboxylic dianhydride with diamine, is subjected to dehydration ring closure by heat treatment. In the heat treatment, a solvent which azeotropes with water, such as meta-xylene, may be added. Alternatively, it may be obtained by adding a dehydration condensing agent such as carboxylic anhydride or dicyclohexylcarbodiimide, a base such as triethylamine, or the like as a ring-closure catalyst, and dehydrating and ring-closing the mixture by chemical heat treatment. Alternatively, the catalyst can be obtained by adding a weakly acidic carboxylic acid compound, and subjecting the mixture to dehydration ring closure by heat treatment at a low temperature of 100 ℃ or lower.

The polybenzoxazole can be obtained, for example, by reacting a bisphenol compound with a dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester, or the like. Polybenzoxazole has dicarboxylic acid residues and bisaminophenol residues. The polybenzoxazole can also be obtained, for example, by the following means: the polyhydroxyamide, which is one of the polybenzoxazole precursors, obtained by reacting a bisaminophenol compound with a dicarboxylic acid is subjected to dehydration ring closure by heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, alkali, carbodiimide compound, etc., and subjecting to dehydration ring closure by chemical treatment.

Examples of the polyimide precursor include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide. For example, the polyamic acid can be obtained by reacting a tetracarboxylic acid, a tetracarboxylic dianhydride, a tetracarboxylic acid diester diacid chloride, or the like with a diamine or a diisocyanate compound, and trimethylsilylated diamine. The polyimide can be obtained, for example, by: the polyamic acid obtained by the above method is subjected to dehydration and ring closure by heating or chemical treatment with an acid, an alkali or the like.

As the polybenzoxazole precursor, polyhydroxyamide and the like can be mentioned. For example, the polyhydroxyamide can be obtained by reacting a bisaminophenol with a dicarboxylic acid, a dicarboxylic acid chloride, a dicarboxylic acid active ester, or the like. The polybenzoxazole can be obtained, for example, by the following means: the polyhydroxyamide obtained by the above method is subjected to dehydration ring closure by heating or chemical treatments such as phosphoric anhydride, alkali, carbodiimide compound, etc.

The polyamideimide precursor can be obtained, for example, by reacting a tricarboxylic acid, a corresponding tricarboxylic anhydride, a tricarboxylic anhydride halide, or the like with a diamine or a diisocyanate. The polyamideimide can be obtained, for example, by the following means: the precursor obtained by the above method is subjected to dehydration ring closure by heating or chemical treatment with an acid, a base or the like.

The copolymer of polyimide, polybenzoxazole, polyamideimide, or a precursor of any of these may be any of block copolymerization, random copolymerization, alternating copolymerization, graft copolymerization, or a combination thereof. For example, the block copolymer can be obtained by reacting a tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, a tetracarboxylic acid diester diacid chloride, or the like with a polyhydroxyamide. In addition, dehydration ring closure can be performed by heating or chemical treatment with an acid, an alkali, or the like.

The polyimide, polybenzoxazole or polyamideimide, a precursor of any of them and copolymers thereof preferably have CF in the residue of the carboxylic acid component and/or the residue of the diamine component ₃ The group more preferably has a structure represented by formula (16). The structure represented by the formula (16) has excellent compatibility with the polysiloxane (a), and thus aggregation of the polysiloxane (a) can be suppressed, and a cured product having few defects can be obtained. Further, the structure represented by (16) has CF ₃ The group can reduce the water absorption of the cured product of the photosensitive resin composition, and further improve the durability of the display device. In addition, due to CF ₃ Since the group does not impart liquid repellency, a cured product having a lyophilic surface can be formed by the "half exposure" described later.

[ chemical formula 9]

* Representing a covalent bond.

From the viewpoints of compatibility with the polysiloxane (a) and water absorption of the resin cured product, the polyimide, polybenzoxazole or polyamideimide, a precursor of any of them, and a copolymer thereof more preferably have a structure represented by formula (16) among the residues of the carboxylic acid component and the diamine component.

The alkali-soluble resin (B) preferably has a structural unit represented by any one of the formulae (17) to (20), more preferably has a structural unit represented by the formula (20). Two or more kinds of resins having these structural units may be contained, or two or more kinds of structural units may be copolymerized. The resin of the alkali-soluble resin (B) preferably contains 3 to 1000 structural units represented by any one of the formulae (17) to (20) in the molecule, more preferably contains 20 to 200 structural units.

[ chemical formula 10]

In the formulae (17) to (20), R ⁶ R is R ⁹ Represents a 4-valent organic group, R ⁷ 、R ⁸ R is R ¹¹ Represents a 2-valent organic group, R ¹⁰ Represents a 3-valent organic group, R ¹² Represents a 2-6 valent organic group, R ¹³ Represents a 2-12 valent organic group. R is R ¹⁴ Represents a hydrogen atom or a 1-valent hydrocarbon group having 1 to 20 carbon atoms. p represents an integer of 0 to 2, and q represents an integer of 0 to 10. n represents an integer of 0 to 2.

R ⁶ ～R ¹³ Preferably having an aromatic ring and/or an aliphatic ring.

The formulae (17) to (20) include R ⁶ 、R ⁸ 、R ¹⁰ 、R ¹² (COOR ¹⁴ ) _n (OH) _p For example, the partial structure of (a) can be obtained by using the respective corresponding carboxylic acid components. I.e. for example, R ⁶ Tetracarboxylic acids, R can be used ⁸ Dicarboxylic acids, R can be used ¹⁰ Tricarboxylic acids, R can be used ¹² Can be obtained using di-, tri-, or tetra-carboxylic acids. As a method for obtaining R ⁶ 、R ⁸ 、R ¹⁰ 、R ¹² (COOR ¹⁴ ) _n (OH) _p Examples of the carboxylic acid component(s) include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyldicarboxylic acid; examples of the tricarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyltricarboxylic acid; examples of the tetracarboxylic acid include pyromellitic acid, 3',4' -biphenyltetracarboxylic acid, 2, 3',4' -biphenyltetracarboxylic acid, 2', 3' -biphenyltetracarboxylic acid, 3',4' -benzophenone tetracarboxylic acid, 2',3,3' -benzophenone tetracarboxylic acid, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane, 1-bis (3, 4-dicarboxyphenyl) ethane, 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 Aromatic tetracarboxylic acids such as 1,2,5, 6-naphthalene tetracarboxylic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 2,3,5, 6-pyridine tetracarboxylic acid, 3,4,9, 10-perylene tetracarboxylic acid, and aliphatic tetracarboxylic acids such as butane tetracarboxylic acid and 1,2,3, 4-cyclopentane tetracarboxylic acid. Of these, in the formula (18), 1 or 2 carboxyl groups of each of the tricarboxylic acid and tetracarboxylic acid correspond to COOR ¹⁴ A base. These acid components may be used as they are or in the form of acid anhydrides, active esters, etc. In addition, two or more of these may be used in combination.

As described above, the alkali-soluble resin (B) preferably has a structure represented by formula (16) at the residue of the carboxylic acid component, and thus, as examples of the carboxylic acid component, bis (carboxyphenyl) hexafluoropropane, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane are preferable.

R is contained in the formulae (17) to (20) ⁷ 、R ⁹ 、R ¹¹ 、R ¹³ (OH) _q For example, can be obtained by using respective corresponding diamine components. As a method for obtaining R ⁷ 、R ⁹ 、R ¹¹ 、R ¹³ (OH) _q In the presence of a diamine component such as, for example, examples thereof include hydroxyl-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, bis (3-amino-4-hydroxyphenyl) fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4, 4' -diaminodiphenyl ether, and thiol-containing diamines such as dimercapto-phenylenediamine, 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl methane, 4' -diaminodiphenyl methane, 3,4' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide, 1, 4-bis (4-phenoxy) benzene, benzidine, 1, 5-diaminobenzene, 6-diaminobenzene, 4- (2, 6-aminophenoxy) diphenyl-4-diphenyl-sulfone, 4-diaminobenzene-4-m-phenylene-4-diphenyl-sulfone, 4-diphenyl-sulfone, 2,2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3', aromatic diamines such as 4,4 '-tetramethyl-4, 4' -diaminobiphenyl and 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, compounds obtained by substituting a part of hydrogen atoms of these aromatic rings with an alkyl group having 1 to 10 carbon atoms, trifluoromethyl group, halogen atom or the like, alicyclic diamines such as cyclohexanediamine and methylenedicyclohexylamine, and siloxane-based diamines such as 1, 3-bis (3-aminopropyl) tetramethyldisiloxane. These diamines may be used as such or in the form of the corresponding diisocyanate compounds, trimethylsilylated diamines. In addition, two or more of these diamine components may be used in combination. In the application requiring heat resistance, the aromatic diamine is preferably used in an amount of 50 mol% or more of the entire diamine.

As described above, the alkali-soluble resin (B) preferably has a structure represented by formula (16) in the residue of the diamine component, and thus bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferable as an example of the diamine component.

In addition, from the viewpoint of adhesion to an electrode, the alkali-soluble resin (B) preferably contains a siloxane-based diamine such as 1, 3-bis (3-aminopropyl) tetramethyldisiloxane in the diamine component. Contributing to the concentration of Si atoms in the characteristic (v) of the resin cured product.

R of formulae (17) to (20) ⁶ ～R ¹³ Phenolic hydroxyl groups, sulfonic acid groups, thiol groups, and the like may be contained in the skeleton thereof. The use of a resin having a suitable phenolic hydroxyl group, a sulfonic acid group or a thiol group results in a positive photosensitive resin composition having a suitable alkali solubility.

In order to improve the storage stability of the photosensitive resin composition, the resin of the alkali-soluble resin (B) is preferably a resin obtained by capping the end of the main chain with a capping agent such as a known monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoacid ester compound. The amount of monoamine used as a blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50 mol% or less, based on the total amount of amine components. The amount of the acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoacyl ester compound to be introduced as the blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 100 mol% or less, particularly preferably 90 mol% or less, based on the diamine component. By reacting a plurality of capping agents, a plurality of different terminal groups may be introduced.

In the resin having the structural unit represented by any one of the formulae (17) to (19), the number of repetitions of the structural unit is preferably 3 to 200. In the resin having the structural unit represented by the formula (20), the number of repeating structural units is preferably 10 to 1000. If the amount is within this range, a thick resin cured product can be easily formed.

The alkali-soluble resin (B) may be composed of only the structural unit represented by any one of the formulae (17) to (20), or may be a copolymer or a mixture with other structural units. In this case, the structural unit represented by any one of the formulae (17) to (20) is preferably contained in an amount of 10% by mass or more, more preferably 30% by mass or more, of the entire resin. The type and amount of the structural unit used for copolymerization or mixing may be selected within a range that does not impair the mechanical properties of the resin cured product obtained by the final heat treatment.

The photosensitive resin composition preferably contains a sensitizer (C). By including the photosensitive agent (C), the opening of the resin cured product located on the 1 st electrode in the laminate of the present invention can be formed by photolithography.

The sensitizer (C) may be a negative type cured by light or a positive type solubilized by light. The photosensitizer (C) may preferably contain a polymerizable unsaturated compound (C-1), a photopolymerization initiator (C-2), or a quinone diazide compound (C-2). In the present invention, the polymerizable unsaturated compound and the photopolymerization initiator (C-1) may be simply referred to as (C-1). The positive photosensitive resin composition can be obtained by containing the quinone diazide compound (C-2), and a resin cured product having a step shape can be formed by 1-time lithography by the "half exposure" described later. Therefore, in the photosensitive resin composition, the photosensitive agent (C) preferably contains a quinone diazide compound.

Examples of the polymerizable unsaturated compound (C-1) include known compounds having an unsaturated double bond functional group such as a vinyl group, an allyl group, an acryl group, a methacryl group, and/or an unsaturated triple bond functional group such as a propynyl group, and among these, a conjugated vinyl group, an acryl group, and a methacryl group are preferable from the viewpoint of polymerizability. The number of the functional groups is preferably 1 to 4 from the viewpoint of stability, and may not be the same. The compound referred to herein is preferably a compound having a molecular weight of 30 to 800. When the molecular weight is in the range of 30 to 800, compatibility with the polymer and the reactive diluent is good. Specifically, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethylacrylate, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2, 6-tetramethylpiperidinyl methacrylate 2, 6-tetramethyl piperidinyl acrylate, N-methyl-2, 6-tetramethyl piperidinyl methacrylate N-methyl-2, 6-tetramethyl piperidinyl acrylate, ethylene oxide modified bisphenol A diacrylate, ethylene oxide modified bisphenol A dimethacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, and the like. These may be used singly or in combination of two or more.

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

The photopolymerization initiator in (C-1) is a substance that initiates polymerization by mainly generating radicals by irradiation with light in the ultraviolet to visible light range. From the viewpoint of availability of a general-purpose light source and rapid curability, a known photopolymerization initiator selected from acetophenone derivatives, benzophenone derivatives, benzoin ether derivatives, and xanthone derivatives is preferable. Examples of the preferable photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexylphenyl ketone, isobutylbenzoin ether, benzoin methyl ether, thioxanthone, isopropylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and the like, but are not limited thereto.

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

Examples of the quinone diazide compound (C-2) include known products such as a product obtained by bonding a quinone diazide sulfonic acid to a polyhydroxy compound via an ester bond, a product obtained by bonding a quinone diazide sulfonic acid to a polyamino compound via a sulfonamide bond, and a product obtained by bonding a quinone diazide sulfonic acid to a polyhydroxy polyamino compound via an ester bond and/or a sulfonamide bond. It is possible that not all of the functional groups in these polyols, polyamino compounds, polyhydroxy polyamino compounds are replaced by quinone diazide groups, preferably on average more than 40 mol% of all functional groups are replaced by quinone diazide groups. In the present invention, the mole% of the functional group substituted with quinone diazide is referred to as the quinone diazide substitution rate. By using such a quinone diazide compound, a positive photosensitive resin composition that sensitizes an i-line (wavelength 365 nm), an h-line (wavelength 405 nm), and a g-line (wavelength 436 nm) of a mercury lamp, which are normal ultraviolet rays, can be obtained.

The polyhydroxy compound used herein is a compound having 2 or more, preferably 3 or more phenolic hydroxyl groups in the molecule. As the polyhydroxy compound, for example, 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-34-X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, triML-P, triML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPBA, HMPHHAL-TPP (trade name of the above), available from chemical industry Co., ltd.), BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, asahi organic materials Co., ltd.), 2, 6-dimethoxymethyl-4-tert-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 Benzhou chemical Co., ltd.), novolac resin and the like, however, the present invention is not limited to these.

Examples of the polyamino compound include 1, 4-phenylenediamine, 1, 3-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane, 4 '-diaminodiphenyl sulfone, and 4,4' -diaminodiphenyl sulfide, but are not limited thereto.

Examples of the polyhydric polyamino compound include 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3' -dihydroxybenzidine, but are not limited thereto.

Examples of the quinone diazide sulfonic acid include 1, 2-naphthoquinone diazide-4-sulfonic acid and 1, 2-naphthoquinone diazide-5-sulfonic acid, but are not limited thereto.

In the present invention, as the quinone diazide compound (C-2), a compound in which quinone diazide sulfonic acid is bonded to a polyhydroxy compound is preferably used. By using such a quinone diazide compound, the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are normal ultraviolet rays, can be sensitized, and high sensitivity and higher resolution can be obtained.

More preferable quinone diazide compound (C-2) is a compound represented by formula (21) or formula (22).

[ chemical formula 11]

In the formula (21) and the formula (22), Q each independently represents a hydrogen atom, a group represented by the structural formula (23), or a group represented by the structural formula (24).

[ chemical formula 12]

From the viewpoint of sensitivity, it is further preferable that Q in the formula (21) and the formula (22) each independently represents a hydrogen atom or a group represented by the structural formula (21).

The quinone diazide substitution rate can be obtained from "(mol number of quinone diazide sulfonate)/(mol number of hydroxyl groups before esterification of the polyhydroxy compound) ×100″ in the case of the polyhydroxy compound, and can be obtained from" (mol number of quinone diazide sulfonamide)/(mol number of amino groups before amidation of the polyhydroxy compound) ×100″ in the case of the polyhydroxy compound, and can be obtained from "{ (mol number of quinone diazide sulfonate) + (mol number of quinone diazide sulfonamide) }/{ (mol number of hydroxyl groups before esterification of the polyhydroxy polyaminocompound) + (mol number of amino groups before amidation of the polyhydroxy polyaminocompound) } ×100″ in the case of the polyhydroxy compound.

In the present invention, two or more kinds of quinone diazide compounds can be used. In this case, as the quinone diazide substitution rate, the total value obtained by multiplying the quinone diazide substitution rate of each quinone diazide compound by the ratio to all the quinone diazide compounds is calculated as shown in the following formula.

Σ (quinone diazide substitution ratio of certain quinone diazide compound) × (ratio of certain quinone diazide compound relative to the entire quinone diazide compound)

The quinone diazide substitution ratio of the quinone diazide compound in the photosensitive resin composition can be determined by removing the resin component of the photosensitive resin composition by a reprecipitation method or the like, separating the component by a column separation method or the like, and identifying the chemical structure by NMR or IR.

The method for producing the quinone diazide compound is not particularly limited, and the quinone diazide sulfonic acid halide (preferably quinone diazide sulfonyl chloride) can be obtained by reacting a polyol with a solvent such as acetone, dioxane, or tetrahydrofuran in the presence of an inorganic base such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, or potassium hydroxide, or an organic base such as trimethylamine, triethylamine, tripropylamine, diisopropylamine, tributylamine, pyrrolidine, piperidine, piperazine, morpholine, pyridine, dicyclohexylamine, or the like, according to a conventional method.

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, relative to 100 parts by mass of the alkali-soluble resin (B). Further, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less. When the content of the quinone diazide compound is within this range, photosensitivity can be obtained without inhibiting liquid repellency.

When the alkali-soluble resin (B) is used as the positive photosensitive resin composition containing the quinone diazide compound (C-2) in the photosensitive agent (C), the alkali-soluble resin (B) preferably contains a phenolic resin and/or a polyhydroxystyrene resin. In addition, two or more of these phenolic resins and/or polyhydroxystyrene resins may be used in combination. Since the reduction in the thickness of the photosensitive resin dried product can be reduced in the development step described later by containing the quinone diazide compound (C-2) and the phenolic resin and/or the polyhydroxystyrene resin, the polysiloxane (a) can be easily retained on the surface of the resin cured product, and further excellent liquid repellency can be obtained.

Examples of the phenolic resin include Novolac phenolic resin and Resol phenolic resin, and they can be obtained by polycondensing various aldehyde compounds alone or in a mixture of a plurality of them by a known method using an aldehyde compound such as formalin.

Examples of phenol compounds constituting the Novolac phenol resin and the resin 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, methylenebis-p-cresol, resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2, 3-dichlorophenol, m-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2, 3-diethylphenol, 2, 5-diethylphenol, p-isopropylphenol, α -naphthol, β -naphthol, and the like, and these may be used singly or as a mixture of plural kinds. Examples of the aldehyde compound include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, in addition to formalin, and these compounds may be used alone or as a mixture of a plurality of compounds.

As the polyhydroxystyrene resin, a homopolymer of vinylphenol or a copolymer with styrene can also be used.

The weight average molecular weight of the phenolic resin or the polyhydroxystyrene resin is preferably 2,000 to 20,000, more preferably 3,000 to 10,000, in terms of polystyrene by GPC (gel permeation chromatography). When the content is within this range, a resin composition having a high concentration and a low viscosity can be obtained.

When the photosensitive resin composition is used as a positive photosensitive resin composition containing a quinone diazide compound (C-2) in the photosensitive agent (C), it is preferable that the alkali-soluble resin (B) contains 20 parts by mass or more, more preferably 30 parts by mass or more of a phenolic resin and/or a polyhydroxystyrene resin in 100 parts by mass from the viewpoint of liquid repellency. From the viewpoint of gas release, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.

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

More specifically, examples thereof include 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 methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; acetate esters such as butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as "PGMEA"), 3-methoxybutyl acetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 3-methoxy-3-methyl-1-butyl acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, propyl acetate, butyl acetate, and γ -butyrolactone; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide; or alcohols such as butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, or diacetone alcohol; etc.

The amount of the organic solvent (D) used is not particularly limited, and is preferably 100 to 2000 parts by mass, particularly preferably 150 to 900 parts by mass, based on 100 parts by mass of the solid content (other components than the organic solvent (D)) of the photosensitive resin composition, because the amount varies depending on the desired thickness and the coating method to be employed.

The photosensitive resin composition may further contain a thermal crosslinking agent. The thermal crosslinking agent is a compound having at least 2 thermally reactive functional groups in the molecule, such as hydroxymethyl, alkoxymethyl, epoxy, oxetanyl, and other known thermal crosslinking agents. The thermal crosslinking agent can crosslink the alkali-soluble resin (B) or other components to improve the durability of the resin cured product.

As preferable examples of the compound having at least 2 alkoxymethyl groups or hydroxymethyl groups, HMOM-TPPHBA, HMOM-TPHAP (trade name, product of Benzhou chemical Co., ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade name, product of Santa Clay, chemical Co., ltd.) are given, and each of them is available from the above-mentioned respective companies.

Examples of the compound having an epoxy group or an oxetanyl group include VG3101L (trade name, manufactured by Printec, inc.), "TEPIC" (trade name, inc.) S, "TEPIC" G, "TEPIC" P (trade name, inc. of Nissan chemical Co., ltd.), "EPICLON" N660, "EPICLON" N695, HP7200 (trade name, manufactured by Dain ink chemical Co., ltd.), DENACOL "EX-321L (trade name, nagase ChemteX, inc.), NC6000, EPPN502H, NC3000 (trade name, etc., examples of the compound having at least 2 oxetanyl groups include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (trade name, manufactured by Toyaku Co., ltd.), ETERNACOL (trade name, manufactured by Toyoku Co., ltd.), ETERNACOL (registered trade name) OXBP, ETERNACOL (trade name, manufactured by Yu Xingzhi Co., ltd.), and the like, which are available from the above-mentioned respective companies.

As the thermal crosslinking agent, a thermal crosslinking agent having a phenolic hydroxyl group in one molecule and hydroxymethyl groups and/or alkoxymethyl groups in both ortho-positions to the phenolic hydroxyl group is preferable. By making the hydroxymethyl group and/or alkoxymethyl group adjacent to the phenolic hydroxyl group, the durability of the resin cured product can be further improved. Examples of the alkoxymethyl group include, but are not limited to, methoxymethyl group, ethoxymethyl group, propoxymethyl group, and butoxymethyl group.

The content of the thermal crosslinking agent is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more, relative to 100 parts by mass of the total amount of the alkali-soluble resin (B). The amount is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less. The heat resistance of the resin cured product is improved by setting the content of the thermal crosslinking agent to 5 parts by mass or more; by setting the content to 50 parts by mass or less, the elongation of the resin cured product can be prevented from decreasing.

A method for producing the photosensitive resin composition will be described. For example, the above-mentioned polysiloxane (A) to sensitizer (C) and other components can be obtained by dissolving them in an organic solvent (D). The dissolution method includes stirring, heating, and the like. In the heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually 20 to 80 ℃. The order of dissolution of the components is not particularly limited, and there is a method of sequentially dissolving compounds having low solubility.

The obtained photosensitive resin composition is preferably filtered using a filter to remove refuse and particles. The filter pore size is, for example, 1 μm, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, etc., but is not limited thereto. The filter is made of polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), or the like, but is preferably made of polyethylene or nylon.

Next, a method for producing a resin cured product of the photosensitive resin composition will be described. The photosensitive resin composition is applied and dried to obtain a resin cured product. Further, by sequentially performing the steps (1) to (4) below, a resin cured product in which at least a part of the 1 st electrode is opened can be formed.

(1) A step of forming a photosensitive resin dried product by applying a photosensitive resin composition to a substrate having a 1 st electrode

(2) Exposing the photosensitive resin dried product to light

(3) Developing the dried product of the exposed photosensitive resin

(4) A step of forming a resin cured product by heat-treating the developed photosensitive resin dried product

First, a process (1) of forming a photosensitive resin dried product by applying a photosensitive resin composition to a substrate having the 1 st electrode will be described.

Examples of the method for applying the photosensitive resin composition to the substrate having the 1 st electrode include spin coating, slit coating, dip coating, spray coating, and printing. The substrate coated with the photosensitive resin composition may be pretreated with the adhesion improver described above before coating. For example, the surface of the substrate is treated with a solution obtained by dissolving 0.5 to 20 mass% of the adhesion improver in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, or the like. Examples of the method for treating the surface of the substrate include spin coating, slot die coating, bar coating, dip coating, spray coating, and vapor treatment.

Then, for example, the dried photosensitive resin is subjected to a reduced pressure drying treatment as needed, and then a heat treatment is performed at 50 to 180 ℃ for 1 minute to several hours using a heating plate, an oven, infrared rays, or the like, whereby a dried photosensitive resin can be obtained.

Next, the step (2) of exposing the photosensitive resin dried product to light will be described.

The photosensitive resin dried product is irradiated with chemical radiation through a photomask having a desired pattern. Examples of chemical rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays, and in the present invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps are preferably used. After the irradiation of the chemical rays, post-exposure baking may be performed. By performing post-exposure baking, effects such as improvement in resolution after development and expansion in the allowable range of development conditions can be expected. The post-exposure baking may be performed using an oven, a hot plate, infrared rays, a flash annealing device, a laser annealing device, or the like. The post-exposure baking temperature is preferably 50 to 180 ℃, more preferably 60 to 150 ℃. 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 may proceed well, and the development time may be shortened. In this case, a lattice-shaped cured product can be obtained by using a lattice-shaped photomask.

In the present invention, "half exposure" may be used. "half-exposure" means: and a process of leaving the substrate of the photosensitive resin dried product of the exposed portion to a certain extent when the development is completed. In other words, the exposure process is performed so that the lower layer of the photosensitive resin dried product is not exposed to light. For example, in the case of forming the resin cured product of fig. 5 from the positive photosensitive resin dried product, it is possible to perform "half exposure" in which the position of the 1 st step 9 of the resin cured product having a relatively thick thickness is not exposed and the position of the 2 nd step 10 of the resin cured product having a relatively thin thickness is exposed by a chemical radiation amount which does not expose the lower layer of the photosensitive resin dried product, and then, the resin cured product is formed by development and heat treatment. Further, by adjusting the amount of chemical radiation irradiated to the photosensitive resin dried product, the thickness of the photosensitive resin dried product remaining after the development is completed can be adjusted. Specifically, in the case where the photosensitive resin dried product is positive, if the amount of chemical radiation is increased, the thickness of the photosensitive resin dried product remaining after the development is completed becomes thin. On the other hand, in the case where the photosensitive resin dried product is negative, if the amount of chemical radiation is increased, the thickness of the photosensitive resin dried product remaining after the development is completed becomes thicker. The amount of chemical radiation may be adjusted by irradiating the chemical radiation through a photomask having two or more regions having different transmittances.

When the photosensitive resin dried product formed from the photosensitive resin composition of the present invention is positive, the surface of the cured product formed by half exposure has no liquid repellency, and can have good ink coatability. That is, a cured product having a liquid repellent surface and a cured product having a lyophilic surface can be formed by one-time photolithography.

Next, the step (3) of developing the dried product of the exposed photosensitive resin will be described.

In the development step of developing the exposed photosensitive resin dried product, the exposed photosensitive resin dried product is developed with a developer, and the portions other than the exposed portion are removed. As the developer, an aqueous solution of a compound exhibiting basicity 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, hexamethylenediamine, or the like is preferable. In addition, as the case may be, to these aqueous alkali solutions, one or a combination of the following may be added: polar solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, gamma-butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, and the like. The development method may be a method such as spraying, spin immersion (pump), dipping, or ultrasonic.

Next, the pattern formed by the development is preferably rinsed with distilled water. Here, the rinsing treatment may be performed by adding alcohols such as ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate to distilled water.

Next, a step (4) of forming a resin cured product by heat-treating the developed photosensitive resin dried product will be described.

The cured film is obtained by a step of heat-treating the developed photosensitive resin dried product. In the present invention, the cured film of the photosensitive resin composition can be suitably used for the partition wall of the organic EL display device. The heat treatment can remove the components having low heat resistance and the residual solvent, and thus can improve the heat resistance and chemical resistance. In addition, by containing the crosslinking agent, the thermal crosslinking reaction can be performed by the heat treatment, and heat resistance and chemical resistance can be improved. The heating treatment is performed for 5 minutes to 5 hours while the temperature is selected and raised stepwise or while a certain temperature range is selected and raised continuously. As an example, a method of performing a heat treatment at 150℃and 250℃for 30 minutes is given. Alternatively, a method of linearly increasing the temperature from room temperature to 300℃over 2 hours may be mentioned. The heating conditions in the present invention are preferably 180℃or higher, more preferably 200℃or higher, and still more preferably 230℃or higher. The heat treatment condition is preferably 400 ℃ or lower, more preferably 350 ℃ or lower, and still more preferably 300 ℃ or lower.

< display device >

The display device of the present invention includes the laminate of the present invention. Specific examples of the display device include an LCD and an organic EL.

The resin cured product provided in the laminate of the present invention has high liquid repellency on the surface of the cured product after UV ozone treatment, and therefore can be suitably used in a display device in which a functional layer is formed by applying functional ink by ink jet in a region where at least a part of the resin cured product on the 1 st electrode is opened. For example, an organic EL display device can be obtained by forming an organic EL light-emitting layer containing at least one or more selected from an organic EL light-emitting material, a hole injection material, and a hole transport material.

The resin cured product provided in the laminate of the present invention has F atoms in the resin cured product, and thus the water absorption of the resin cured product is reduced, and corrosion of the electrode is suppressed, so that a display device having small pixel shrinkage and excellent durability can be obtained.

Since the resin cured product provided in the laminate of the present invention has a small outgas amount at a high temperature, it is preferable to use the resin cured product in an organic EL display device in which at least one kind selected from the group consisting of an organic EL light-emitting material, a hole injection material, and a hole transport material is contained in the functional layer. An organic EL display device with small pixel shrinkage and excellent durability can be obtained.

The organic EL display device has a drive circuit, a planarizing layer, a 1 st electrode, a partition wall, an organic EL light-emitting layer, and a 2 nd electrode on a substrate. In the case of an active matrix display device, a TFT and a wiring which is located on a side of the TFT and connected to the TFT are provided on a substrate such as glass or a resin film, a planarizing layer is provided so as to cover irregularities thereon, and a display element is provided on the planarizing layer. The display element and the wiring are connected via a contact hole formed in the planarization layer.

< method for manufacturing display device >

The first embodiment of the method for manufacturing a display device of the present invention includes steps (5) and (6) in this order.

(5) In the laminate of the present invention, a step of forming a functional layer by applying a functional ink to the 1 st electrode by ink jet

(6) And forming a 2 nd electrode on the functional layer.

In the step (5), the functional ink is applied to the 1 st electrode of the laminate of the present invention by ink jet to form a functional layer. For example, in the case of an organic EL display device, a composition containing at least one selected from the group consisting of an organic EL light-emitting material, a hole injection material, and a hole transport material is dropped as a functional ink into a pixel, and is dried, whereby an organic EL light-emitting layer can be formed. A heating plate and an oven are preferably used for drying, and the drying is carried out by heating at 150-250 ℃ for 0.5-120 minutes.

In the step (6), the 2 nd electrode is formed on the functional layer. The 2 nd electrode is preferably formed so as to cover the whole of the partition wall and the functional layer. Examples of the method for forming the 2 nd electrode include a sputtering method and a vapor deposition method. It is preferable that the 2 nd electrode is formed in a uniform layer thickness without disconnection.

When the laminate of the present invention includes a resin cured product having the step-difference shape of the 1 st and 2 nd steps, the second embodiment of the method for manufacturing a display device of the present invention includes steps (7) and (8) in this order.

(7) In the laminate of the present invention, a step of forming a functional layer by applying a functional ink on the 1 st electrode and the 2 nd stage of the resin cured product by ink jet

(8) And forming a 2 nd electrode on the functional layer.

In the step (7), the functional ink is applied by ink jet to the 1 st electrode of the laminate of the present invention and the 2 nd step of the resin cured product to form a functional layer. For example, in the case of an organic EL display device, a composition containing at least one selected from the group consisting of an organic EL light-emitting material, a hole-injecting material, and a hole-transporting material may be dropped as a functional ink into a pixel, and dried, thereby forming an organic EL light-emitting layer. A heating plate and an oven are preferably used for drying, and the drying is carried out by heating at 150-250 ℃ for 0.5-120 minutes.

For example, the laminated body having the patterned 1 st electrode 8 on the substrate and the resin cured product sequentially laminated as shown in fig. 2, and the resin cured product having the 1 st step 9 defining the ink-jet coated region and the 2 nd step 10 defining the 2 or more pixel regions arranged in the ink-jet coated region can be applied to a method for manufacturing a display device in which the functional layer 11 continuously arranged on the patterned 1 st electrode 8 on the substrate and the 2 nd step 10 of the resin cured product is formed by the ink-jet coating method.

In the step (8), the 2 nd electrode is formed on the functional layer. The 2 nd electrode is preferably formed so as to cover the whole of the partition wall and the functional layer. Examples of the method for forming the 2 nd electrode include a sputtering method and a vapor deposition method. It is preferable that the 2 nd electrode is formed in a uniform layer thickness without disconnection.

Examples

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

< partition wall Pattern used in examples >

Partition wall pattern 4: a barrier rib pattern for exposing the patterned 1 st electrode on the substrate from the opening of the resin cured product, wherein the size of the opening is 70 μm wide and 260 μm long, and the opening is arranged at one position in the center of the resin cured product

Partition wall pattern 5: the 1 st electrode patterned on the substrate was exposed from the opening of the cured resin material, and the opening was 70 μm wide and 260 μm long, and the cured resin material was arranged at a pitch of 155 μm in the width direction and at a pitch of 465 μm in the length direction

Partition wall pattern 12: the barrier rib pattern shown in FIG. 2 or FIG. 3 is a barrier rib pattern in which the 2 nd step 10 of the resin cured product having a width a of 205 μm and the 1 st step 9 of the resin cured product having a width b of 85 μm are arranged on a substrate having a width of 70 μm and a length of 260 μm so as to expose the patterned 1 st electrode 8

First, a measurement method and an evaluation method will be described.

(1) Average molecular weight determination

The molecular weights of the polysiloxane (P-1) synthesized in Synthesis example 1, the acrylic liquid repellent material (Ac-1) synthesized in Synthesis example 2, the alkali soluble resin (d 1) 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) apparatus (Waters 2690-996; manufactured by Waters Co., ltd.) and tetrahydrofuran as an eluting solvent, and the weight average molecular weight (Mw) was calculated by a polystyrene conversion.

The molecular weights of the alkali-soluble resins (b 1) to (b 3) synthesized in synthesis examples 4 to 6 were measured using the above GPC apparatus with N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as an eluting solvent, and the number average molecular weight (Mn) was calculated by polystyrene conversion.

(2) Evaluation of liquid repellency

In the measurement of the contact angle, a laminate having the barrier wall pattern in fig. 1 was formed by a method described later, and 3 μl of PGMEA was dropped onto the resin cured product of the barrier wall pattern 4 to measure the contact angle. A contact angle measuring device (DMs-401; manufactured by Kyowa Co., ltd.) was used for measurement, and the measurement was carried out in accordance with JIS-R3257:1999, measured by the still drop method at 23 ℃.

The measurement results of the PGMEA contact angle on the cured product were determined as follows, with a being optimal, B being good, C being ok, and D being not ok.

A: contact angle of 45 DEG or more

B: contact angle of 35 DEG or more and less than 45 DEG

C: a contact angle of 25 DEG or more and less than 35 DEG

D: contact angle less than 25 DEG

(3) Evaluation of UV ozone resistance

The laminate subjected to the evaluation of liquid repellency of (2) above was subjected to UV ozone treatment under the following conditions. Then, 3. Mu.L of PGMEA was dropped onto the resin cured product of the partition wall pattern 4, and the contact angle was measured. In the measurement, a contact angle measuring device (DMs-401; manufactured by Kyowa Kagaku Co., ltd.) was used, and the measurement was carried out by a still drop method at 23℃in accordance with JIS-R3257.

In comparison with the evaluation result of the liquid repellency of the above (2), a (pass) was found when the contact angle was 10% or less, and B (fail) was found when the contact angle was 10% or more.

UV ozone conditions

The device comprises: PL16 (SEN LIGHTS Corp. Product)

Illuminance: 15mW/cm ²

Irradiation distance: 75mm

Irradiation time: 120sec

(4) Analysis of a resin cured product by X-ray photoelectron spectroscopy (XPS) shows a method of analyzing a resin cured product by X-ray photoelectron spectroscopy (XPS).

< preparation of cured product for X-ray photoelectron Spectrometry (XPS) analysis >

The laminate in fig. 1 on which the barrier rib pattern 4 was formed was produced by a method described later, and XPS analysis was performed at any position within a range of 100 μm from the end of the opening of the cured product in the barrier rib pattern 4.

< method for X-ray photoelectron Spectroscopy (XPS) analysis of resin cured product >

(4-1) method for measuring XPS analysis of properties (i) and (v) of surface of resin cured product

Analysis by X-ray photoelectron spectroscopy (XPS) was performed from the surface of the resin cured product of the barrier rib pattern 4 or the barrier rib pattern 12 in fig. 1 under the measurement conditions described below. The measurement conditions and the data processing conditions are as follows.

Measurement conditions

Device Quantera SXM (PHI company)

Exciting X-rays monochromatic Al K, 2 rays (1486.6 eV)

X-ray diameter 200 μm

Optoelectronic detection angle 45 ° (inclination of detector relative to sample surface)

Data processing conditions

Smoothing 9-Point smoothing (9-Point smoothing)

The horizontal axis correction sets the C1s main peak (CHx, C-C, c=c) to 284.6eV.

(4-2) method for measuring XPS analysis characteristic (ii) in cured resin product

In the resin cured product of the barrier rib pattern 4 in fig. 1, an Ar gas cluster ion beam (Ar-GCIB) is performed so that an interface between the patterned 1 st electrode 8 and the resin cured product of the barrier rib pattern 4 is exposed at any position within a range of 100 to 200nm as a starting point in a direction perpendicular to the interface between the patterned 1 st electrode 8 and the resin cured product of the barrier rib pattern 4 and toward the barrier rib pattern 4 from the alkali-free glass substrate 1. Then, X-ray photoelectron spectroscopy (XPS) analysis was performed at the site where Ar-GCIB was performed. The measurement conditions and data processing are as follows.

Measurement conditions

Device K-Alpha (Thermo Fisher Scientific Co., ltd.)

Exciting X-rays monochromatic Al K, 2 rays (1486.6 eV)

X-ray diameter 400 μm

Photoelectron escape angle 90 ° (inclination of detector relative to sample surface)

Ion etching conditions Ar gas cluster ion Beam (Ar-GCIB)

Etching rate of 3.5nm/min

Data processing

Smoothing 11-Point smoothing (11-Point smoothing)

The horizontal axis correction sets the C1s main peak (CHx, C-C) to 284.6eV.

(4-3) XPS method for comparing surface and interior properties (iii) and (iv) of resin cured product

Analysis by X-ray photoelectron spectroscopy (XPS) was performed from the surface of the resin cured product of the partition wall pattern 4 in fig. 1 under the measurement conditions described below. Next, the resin cured product of the barrier rib pattern 4 is subjected to an Ar gas cluster ion beam (Ar-GCIB) so that the interface between the patterned 1 st electrode 8 and the resin cured product of the barrier rib pattern 4 is exposed at any position within a range of 100 to 200nm from the interface between the patterned 1 st electrode 8 and the resin cured product of the barrier rib pattern 4 in a direction perpendicular to the interface between the patterned 1 st electrode 8 and the resin cured product of the barrier rib pattern 4 and in a direction from the alkali-free glass substrate 1 toward the barrier rib pattern 4. Then, X-ray photoelectron spectroscopy (XPS) analysis was performed at the site where Ar-GCIB was performed. The measurement conditions and data processing are as follows.

Measurement conditions

Device K-Alpha (Thermo Fisher Scientific Co., ltd.)

Exciting X-rays monochromatic Al K, 2 rays (1486.6 eV)

X-ray diameter 400 μm

Ion etching conditions Ar gas cluster ion Beam (Ar-GCIB)

Etching rate of 3.5nm/min

Data processing

Smoothing 11-Point smoothing (11-Point smoothing)

The horizontal axis correction sets the C1s main peak (CHx, C-C) to 284.6eV.

(5) Evaluation of durability

Under the condition for evaluating the UV ozone resistance of (3), the laminate of fig. 1, in which the barrier rib pattern 5 or the barrier rib pattern 12 is formed using the cured product of the photosensitive resin composition, is subjected to UV ozone treatment. Then, in the case of the partition wall pattern 5, an ink jet device (Litlex 142 manufactured by ULVAC corporation) was used as the hole injection layer, and an ink of the compound (HT-1) using methyl benzoate as a solvent was dropped onto the 1 st electrode 8 patterned on the substrate surrounded by the resin cured product, and then fired at 200 ℃. Next, as the hole transport layer, a compound (HT-2) using 4-methoxytoluene as a solvent was dropped into a region surrounded by a cured resin using an inkjet device, and then fired at 190 ℃. Further, as the light-emitting layer, a mixture of the compound (GH-1) and the compound (GD-1) using 4-methoxytoluene as a solvent was dropped into a region surrounded by a resin cured product using an inkjet device, and then fired at 130 ℃. In the case of the partition wall pattern 12, an ink jet device (Litlex 142, ULVAC corporation) was used as the hole injection layer, and an ink of a compound (HT-1) using methyl benzoate as a solvent was continuously dropped onto the patterned 1 st electrode 8 on the substrate located in the region sandwiched by the 1 st steps of the resin cured product and the 2 nd step 10 of the resin cured product, followed by firing at 200 ℃. Next, as the hole transport layer, a compound (HT-2) using 4-methoxytoluene as a solvent was dropped into the same region using an inkjet device, and then baked at 190 ℃. Further, as the light-emitting layer, an inkjet device was used, and a mixture of the compound (GH-1) and the compound (GD-1) using 4-methoxytoluene as a solvent was dropped into the same region, followed by firing at 130 ℃.

Then, as an electron transport material, the compound (ET-1) and the compound (LiQ) were sequentially stacked at a volume ratio of 1:1 by a vacuum vapor deposition method, to form the organic EL layer 6. Next, a compound (LiQ) of 2nm was vapor-deposited, and Mg and Ag were vapor-deposited at a volume ratio of 10:1 for 10nm as the 2 nd electrode 7. Finally, the cover glass plate was bonded with an epoxy resin adhesive under a low-humidity nitrogen atmosphere to seal the glass plate, and a 5mm square organic EL display device was fabricated on 1 substrate.

[ chemical formula 13]

/>

At 10mA/cm ² The organic EL display device manufactured by the above method was caused to emit light by dc driving, and an initial light emitting area was measured. Further, the mixture was kept at 80℃for 500 hours at 10mA/cm ² By driving the light-emitting element with a direct current, whether or not there is a change in the light-emitting area was confirmed, and durability was determined as shown below, with A being the optimum and B being the optimumGood, C is set to ok, D is set to not.

A: no change in light-emitting area

B: the change of the luminous area is 90 to 99 percent

C: the change of the luminous area is 80 to 89 percent

D: the light emitting area was changed to 79% or less

(6) Composition analysis of resin cured product

The method of analyzing the components contained in the resin cured product is shown, but is not limited to the method described above as long as the composition analysis can be performed.

< preparation of resin cured product for compositional analysis >

The photosensitive resin composition was applied by spin coating to an 8-inch silicon wafer using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Co., ltd.) and baked at 120℃for 3 minutes using a heating plate. Then, development was performed using a 2.38 mass% aqueous TMAH solution using the ACT-8 developing apparatus, and spin-drying was performed after rinsing with distilled water. Next, the developed photosensitive resin dried product was subjected to a heat curing treatment in a nitrogen atmosphere (oxygen concentration: 100ppm or less) using a high-temperature inert gas oven (INH-9 CD-S; manufactured by Guangyang THERMO SYSTEM Co., ltd.) at a temperature of 5℃per minute to 250℃for 1 hour, and the heat-cured product of the varnish was produced. The thickness of the cured resin was about 2.0. Mu.m.

< analysis of composition Using FT-IR >

The obtained resin cured product was subjected to a wave number of 4000 to 650cm using an infrared microscope Nicolet iN10 (manufactured by Thermo Fisher SCIENTIFIC) ^-1 The detector uses MCT, the resolution is set to 8cm ^-1 The IR spectrum was obtained by counting 64 times and measuring 1-time reflection ATR (Ge, 45 °).

< analysis of composition by pyrolysis GC/MS >

The obtained resin cured product was thermally decomposed using Multi-Shot Pyrolyzer PY-3030D (manufactured by front Lab) at a heating temperature of 600℃and analyzed using a gas chromatograph mass spectrometer JMS-Q1050GC (manufactured by Japan electronics), a GC column was heated from 40℃to 320℃at a rate of 20℃per minute using a stainless steel capillary column (0.25 mm inner diameter. Times.30 m, stationary phase; 5% phenyl polydimethylsiloxane), an inlet temperature of 300℃and a column flow rate of 1.5 mL/min, an ionization method of EI (electron ionization) method, a mass number range of m/z of 10 to 800, and a scanning speed of 0.5 sec/scan.

The following shows the abbreviations of the components used in the examples.

< alkoxysilyl group >

MTMS: methyltrimethoxysilane

NapTMS: 1-naphthyl trimethoxysilane

Tmsu ca: 3-trimethoxysilylpropyl succinic anhydride

TfTMS: tridecafluorooctyl trimethoxysilane

< crosslinking agent >

HMOM-TPHAP: (Compound represented by the following chemical formula, manufactured by Benzhou chemical industry Co., ltd.)

[ chemical formula 14]

VG3101L: "TECHMORE" (registered trademark) VG3101L (Compound represented by the following chemical formula, manufactured by Printec, inc.)

[ chemical formula 15]

< 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.

Synthesis example 1 Synthesis of polysiloxane (P-1)

A500 mL three-necked flask was charged with 27.90g of water and 1.31g (1.0 mass% based on the charged monomer) of phosphoric acid while stirring at 40℃to obtain 27.90g of phosphoric acid solution, which was added to a 500mL three-necked flask with 39.80g (0.17 mol) of TfTMS, 62.09g (0.50 mol) of NapTMS62.09g (0.10 mol) of TMSSucA, 15.66g (0.23 mol) of MTMS15.05 g, 131.05g of MAK and 14.56g of IPA. Then, after immersing the flask in an oil bath at 70 ℃ and stirring for 60 minutes, the oil bath was warmed up to 130 ℃ for 15 minutes. After 10 minutes from the start of the temperature rise, the internal temperature of the solution reached 100℃and was then heated and stirred for 1 hour (internal temperature 100 to 125 ℃) to obtain polysiloxane (P-1). During the heating and stirring, nitrogen gas was flowed at 0.07l (liter)/min. The weight average molecular weight obtained by GPC was 3000.

Synthesis example 2 Synthesis of acrylic liquid repellent Material (Ac-1)

100g of cyclohexanone was charged into a glass reaction vessel equipped with a stirring device, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, and the temperature was raised to 110℃under a nitrogen gas atmosphere. The temperature of cyclohexanone was maintained at 110℃and a monomer mixture solution containing 44g (0.65 mol) of N, N-dimethylacrylamide, 30g (0.10 mol) of 2- (perfluorohexyl) ethyl methacrylate, 21g (0.22 mol) of glycidyl methacrylate and 5g (0.03 mol) of 3-phenoxybenzyl acrylate was added dropwise via a dropping funnel at a constant rate of 2 hours to prepare each monomer solution. After the completion of the dropwise addition, the monomer solution was heated to 115℃and reacted for 2 hours to obtain an acrylic liquid repellent material (Ac-1). The weight average molecular weight obtained by GPC was 5500.

Synthesis example 3 Synthesis of hydroxyl group-containing diamine Compound

18.3g (0.05 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 100mL of acetone and 17.4g (0.3 mol) of propylene oxide, and cooled to-15 ℃. To this was added dropwise a solution of 20.4g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100mL of acetone. After the completion of the dropwise addition, the reaction was carried out at-15℃for 4 hours, and then the reaction was allowed to return to room temperature. The white solid precipitated was collected by filtration and dried at 50℃under vacuum.

30g of the solid was charged into a 300mL stainless steel autoclave, dispersed in 250mL of methyl cellosolve, and 2g of 5% palladium-carbon was added. Hydrogen was introduced into the reaction vessel by a balloon, and the reaction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon was not contracted any more and the reaction was ended. After the completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

[ chemical formula 16]

Synthesis example 4 Synthesis of alkali-soluble resin (b 1)

88.8g (0.20 mol) of 2,2- (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride was dissolved in 500g of NMP under a dry nitrogen flow. To this were added 96.7g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis example 3, 1.24g (0.005 mol) of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and 100g of NMP, and the mixture was reacted at 20℃for 1 hour, followed by 50℃for 2 hours. Next, 8.7g (0.08 mol) of 3-aminophenol as a blocking agent and 50g of NMP were added and reacted at 50℃for 2 hours. Then, a solution obtained by diluting 47.7g (0.40 mol) of N, N-dimethylformamide dimethyl acetal with 100g of NMP was added. After the addition, stirring was carried out at 50℃for 3 hours. After the completion of stirring, the solution was cooled to room temperature, and then the solution was added to 5L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and dried with a vacuum dryer at 80℃for 24 hours to give an alkali-soluble resin (b 1) as the objective polyimide precursor. The number average molecular weight of the alkali-soluble resin (b 1) was 12000.

Synthesis example 5 Synthesis of alkali-soluble resin (b 2)

62.0g (0.20 mol) of 3,3', 4' -diphenyl ether tetracarboxylic dianhydride was dissolved in 500g of NMP under a dry nitrogen flow. To this were added 96.7g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis example 3, 1.24g (0.005 mol) of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and 100g of NMP, and the mixture was reacted at 20℃for 1 hour, followed by 50℃for 2 hours. Next, 8.7g (0.08 mol) of 3-aminophenol as a blocking agent and 50g of NMP were added and reacted at 50℃for 2 hours. Then, a solution obtained by diluting 47.7g (0.40 mol) of N, N-dimethylformamide dimethyl acetal with 100g of NMP was added. After the addition, the mixture was stirred at 50℃for 3 hours. After the completion of stirring, the solution was cooled to room temperature, and then the solution was added to 5L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and dried with a vacuum dryer at 80℃for 24 hours to give an alkali-soluble resin (b 2) as the objective polyimide precursor. The number average molecular weight of the alkali-soluble resin (b 2) was 11000.

Synthesis example 6 Synthesis of alkali-soluble resin (b 3)

62.0g (0.20 mol) of 3,3', 4' -diphenyl ether tetracarboxylic dianhydride was dissolved in 500g of NMP under a dry nitrogen flow. To this was added 44.85g (0.16 mol) of bis (3-amino-4-hydroxyphenyl) sulfone, 1.24g (0.005 mol) of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and 100g of NMP, and the mixture was reacted at 20℃for 1 hour and then at 50℃for 2 hours. Next, 8.7g (0.08 mol) of 3-aminophenol as a blocking agent and 50g of NMP were added and reacted at 50℃for 2 hours. Then, a solution obtained by diluting 47.7g (0.40 mol) of N, N-dimethylformamide dimethyl acetal with 100g of NMP was added. After the addition, stirring was carried out at 50℃for 3 hours. After the completion of stirring, the solution was cooled to room temperature, and then the solution was added to 5L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and dried with a vacuum dryer at 80℃for 24 hours to give an alkali-soluble resin (b 3) as the objective polyimide precursor. The number average molecular weight of the alkali-soluble resin (b 3) was 11000.

Synthesis example 7 Synthesis of quinone diazide compound (c 2)

21.23g (0.05 mol) of TrisP-PA (trade name, manufactured by Benzhou chemical Co., ltd.) and 33.58g (0.125 mol) of 4-naphthoquinone diazide sulfonyl chloride were dissolved in 450g of 1, 4-dioxane under a dry nitrogen flow, and the mixture was brought to room temperature. To this, 12.65g (0.125 mol) of triethylamine mixed with 50g of 1, 4-dioxane was added dropwise so that the temperature in the reaction system did not become 35℃or higher. After the dropwise addition, the mixture was stirred at 30℃for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. The precipitated precipitate was then collected by filtration. The precipitate was dried with a vacuum dryer to obtain naphthoquinone diazide compound (c 2). The quinone diazide substitution rate of the naphthoquinone diazide compound was 83%.

[ chemical formula 17]

Synthesis example 8 Synthesis of alkali-soluble resin (d 1)

Under a dry nitrogen gas flow, 108.0g (1.00 mol) of m-cresol, 75.5g (0.93 mol) of 37 mass% aqueous formaldehyde solution, 0.63g (0.005 mol) of oxalic acid dihydrate and 264g of methyl isobutyl ketone were added, and the mixture was immersed in an oil bath to reflux the reaction solution, and a polycondensation reaction was carried out for 4 hours. Then, the temperature of the oil bath was raised for 3 hours, and then the pressure in the flask was reduced to 4.0kPa to 6.7kPa to remove volatile components, and the dissolved resin was cooled to room temperature to obtain an alkali-soluble resin (d 1) as a novolacs type phenol resin. The weight average molecular weight obtained by GPC was 3,500.

Synthesis example 9 Synthesis of alkali-soluble resin (Ac-2)

100g of isopropyl alcohol was charged into a 1000cc four-necked flask, kept at 80℃in an oil bath and sealed with nitrogen gas, and while stirring, 2g of N, N-azobisisobutyronitrile was mixed with 30g of methyl methacrylate, 40g of styrene and 30g of methacrylic acid and added dropwise via a dropping funnel over 30 minutes. Then, after the reaction was continued for 4 hours, 1g of hydroquinone monomethyl ether was added thereto, and the reaction was returned to normal temperature to complete the polymerization. Then, after 100g of isopropyl alcohol was added, 40g of glycidyl methacrylate and 3g of triethylbenzyl ammonium chloride were added and reacted for 3 hours while maintaining the temperature at 75℃to obtain a copolymer solution. Then, after cooling the copolymer solution to room temperature, the copolymer solution was added to 5L of water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and dried with a vacuum dryer at 80℃for 24 hours to give an alkali-soluble resin (Ac-2) of the objective acrylic resin. The alkali-soluble resin (Ac-2) had a weight average molecular weight of 10000.

Examples 1 to 6 and 15, comparative examples 1 to 4 and 8

Fig. 1 shows a schematic diagram of a laminate used for evaluation.

An ITO transparent conductive film 10nm was formed on the entire surface of the alkali-free glass plate 1 by sputtering, and etched as a patterned 1 st electrode 8 on the substrate. In addition, in order to take out the 2 nd electrode, an auxiliary electrode 3 is also formed at the same time. The obtained substrate was subjected to ultrasonic washing with "semiconductor Clean" (registered trademark) 56 (manufactured by Furuuchi Chemical corporation) for 10 minutes, and then washed with ultrapure water, and dried to obtain an intermediate for evaluation.

Next, the components were mixed in the mixing ratio shown in table 1 under a yellow lamp, and the mixture was sufficiently stirred at room temperature to be dissolved. Then, the obtained solution was filtered through a filter having a pore size of 0.45 μm to obtain photosensitive resin compositions W1 to W12.

TABLE 1

Next, on the intermediate for evaluation, the photosensitive resin compositions W1 to W12 obtained by spin coating were pre-baked on a heating plate at 120℃for 2 minutes to form a photosensitive resin dried product having a thickness of about 2 μm, and then irradiated with an exposure of 120mJ/cm at the full wavelength of a mercury lamp via a photomask having a predetermined pattern ² After ultraviolet rays (converted by the h line), development was performed with a 2.38 mass% TMAH aqueous solution for 60 seconds, and rinsing was performed with water, whereby 2 sheets of uncured material having the barrier rib pattern 4 formed thereon and 2 sheets of uncured material having the barrier rib pattern 5 formed thereon were produced, respectively. Next, a cleaning oven (manufactured by Koyo Thermo Systems corporation) was used, and the laminate a was cured by heating at 250 ℃ for 1 hour under a nitrogen atmosphere, to thereby form a barrier rib pattern 4 or a barrier rib pattern 5.

Using the laminate a having the barrier rib pattern 4 formed, the liquid repellency was evaluated (2), and then the UV ozone resistance was evaluated (3). The results are shown in Table 2. Further, XPS analysis of the surface of the (4-1) resin cured product was performed using the laminate A having the partition wall pattern 4 formed in the 2 nd sheet, and then XPS analysis of the inside of the (4-2) resin cured product was performed. The elemental concentrations (atom%) of the F atom and the Si atom obtained are shown in Table 2.

Next, (5) evaluation of durability was performed using the laminate a formed with the partition wall pattern 5, and the results are shown in table 2.

TABLE 2

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Example 7

The laminate a with the partition wall pattern 4 formed as described in example 1 was produced using the photosensitive resin composition W3, and the surface and the interior of the resin cured product were evaluated by XPS comparison (4-3). The resin cured product of the photosensitive resin composition W3 is referred to as a resin cured product W3. Fig. 6 shows a C1s spectrum 22 on the surface of the obtained resin cured product W3 and a C1s spectrum 23 inside the resin cured product W3.

For those from CF having peaks in the range of bond energy 290-292 eV ₂ As a result, the C1s spectrum 22 of the surface of the resin cured product W3 was high as a result of the peak height of the group peak. On the other hand, for CF-derived materials having peaks in the bond energy range of 292 to 294eV ₃ The peak height of the group peak resulted in a high C1s spectrum 23 inside the resin cured product W3. In addition, the resin cured product W3 has high liquid repellency after UV ozone treatment, and as a result, durability when used in a display device is high.

Comparative example 5

The substrate with the partition wall pattern 4 formed thereon described in example 1 was produced using the photosensitive resin composition W10, and the surface and the interior of the resin cured product were evaluated by XPS comparison (4-3). The resin cured product of the photosensitive resin composition W10 is referred to as a resin cured product W10. Fig. 7 shows a C1s spectrum 24 of the surface of the obtained resin cured product W10 and a C1s spectrum 25 of the inside of the resin cured product W10. From CF by comparing C1s spectrum 24 on the surface of resin cured product W10 with C1s spectrum 25 in resin cured product W10 ₂ Peak height of group peak and from CF ₃ The peak heights of the peaks of (2) are the same. In addition, the liquid repellency of the resin cured product W10 was evaluated as poor.

Example 8 comparative examples 6 and 7

By the above<Compositional analysis using FT-IR>The method described in (a) was carried out by measuring the IR spectrum of a cured resin formed from the photosensitive resin compositions W3 (example 8), W7 (comparative example 6) and W8 (comparative example 7). According to the IR spectrum of the resin composition of the photosensitive resin compositions W3 and W7, the range of 1775-1780 cm ^-1 1720 to 1725cm ^-1 Peaks from carbonyl stretching vibration in the imide ring structure were obtained. On the other hand, according to the IP spectrum of the resin cured product of the photosensitive resin composition W8, no spectrum showing the presence of the imide ring structure was confirmed.

The thermally decomposed products of the resin cured products of the photosensitive resin compositions W3, W7 and W8 were analyzed by the method described in the above < composition analysis by thermal decomposition GC/MS >. As a result of the analysis, peaks (840 to 850 seconds) ascribed to the imide ring structure were obtained from the resin cured products of the photosensitive resin compositions W3 and W7. On the other hand, no peak ascribed to the imide ring structure was observed from the cured product of the photosensitive resin composition W8.

The evaluation result of the durability of (5) of the photosensitive resin composition W3 used in example 8 was example 3, and the light-emitting area was not changed, and was determined as a.

The evaluation result of the durability of (5) of the photosensitive resin composition W7 used in comparative example 6 was comparative example 1, and the light-emitting area was reduced to 83%, and thus was determined as C. The presence of the imide ring structure was confirmed from the resin cured product of the photosensitive resin composition W7, but in XPS analysis of the inside of the (4-2) resin cured product of comparative example 1, the fluorine atom was 0atom%, and therefore, it was assumed that the light emitting area was reduced.

The evaluation result of the durability of (5) of the photosensitive resin composition W8 used in comparative example 7 was comparative example 2, and the light-emitting area was reduced to 60%, and thus was determined as D.

From this, it was confirmed that when a resin cured product containing a compound having an imide ring structure was used for the partition wall, the performance as a light-emitting element was maintained even after a durability test under acceleration conditions, and an organic EL display device having high durability was obtained.

Examples 9 and 10

The thermally decomposed products of the resin cured products of the photosensitive resin compositions W3 (example 9) and W6 (example 10) were analyzed by the method described in the above < composition analysis by thermal decomposition GC/MS >. As a result of the analysis, a peak (450 to 455 seconds) ascribed to indene was obtained from the resin cured product of the photosensitive resin composition W3. On the other hand, no peak ascribed to indene was observed from the cured resin of the photosensitive resin composition W6.

Next, photosensitive resin compositions W3 and W6 were applied to the substrate by spin coating, and prebaked on a heating plate at 120℃for 2 minutes to form a photosensitive resin dried product having a thickness of about 2. Mu.m. Next, "half exposure" in which ultraviolet light was irradiated with the full wave of the mercury lamp was performed so that the thickness after development became 0.5 μm for half of the area of the photosensitive resin dried product. The remaining half area of the W3 photosensitive resin dried product having the positive photosensitive characteristic was left unexposed so that the thickness thereof was not reduced in the developing step. On the other hand, W6 having negative photosensitive characteristics was irradiated with an exposure of 120mJ/cm so that the thickness in the developing step was not reduced ² (conversion of h line). Then, development was performed with a 2.38 mass% TMAH aqueous solution for 60 seconds, followed by rinsing with water, to prepare an intermediate with a photosensitive resin dried product. Next, the obtained intermediate of the photosensitive resin-provided dried product was heated at 250 ℃ for 1 hour in a nitrogen atmosphere using a cleaning oven (manufactured by Koyo Thermo Systems corporation) to be cured, thereby producing a laminate B with a resin cured product.

The contact angle measured on the surface of the resin cured product of the photosensitive resin composition W3 with PGMEA was 46 ° at the unexposed portion and 5 ° or less at the half-exposed portion. Thus, it was confirmed that the surface of the resin cured product produced by half-exposing the photosensitive resin composition containing the indene-containing compound exhibited lyophilic properties. That is, a resin cured product having a liquid repellent surface and a resin cured product having a lyophilic surface can be formed by one-time photolithography. On the other hand, regarding the contact angle measured with PGMEA on the surface of the resin cured product of the photosensitive resin composition W6, the exposure portion was 46 °, the half exposure portion was 40 °, and liquid repellency was confirmed in two regions.

Example 11

Fig. 1 shows a schematic diagram of a laminate used for evaluation.

Further, the photosensitive resin composition W3 obtained by spin coating was pre-baked on a heating plate at 120 ℃ for 2 minutes on the intermediate for evaluation to form a photosensitive resin dried product having a thickness of about 2 μm. Then, the exposure amount was 120mJ/cm by irradiating the full wavelength of the mercury lamp with a photomask having a predetermined pattern and a position where the transmittance was adjusted so as to be able to perform half exposure ² After ultraviolet rays (converted into h line), development was performed for 60 seconds with a 2.38 mass% TMAH aqueous solution, and the resultant was rinsed with water to form an uncured material of the barrier rib pattern 12. Next, the substrate on which the barrier rib pattern 12 was formed was heated at 250 ℃ for 1 hour in a nitrogen atmosphere using a cleaning oven (manufactured by Koyo Thermo Systems corporation) to be cured, thereby obtaining a laminate a on which the barrier rib pattern 12 was formed. In the barrier rib pattern 12 formed, the thickness of the 1 st step was 1.8 μm, and the thickness of the 2 nd step was 0.5 μm.

XPS analysis was performed on the surface of the resin cured product (4-1) with respect to the resin cured product W3 (2 nd order) formed by half exposure and the resin cured product W3 (1 st order) formed by non-exposure, and the obtained elemental concentrations (atom%) of F atoms and Si atoms are shown in Table 3. Fig. 8 shows a C1s spectrum 26 of the surface of the resin cured product W3 (2 nd order) formed by half exposure. The evaluation results of (5) durability are shown in table 3.

The XPS analysis result of the surface of the resin cured product W3 (2 nd order) formed by half exposure was a result satisfying the characteristic (v). In the evaluation of durability (5), the functional ink 11 can be continuously dropped onto the patterned 1 st electrode 8 on the substrate and the 2 nd step 10 of the resin cured product without occurrence of white spots, as shown in fig. 2.

TABLE 3

Example 12

An evaluation was made in the same manner as in example 11 except that the photosensitive resin composition was changed to W5. XPS analysis was performed on the surface of the resin cured product (4-1) with respect to the resin cured product W5 (2 nd order) formed by half exposure and the resin cured product W5 (1 st order) formed by non-exposure, and the obtained elemental concentrations (atom%) of F atoms and Si atoms are shown in Table 3. Fig. 9 shows a C1s spectrum 27 of the surface of the resin cured product W5 (2 nd order) formed by half exposure. The evaluation results of (5) durability are shown in table 3.

The XPS analysis result of the surface of the resin cured product W5 (2 nd order) formed by half exposure was a result satisfying the characteristic (v). In the evaluation of durability (5), as shown in fig. 2, the functional ink 11 can be continuously dropped onto the patterned 1 st electrode 8 on the substrate and the 2 nd step 10 of the resin cured product without occurrence of white spots, because the surface of the resin cured product W5 (2 nd step) formed by half exposure is lyophilic.

It is assumed that the durability test was poor because the F atom concentration of the resin cured product (2 nd order) formed by half exposure was lower than that of example 11.

Example 13

Evaluation was performed in the same manner as in example 11 except that the method for producing the partition wall pattern 12 was changed as follows.

The photosensitive resin composition W10 was applied to the intermediate for evaluation by spin coating, and prebaked on a heating plate at 120 ℃ for 2 minutes to form a photosensitive resin dried product having a thickness of about 0.6 μm. Then, a photomask having a predetermined pattern is interposed therebetweenA mold for irradiating exposure of 60mJ/cm with full wavelength of mercury lamp ² After ultraviolet rays (conversion to h line), development was performed for 50 seconds with a 2.38 mass% aqueous TMAH solution, and rinsing was performed with water. Then, the cured product was cured by heating at 250℃for 1 hour in a nitrogen atmosphere using a clean oven (manufactured by Koyo Thermo Systems Co., ltd.) to form a resin cured product, as shown in FIG. 3, on the 1 st electrode, at the 2 nd stage 10. Next, the photosensitive resin composition W3 was applied by spin coating, and prebaked on a hot plate at 120℃for 2 minutes to form a dried photosensitive resin having a thickness of about 2.0. Mu.m. Then, the exposure was 120mJ/cm at the full wavelength of the mercury lamp through a photomask having a predetermined pattern ² After ultraviolet rays (conversion to h line), development was performed for 60 seconds with a 2.38 mass% aqueous TMAH solution, and rinsing was performed with water. Next, a cleaning oven (manufactured by Koyo Thermo Systems corporation) was used, and the resultant was heated at 250 ℃ for 1 hour under a nitrogen atmosphere to cure the resultant, and as shown in fig. 3, a 1 st step 9 of a resin cured product was formed on a 1 st electrode and a 2 nd step 10 of the resin cured product, whereby a laminate a having 2 sheets of barrier rib patterns 12 was produced.

In the barrier rib pattern 12 formed, the thickness of the 1 st step was 1.8 μm, and the thickness of the 2 nd step was 0.5 μm.

XPS analysis was performed on the surfaces of the resin cured products of the (4-1) th order 2 with respect to the resin cured product W10 (2 nd order) and the resin cured product W3 (1 st order), and the obtained elemental concentrations (atom%) of the F atom and the Si atom are shown in Table 3. Fig. 10 shows a C1s spectrum 28 of the surface of the 2 nd-order resin cured product W10. The evaluation results of (5) durability are shown in table 3.

The XPS analysis result of the surface of the resin cured product W10 (2 nd order) shows that the characteristic (v) is satisfied. In the evaluation of durability (5), as shown in fig. 3, the functional ink 11 can be continuously dropped onto the 1 st electrode 8 patterned on the substrate and the 2 nd step 9 of the resin cured product without occurrence of white spots, while the surface of the resin cured product W10 (2 nd step) is lyophilic.

Example 14

Evaluation was performed in the same manner as in example 13 except that the photosensitive resin composition was changed to the type shown in table 3. XPS analysis was performed on the surface of the (4-1) resin cured product of the 1 st and 2 nd orders, and the elemental concentrations (atom%) of the F atoms and Si atoms obtained are shown in Table 3. Fig. 11 shows a C1s spectrum 29 of the surface of the 2 nd-order resin cured product W10. The evaluation results of (5) durability are shown in table 3.

In example 14, a reduction in the light emitting area was confirmed in the durability evaluation of the display device as compared with example 13. Regarding the photosensitive resin composition W8 used in the 1 st stage, the light emitting area was presumed to be reduced by analysis of the inside of the resin cured product by XPS of comparative example 2, since the concentration of F atoms was 0 atom%.

Example 16

An evaluation was made in the same manner as in example 11 except that the photosensitive resin composition was changed to W11. XPS analysis was performed on the surface of the resin cured product W11 (2 nd order) formed by half exposure and the resin cured product W11 (1 st order) formed by non-exposure (4-1), and the obtained elemental concentrations (atom%) of F atoms and Si atoms are shown in Table 3. Fig. 12 shows a C1s spectrum 31 of the surface of the resin cured product W5 (2 nd order) formed by half exposure. The evaluation results of (5) durability are shown in table 3.

The XPS analysis result of the surface of the resin cured product W11 (2 nd order) formed by half exposure was a result satisfying the characteristic (v). In the evaluation of durability (5), the functional ink 11 can be continuously dropped onto the patterned 1 st electrode 8 on the substrate and the 2 nd step 10 of the resin cured product without occurrence of white spots, as shown in fig. 2, because the surface of the resin cured product W11 (2 nd step) formed by half exposure is lyophilic.

Example 17

Evaluation was performed in the same manner as in example 13 except that the photosensitive resin composition was changed to the type described in table 3. XPS analysis was performed on the surface of the (4-1) resin cured product of the 1 st and 2 nd orders, and the obtained elemental concentrations (atom%) of F atoms and Si atoms are shown in Table 3. Fig. 13 shows a C1s spectrum 32 of the surface of the 2 nd-order resin cured product W10. The evaluation results of (5) durability are shown in table 3.

In example 17, a reduction in the light emitting area was confirmed in the durability evaluation of the display device as compared with example 13. Regarding the photosensitive resin composition W12 used in the 1 st stage, the light emitting area was presumed to be reduced by analysis of the inside of the resin cured product by XPS of comparative example 8, since the concentration of F atoms was 0 atom%.

Reference numerals

1. Alkali-free glass substrate

3. Auxiliary electrode

4. Partition wall pattern

5. Partition wall pattern

6 organic EL layer

7 nd electrode

Patterned 1 st electrode on 8 substrate

9 st order of resin cured product

10 2 nd order of resin cured product

11. Functional layer

12. Partition wall pattern

13. Substrate board

14. Planarization layer

16. Resin cured product

17 and the surface of the 1 st electrode opposite to the interface with the resin cured product

18 interface between the 1 st electrode and the resin cured product

19 are perpendicular to the interface between the first electrode and the resin cured product, and in the direction from the substrate toward the resin cured product, the range of 100-200 nm is taken as the starting point of the interface between the first electrode and the resin cured product

20 resin cured product 1 st stage and surface opposite to interface between 1 st electrode and resin cured product

21 the surface of the resin cured product on the opposite side of the interface between the 1 st electrode and the resin cured product of the 2 nd step

C1s spectrum of surface of 22 resin cured W3

23C 1s spectrum inside the resin cured product W3

24C 1s spectrum of the surface of the resin cured product W10

25C 1s spectrum inside the resin cured product W10

26C 1s spectrum of surface of resin cured product W3 (2 nd order) formed by half exposure

27C 1s spectrum of surface of resin cured product W5 (2 nd order) formed by half exposure

28C 1s spectrum of the surface of the 2 nd order resin cured product W10

29C 1s spectrum of the surface of the 2 nd order resin cured product W10

30 is perpendicular to the interface between the first electrode and the resin cured product, and is 100nm from the interface between the first electrode and the resin cured product in the direction from the substrate toward the resin cured product

31C 1s spectrum of surface of resin cured product W5 (2 nd order) formed by half exposure

32 as the C1s spectrum of the surface of the 2 nd order resin cured product W10.

Claims

1. A laminated body in which a substrate, a patterned 1 st electrode on the substrate, and a resin cured product are laminated in this order, and at least a part of the resin cured product located on the 1 st electrode is opened,

analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS) satisfies the characteristics (i) and (ii),

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

3. The laminate according to claim 1 or 2, wherein, in analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS), C1s spectra [ A ] and C1s spectra [ B ] satisfy characteristics (iii) and (iv),

wherein the C1s spectrum [ A ] is a C1s spectrum of the resin cured product measured from at least a part of a surface on the opposite side of the interface with the 1 st electrode and the resin cured product,

(iii) With C1s spectrum [ B]From CF having peaks in the range of bond energy 290-292 eV ₂ Peak height of group peak compared with C1s spectrum [ A]Is higher than the peak height of the die,

(iv) With C1s spectrum [ A]From CF having peaks in the bond energy range of 292-294 eV ₃ Peak height of group peak compared with C1s spectrum [ B]Is higher.

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

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

6. The laminate according to any one of claims 1 to 5, wherein the resin cured product is a resin cured product having a step shape having a 1 st order of 0.8 μm to 10.0 μm in thickness starting from an interface between the 1 st electrode and the resin cured product and a 2 nd order of 0.1 μm to 0.7 μm in thickness starting from an interface between the 1 st electrode and the resin cured product, and further wherein in analysis of the resin cured product by X-ray photoelectron spectroscopy (XPS), the 1 st order of the resin cured product satisfies the characteristic (i) and the 2 nd order of the resin cured product satisfies the characteristic (v),

(v) A concentration of F atoms measured from at least a part of a surface opposite to an interface of the 1 st electrode and the resin cured product is 0.1atom% or more and 20.0atom% or less, and a concentration of Si atoms is 0.1atom% or more and 0.9atom% or less, and a peak having a maximum peak height measured in a range of 290 to 295eV in a C1s spectrum is a CF derived from a peak top in a range of 292 to 294eV ₃ Peaks of the groups.

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

8. A display device comprising the laminate according to any one of claims 1 to 7.

9. A method for manufacturing a display device, comprising the steps (5) and (6) in this order,

(5) A step of forming a functional layer by applying a functional ink to the 1 st electrode by ink jet in the laminate according to any one of claims 1 to 7;

(6) And forming a 2 nd electrode on the functional layer.

10. A method for manufacturing a display device, comprising the steps (7) and (8) in this order,

(7) A step of forming a functional layer by applying a functional ink on the 1 st electrode and the 2 nd step of the resin cured product by ink jet in the laminate according to claim 6 or 7;

(8) And forming a 2 nd electrode on the functional layer.