KR20230148808A - Laminate, display device and method of manufacturing display device - Google Patents

Abstract

The purpose of the present invention is to obtain a laminate that has a cured resin material that has high liquid repellency after UV ozone treatment and is highly durable when used in a display device. In order to achieve the above object, the laminate of the present invention is laminated in the order of a substrate, a first electrode patterned on the substrate, and a cured resin, and at least a portion of the cured resin on the first electrode is open. It is a laminate, and analysis of the cured resin by X-ray photoelectron spectroscopy (XPS) satisfies specific characteristics.

Description

Laminate, display device and method of manufacturing display device

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

In display devices with thin displays, such as smartphones, tablet PCs, and televisions, many products are being developed in which functional layers are formed by a printing method typified by the inkjet method. For example, in the case of an organic electroluminescence (hereinafter referred to as “organic EL”) display device, after forming a barrier rib pattern on a substrate, an inkjet method is used to fill the openings between the barrier ribs with a light emitting material, a hole transport material, There is a known method of dropping a solution of a functional material such as an electron transport material and forming an organic EL display device having a functional layer.

Generally, an organic EL display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate, and is operated by applying a voltage between the opposing first and second electrodes. It can emit light. Among these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are generally used as materials for the planarization layer and the insulating layer. Among them, photosensitive resin compositions using polyimide resin or polybenzoxazole resin are suitable for providing highly durable organic EL display devices because the heat resistance of the resin is high and the gas component generated from the cured product is small. It is widely used (patent document 1).

When forming a functional layer by an inkjet method, it is necessary to provide liquid repellency to the upper surface of the partition for the purpose of preventing color mixing of ink injected into adjacent openings. Additionally, in order to prevent white leakage of the organic EL display device, the openings between the partitions must have good wettability for ink.

In order to realize this, a method of developing liquid repellency by subjecting the upper layer surface of the partition pattern on the substrate to fluorination treatment by plasma irradiation is being studied (patent document 2).

In addition, a method of forming a partition using a photosensitive resin composition containing an alkali-soluble resin and a liquid-repelling compound is being studied. For example, a resist composition containing a fluorine-based acrylic polymer (Patent Document 3) and a photosensitive resin composition containing a polysiloxane having a fluorinated alkyl group (Patent Document 4) are being studied.

Japanese Patent Publication No. 2002-91343 Japanese Patent Publication No. 2002-207114 Japanese Patent Publication No. 2012-220855 International Publication No. 2019/159000

Since the technology of Patent Document 1 does not have liquid repellency on the upper surface of the formed partition, there is a problem in that the functional material solution dropped by the inkjet method crosses the partition and mixes into nearby pixels, causing poor light emission.

In the technique of Patent Document 2, a problem arises in that the liquid-repellent component also adheres to the openings between the partitions due to the fluorination treatment, and the ink wettability of the openings becomes insufficient.

The techniques of Patent Document 3 and Patent Document 4 have sufficient liquid repellency and enable pattern formation as a photosensitive resin composition. 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 is insufficient after UV ozone treatment.

The polysiloxane having a fluorine atom in Patent Document 4 is excellent in UV ozone resistance and can provide sufficient liquid repellency to the upper surface of the partition after UV ozone treatment. On the other hand, the cured product has high water absorption, and there is a problem with durability when used in a partition of a display device.

Therefore, the purpose of the present invention is to obtain a laminate that has a cured resin material that has high liquid repellency after UV ozone treatment and is highly durable when used in a display device.

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 in which a substrate, a first electrode patterned on the substrate, and a cured resin are laminated in that order, and at least a portion of the cured resin on the first electrode is open,

A laminate wherein analysis of the cured resin by X-ray photoelectron spectroscopy (XPS) satisfies properties (i) and (ii).

(i) the F atom concentration of the cured resin measured from at least a portion of the surface opposite to the interface where the first electrode and the cured resin are in contact is 8.1 atom% or more and 30.0 atom% or less and the Si atom concentration is 1.0 atom % or more and 6.0 atom% or less

(ii) perpendicular to the interface where the first electrode and the cured resin are in contact, and in the direction of the cured resin from the substrate, and of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. The concentration of F atoms in the cured resin as measured within the range is 0.1 atom% or more and 8.0 atom% or less.

According to the present invention, it is possible to obtain a laminate that has a cured resin material that has high liquid repellency after UV ozone treatment and is highly durable when used in a display device.

1 is a schematic diagram of a laminate used for evaluation in examples.
Fig. 2 is a schematic diagram of the partition pattern 12 used for evaluation in the example.
Fig. 3 is a schematic diagram of the partition pattern 12 used for evaluation in the example.
4 is a schematic diagram of a cross section of an example of a laminate.
Figure 5 is a schematic diagram of a cross section of another example of a laminate.
Figure 6 is a C1s spectrum from XPS analysis in Example 7.
Figure 7 is a C1s spectrum from XPS analysis in Comparative Example 5.
Figure 8 is a C1s spectrum from XPS analysis in Example 11.
Figure 9 is a C1s spectrum from XPS analysis in Example 12.
Figure 10 is a C1s spectrum from XPS analysis in Example 13.
Figure 11 is a C1s spectrum from XPS analysis in Example 14.
Figure 12 is a C1s spectrum from XPS analysis in Example 16.
Figure 13 is a C1s spectrum from XPS analysis in Example 17.

Embodiments of the present invention will be described in detail.

<Laminate>

The laminate of the present invention is a laminate in which a substrate, a first electrode patterned on the substrate, and a cured resin are laminated in that order, and at least a portion of the cured resin on the first electrode is open,

Analysis of the cured resin by X-ray photoelectron spectroscopy (XPS) shows that the laminate satisfies properties (i) and (ii).

(i) the F atom concentration of the cured resin measured from at least a portion of the surface opposite to the interface where the first electrode and the cured resin are in contact is 8.1 atom% or more and 30.0 atom% or less and the Si atom concentration is 1.0 atom % or more and 6.0 atom% or less.

(ii) perpendicular to the interface where the first electrode and the cured resin are in contact, and in the direction of the cured resin from the substrate, and of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. The concentration of F atoms in the cured resin as measured within the range is 0.1 atom% or more and 8.0 atom% or less.

The cured resin of the laminate of the present invention has characteristic (i) as a surface characteristic and has characteristic (ii) inside the cured resin. Due to the characteristics of this composition, the laminate of the present invention has a cured resin material with high liquid repellency after UV ozone treatment and is excellent in durability when used in a display device.

Next, the characteristics (i) of the cured resin product according to X-ray photoelectron spectroscopy (XPS) will be explained.

Property (i) is measured from at least a portion of the surface of the cured resin opposite to the interface where the first electrode and the cured resin are in contact. Additionally, it is preferable to measure within a range of 100 ㎛ from the edge of the opening of the cured resin. By measuring this range, the liquid repellency of the surface of the cured resin material for functional ink can be analyzed.

As the first characteristic (i), the concentration of F atoms is 8.1 atom% or more and 30.0 atom% or less, and more preferably 15.0 atom% or more and 26 atom% or less. Since the concentration of F atoms is 8.1 atom% or more, the surface of the cured resin material has excellent liquid repellency. On the other hand, if the concentration of F atoms is 30 atom% or less, aggregation of F atoms can be suppressed and a cured resin product with fewer defects can be obtained. Additionally, as the second characteristic (i), the Si atom concentration is 1.0 atom% or more and 6.0 atom% or less, and more preferably 1.5 atom% or more and 4.5 atom% or less. When the concentration of Si atoms is 1.0 atom% or more, the UV ozone resistance of the cured resin is improved, and good liquid repellency can be obtained even after UV ozone treatment. On the other hand, if the concentration of Si atoms is 6.0 atom% or less, aggregation of Si atoms can be suppressed and a cured resin product with fewer defects can be obtained.

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

As a method for adjusting the concentration of the F atom of characteristic (i) to the above range, for example, the content of compound (a-1) having a fluorinated alkyl group of 7 to 21 fluorine numbers and 5 to 12 carbon atoms in the photosensitive resin composition is adjusted. There is a way to adjust it. By increasing the content, the concentration of F atoms of characteristic (i) can be increased, and by decreasing the content, the concentration of F atoms of characteristic (i) can be reduced. Additionally, there is also a method of adjusting the concentration of the fluorinated alkyl group contained in compound (a-1). By increasing the concentration of the fluorinated alkyl group, the concentration of the F atoms of characteristic (i) can be increased, and by decreasing the concentration of the fluorinated alkyl group, the concentration of the F atoms of characteristic (i) can be reduced.

As a method for adjusting the Si atom concentration of characteristic (i) to the above range, for example, there is a method of adjusting the content of the compound (a-2) having a siloxane structure in the photosensitive resin composition. By increasing the content, the concentration of Si atoms of characteristic (i) can be increased, and by decreasing the content, the concentration of Si atoms of characteristic (i) can be reduced. Additionally, there is also a method of adjusting the concentration of the siloxane structure of compound (a-2). By increasing the concentration of the siloxane structure, the concentration of Si atoms of characteristic (i) can be increased, and by decreasing the concentration of the siloxane structure, the concentration of Si atoms of characteristic (i) can be reduced.

The structure of compound (a-1) having a fluorinated alkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms is not particularly limited. For example, consisting of 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, and 2-(perfluorooctyl)ethyl (meth)acrylate. Acrylic resins copolymerized with one or more types selected from the group and polysiloxane (A) described later can be mentioned. From the viewpoint of UV ozone resistance, polysiloxane (A) described later is preferred.

The structure of compound (a-2) having a siloxane structure is not particularly limited. For example, alkyl-modified silicone, polyether-modified silicone, and polysiloxane (A) described later. From the viewpoint of localization on the surface of the cured resin, polyether-modified silicone and polysiloxane (A) described later are preferred. Moreover, polysiloxane (A) described later is more preferable from the viewpoint of liquid repellency.

Products commercially available as polyether-modified silicone include, for example, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-642 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH8400, SH8700, SF8410 (manufactured by Dow Corning Toray Co., Ltd.), BYK-300, BYK-306, BYK-307, BYK-320, BYK-325, BYK-330 (manufactured by Big Chemistry), etc.

Characteristic (i) is preferably analyzed with an XPS device with a detector tilt of 45° with respect to the sample surface. Since the detector has an inclination of 45°, the area near the surface of the cured resin material can be analyzed.

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

Property (ii) is perpendicular to the interface where the first electrode and the cured resin are in contact, and is in the direction of the cured material from the substrate, and is measured anywhere in the range of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. do. When the thickness of the cured resin material is 200 nm or less, measurement is made at the median value of the thickness of the cured resin material. By having an F atom inside the cured resin, the water absorption of the cured resin is reduced and corrosion of the electrode is suppressed, thereby improving the durability of the display device.

In characteristic (ii), the concentration of F atoms is 0.1 atom% or more and 8.0 atom% or less, and preferably 4.0 atom% or more and 7.5 atom% or less. When the concentration of F atoms is 0.1 atom% or more, the water absorption of the cured resin decreases and corrosion of the electrode is suppressed, thereby improving the durability of the display device. On the other hand, when the concentration of F atoms is 8.0 atom% or less, the durability of the display device and the good mechanical properties of the cured resin can be achieved at the same time.

As a method for the laminate of the present invention to satisfy characteristic (ii), for example, a method of forming a cured resin from a photosensitive resin composition containing an alkali-soluble resin (b-1) having a CF ₃ group can be cited. . The CF ₃ group has a small tendency to be localized on the surface of the cured resin, so it can fix the F atom inside the cured resin.

As a method for adjusting the concentration of the F atom of characteristic (ii) to the above range, for example, there is a method of adjusting the content of the alkali-soluble resin (b-1) having a CF ₃ group in the photosensitive resin composition. By increasing the content, the concentration of F atoms of characteristic (ii) can be increased, and by decreasing the content, the concentration of F atoms of characteristic (ii) can be reduced. Additionally, there is also a method of adjusting the concentration of the CF ₃ group contained in the alkali-soluble resin (b-1). By increasing the concentration of CF ₃ groups, the concentration of F atoms of characteristic (ii) can be increased, and by decreasing the concentration of CF ₃ groups, the concentration of F atoms of characteristic (ii) can be reduced. For the alkali-soluble resin (b-1) having a CF ₃ group, the types of the main chain skeleton and side chains of the polymer constituting the resin are not limited. Examples include, but are not limited to, polyimide resin, polybenzoxazole resin, polyamidoimide resin, acrylic resin, novolak resin, polyhydroxystyrene resin, phenol resin, and polysiloxane resin. From the viewpoint of heat resistance, the alkali-soluble resin (b-1) having a CF ₃ group includes at least one selected from the group consisting of polyimide, polybenzoxazole, polyamidoimide, precursors of any of these, and copolymers thereof. It is desirable to do so. Since these alkali-soluble resins have high heat resistance, when used in a display device, the amount of outgassing at a high temperature of 200°C or higher after heat treatment is reduced, thereby improving the durability of the display device.

Characteristic (ii) is that the cured product is excavated by Ar gas cluster ions (Ar-GCIB), and is perpendicular to the interface where the first electrode and the cured product are in contact, and is in the direction of the cured material from the substrate, and is 100 to 100 degrees from the first electrode. It can be obtained by performing analysis by X-ray photoelectron spectroscopy (XPS) after exposing something in the range of 200 nm.

In the laminate of the present invention, the thickness of the cured resin starting from the interface where the first electrode and the cured resin are in contact is preferably 0.8 to 10 μm. If it is 0.8 μm or more, it is possible to easily fix the functional ink when applying the functional ink to an area where at least a portion of the cured resin on the first electrode is open. Additionally, from the viewpoint of facilitating processing in photolithography or the like, it is preferable that the thickness is 10 μm or less.

In the laminate of the present invention, the method of forming the cured resin in which at least a portion of the first electrode is open is not particularly limited. For example, it can be formed by using the method for producing a cured resin of the photosensitive resin composition described below. As another method, for example, there is a method of forming a cured resin on the front surface of the substrate, then masking an arbitrary area with photoresist, and then etching the opening.

The cured resin material included in the laminate of the present invention is not particularly limited as long as it has the above-mentioned properties (i) and properties (ii) as determined by analysis using XPS. A cured resin product having the corresponding properties can be formed, for example, by using the photosensitive resin composition described below, and achieving both properties (i) and (ii). Additionally, it may be formed by laminating a cured resin material having characteristic (i) and a cured resin material having characteristic (ii).

The laminate of the present invention includes a substrate. As the substrate, one suitable for supporting the display device or conveying it in subsequent processes, such as metal, glass, or resin film, can be appropriately selected. If it is a glass substrate, soda-lime glass, alkali-free glass, etc. can be used, and the thickness may be sufficient to maintain mechanical strength. Regarding the material of the glass, alkali-free glass is preferable because fewer ions are eluted from the glass. However, soda-lime glass coated with a barrier coat such as SiO ₂ is also commercially available, so this can be used. If it is a resin film, it preferably contains a resin material selected from polyimide, polyamide, polybenzoxazole, polyamidoimide, and poly(p-xylylene), and may contain these resin materials alone. Multiple species may be combined. For example, when forming a resin film with polyimide, a solution containing polyamic acid, which is a precursor of polyimide (including polyamic acid partially imidized) or soluble polyimide, is applied to a support substrate and fired. After this, it can also be formed by peeling the polyimide resin film from the support substrate.

The laminate of the present invention includes a first electrode patterned on a substrate. The first electrode preferably contains ITO (indium/tin oxide), IZO (indium/zinc oxide), ZnO (zinc oxide), Ag, Al, etc. Additionally, patterning of the first electrode can be performed by a known method. For example, there is a method of forming a first electrode on the entire surface of the substrate by a sputtering method, then masking an arbitrary area with photoresist, and then etching the opening.

In the laminate of the present invention, a planarization layer may be further laminated between the substrate and the first electrode patterned on the substrate. When the laminate of the present invention is used in a display device, a TFT (thin film transistor) and a wiring located on the side of the TFT and connected to the TFT are often provided on a substrate such as glass. If the first electrode follows the unevenness of the wiring, appearance defects such as uneven light emission occur. Therefore, a planarization layer is formed on the drive circuit to cover the unevenness, and a first electrode is further provided on the planarization layer. The flattening layer preferably contains a resin material selected from polyimide, polyamide, polybenzoxazole, polyamidoimide, acrylic, cardo, and poly(p-xylylene), and these resin materials may be used alone. It may be included, or multiple species may be combined.

Figure 4 shows a schematic cross-section of an example of the laminate of the present invention. The planarization layer 14, the patterned first electrode 8, and the cured resin material 16 are laminated in that order on the substrate 13, and the cured resin material 16 is on the patterned first electrode 8. At least part of the is open. Characteristics (i) of the cured resin product by analysis of X-ray photoelectron spectroscopy (XPS) are measured from the surface 17 on the opposite side to the interface where the first electrode and the cured resin are in contact. XPS is preferably measured within a range of 100 μm from the edge of the opening of the cured resin 16. Additionally, characteristic (ii) is perpendicular to the interface 18 where the first electrode and the cured resin are in contact, and is in the direction of the cured resin from the substrate, starting from the interface where the first electrode and the cured resin are in contact. Range from 100 nm (30) to 100 nm, that is, perpendicular to the interface between the first electrode and the cured resin, and in the direction of the cured resin from the substrate, from 100 to 200 nm starting from the interface between the first electrode and the cured resin. It is measured anywhere in the range 19 nm. In the opening of the first electrode patterned on the substrate, it is perpendicular to the interface between the first electrode and the cured resin, and is oriented from the substrate to the cured resin, and is 100 to 200 degrees from the interface between the first electrode and the cured resin. As in the nm range (19), when the first electrode is present, the height is measured anywhere from 100 to 200 nm from the height of the first electrode. Additionally, when there is a change in the thickness of the first electrode, it is assumed that in the opening of the patterned first electrode, a first electrode having an average thickness at the end of the opening is present.

The laminate of the present invention is used in the analysis of the cured resin material by X-ray photoelectron spectroscopy (XPS),

A C1s spectrum [A] of the cured resin measured from at least a portion of the surface of the cured resin opposite to the interface where the first electrode and the cured resin are in contact,

It is perpendicular to the interface where the first electrode and the cured resin are in contact, and is in the direction of the cured resin from the substrate, and is measured anywhere in the range of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. The C1s spectrum [B] of the cured resin is,

It is desirable to satisfy properties (iii) and (iv).

(iii) The same peak height in the C1s spectrum [A] is higher than the peak height of the peak derived from the CF ₂ group with a peak top within the range of binding energy 290 to 292 eV in the C1s spectrum [B].

(iv) The peak height of the same peak in the C1s spectrum [B] is higher than the peak height of the peak derived from the CF ₃ group with a peak top within the range of binding energy 292 to 294 eV in the C1s spectrum [A].

The C1s spectrum [A] is a spectrum of the surface of the cured resin measured from at least a portion of the surface of the cured resin opposite to the interface where the first electrode and the cured product are in contact. Meanwhile, the C1s spectrum [B] is perpendicular to the interface where the first electrode and the cured resin are in contact, and is in the direction of the resin cured material from the substrate, and is in the range of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. This is the spectrum inside the cured material measured from something. When the thickness of the cured resin is 200 nm or less, measurement is made at the median of the thickness of the cured resin.

Since the cured resin of the laminate of the present invention exhibits characteristic (iii), the surface of the cured resin has excellent liquid repellency. Structures showing peaks derived from the CF ₂ group with peak tops within the range of binding energy 290 to 292 eV include, for example, heptafluoropentyl group, nonafluorohexyl group, tridecafluorooctyl group, and heptadecafluorode. It has a real group, a 5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl group, etc., and has the property of being localized on the surface of the cured resin. It can provide good liquid repellency to the cargo surface.

Since the cured resin of the laminate of the present invention exhibits characteristic (iv), the water absorption of the cured resin decreases and corrosion of the electrode is suppressed, thereby improving the durability of the display device. The CF ₃ group has a small tendency to be localized on the surface of the cured resin, so it can fix the F atom inside the cured resin.

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

Figure 4 shows a schematic cross-section of an example of the laminate of the present invention. The planarization layer 14, the patterned first electrode 8, and the cured resin 16 are laminated on the substrate 13 in that order, and at least one of the cured resin 16 on the first electrode 8 Some parts are open. In the analysis of the cured resin material by It is preferable to measure within a range of 100 μm from the edge of the opening of the cured resin 16. In addition, the C1s spectrum [B] is perpendicular to the interface 18 where the first electrode and the cured resin are in contact, and is in the direction of the cured resin from the substrate, and starts at the interface where the first electrode and the cured resin are in contact. In the range of 100 nm (30) to 100 nm, that is, perpendicular to the interface of the first electrode and the cured resin, and in the direction of the cured resin from the substrate, starting from the interface of the first electrode and the cured resin, 100 It is measured anywhere in the range (19) from 200 nm to 200 nm. The opening of the patterned first electrode is perpendicular to the interface between the first electrode and the cured resin, and is oriented from the substrate to the cured resin, and ranges from 100 to 200 nm starting from the interface between the first electrode and the cured resin. As shown in (19), when the first electrode is present, the height is measured within the range (19) of 100 to 200 nm from the height of the first electrode. Additionally, when there is a change in the thickness of the first electrode, it is assumed that in the opening of the patterned first electrode, a first electrode having an average thickness at the end of the opening is present.

As a method of forming the resin cured product of the laminate of the present invention, for example, a resin cured product that satisfies characteristics (i) to (iv) can be formed by using the photosensitive resin composition described below. . Additionally, it may be formed by laminating a cured resin material having properties (i) and (iii) and a cured resin material having properties (ii) and (iv).

In the laminate of the present invention, it is preferable that the cured resin contains a compound having an imide ring structure. The compound having an imide ring structure is preferably a structure derived from polyimide resin or a residue thereof. Examples of the polyimide resin include the polyimide described in the alkali-soluble resin (B) described later, polyamidoimide, these precursors, and their copolymers. Since the cured resin contains a compound having an imide ring structure, the amount of outgassing 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. there is.

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

In the laminate of the present invention, when the cured resin is a cured product of a positive type photosensitive resin composition, the surface of the cured resin formed by “half exposure” described later has no liquid repellency and can have good ink applicability. there is. That is, in one photolithography, a cured resin material with a liquid-repellent surface and a cured resin material with a lyophilic surface can be formed.

In the laminate of the present invention, the cured resin material has a first stage having a thickness of 0.8 ㎛ to 10.0 ㎛ starting from the interface between the first electrode and the cured resin, and a first stage starting from the interface between the first electrode and the cured resin. It is a step-shaped cured resin material having a second stage with a thickness of 0.1 μm to 0.7 μm, and in the analysis of the cured resin material by X-ray photoelectron spectroscopy (XPS), the first stage of the cured resin material has the characteristic (i) It is preferable that the second stage of the cured resin satisfies characteristic (v).

(v) The concentration of F atoms measured from at least a portion of the surface of the cured resin opposite to the interface where the first electrode and the cured resin are in contact is 0.1 atom% or more and 20.0 atom% or less, and the concentration of Si atoms is 0.1 atom%. % or more but 0.9 atom% or less, and the maximum peak height measured in the range of 290 to 295 eV of binding energy in the C1s spectrum is a peak derived from the CF ₃ group with the peak top in the range of 292 to 294 eV.

The first stage, which has a thickness of 0.8 ㎛ to 10.0 ㎛ starting from the interface between the first electrode and the cured resin, is a cured resin with a liquid-repellent surface having characteristic (i). If the thickness is 0.8 μm or more, the functional ink can be easily fixed when the functional ink is applied to an area where at least a portion of the cured resin on the first electrode is open. Additionally, from the viewpoint of facilitating processing in photolithography or the like, it is preferable that the thickness is 10.0 μm or less.

The second stage, which has a thickness of 0.1 ㎛ to 0.7 ㎛ starting from the interface between the first electrode and the cured resin, is a cured resin with a hydrophilic surface having characteristic (v). Property (v) is a property of the surface of the cured product measured from at least a portion of the surface on the second stage of the cured resin product opposite to the interface where the first electrode and the cured resin are in contact. When the cured resin exhibits characteristic (v), a laminate can be obtained that has a lyophilic surface, a low water absorption rate, and excellent durability when used in a display device. When the thickness is 0.1㎛ or more, the cured resin material can exhibit insulating properties. On the other hand, when the functional ink is continuously inkjet applied to the second stage of the resin cured material with a thickness of 0.7 μm or less from the area where at least a portion of the cured resin material on the first electrode is open to form a functional layer, the functional layer Defects that cause white omission can be suppressed.

In characteristic (v), the concentration of F atoms measured from at least a portion of the surface of the cured resin opposite to the interface where the first electrode and the cured resin are in contact is 0.1 atom% or more and 20.0 atom% or less, preferably is 8.0 atom% or more and 18.0 atom% or less. When the concentration of F atoms is 0.1 atom% or more, the water absorption rate of the cured resin is low, and durability when used in a display device can be improved. On the other hand, when the concentration of F atoms is 20.0 atom%, aggregation of F atoms can be suppressed. In addition, characteristic (v) is a peak having a maximum peak height measured in the range of 290 to 295 eV of binding energy in the C1s spectrum measured from at least a portion of the surface opposite to the interface where the first electrode and the cured resin are in contact. , a peak derived from the CF ₃ group with a peak top in the range of 292 to 294 eV. Since the fluorine structure is CF ₃ group, it is possible to achieve both the lyophilicity of the surface of the cured resin and the durability of the display device.

In characteristic (v), the concentration of Si atoms of the cured resin measured from the surface opposite to the interface where the first electrode and the cured resin are in contact is 0.1 atom% or more and 0.9 atom% or less, more preferably 0.1 atom%. It is more than atom% and less than 0.5atom%. When the concentration of Si atoms is 0.1 atom% or more, adhesion to the electrode is improved and the durability of the display device can be improved. When the concentration of Si atoms is 0.9 atom% or less, the surface of the cured resin material can exhibit good lyophilicity.

Property (i) is preferably measured within a range of 100 ㎛ from the end of the opening of the first stage of the cured resin. By measuring this range, the surface liquid repellency of the first stage of the cured resin material for functional ink can be analyzed. Additionally, property (v) is preferably measured within a range of 100 μm from the end of the opening of the second stage of the cured resin. By measuring this range, the surface hydrophilicity of the second stage of the cured resin material for the functional ink can be analyzed.

As a method for the laminate of the present invention to satisfy characteristic (v), for example, a photosensitive resin comprising an alkali-soluble resin (b-1) having a CF ₃ group and an alkali-soluble resin (b-2) having a siloxane structure. A method of forming a cured resin product from the composition is included. The alkali-soluble resin (b-1) having a CF ₃ group may have a siloxane structure. By containing an alkali-soluble resin (b-1) having a CF ₃ group, a peak with a maximum peak height measured in the range of 290 to 295 eV of binding energy in the C1s spectrum is CF with a peak top in the range of 292 to 294 eV. The peak originates from stage ₃ . The CF ₃ group has a small tendency to be localized on the surface of the cured resin, so it can fix the F atom inside the cured resin.

As a method for adjusting the concentration of the F atom of characteristic (v) to the above range, for example, there is a method of adjusting the content of the alkali-soluble resin (b-1) having a CF ₃ group in the photosensitive resin composition. By increasing the content, the concentration of F atoms of characteristic (v) can be increased, and by decreasing the content, the concentration of F atoms of characteristic (v) can be reduced. Additionally, there is also a method of adjusting the concentration of the CF ₃ group contained in the alkali-soluble resin (b-1). By increasing the concentration of CF3 groups, the concentration of F atoms of characteristic (v) can be increased, and by decreasing the concentration of _CF3 groups, the concentration of F atoms of characteristic (v) can be reduced.

As a method for adjusting the Si atom concentration of characteristic (v) to the above range, for example, there is a method of adjusting the content of alkali-soluble resin (b-2) having a siloxane structure in the photosensitive resin composition. By increasing the content, the concentration of Si atoms of characteristic (v) can be increased, and by decreasing the content, the concentration of Si atoms of characteristic (v) can be reduced. There is also a method of adjusting the concentration of the siloxane structure of the alkali-soluble resin (b-2). By increasing the concentration of the siloxane structure, the concentration of Si atoms of characteristic (v) can be increased, and by decreasing the concentration of the siloxane structure, the concentration of Si atoms of characteristic (v) can be reduced.

Characteristic (v) is preferably analyzed with an XPS device with a detector tilt of 45° with respect to the sample surface. Since the detector has an inclination of 45°, the area near the surface of the cured resin material can be analyzed.

The laminate including the step-shaped cured resin having the first step and the second step is, for example, formed of a cured resin having at least properties (i), (ii), and (v). can do. Such a laminate can be formed, for example, by using the photosensitive resin composition described below. Specifically, when a positive type photosensitive resin composition is used, a first stage having characteristic (i) is formed in the unexposed area, and a second stage having characteristic (v) is formed in the “half-exposed part” described later. It can be done, and the inside of the cured resin can exhibit characteristic (ii). Additionally, it may be formed by laminating a cured resin material having characteristic (i) and a cured resin material having characteristic (v). When two types of cured resins are laminated, at least one type of cured resin has characteristic (ii). From the viewpoint of durability of the display device, it is more preferable that the two types of cured resins have characteristic (ii).

A laminate comprising a step-shaped cured resin having the first step and the second step, for example, a first electrode (8) patterned on a substrate as shown in FIG. 2 or FIG. 3. , a laminate comprising a first stage 9 that defines an area where the cured resin material is applied by inkjet, and a second stage 10 that defines two or more regions arranged within the region. there is. The functional layer 11 continuously disposed on the first electrode 8 patterned on the substrate and the second end 10 of the cured resin can be formed by an inkjet coating method.

A laminate including a step-shaped cured resin product having the first step and the second step can be formed by using a photosensitive resin composition. Specifically, a photosensitive resin dried product obtained from a positive type photosensitive resin composition is produced on the first electrode 8 patterned on a substrate, and an unexposed portion, a half-exposed portion, and an exposed portion are formed in the subsequent exposure process. Subsequently, by performing the development process and heat treatment process, the first stage 9 of the cured resin can be formed in the unexposed area, and the second stage 10 of the cured resin can be formed in the half-exposed area, and the exposed area can be patterned on the substrate. The first electrode 8 is exposed. also. As shown in FIG. 3, the second stage 10 of the cured resin material and the first stage 9 of the cured resin material may be laminated on the first electrode 8 patterned on the substrate in that order.

Figure 5 shows a schematic cross section of another example of the laminate of the present invention. The planarization layer 14, the patterned first electrode 8, and the cured resin are laminated on the substrate 13 in that order, and the cured resin has at least a portion of the first electrode 8 open, and the cured resin also has It has a first stage (9) and a second stage (10) of cured resin. Characteristics (i) of the cured resin product by analysis of X-ray photoelectron spectroscopy (XPS) are measured from the surface 20 on the opposite side to the interface where the first electrode of the first stage of the cured resin product contacts the cured resin product. The characteristic (v) is measured from the surface 21 on the side opposite to the interface where the first electrode of the second stage of the cured resin and the cured resin come into contact. Characteristic (ii) is perpendicular to the interface 18 where the first electrode and the cured resin are in contact, and is in the direction of the cured resin from the substrate, and is 100 nm (30) starting from the interface where the first electrode and the cured resin are in contact. Also in the range of 100 nm, that is, perpendicular to the interface of the first electrode and the cured resin, and in the direction of the cured resin from the substrate, in the range of 100 to 200 nm starting from the interface of the first electrode and the cured resin (19 ) is measured in any of the In the opening of the patterned first electrode, it is perpendicular to the interface between the first electrode and the cured resin, and in the direction of the cured resin from the substrate, and has an opening of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. As in range 19, the first electrode is present, and the height is measured anywhere in range 19 from 100 to 200 nm from the height of the first electrode. Additionally, when there is a change in the thickness of the first electrode, it is assumed that in the opening of the patterned first electrode, a first electrode having an average thickness at the end of the opening is present. Subsequently, the functional layer 11 continuously disposed on the first electrode 8 patterned on the substrate and the second stage 10 of the cured resin can be formed by an inkjet coating method.

In the laminate of the present invention, the cured resin material is not particularly limited as long as it has the above-mentioned characteristics. A method of forming a cured resin that satisfies characteristics (i) to (v), for example, compound (a-1) having a fluorinated alkyl group having 7 to 21 fluorine atoms and 5 to 12 carbon atoms, having a siloxane structure A method of forming a cured resin product from a photosensitive resin composition comprising compound (a-2), an alkali-soluble resin (b-1) having a CF ₃ group, and an alkali-soluble resin (b-2) having a siloxane structure can be cited. .

From the viewpoint of UV ozone resistance and liquid repellency of the cured resin, the preferred structures of the compound (a-1) having a fluorinated alkyl group having 7 to 21 fluorine numbers and 5 to 12 carbon atoms and the compound (a-2) having a siloxane structure are: and siloxane (A) described later. In addition, from the viewpoint of heat resistance, preferred structures of the alkali-soluble resin (b-1) having a CF ₃ group and the alkali-soluble resin (b-2) having a siloxane structure include the alkali-soluble resin (B) described later.

Polysiloxane (A) will be explained.

By containing polysiloxane (A) in the photosensitive resin composition, high liquid repellency can be imparted to the upper surface of the cured resin material. In addition, the polysiloxane of the main chain has high UV ozone resistance and can easily provide high liquid repellency to the upper surface of the cured resin after UV ozone treatment.

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

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

The fluorinated alkyl group of R ^f preferably has a CF ₂ group. When the fluorinated alkyl group has a CF ₂ group, the cured resin tends to satisfy characteristic (iii), and the upper surface of the cured resin can exhibit good liquid repellency. Specific examples of fluorinated alkyl groups having a CF ₂ group include heptafluoropentyl group, nonafluorohexyl group, tridecafluorooctyl group, heptadecafluorodecyl group, 5,5,6,6,7,7,7- Heptafluoro-4,4-bis(trifluoromethyl)heptyl group, etc. are mentioned. From the viewpoint of liquid repellency and environmental load, nonafluorohexyl and tridecafluorooctyl groups having 9 to 13 fluorine atoms and 6 to 8 carbon atoms are preferable.

Polysiloxane (A) contains 5 to 30 mol% of the total of the repeating unit structure represented by formula (1) and the repeating unit structure represented by formula (2) out of 100 mol% of the total repeating unit structure of polysiloxane (A). It is desirable. More preferably, it is 10 to 25 mol%. By containing 5 mol% or more of the repeating unit structure represented by formula (1) and/or the structure represented by formula (2), the cured resin becomes easier to satisfy characteristic (i) and can exhibit better liquid repellency. there is. Additionally, if the amount is 30 mol% or less, aggregation of fluorinated alkyl groups can be reduced.

Additionally, polysiloxane (A) preferably has the repeating unit structures of (I) and (II).

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

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

R ¹ is a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an acyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 15 carbon atoms. R ² is an aryl group having 6 to 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 ⁴ is an organic group having 2 to 20 carbon atoms containing an acidic group. * indicates a covalent bond.

Polysiloxane (A) preferably has a repeating unit structure represented by (I) formula (3) and/or a repeating unit structure represented by formula (4). Since the repeating unit structure represented by formula (3) and/or the repeating unit structure represented by formula (4) has an aryl group, aggregation of the above-described fluorinated alkyl group is suppressed due to steric hindrance of the aryl group, and defects are reduced. Hardened products become easier to obtain.

In the repeating unit structure represented by formula (3) and/or the repeating unit structure represented by formula (4), R ² is an aryl group having 6 to 15 carbon atoms, and specific examples include phenyl group, 4-methylphenyl group, and 4-hydride. Roxyphenyl group, 4-methoxyphenyl group, 4-t-butylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-phenylethyl group, 4-hydroxybenzyl group and the structure represented by formula (7), etc. there is.

Here, * represents a covalent bond directly connected to R ³ . When R ³ is a single bond, it represents a covalent bond directly linked to a silicon atom. a is an integer from 1 to 3. From the viewpoint of chemical resistance, a is preferably 1 to 2, and a is more preferably 1. If these specific examples are represented by a general formula, the following structures can be given.

Among the repeating unit structures represented by formula (3) and/or the repeating unit structures represented by formula (4), at least one of R ² is a 1-naphthyl group from the viewpoint of the effect of suppressing aggregation of fluorinated alkyl groups and controlling polymerizability. , 2-naphthyl group or a structure represented by formula (7). Moreover, from the viewpoint of polymerizability control, it is more preferable that Y in the repeating unit structure represented by formula (4) is 1.

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

Of the total repeating unit structures of polysiloxane (A), 100 mol% preferably contains 20 to 70 mol% of the total of the repeating unit structures represented by formula (3) and the repeating unit structures represented by formula (4). More preferably, it is 30 to 60 mol%. By containing a total of 20 mol% or more of the repeating unit structure represented by formula (3) and the repeating unit structure represented by formula (4), it becomes easy to exhibit a good effect of suppressing aggregation of fluorinated alkyl groups. Additionally, from the viewpoint of polymerizability control, 70 mol% or less is preferable.

Polysiloxane (A) (II) has a repeating unit structure represented by formula (5) and/or a repeating unit structure represented by formula (6). Since the repeating unit structure represented by formula (5) and/or the repeating unit structure represented by formula (6) has an organic group having 2 to 20 carbon atoms including an acidic group, solubility in an alkaline developer is easy to improve, Residue in the opening can be reduced. Additionally, it becomes easy to suppress the aggregation of the above-described fluorinated alkyl groups, making it easy to obtain a cured product with fewer defects.

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 of carboxyl group, carboxylic acid anhydride group, hydroxyl group and sulfonic acid group. Preferably, it is a structure represented by formula (8) or formula (9).

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

From the viewpoint of the residue in the opening, it is more preferable that R ⁴ has a carboxyl group. Moreover, it is more preferable that it is a dicarboxy group obtained by hydrolyzing a carboxylic acid anhydride group. Specific examples of organic groups having 2 to 20 carbon atoms containing an acidic group include 2-hydroxyethyl group, 3-hydroxypropyl group, bis(2-hydroxyethyl)-3-aminopropyl group, carboxymethyl group, 2-carboxyethyl group, Examples include 3-carboxypropyl group and structures (α) and structures (β) shown below. As structures having a carboxyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, structure (α) and structure (β) are preferable, and structure (α) and structure (β) are more preferable.

Here, * represents a covalent bond directly connected to a silicon atom.

Of the total repeating unit structures of polysiloxane (A), 100 mol% preferably contains 1 to 40 mol% of the total of the repeating unit structures represented by formula (5) and the repeating unit structures represented by formula (6). More preferably, it is 5 to 30 mol%. By containing a total of 1 mol% or more of the repeating unit structure represented by formula (5) and the repeating unit structure represented by formula (6), better ink wettability and compatibility of the opening can be exhibited. Additionally, better liquid repellency can be obtained when the amount is 40 mol% or less.

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

R ¹ is a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an acyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 15 carbon atoms, and R ⁵ has 1 to 1 carbon atoms other than R ^f , R ² -R ³ -, and R ⁴ It represents the organic group of 10.

R ⁵ is not particularly limited as long as it is an organic group having 1 to 10 carbon atoms other than R ^f , R ² -R ³ -, and R ⁴ . Specific examples of R ⁵ include hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and cyclohexyl; Amino group-containing groups such as 3-aminopropyl group, N-(2-aminoethyl)-3-aminopropyl group, and N-β-(aminoethyl)-γ-aminopropyl group; Cyano group-containing groups such as β-cyanoethyl group; Glycidoxymethyl group, α-glycidoxyethyl group, α-glycidoxypropyl group, β-glycidoxypropyl group, γ-glycidoxypropyl group, α-glycidoxybutyl group, β-glycidoxybutyl group group, γ-glycidoxybutyl group, σ-glycidoxybutyl group, (3,4-epoxycyclohexyl)methyl group, 3-(3,4-epoxycyclohexyl)propyl group, 4-(3,4- Epoxy group-containing groups such as epoxycyclohexyl)butyl group; Chloro group-containing groups such as 3-chloropropylmethyl group; Fluoro group-containing groups such as 2,2,2-trifluoroethyl group and 3,3,3-trifluoropropyl group; α,β-unsaturated ester group-containing groups such as γ-acryloylpropyl group, γ-methacryloylpropyl group, etc.; Vinyl group-containing groups such as vinyl group, styryl group, etc.; etc. can be mentioned.

In formulas (1), (3), (5), and (10), R ¹ is a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an acyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 15 carbon atoms, and polymerization From the viewpoint of control of properties, preferred specific examples of alkyl groups having 1 to 6 carbon atoms and hydrogen atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl. etc. can be mentioned. Among these, from the viewpoint of polymerizability control, 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 polysiloxane (A) is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (B). More preferably, it is 0.2 parts by mass or more and 5 parts by mass or less. When the content of polysiloxane (A) is 0.1 parts by mass or more, the cured resin product easily satisfies characteristic (i), and better liquid repellency becomes easier to obtain. Moreover, if it is 10 parts by mass or less, it becomes easy to suppress the aggregation of the above-mentioned fluorinated alkyl groups.

(A) Polysiloxane can be obtained by hydrolyzing and polycondensing alkoxysilanes represented by the following general formulas (12), (13), (14) and (15) in a solvent. (A) Polysiloxane is preferably polysiloxane obtained in this way.

R ^f is a fluorinated alkyl group with 7 to 21 fluorine atoms and 5 to 12 carbon atoms, and R ¹ is a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an acyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 15 carbon atoms. R ² is an aryl group having 6 to 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 ⁴ is an organic group having 2 to 20 carbon atoms containing an acidic group. R ⁵ is an organic group having 1 to 10 carbon atoms.

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

Additionally, after obtaining the silanol compound through a hydrolysis reaction, it is preferable to heat the reaction solution at 50°C or higher and below the boiling point of the solvent for 1 to 100 hours to perform a condensation reaction. Additionally, in order to increase the degree of polymerization of the siloxane compound obtained by the condensation reaction, it is also possible to add an acid or base catalyst or perform reheating.

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

As water used in the hydrolysis reaction, ion-exchanged water is preferable. The amount of water can be selected arbitrarily, but it is preferably used in the range of 1.0 to 4.0 mol per 1 mol of the alkoxysilane compound.

Solvents used in the hydrolysis reaction include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 3-hydroxy-3-methyl-2-butanone, and 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 monon-propyl ether, propylene. Glycol monon-butyl ether, propylene glycol monot-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3 -Methoxy-1-butanol, ethylene glycol, propylene glycol, benzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 4-isopropylbenzyl alcohol, 1-phenylethyl alcohol, 2- Alcohol-based solvents such as phenyl-2-propanol, 2-ethylbenzyl alcohol, 3-ethylbenzyl alcohol, and 4-ethylbenzyl alcohol; 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, di Ether-based solvents such as propylene glycol dimethyl ether; γ-Butyrolactone, δ-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1- Ester solvents such as butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetoacetate, and cyclohexanol acetate; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyric acid amide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, amide-based solvents such as N-dimethylpropylene urea; Aromatic hydrocarbons such as toluene and xylene can be mentioned.

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, polyhydric carboxylic acid or its anhydride, and ion exchange resin. In particular, an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferred.

The preferred content of the acid catalyst is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of all alkoxysilane compounds used during the hydrolysis reaction. Moreover, the content of the acid catalyst is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. Here, the total alkoxysilane compound amount means the amount including all of the alkoxysilane compound, its hydrolyzate, and its condensate, and the same applies hereinafter. By setting the amount of the acid catalyst to 0.05 parts by mass or more, hydrolysis proceeds smoothly, and by setting it to 10 parts by mass or less, control of the hydrolysis reaction becomes easy.

Additionally, from the viewpoint of storage stability of the composition, it is preferable that the polysiloxane solution after hydrolysis and partial condensation does not contain the catalyst, and the catalyst can be removed as necessary. There are no particular restrictions on the removal method, but in terms of ease of operation and removal, water washing and/or treatment with ion exchange resin are preferable. Water washing is a method of diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing the resulting organic layer several times with water and concentrating it in an evaporator or the like. Treatment with an ion exchange resin is a method of bringing a polysiloxane solution into contact 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 in terms of polystyrene as measured by gel permeation chromatography (GPC). Additionally, it is preferably 20,000 or less, and more preferably 10,000 or less.

Next, the alkali-soluble resin (B) is explained.

Alkali-soluble resin in the present invention refers to a resin having a dissolution rate of 50 nm/min or more, as defined below. In detail, a solution in which the resin is dissolved in γ-butyrolactone is applied on a silicon wafer, prebaked at 120°C for 4 minutes to form a prebaked film with a thickness of 10 μm ± 0.5 μm, and the prebaked film is heated at 23 ± 0.5 μm. It refers to a resin with a dissolution rate of 50 nm/min or more, which is determined from the thickness reduction when immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 1°C for 1 minute and then rinsed with pure water.

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

The alkali-soluble resin (B) is not limited to the types of the main chain skeleton and side chains of the polymer constituting the resin, as long as it has a structure having the alkali-soluble group described above. Examples include, but are not limited to, polyimide resin, polybenzoxazole resin, polyamidoimide resin, acrylic resin, novolak resin, polyhydroxystyrene resin, phenol resin, and polysiloxane resin.

Additionally, the alkali-soluble resin (B) preferably has a CF ₃ group. By having a CF ₃ group, the cured resin becomes more likely to satisfy characteristics (ii) and (iv), and the durability of the display device can be further improved by suppressing corrosion of the electrode due to a decrease in water absorption of the cured resin. . The CF ₃ group has a small tendency to be localized on the surface of the cured resin, so it can fix the F atom inside the cured resin. Additionally, by having a CF ₃ group, it contributes to the concentration of F atoms in the characteristic (v) of the cured resin and to the C1s spectrum. Since the CF ₃ group does not exhibit liquid repellency, it is easy to achieve both the lyophilicity of the surface of the cured resin and the durability of the display device.

The alkali-soluble resin (B) preferably has a siloxane structure. By having a siloxane structure, it contributes to the concentration of Si atoms in characteristic (v) of the cured resin. Additionally, adhesion to electrodes is improved, and the durability of the display device can be further improved.

It is preferable that the alkali-soluble resin (B) contained in the photosensitive resin composition has an imide ring structure. It is more preferable to contain at least one type selected from the group consisting of polyimide, polyamidoimide, their precursors, and their copolymers. These alkali-soluble resins may be used individually, or a plurality of alkali-soluble resins may be used in combination. By having an imide ring structure, the amount of outgassing 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 more excellent durability can be obtained. Moreover, as a resin with high heat resistance, polybenzoxazole and/or its precursor may be contained.

Polyimide can be obtained, for example, by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc. with diamine or diisocyanate compounds, trimethylsilylated diamine, etc. Polyimide has tetracarboxylic acid residues and diamine residues. In addition, polyimide can be obtained, for example, by dehydrating and ring-closing polyamic acid, which is one of the polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, by heat treatment. During this heat treatment, a solvent azeotropic to water, such as m-xylene, may be added. Alternatively, it can also be obtained by adding a dehydration condensation agent such as carboxylic acid anhydride or dicyclohexylcarbodiimide or a base such as triethylamine as a ring-closure catalyst and dehydrating ring-closure by chemical heat treatment. Alternatively, it can be obtained by adding a weakly acidic carboxylic acid compound and subjecting it to dehydration and ring closure by heat treatment at a low temperature of 100°C or lower.

Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol compound with dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester, etc. Polybenzoxazole has a dicarboxylic acid residue and a bisaminophenol residue. In addition, polybenzoxazole can be obtained, for example, by dehydrating polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid, by heat treatment to ring-close it. . Alternatively, it can be obtained by adding anhydrous phosphoric acid, a base, a carbodiimide compound, etc., and dehydrating and ring-closing it through chemical treatment.

Examples of polyimide precursors include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide. For example, polyamic acid can be obtained by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc. with diamine or diisocyanate compound, trimethylsilylated diamine. Polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid obtained by the above method by heating or chemical treatment with an acid or base.

Examples of polybenzoxazole precursors include polyhydroxyamide. For example, polyhydroxyamide can be obtained by reacting bisaminophenol with dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester, etc. Polybenzoxazole can be obtained, for example, by dehydrating and ring-closing the polyhydroxyamide obtained by the above method by heating or chemical treatment with anhydrous phosphoric acid, a base, or a carbodiimide compound.

The polyamideimide precursor can be obtained, for example, by reacting tricarboxylic acid, the corresponding tricarboxylic acid anhydride, tricarboxylic acid anhydride halide, etc. with diamine or diisocyanate. Polyamidoimide can be obtained, for example, by dehydrating and ring-closing the precursor obtained by the above method by heating or chemical treatment with an acid or base.

The copolymer of polyimide, polybenzoxazole, polyamidoimide, and precursors of any of these may be any of block copolymerization, random copolymerization, alternating copolymerization, and graft copolymerization, or a combination thereof. For example, a block copolymer can be obtained by reacting polyhydroxyamide with tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc. Additionally, dehydration and ring closure can be achieved by heating or chemical treatment such as acid or base.

Polyimide, polybenzoxazole or polyamidoimide, precursors of any of these and their copolymers preferably have CF ₃ groups in the residues of the carboxylic acid component and/or the residues of the diamine component, and are represented by formula (16) It is more desirable to have a structure that is Since the structure represented by formula (16) has excellent compatibility with the polysiloxane (A) described above, aggregation of the polysiloxane (A) can be suppressed and a cured product with few defects can be obtained. In addition, the CF ₃ group of the structure represented by (16) reduces the water absorption of the cured product of the photosensitive resin composition and can further improve the durability of the display device. In addition, since the CF ₃ group does not impart liquid repellency, a cured product with a lyophilic surface can be formed by “half exposure” described later.

* indicates a covalent bond.

From the viewpoint of compatibility with the above-mentioned polysiloxane (A) and water absorption of the cured resin, polyimide, polybenzoxazole or polyamidoimide, any of these precursors, and their copolymers contain the residue of the carboxylic acid component and the diamine component. It is more preferable that the residue has a structure represented by formula (16).

The alkali-soluble resin (B) preferably has a structural unit represented by any of formulas (17) to (20), and more preferably has a structural unit represented by formula (20). Two or more types of resins having these structural units may be contained, and two or more types of structural units may be copolymerized. The alkali-soluble resin (B) preferably contains 3 to 1,000 structural units represented by any of the formulas (17) to (20) in the molecule, and more preferably contains 20 to 200 structural units.

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

It is preferable that R ⁶ to R ¹³ all have an aromatic ring and/or an aliphatic ring.

The partial structure containing R ⁶ , R ⁸ , R ¹⁰ , R ¹² (COOR ¹⁴ ) _n (OH) _p in formulas (17) to (20) can be formed, for example, by using the corresponding carboxylic acid component, respectively. You can get it. That is, for example, R ⁶ can be obtained by using tetracarboxylic acid, R ⁸ is dicarboxylic acid, R ¹⁰ is tricarboxylic acid, and R ¹² is di-, tri- or tetra-carboxylic acid. Examples of carboxylic acid components used to obtain R ⁶ , R ⁸ , R ¹⁰ , R ¹² (COOR ¹⁴ ) _n (OH) _p include dicarboxylic acids such as terephthalic acid, isophthalic acid, and diphenyl ether dicarboxylic acid. Boxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc. Examples of tricarboxylic acids include trimellitic acid and trimesic acid. , diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc., examples of tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3, 3',4'-Biphenyltetracarboxylic acid, 2,2',3,3'-Biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2 ',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoro Propane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2, 3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3, Aromatic tetracarboxylic acids such as 6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, and 3,4,9,10-perylenetetracarboxylic acid, or butane tetracarboxylic acid. and aliphatic tetracarboxylic acids such as boxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Among these, in formula (18), one or two carboxyl groups of tricarboxylic acid and tetracarboxylic acid respectively correspond to COOR ¹⁴ groups. These acid components can be used as is or as acid anhydrides, activated esters, etc. Additionally, these two or more types of acid components may be used in combination.

As described above, the alkali-soluble resin (B) preferably has the structure represented by formula (16) in the residue of the carboxylic acid component. As an example of the carboxylic acid component, bis(carboxyphenyl)hexafluoro Propane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane are preferred.

The partial structure containing R ⁷ , R ⁹ , R ¹¹ , and R ¹³ (OH) _q in formulas (17) to (20) can be obtained, for example, by using the diamine component corresponding to each. Examples of diamine components used to obtain R ⁷ , R ⁹ , R ¹¹ , R ¹³ (OH) _q include 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( Hydroxyl group-containing diamines such as 3-amino-4-hydroxy)biphenyl and bis(3-amino-4-hydroxyphenyl)fluorene, 3-sulfonic acid-4,4'-diaminodiphenyl ether, etc. Sulfonic acid-containing diamines, thiol group-containing diamines such as dimercaptophenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4 ,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-dia minodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis( 4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4- Bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diamino Biphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, etc. Aromatic diamines, compounds in which some of the hydrogen atoms of these aromatic rings are replaced with an alkyl group having 1 to 10 carbon atoms, a trifluoromethyl group, a halogen atom, etc., alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine, 1, Siloxane-based diamines such as 3-bis(3-aminopropyl)tetramethyldisiloxane can be mentioned. These diamines can be used as is or as the corresponding diisocyanate compound, trimethylsilylated diamine. Additionally, you may use these two or more types of diamine components in combination. For applications requiring heat resistance, it is preferable to use aromatic diamine in an amount of 50 mol% or more of the total diamine.

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

In addition, the alkali-soluble resin (B) preferably has a siloxane-based diamine such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane as the diamine component from the viewpoint of adhesiveness with the electrode. Contributes to the concentration of Si atoms in the properties (v) of the cured resin.

R ⁶ to R ¹³ in formulas (17) to (20) may contain a phenolic hydroxyl group, a sulfonic acid group, a thiol group, etc. in the skeleton. By using a resin appropriately having a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, a positive photosensitive resin composition with appropriate alkali solubility can be obtained.

In addition, in order to improve the storage stability of the photosensitive resin composition, the main chain terminal of the alkali-soluble resin (B) is a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound terminal. It is desirable to seal with a sealant. The introduction ratio of the monoamine used as the end cap agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, especially preferably 50 mol% or more, relative to the total amine component. It is less than mol%. The introduction rate of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end cap agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, relative to the diamine component. , Preferably it is 100 mol% or less, especially preferably 90 mol% or less. A plurality of different end groups may be introduced by reacting a plurality of end capping agents.

In the resin having a structural unit represented by any of formulas (17) to (19), the repeating number of the structural unit is preferably 3 or more and 200 or less. In addition, in the resin having the structural unit represented by formula (20), the number of repeats of the structural unit is preferably 10 or more and 1000 or less. Within this range, a thick cured resin can be easily formed.

The alkali-soluble resin (B) may contain only structural units represented by any of formulas (17) to (20), or may be a copolymer or mixture with other structural units. At that time, it is preferable to contain 10% by mass or more of the entire resin, and more preferably 30% by mass or more of the structural unit represented by any of formulas (17) to (20). The type and amount of structural units used for copolymerization or mixing can be selected within a range that does not impair the mechanical properties of the cured resin product obtained by final heat treatment.

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

The photosensitizer (C) may be a negative type that hardens with light, or a positive type that solubilizes with light. As the photosensitizer (C), a polymerizable unsaturated compound, a photopolymerization initiator (C-1), or a quinonediazide compound (C-2) may be preferably contained. In addition, in the present invention, the polymerizable unsaturated compound and photopolymerization initiator (C-1) may be simply referred to as (C-1). By containing the quinonediazide compound (C-2), a positive type photosensitive resin composition can be obtained, and a stepped resin cured product can be formed in one photolithography by “half exposure” described later. desirable. Therefore, in the photosensitive resin composition, it is preferable that the photosensitive agent (C) contains a quinonediazide compound.

Examples of the polymerizable unsaturated compound in (C-1) include compounds having an unsaturated double bond functional group such as a vinyl group, allyl group, acryloyl group, or methacryloyl group, and/or an unsaturated triple bond functional group such as a propargyl group. These include known ones, and among these, conjugated vinyl, acryloyl, and methacryloyl groups are preferable in terms of polymerizability. In addition, the number of functional groups contained is preferably 1 to 4 from the viewpoint of stability, and each group may not be the same group. In addition, the compound referred to here preferably has a molecular weight of 30 to 800. When the molecular weight is in the range of 30 to 800, compatibility with polymers and reactive diluents is good. Specifically, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, penta. Erythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide , N,N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N -Methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A diacrylate, Examples include ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, and N-vinylcaprolactam. These are used individually or in combination of two or more types.

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 from the viewpoint of improving alkali solubility, based on 100 parts by mass of the alkali-soluble resin (B). From the viewpoint of pattern formation, 50 parts by mass or less is preferable.

The photopolymerization initiator in (C-1) means that polymerization is initiated mainly by generating radicals when irradiated with light in the ultraviolet to visible light range. From the viewpoint of being able to use a general-purpose light source and fast curing properties, a known photopolymerization initiator selected from acetophenone derivatives, benzophenone derivatives, benzoin ether derivatives, and xanthone derivatives is preferred. Examples of preferred photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxy-cyclohexylphenyl. Ketone, isobutyl benzoin ether, benzoin methyl ether, thioxanthone, isopropyl thioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, Examples include, but are not limited to, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.

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 with respect to 100 parts by mass of the alkali-soluble resin (B). Within this range, it becomes easy to ensure interaction with the resin necessary for forming a good pattern and transmittance for obtaining appropriate sensitivity.

The quinonediazide compound (C-2) includes an ester bond of quinonediazide sulfonic acid to a polyhydroxy compound, a sulfonamide bond of quinonediazide sulfonic acid to a polyamino compound, and quinonediazide bond to a polyhydroxypolyamino compound. Known examples include those in which the sulfonic acid of azide is linked to an ester linkage and/or a sulfonamide linkage. Although not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds need to be substituted with quinonediazide, it is preferable that on average, 40 mol% or more of all functional groups are substituted with quinonediazide. . In the present invention, the mole percent of the functional group substituted with quinonediazide is referred to as the quinonediazide substitution rate. By using such a quinonediazide compound, a positive photosensitive resin composition that is sensitive to the i-ray (wavelength 365 nm), h-ray (wavelength 405 nm), and g-ray (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays, can be obtained.

The polyhydroxy compound used herein has two or more, preferably three or more, phenolic hydroxyl groups in the molecule. Polyhydroxy compounds include, 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, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, 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-TPPHBA, HML-TPHAP (trade names above, manufactured by Honshu Kagaku Kogyo Co., Ltd.), BIR-OC, BIP-PC, BIR- PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above product names, Asahi Yukizai High School Co., Ltd.) 1st), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone , methyl gallate ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (brand name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc., but is not limited to these.

Polyamino compounds include, for example, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4' -Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, etc. are mentioned, but are not limited to these.

In addition, polyhydroxypolyamino compounds include, for example, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, etc. It is not limited to

In addition, examples of the sulfonic acid of quinonediazide include, but are not limited to, 1,2-naphthoquinonediazide-4-sulfonic acid and 1,2-naphthoquinonediazide-5-sulfonic acid.

In the present invention, a quinonediazide compound (C-2) in which quinonediazide sulfonic acid is bonded to a polyhydroxy compound is preferably used. By using these quinonediazide compounds, it is possible to obtain high sensitivity and higher resolution by being sensitive to the i-ray (wavelength 365 nm), h-ray (wavelength 405 nm), and g-ray (wavelength 436 nm) of mercury lamps, which are common ultraviolet rays. there is.

A more preferable quinonediazide compound (C-2) includes a compound represented by formula (21) or formula (22).

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

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

The quinonediazide substitution rate is set as “(number of moles of quinonediazide sulfonic acid ester group)/(number of moles of hydroxy groups before esterification of the polyhydroxy compound) Number of moles of azide sulfonic acid amide group)/(number of moles of amino group before amidation of polyamino compound) Number of moles)}/{(Number of moles of hydroxy groups before esterification of the polyhydroxypolyamino compound)+(Number of moles of amino groups before amidation of the polyhydroxypolyamino compound)}×100.”

In the present invention, two or more types of quinonediazide compounds can be used. In this case, the quinonediazide substitution rate is calculated by summing the quinonediazide substitution rate of each quinonediazide compound multiplied by the ratio to all quinonediazide compounds, as shown in the following formula.

Σ((Quinonediazide substitution rate of a certain quinonediazide compound) × (Ratio of a certain quinonediazide compound to all quinonediazide compounds))

In addition, the quinonediazide substitution rate of the quinonediazide 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 contained components by a column preparative method, etc., and identifying the chemical structure by NMR or IR. You can get it.

The method for producing the quinonediazide compound is not particularly limited, but according to a conventional method, quinonediazide sulfonic acid halide (preferably quinonediazide sulfonic acid chloride) is dissolved in sodium carbonate or sodium bicarbonate in a solvent such as acetone, dioxane, or tetrahydrofuran. , inorganic bases such as sodium hydroxide or potassium hydroxide, or trimethylamine, triethylamine, tripropylamine, diisopropylamine, tributylamine, pyrrolidine, piperidine, piperazine, morpholine, pyridine, dicyclo It can be obtained by reacting with a polyhydroxy compound in the presence of an organic base such as hexylamine.

The content of the quinonediazide compound (C-2) is not particularly limited, but the content of the quinonediazide compound (C-2) is preferably 10 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin (B). 20 parts by mass or more is more preferable. Moreover, 50 parts by mass or less is preferable, and 40 parts by mass or less is more preferable. By setting the content of the quinonediazide compound within this range, photosensitivity can be obtained without impairing the liquid repellency.

When used as a positive type photosensitive resin composition containing a quinonediazide compound (C-2) in the photosensitizer (C), it is preferable that the alkali-soluble resin (B) contains a phenol resin and/or a polyhydroxystyrene resin. do. Additionally, you may use these two or more types of phenol resin and/or polyhydroxystyrene resin in combination. By including the quinonediazide compound (C-2) and the phenol resin and/or polyhydroxystyrene resin, the amount of thickness reduction of the photosensitive resin dried product can be reduced in the developing process described later, so polysiloxane (A) is used in the cured resin. It has the effect of making it easier to fix to the surface, and better liquid repellency can be obtained.

Phenol resins include novolac phenol resins and resol phenol resins, and are obtained by polycondensing various phenol compounds alone or a mixture of multiple types thereof using an aldehyde compound such as formalin by a known method.

Phenol compounds constituting the novolac phenol resin and resol phenol resin include, for example, phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5- Dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol , 2,4,5-trimethylphenol, methylenebisphenol, methylenebisp-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chloro Phenol, 2,3-dichloro phenol, m-methoxy phenol, p-methoxy phenol, p-butoxy phenol, o-ethyl phenol, m-ethyl phenol, p-ethyl phenol, 2,3-diethyl phenol, Examples include 2,5-diethylphenol, p-isopropylphenol, α-naphthol, and β-naphthol, and these can be used individually or in a mixture of two or more. In addition to formalin, aldehyde compounds include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde, and these can be used individually or in a mixture of two or more.

As the polyhydroxystyrene resin, it is also possible to use a homopolymer of vinyl phenol or a copolymer of styrene.

The preferred weight average molecular weight of the phenol resin and polyhydroxystyrene resin is 2,000 to 20,000, preferably 3,000 to 10,000, in terms of polystyrene by GPC (gel permeation chromatography). Within this range, a resin composition with high concentration and low viscosity can be obtained.

When the photosensitive resin composition is used as a positive type photosensitive resin composition containing a quinonediazide compound (C-2) as the photosensitive agent (C), from the viewpoint of liquid repellency, phenol is added to 100 parts by mass of the alkali-soluble resin (B). It is preferable that it contains 20 parts by mass or more of resin and/or polyhydroxystyrene resin, and 30 parts by mass or more is more preferable. Moreover, from the viewpoint of outgassing, 50 parts by mass or less is preferable, and 40 parts by mass or less is more preferable.

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, for example, 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. Ethers such as methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or tetrahydrofuran, butyl acetate, ethylene glycol mono. Methyl 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, Acetates such as dipropylene glycol methyl ether acetate and 3-methoxy-3-methyl-1-butyl acetate, ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone, and 2-hydroxy Lactic acid alkyl esters such as methyl propionate or 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3- Ethyl ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxy acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3 -Other esters such as methoxybutylpropionate, ethyl acetate, propyl acetate, butyl acetate, γ-butyrolactone, aromatic hydrocarbons such as toluene or xylene, N-methylpyrrolidone, N,N-dimethyl Amides such as formamide or N,N-dimethylacetamide, or butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-meth Alcohols such as toxybutanol or diacetone alcohol can be mentioned.

The amount of the organic solvent (D) used is not particularly limited as it can be changed depending on the required thickness or the application method employed, but is based on 100 parts by mass of the solid content (other components excluding the organic solvent (D)) of the photosensitive resin composition. , 100 to 2000 parts by mass is preferable, and 150 to 900 parts by mass is particularly preferable.

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

Preferred examples of compounds having at least two alkoxymethyl groups or methylol groups include HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, and NIKALAC. Examples include MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (above, brand name, manufactured by Sanwa Chemical Co., Ltd.), each of which can be obtained from the companies mentioned above.

Compounds having an epoxy group or oxetanyl group include VG3101L (trade name, manufactured by Printec Co., Ltd.), “Tepic” (registered trademark) S, “Tepic” G, and “Tepic” P (trade name, Nissan Chemical Industries, Ltd.) (manufactured by), "Epiclon" N660, "Epiclon" N695, HP7200 (trade name above, manufactured by Dainippon Ink Chemicals Co., Ltd.), "Denacol" EX-321L (trade name, manufactured by Nagase Chemtex Co., Ltd.) , NC6000, EPPN502H, NC3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), "EPOTOT" (registered trademark) YH-434L (trade name, manufactured by Doto Kasei Co., Ltd.), EHPE-3150 (trade name, manufactured by Doto Kasei Co., Ltd.) ), manufactured by Daicel), compounds having two or more oxetanyl groups include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (trade names above, manufactured by Toagosei Co., Ltd.) , “Eternacol” (registered trademark) OXBP, “Eternacol” OXTP (trade name above, manufactured by Ube Kosan Co., Ltd.), etc., and each is available from each company.

As a thermal crosslinking agent, it is preferable to have a phenolic hydroxyl group in one molecule and also to have a methylol group and/or an alkoxymethyl group at both ortho positions of the phenolic hydroxyl group. By having a methylol group and/or an alkoxymethyl group adjacent to a phenolic hydroxyl group, the durability of the cured resin 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, based on 100 parts by mass of the total amount of the alkali-soluble resin (B). Moreover, 50 parts by mass or less is preferable, 40 parts by mass or less is more preferable, and 30 parts by mass or less is still more preferable. By setting the content of the thermal crosslinking agent to 5 parts by mass or more, the heat resistance of the cured resin product is improved, and by setting it to 50 parts by mass or less, a decrease in elongation of the cured resin product can be prevented.

A method for manufacturing the photosensitive resin composition will be described. For example, it can be obtained by dissolving the polysiloxane (A) to photosensitizer (C) and other components in an organic solvent (D). Dissolution methods include stirring and heating. In the case of heating, the heating temperature is preferably set in a range that does not impair the performance of the resin composition, and is usually 20°C to 80°C. Additionally, the order of dissolution of each component is not particularly limited, and for example, there is a method of sequentially dissolving the components starting from the less soluble compounds.

It is preferable to filter the obtained photosensitive resin composition using a filtration filter to remove dust and particles. Filter hole diameters include, for example, 1 μm, 0.5 μm, 0.2 μm, 0.1 μm, and 0.05 μm, but are not limited to these. The materials of the filtration filter include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE), but it is preferable to use polyethylene or nylon for filtration.

Next, a method for producing a cured resin product of the photosensitive resin composition will be described. A cured resin product is obtained by applying the photosensitive resin composition and drying it. Furthermore, by performing the steps (1) to (4) below in this order, it is possible to form a cured resin in which at least a portion of the first electrode is open.

(1) A process of applying a photosensitive resin composition on a substrate having a first electrode and forming a dried photosensitive resin product.

(2) Process of exposing the dried photosensitive resin material to light.

(3) Process of developing the exposed photosensitive resin dried product

(4) Process of forming a cured resin product by heat treating the developed photosensitive resin dried product.

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

Methods for applying the photosensitive resin composition on the substrate having the first electrode include spin coating, slit coating, dip coating, spray coating, and printing. Prior to application, the substrate to which the photosensitive resin composition is applied may be pretreated with the adhesion improving agent described above. For example, 0.5 to 20 mass% of the adhesion improving agent was dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. A method of treating the surface of a substrate using a solution is included. Methods for treating the surface of the substrate include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

Next, for example, the applied photosensitive resin dried product is subjected to reduced pressure drying as needed, and then dried at a temperature of 50°C to 180°C for 1 minute to several hours using a hot plate, oven, infrared rays, etc. By performing heat treatment, a dried photosensitive resin product can be obtained.

Next, (2) the process of exposing the dried photosensitive resin material to light is explained.

Actinic rays are irradiated onto the photosensitive resin dried product through a photomask with a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and do. It does not matter if you bake after exposure to actinic rays. By performing baking after exposure, effects such as improved resolution after development or increased allowable width of developing conditions can be expected. For baking after exposure, an oven, hot plate, infrared ray, flash annealing device, or laser annealing device can be used. The post-exposure bake temperature is preferably 50 to 180°C, and more preferably 60 to 150°C. The baking time after exposure is preferably 10 seconds to several hours. If the post-exposure bake time is within the above range, the reaction may proceed favorably and the development time may be shortened. At this time, a grid-shaped cured product can be obtained by using a grid-shaped photomask.

In the present invention, “half exposure” may be used. “Half exposure” refers to a process in which the base of the photosensitive resin dried material in the exposed portion remains to some extent upon completion of development. In other words, it refers to a process of performing exposure so that the lower layer of the photosensitive resin dried product is not exposed to light. For example, when forming the cured resin of FIG. 5 with a dried positive-type photosensitive resin, the portion that becomes the first end 9 of the thick cured resin is said to be unexposed, and the portion of the cured resin of thin thickness is said to be unexposed. The portion that becomes the second stage 10 can be formed by performing “half exposure” in which the lower layer of the photosensitive resin dried material is exposed to a chemical dose that does not sensitize it, followed by development and heat treatment. Additionally, by adjusting the chemical dose irradiated to the photosensitive resin dried product, the thickness of the photosensitive resin dried product remaining after completion of development can be adjusted. Specifically, when the photosensitive resin dried product is a positive type, if the chemical dose is increased, the thickness of the photosensitive resin dried product remaining after development is completed becomes thinner. On the other hand, when the photosensitive resin dried product is a negative type, increasing the chemical dose increases the thickness of the photosensitive resin dried product remaining after development is completed. Actinic rays may be irradiated through a photomask having two or more areas with different transmittances, and the actinic dose may be adjusted.

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

Next, (3) the process of developing the exposed photosensitive resin dried product is explained.

In the development process of developing the exposed photosensitive resin dried product, the exposed photosensitive resin dried product is developed using a developing solution, and areas other than the exposed portion are removed. As a developer, tetramethylammonium hydroxide (TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, and dimethylamino acetate. An aqueous solution of an alkaline compound such as ethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred. In some cases, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, etc. are added to these aqueous alkaline solutions. polar solvents, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, etc. Or, you can add a combination of species. As a developing method, methods such as spray, paddle, immersion, and ultrasonic waves are possible.

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

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

A cured product is obtained through a process of heat treating the developed photosensitive resin dried product. In the present invention, the cured product of the photosensitive resin composition can be suitably used for the partition wall of an organic EL display device. Since residual solvents and components with low heat resistance can be removed by heat treatment, heat resistance and chemical resistance can be improved. Additionally, by containing a crosslinking agent, a thermal crosslinking reaction can be promoted by heat treatment, and heat resistance and chemical resistance can be improved. This heat treatment is performed for 5 minutes to 5 hours by selecting a temperature and gradually increasing the temperature, or by selecting a certain temperature range and continuously increasing the temperature. An example is a method of heat treatment at 150°C and 250°C for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 300°C over 2 hours may be used. As heat treatment conditions in the present invention, 180°C or higher is preferable, 200°C or higher is more preferable, and 230°C or higher is still more preferable. Additionally, the heat treatment conditions are preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower.

<Display device>

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

Since the cured resin of the laminate of the present invention has high liquid repellency on the surface of the cured product after UV ozone treatment, functional ink is applied by inkjet to the area where at least a portion of the cured resin on the first electrode is open. It can be suitably used in display devices that form a functional layer by coating. For example, it can be used as an organic EL display device by forming an organic EL light-emitting layer containing at least one type selected from organic EL light-emitting materials, hole injection materials, and hole transport materials.

The cured resin material included in the laminate of the present invention has an F atom inside the cured resin material, which lowers the water absorption of the cured resin material and suppresses corrosion of the electrode, thereby producing a display device with small pixel shrinkage and excellent durability. You can get it.

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

An organic EL display device has a driving circuit, a planarization layer, a first electrode, a partition, an organic EL light-emitting layer, and a second electrode on a substrate. Taking an active matrix display device as an example, on a substrate such as glass or resin film, there is a TFT, a wiring connected to the TFT located on the side of the TFT, and a planarization layer is placed on the top to cover the unevenness, further flattening the surface. A display element is provided on the layer. The display element and the wiring are connected through a contact hole formed in the planarization layer.

<Method of manufacturing display device>

The first aspect of the display device manufacturing method of the present invention has steps (5) and (6) in this order.

(5) In the laminate of the present invention, a step of forming a functional layer by applying functional ink to the first electrode by inkjet.

(6) A process of forming a second electrode on the functional layer.

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

(6) In step, a second electrode is formed on the functional layer. The second electrode is preferably formed to cover the entire partition and the functional layer. Methods for forming the second electrode include sputtering and vapor deposition. Additionally, it is desirable to form the second electrode without disconnection and with a uniform layer thickness.

When the laminate of the present invention includes a step-shaped cured resin having the above-described first and second steps, the second aspect of the display device manufacturing method of the present invention includes steps (7) and (8). They are in order.

(7) In the laminate of the present invention, a process of forming a functional layer by applying functional ink to the first electrode and the second stage of the cured resin by inkjet.

(8) A process of forming a second electrode formation on the functional layer.

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

For example, as shown in FIG. 2, a first electrode 8 patterned on a substrate is stacked in that order with a cured resin, and a first stage 9 defines an area where the cured resin is applied by inkjet; , for a laminate having a second stage 10 defining two or more pixel regions arranged in the inkjet application area, a first electrode 8 patterned on a substrate and a second stage 10 of the cured resin. It can be suitably used in a manufacturing method of a display device in which the functional layer 11 disposed continuously on the surface is formed by an inkjet coating method.

In step (8), a second electrode is formed on the functional layer. The second electrode is preferably formed to cover the entire partition and the functional layer. Methods for forming the second electrode include sputtering and vapor deposition. Additionally, it is desirable to form the second electrode without disconnection and with a uniform layer thickness.

Example

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

<Partition wall pattern used in the example>

Barrier pattern (4): A partition pattern that exposes the first electrode patterned on the substrate from the opening of the cured resin. The size of the opening is 70㎛ in width and 260㎛ in length, and the opening is located at one location in the center of the cured resin. bulkhead pattern

Barrier pattern (5): A partition pattern that exposes the first electrode patterned on the substrate from the opening of the cured resin. The size of the opening is 70㎛ in width and 260㎛ in length, and the pitch in the width direction is 155㎛ and the pitch in the longitudinal direction is 155㎛. Bulkhead pattern with cured resin placed at 465㎛

Barrier pattern 12: This is the partition pattern shown in FIG. 2 or 3, and is made of cured resin with a width a of 205 μm to expose the patterned first electrode 8 on a substrate with a width of 70 μm and a length of 260 μm. A partition pattern in which a second stage (10) and a first stage (9) of a cured resin material with a width b of 85 μm are arranged.

First, the measurement and evaluation methods are explained.

(1) Average molecular weight measurement

Polysiloxane (P-1) synthesized in Synthesis Example 1, acrylic liquid repellent (Ac-1) synthesized in Synthesis Example 2, alkali-soluble resin (d1) synthesized in Synthesis Example 8, and alkali-soluble resin synthesized in Synthesis Example 9 The molecular weight of (Ac-2) was measured using a GPC (gel permeation chromatography) device (Waters2690-996; manufactured by Nippon Waters Co., Ltd.) using tetrahydrofuran as a developing solvent, and the weight average molecular weight was converted to polystyrene. (Mw) was calculated.

In addition, the molecular weights of the alkali-soluble resins (b1) to (b3) synthesized in Synthesis Examples 4 to 6 were determined using the GPC apparatus described above, and the developing solvent was N-methyl-2-pyrrolidone (hereinafter referred to as NMP). and calculated the number average molecular weight (Mn) in terms of polystyrene.

(2) Evaluation of liquid repellency

To measure the contact angle, a laminate having the partition pattern 4 in FIG. 1 was formed by a method described later, 3 μL of PGMEA was dropped onto the resin cured material of the partition pattern 4, and the contact angle was measured. For the measurement, a contact angle measuring device (DMs-401; manufactured by Kyowa Kaimen Chemical Co., Ltd.) was used to measure the contact angle using the static method at 23°C in accordance with JIS-R3257:1999.

The measurement results of the PGMEA contact angle on the cured product were determined as follows, with A being excellent, B being good, C being possible, and D being unacceptable.

A: Contact angle is more than 45°

B: Contact angle is 35° or more but less than 45°

C: Contact angle is 25° or more but less than 35°

D: Contact angle is less than 25°.

(3) Evaluation of UV ozone resistance

The laminate for which the above-mentioned (2) liquid repellency evaluation was performed was subjected to UV ozone treatment under the following conditions. After that, 3 μL of PGMEA was dropped onto the cured resin material of the partition pattern 4, and the contact angle was measured. For the measurement, a contact angle measuring device (DMs-401; manufactured by Kyowa Kaimen Chemical Co., Ltd.) was used, and the measurement was carried out by a static method at 23°C in accordance with JIS-R3257.

Compared with the above-mentioned (2) liquid repellency evaluation results, if the change in contact angle was 10% or less, it was rated as A (pass), and if the change in contact angle was 10% or more, it was rated as B (fail).

·UV ozone conditions

Device: PL16 (manufactured by SEN LIGHTS Corp.)

Illuminance: 15mW/㎠

Irradiation distance: 75mm

Investigation time: 120sec

(4) Analysis of cured resin material by X-ray photoelectron spectroscopy (XPS)

A method for analyzing cured resin products by X-ray photoelectron spectroscopy (XPS) is shown.

<Production of cured material for X-ray photoelectron spectroscopy (XPS) analysis>

By the method described later, a laminate forming the partition pattern 4 in FIG. 1 is produced, and It was done.

<X-ray photoelectron spectroscopy (XPS) analysis method of cured resin>

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

Analysis was performed on the surface of the resin cured product of the partition pattern 4 or partition pattern 12 in FIG. 1 by X-ray photoelectron spectroscopy (XPS) under the measurement conditions described below. Measurement conditions and data processing conditions are described below.

·Measuring conditions

Device Quantera SXM (manufactured by PHI)

Excitation X-ray monochromatic Al K 1, 2 lines (1486.6 eV)

X-ray diameter 200㎛

Photoelectric detection angle 45° (tilt of detector relative to sample surface)

·Data processing conditions

Smoothing 9-point smoothing

The horizontal axis corrected C1s main peak (CHx, C-C, C=C) was set to 284.6 eV.

(4-2) Measurement method for XPS analysis characteristics (ii) inside the cured resin material

The alkali-free glass substrate 1 is perpendicular to the interface where the patterned first electrode 8 and the resin cured material of the partition pattern 4 in FIG. 1 are in contact with the cured resin material of the partition pattern 4 in FIG. In the direction of the partition pattern 4, Ar gas cluster ions (Ar gas cluster ions ( Ar-GCIB) was performed. Afterwards, analysis by X-ray photoelectron spectroscopy (XPS) was performed at the location where Ar-GCIB was performed. Measurement conditions and data processing are described below.

·Measuring conditions

Device K-Alpha (manufactured by Thermo Fisher Scientific)

Excitation X-ray monochromatic Al K 1, 2 lines (1486.6 eV)

X-ray diameter 400㎛

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

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

Etching rate 3.5㎚/min

·Data processing

Smoothing 11-point smoothing

The horizontal axis corrected C1s main peak (CHx, C-C) was set to 284.6 eV.

(4-3) XPS comparative measurement method for characteristics (iii) and characteristics (iv) of the surface and interior of the cured resin material

Analysis by X-ray photoelectron spectroscopy (XPS) was performed on the surface of the cured resin material of the partition pattern 4 in FIG. 1 under the measurement conditions described below. Subsequently, with respect to the resin cured material of the partition pattern 4, the patterned first electrode 8 is perpendicular to the interface where the resin cured material of the partition pattern 4 is in contact, and the partition wall is formed from the alkali-free glass substrate 1. In the direction of the pattern 4, Ar gas cluster ions (Ar- GCIB) was performed. Afterwards, analysis by X-ray photoelectron spectroscopy (XPS) was performed at the location where Ar-GCIB was performed. Measurement conditions and data processing are described below.

·Measuring conditions

Device K-Alpha (manufactured by Thermo Fisher Scientific)

Excitation X-ray monochromatic Al K 1, 2 lines (1486.6 eV)

X-ray diameter 400㎛

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

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

Etching rate 3.5㎚/min

·Data processing

Smoothing 11-point smoothing

The horizontal axis corrected C1s main peak (CHx, C-C) was set to 284.6 eV.

(5) Evaluation of durability

The laminate shown in FIG. 1 in which the partition pattern 5 or the partition pattern 12 was formed using a cured product of the photosensitive resin composition was subjected to UV ozone treatment under the UV ozone resistance evaluation conditions (3) described above. Thereafter, in the case of the partition pattern 5, as a hole injection layer, an ink of a compound (HT-1) using methyl benzoate as a solvent was applied to the substrate surrounded by the cured resin using an inkjet device (Litlex142, manufactured by ULVAC). was dropped onto the patterned first electrode 8 and then fired at 200°C to form a hole injection layer. Next, as a hole transport layer, a compound (HT-2) using 4-methoxytoluene as a solvent was dropped onto the area surrounded by the cured resin using an inkjet device, and then fired at 190°C to form a hole transport layer. did. Additionally, as a light-emitting layer, a mixture of compound (GH-1) and compound (GD-1) using 4-methoxytoluene as a solvent was dropped onto the area surrounded by the cured resin using an inkjet device, and then cooled at 130°C. and fired to form a light-emitting layer. In the case of the partition pattern 12, as a hole injection layer on the first electrode 8 patterned on the substrate in the area sandwiched by the first end of the cured resin and on the second end 10 of the cured resin, methyl benzoate The ink of compound (HT-1) using as a solvent was continuously added dropwise using an inkjet device (Litlex142 manufactured by ULVAC) and then baked at 200°C to form a hole injection layer. Next, as a hole transport layer, a compound (HT-2) using 4-methoxytoluene as a solvent was dropped onto the same area using an inkjet device and then baked at 190°C to form a hole transport layer. Additionally, as a light-emitting layer, a mixture of compound (GH-1) and compound (GD-1) using 4-methoxytoluene as a solvent was dropped onto the same area using an inkjet device, and then fired at 130°C. A light emitting layer was formed.

Thereafter, as an electron transport material, compound (ET-1) and compound (LiQ) were sequentially laminated at a volume ratio of 1:1 by vacuum evaporation to form the organic EL layer 6. Next, 2 nm of compound (LiQ) was deposited, and then 10 nm of Mg and Ag were deposited at a volume ratio of 10:1 to form the second electrode 7. Finally, the cap-shaped glass plate was sealed by bonding it with an epoxy resin adhesive under a low-humidity nitrogen atmosphere, and a 5 mm square organic EL display device was produced on one substrate.

The organic EL display device produced by the above-described method was driven to emit light by direct current at 10 mA/cm2, and the initial light emission area was observed. In addition, the light was maintained at 80°C for 500 hours, and the light was emitted again by direct current driving at 10 mA/cm2 to confirm that there was no change in the light emitting area, and the durability was judged as follows, with A as excellent, B as good, and C as possible. And D was made impossible.

A: No change in light emitting area

B: Light emitting area changes from 90% to 99%

C: Light emitting area changes from 80% to 89%

D: Light emitting area changes to 79% or less

(6) Composition analysis of cured resin material

Although a method for analyzing components contained in a cured resin is shown, any method that allows for composition analysis is sufficient and is not limited to the method described.

<Production of cured resin for composition analysis>

The photosensitive resin composition was applied by spin coating onto an 8-inch silicon wafer using a coating developer ACT-8 (manufactured by Tokyo Electron Co., Ltd.), and baked on a hot plate at 120°C for 3 minutes. After that, using the ACT-8 developing device, it was developed using a 2.38% by mass TMAH aqueous solution, rinsed with distilled water, and then shaken off and dried. Subsequently, the dried photosensitive resin after development was heated at 5°C/min under a nitrogen atmosphere (oxygen concentration: 100ppm or less) using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.). The temperature was raised to 250°C, and a heat curing process of heating at 250°C for 1 hour was performed to produce a cured varnish resin. The thickness of the cured resin was about 2.0 μm.

<Composition analysis by FT-IR>

The obtained cured resin was subjected to integration using an infrared microscope Nicolet iN10 (manufactured by Thermo Fisher SCIENTIFIC), using MCT as a detector, with a resolution of 8 cm ^-1 , in the range of wave numbers 4000 to 650 cm ^-1 . At number 64, the IR spectrum was obtained by the measurement mode: single reflection ATR method (Ge, 45°).

<Composition analysis by pyrolysis GC/MS>

The obtained resin cured product was subjected to thermal decomposition using a Multishot Pyrolizer PY-3030D (manufactured by Frontier Laboratories) under the conditions of a heating temperature of 600°C, followed by gas chromatography mass spectrometer JMS-Q1050GC (manufactured by Nippon Electronics). Using a GC column, a stainless steel capillary column (0.25 mm inner diameter The temperature was raised to 320℃, the inlet temperature was 300℃, the column flow rate was 1.5mL/min, the ionization method was EI (electron ionization), the mass number range was m/z10 to 800, and the analysis was performed at a scan speed of 0.5sec/scan. It was done.

Below, the abbreviated names of the components used in the examples are shown.

<Alkoxysilyl>

MTMS: Methyltrimethoxysilane

NapTMS: 1-naphthyl trimethoxysilane

TMSSucA: 3-trimethoxysilylpropylsuccinic anhydride

TfTMS: Tridecafluorooctyltrimethoxysilane

<Cross-linking agent>

HMOM-TPHAP: (Compound represented by the following chemical formula, manufactured by Honshu Chemical Industry Co., Ltd.)

VG3101L: "Techmore" (registered trademark) VG3101L (compound shown in the following chemical formula, manufactured by Printec Co., Ltd.).

<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)

In a 500 mL three-neck flask, 39.80 g (0.17 mol) of TfTMS, 62.09 g (0.50 mol) of NapTMS, 13.12 g (0.10 mol) of TMSSucA, 15.66 g (0.23 mol) of MTMS, 131.05 g of MAK, and 14.56 g of IPA. g was added, and while stirring at 40°C, a phosphoric acid solution containing 27.90 g of water and 1.31 g of phosphoric acid (1.0 mass% based on the charged monomer) was added. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the temperature of the oil bath was raised to 130°C over 15 minutes. 10 minutes after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the solution was heated and stirred for 1 hour (internal temperature was 100 to 125°C) to obtain polysiloxane (P-1). Additionally, nitrogen was flowed at 0.07 l (liter)/min during temperature increase and heating and stirring. As a result of determining the weight average molecular weight using GPC, the weight average molecular weight was 3000.

Synthesis Example 2 Synthesis of acrylic liquid repellent (Ac-1)

100 g of cyclohexanone was added to a glass reaction vessel equipped with a stirring device, a reflux cooling pipe, a dropping funnel, a thermometer, and a nitrogen gas inlet, and the temperature was raised to 110°C in a nitrogen gas atmosphere. The temperature of cyclohexanone was maintained at 110°C, and 44 g (0.65 mol) of N,N-dimethylacrylamide, 30 g (0.10 mol) of 2-(perfluorohexyl)ethyl methacrylate, and 21 g (0.10 mol) of glycidyl methacrylate were added. A monomer mixed solution containing 0.22 mol) and 5 g (0.03 mol) of 3-phenoxybenzyl acrylate was dropped at a constant rate over 2 hours using a dropping funnel to prepare each monomer solution. After completion of the dropwise addition, the temperature of the monomer solution was raised to 115°C and reaction was carried out for 2 hours to obtain an acrylic liquid repellent material (Ac-1). As a result of determining the weight average molecular weight using GPC, the weight average molecular weight was 5500.

Synthesis Example 3 Synthesis of diamine compound containing hydroxyl group

18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15°C. A solution of 20.4 g (0.11 mole) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise here. After the dropwise addition was completed, the reaction was performed at -15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried under vacuum at 50°C.

30 g of solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced using a balloon, and the reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon was no longer deflated, and the reaction was terminated. After completion of the reaction, it was filtered to exclude the palladium compound as a catalyst, and concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

Synthesis Example 4 Synthesis of alkali-soluble resin (b1)

Under a dry nitrogen stream, 88.8 g (0.20 mol) of 2,2-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride was dissolved in 500 g of NMP. Here, 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added along with 100 g of NMP, and the mixture was heated at 20°C. It was reacted for 1 hour, and then reacted at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as an end capping agent was added along with 50 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. After that, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal diluted with 100 g of NMP was added. After addition, it was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80°C for 24 hours to obtain alkali-soluble resin (b1), which is the target polyimide precursor. The number average molecular weight of the alkali-soluble resin (b1) was 12000.

Synthesis Example 5 Synthesis of alkali-soluble resin (b2)

Under a dry nitrogen stream, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was dissolved in 500 g of NMP. Here, 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added along with 100 g of NMP, and the mixture was heated at 20°C. It was reacted for 1 hour, and then reacted at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as an end capping agent was added along with 50 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. After that, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal diluted with 100 g of NMP was added. After addition, it was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain alkali-soluble resin (b2), which is the target polyimide precursor. The number average molecular weight of the alkali-soluble resin (b2) was 11000.

Synthesis Example 6 Synthesis of alkali-soluble resin (b3)

Under a dry nitrogen stream, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was dissolved in 500 g of NMP. Here, 44.85 g (0.16 mol) of bis(3-amino-4-hydroxyphenyl)sulfone and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added together with 100 g of NMP, It was reacted at 20°C for 1 hour, and then reacted at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as an end capping agent was added along with 50 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. After that, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal diluted with 100 g of NMP was added. After addition, it was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain alkali-soluble resin (b3), which is the target polyimide precursor. The number average molecular weight of the alkali-soluble resin (b3) was 11000.

Synthesis Example 7 Synthesis of quinonediazide compound (c2)

Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 33.58 g (0.125 mol) of 4-naphthoquinone diazidesulfonylic acid chloride were mixed with 1,4-dioxane. It was dissolved in 450 g and brought to room temperature. Here, 12.65 g (0.125 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the reaction system did not exceed 35°C. After dropwise addition, it was stirred at 30°C for 2 hours. Triethylamine salt was filtered, and the filtrate was added to water. Afterwards, the precipitate that precipitated was collected by filtration. This precipitate was dried in a vacuum dryer to obtain naphthoquinonediazide compound (c2). The quinonediazide substitution rate of this naphthoquinonediazide compound was 83%.

Synthesis Example 8 Synthesis of alkali-soluble resin (d1)

Under a dry nitrogen stream, 108.0 g (1.00 mol) of m-cresol, 75.5 g (0.93 mol of formaldehyde) of 37 mass% formaldehyde aqueous solution, 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone were added, followed by an oil bath. A polycondensation reaction was performed for 4 hours while immersed in the solution and refluxing the reaction solution. After that, the temperature of the oil bath was raised over 3 hours, and then the pressure in the flask was reduced to 4.0 kPa to 6.7 kPa, volatile matter was removed, the dissolved resin was cooled to room temperature, and the novolak-type phenol resin Phosphorus alkali-soluble resin (d1) was obtained. The weight average molecular weight from GPC was 3,500.

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

Add 100 g of isopropyl alcohol to a 1000 cc four-necked flask, maintain it at 80°C in an oil bath, seal with nitrogen, and stir while adding N.N-azobisisobuty to 30 g of methyl methacrylate, 40 g of styrene, and 30 g of methacrylic acid. 2 g of Ronitrile was mixed and added dropwise over 30 minutes through a dropping funnel. After this, the reaction was continued for 4 hours, 1 g of hydroquinone monomethyl ether was added, and the temperature was returned to room temperature to complete polymerization. Next, 100 g of isopropyl alcohol was added, and while maintaining the temperature at 75°C, 40 g of glycidyl methacrylate and 3 g of triethylbenzylammonium chloride were added and reacted for 3 hours to obtain a copolymer solution. Subsequently, after cooling the copolymer solution to room temperature, the copolymer solution was added to 5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the alkali-soluble resin (Ac-2), which is the acrylic resin of interest. The weight average molecular weight of this alkali-soluble resin (Ac-2) was 10000.

Examples 1 to 6 and 15, Comparative Examples 1 to 4 and 8

Figure 1 shows a schematic diagram of the laminate used for evaluation.

10 nm of an ITO transparent conductive film was formed on the entire surface of the alkali-free glass plate 1 by sputtering, and was etched as the first electrode 8 patterned on the substrate. Additionally, in order to take out the second electrode, the auxiliary electrode 3 was also formed at the same time. The obtained substrate was ultrasonically cleaned with "Semicoclean" (registered trademark) 56 (manufactured by Furuchi Chemical Co., Ltd.) for 10 minutes, then washed with ultrapure water and dried to prepare an intermediate for evaluation.

Next, each component was mixed in the mixing ratio shown in Table 1, and stirred sufficiently at room temperature to dissolve the yellow color. Thereafter, the obtained solution was filtered through a filter with a pore diameter of 0.45 μm, and photosensitive resin compositions W1 to W12 were obtained.

Subsequently, the obtained photosensitive resin compositions W1 to W12 were applied onto the intermediate for evaluation by spin coating, prebaked for 2 minutes on a hot plate at 120°C to form a photosensitive resin dried product with a thickness of about 2 μm, and then pre-baked for 2 minutes on a hot plate at 120°C. After irradiating ultraviolet rays with an exposure amount of 120 mJ/cm2 (equivalent to h-rays) with the entire wavelength of a mercury lamp through a photomask with a pattern of Two pieces were produced, one in which the cargo was manufactured and the other in which the uncured cargo of the partition pattern 5 was formed. Next, it was cured by heating at 250°C for 1 hour in a nitrogen atmosphere using a clean oven (manufactured by Koyo Thermo System Co., Ltd.) to obtain a laminate A in which the partition pattern 4 or the partition pattern 5 was formed.

Using the laminate A in which the partition pattern (4) was formed, (2) liquid repellency was evaluated, and then (3) UV ozone resistance was evaluated. The results are shown in Table 2. In addition, using the laminate A on which the second partition pattern 4 was formed, (4-1) XPS analysis of the surface of the resin cured material was performed, and then (4-2) XPS analysis of the interior of the resin cured material was performed. It was done. The obtained element concentrations (atom%) of F atoms and Si atoms are shown in Table 2.

Next, using the laminate A on which the partition pattern 5 was formed, (5) durability was evaluated, and the results are shown in Table 2.

Example 7

A laminate A having the partition pattern 4 described in Example 1 was produced using the photosensitive resin composition W3, and XPS comparison of the surface and interior of the cured resin (4-3) was evaluated. The resin cured product of photosensitive resin composition W3 is referred to as resin cured product W3. The C1s spectrum 22 on the surface of the obtained cured resin W3 and the C1s spectrum 23 inside the cured resin W3 are shown in Figure 6.

The peak height of the peak derived from the CF ₂ group with a peak top in the range of binding energy 290 to 292 eV was found to be higher in the C1s spectrum (22) of the surface of the cured resin W3. On the other hand, the peak height of the peak derived from the CF ₃ group with the peak top within the range of binding energy 292 to 294 eV was found to be higher in the C1s spectrum (23) inside the cured resin material W3. In addition, the cured resin W3 had high liquid repellency after UV ozone treatment and was highly durable when used in a display device.

Comparative Example 5

A substrate on which the partition pattern 4 described in Example 1 was formed was produced using photosensitive resin composition W10, and XPS comparison of the surface and interior of the cured resin (4-3) was evaluated. The cured resin product of photosensitive resin composition W10 is referred to as cured resin product W10. The C1s spectrum (24) on the surface of the obtained cured resin material W10 and the C1s spectrum (25) inside the cured resin material W10 are shown in Figure 7. Comparison of the C1s spectrum (24) on the surface of the cured resin W10 and the C1s spectrum (25) inside the cured resin W10 showed that the peak heights of the peaks derived from the CF ₂ group and the peak heights of the peaks derived from the CF ₃ group were the same. In addition, the cured resin W10 had a poor evaluation of liquid repellency.

Example 8 Comparative Examples 6 and 7

In the method described in <Composition analysis by FT-IR>, the IR spectra of cured resin products formed from photosensitive resin compositions W3 (Example 8), W7 (Comparative Example 6), and W8 (Comparative Example 7) were measured. From the IR spectra of the cured resins of the photosensitive resin compositions W3 and W7, peaks at 1775 to 1780 cm ^-1 and 1720 to 1725 cm ^-1 resulting from the stretching vibration of the carbonyl group in the imide ring structure were obtained. On the other hand, the IR spectrum of the cured resin of photosensitive resin composition W8 did not show a spectrum confirming the presence of an imide ring structure.

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

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

The evaluation result of (5) durability of photosensitive resin composition W7 used in Comparative Example 6 was Comparative Example 1, and since the light emitting area was reduced to 83%, the judgment was C. Although the presence of an imide ring structure could be confirmed from the cured resin of photosensitive resin composition W7, the XPS analysis inside the cured resin of (4-2) of Comparative Example 1 showed that the fluorine atom was 0 atom%, so it is assumed that the emission area was reduced.

The evaluation result of (5) durability of photosensitive resin composition W8 used in Comparative Example 7 was Comparative Example 2, and since the light emitting area was reduced to 60%, the judgment was D.

In this way, it was confirmed that when a resin cured material containing a compound having an imide ring structure is used for a partition, the performance as a light emitting element is maintained even after a durability test under accelerated conditions, and an organic EL display device with high durability is obtained.

Examples 9 and 10

By the method described in <Composition analysis by thermal decomposition GC/MS>, the thermal decomposition products of the cured resins of photosensitive resin compositions W3 (Example 9) and W6 (Example 10) were analyzed. As a result of the analysis, a peak (450 to 455 seconds) attributed to indene was obtained from the cured resin of photosensitive resin composition W3. On the other hand, no peak attributable to indene was observed from the cured resin of photosensitive resin composition W6.

Next, the photosensitive resin compositions W3 and W6 were applied onto the substrate by spin coating and prebaked for 2 minutes on a hot plate at 120°C to form a dried photosensitive resin product with a thickness of about 2 μm. Subsequently, “half exposure” was performed in which half the area of the photosensitive resin dried material was irradiated with ultraviolet rays at all wavelengths of a mercury lamp so that the thickness after development was 0.5 μm. For the remaining half area, the dried photosensitive resin of W3, which has positive photosensitive characteristics, was left unexposed so as not to reduce its thickness during the development process. Meanwhile, W6, which has negative photosensitive characteristics, was irradiated with ultraviolet rays at an exposure amount of 120 mJ/cm2 (equivalent to h-rays) to prevent its thickness from decreasing during the development process. Next, it was developed with a 2.38% by mass TMAH aqueous solution for 60 seconds and then rinsed with water to produce an intermediate with a photosensitive resin dried product. Next, the obtained intermediate with the photosensitive resin dried product was cured by heating for 1 hour in a nitrogen atmosphere using a clean oven (manufactured by Koyo Thermo System Co., Ltd.) at 250°C to produce a laminate B with a cured resin product.

With respect to the contact angle in PGMEA measured on the surface of the cured resin of photosensitive resin composition W3, the unexposed area was 46° and the half-exposed area was 5° or less. In this way, it was confirmed that the surface of a cured resin product produced by half exposure of a photosensitive resin composition containing an indene-containing compound exhibits lyophilicity. That is, in one photolithography, a cured resin material with a liquid-repellent surface and a cured resin material with a lyophilic surface can be formed. On the other hand, the contact angle in PGMEA measured on the surface of the cured resin of photosensitive resin composition W6 was 46° in the exposed area and 40° in the half-exposed area, and liquid repellency was confirmed in both areas.

Example 11

Figure 1 shows a schematic diagram of the laminate used for evaluation.

10 nm of an ITO transparent conductive film was formed on the entire surface of the alkali-free glass plate 1 by sputtering, and was etched as the first electrode 8 patterned on the substrate. Additionally, in order to take out the second electrode, the auxiliary electrode 3 was also formed at the same time. The obtained substrate was ultrasonic cleaned with "Semicoclean" (registered trademark) 56 (manufactured by Furuchi Chemical Co., Ltd.) for 10 minutes, then washed with ultrapure water and dried to prepare an intermediate for evaluation.

Additionally, the obtained photosensitive resin composition W3 was applied onto the intermediate for evaluation by spin coating and prebaked for 2 minutes on a hot plate at 120°C to form a dried photosensitive resin product with a thickness of about 2 μm. Next, after irradiating ultraviolet rays with an exposure amount of 120 mJ/cm2 (equivalent to h-rays) at the full wavelength of a mercury lamp through a photomask with a point where the transmittance is adjusted to enable a predetermined pattern and half exposure, 60% UV rays are added with a 2.38% by mass TMAH aqueous solution. It was developed for a few seconds, rinsed with water, and an uncured product of the partition pattern 12 was formed. Next, the substrate on which the partition pattern 12 was formed was cured by heating at 250° C. for 1 hour in a nitrogen atmosphere using a clean oven (manufactured by Koyo Thermo System Co., Ltd.), thereby forming the partition pattern 12. Sieve A was obtained. The formed partition wall pattern 12 had a thickness of 1.8 μm at the first stage and 0.5 μm at the second stage.

For the cured resin material W3 (second stage) formed by half exposure and the cured resin material W3 (first stage) formed by unexposed, (4-1) XPS analysis of the surface of the cured resin material was performed, and the obtained F The elemental concentrations (atom%) of atoms and Si atoms are shown in Table 3. Additionally, the C1s spectrum 26 of the surface of the cured resin W3 (second stage) formed by half exposure is shown in FIG. Additionally, (5) the durability evaluation results are shown in Table 3.

The XPS analysis results of the surface of the cured resin W3 (second stage) formed by half exposure were results that satisfied characteristic (v). The surface of the cured resin W3 (second stage) formed by half exposure is lyophilic, and (5) in the evaluation of durability, as shown in FIG. 2, the first electrode 8 patterned on the substrate and the resin The functional ink 11 was able to be continuously dripped onto the second stage 10 of the cured product without leaving any white spots.

Example 12

Evaluation was performed in the same manner as in Example 11, except that the photosensitive resin composition was changed to W5. For the cured resin material W5 (second stage) formed by half exposure and the cured resin material W5 (first stage) formed by unexposed, (4-1) XPS analysis of the surface of the cured resin material was performed, and the obtained F The elemental concentrations (atom%) of atoms and Si atoms are shown in Table 3. The C1s spectrum (27) of the surface of the cured resin W5 (second stage) formed by half exposure is shown in Figure 9. Additionally, (5) the durability evaluation results are shown in Table 3.

The XPS analysis results of the surface of the cured resin W5 (second stage) formed by half exposure were results that satisfied characteristic (v). The surface of the cured resin W5 (second stage) formed by half exposure is lyophilic, and (5) in the evaluation of durability, as shown in FIG. 2, the first electrode 8 patterned on the substrate and the resin The functional ink 11 was able to be continuously dripped onto the second stage 10 of the cured product without leaving any white spots.

Compared to Example 11, it is assumed that the durability test deteriorated because the F atom concentration of the cured resin (second stage) formed by half exposure was low.

Example 13

The evaluation was performed in the same manner as in Example 11, except that the manufacturing method of the partition pattern 12 was changed as follows.

Photosensitive resin composition W10 was applied onto the intermediate for evaluation by spin coating, and prebaked for 2 minutes on a hot plate at 120°C to form a dried photosensitive resin product with a thickness of about 0.6 μm. Next, after irradiating ultraviolet rays with an exposure amount of 60 mJ/cm2 (h-ray equivalent) with all wavelengths of a mercury lamp through a photomask with a predetermined pattern, it was developed with a 2.38% by mass TMAH aqueous solution for 50 seconds and rinsed with water. Next, it was cured by heating at 250°C for 1 hour under a nitrogen atmosphere using a clean oven (manufactured by Koyo Thermo System Co., Ltd.), and the second stage (10) of the cured resin was placed on the first electrode as shown in FIG. 3. ) was formed. Next, photosensitive resin composition W3 was applied by spin coating and prebaked for 2 minutes on a hot plate at 120°C to form a dried photosensitive resin product with a thickness of about 2.0 μm. Next, after irradiating ultraviolet rays with an exposure amount of 120 mJ/cm2 (h-ray equivalent) with all wavelengths of a mercury lamp through a photomask with a predetermined pattern, it was developed with a 2.38% by mass TMAH aqueous solution for 60 seconds and rinsed with water. Next, it was cured by heating at 250°C for 1 hour under a nitrogen atmosphere using a clean oven (manufactured by Koyo Thermo System Co., Ltd.), and as shown in FIG. 3, the first electrode and the second stage 10 of the cured resin were formed. Two layers of laminate A were produced on which the first stage 9 of the cured resin was formed and the partition pattern 12 was formed.

The formed partition wall pattern 12 had a thickness of 1.8 μm at the first stage and 0.5 μm at the second stage.

For the cured resin W10 (second stage) and the cured resin W3 (first stage), XPS analysis was performed on the surface of the second stage (4-1) resin cured material, and the elements of the F atoms and Si atoms were obtained. Concentrations (atom%) are shown in Table 3. Additionally, C1s spectrum 28 of the surface of the second stage cured resin material W10 is shown in Figure 10. Additionally, (5) the durability evaluation results are shown in Table 3.

The XPS analysis results of the surface of the cured resin W10 (second stage) were results that satisfied characteristic (v). The surface of the cured resin W10 (second stage) is lyophilic, and (5) in the evaluation of durability, as shown in FIG. 3, the first electrode 8 patterned on the substrate and the second stage of the cured resin (9) The functional ink (11) was able to be continuously dripped onto the surface without leaving white spots.

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 cured resin (4-1) in the first and second stages, and the obtained element concentrations (atom%) of F atoms and Si atoms are shown in Table 3. Additionally, the C1s spectrum (29) of the surface of the second stage cured resin W10 is shown in FIG. 11. Additionally, (5) the durability evaluation results are shown in Table 3.

The XPS analysis results of the surface of the cured resin W10 (second stage) were results that satisfied characteristic (v). The surface of the cured resin W10 (second stage) is lyophilic, and (5) in the evaluation of durability, as shown in FIG. 3, the first electrode 8 patterned on the substrate and the second stage of the cured resin (9) The functional ink (11) was able to be continuously dripped onto the surface without leaving white spots.

Compared to Example 13, Example 14 showed a reduction in the light emitting area in the durability evaluation of the display device. In the photosensitive resin composition W8 used in the first stage, it is assumed that the emission area was reduced because the concentration of F atoms was 0 atom%, based on analysis of the inside of the cured resin material by XPS in Comparative Example 2.

Example 16

Evaluation was performed in the same manner as in Example 11, except that the photosensitive resin composition was changed to W11. For the cured resin material W11 (second stage) formed by half exposure and the cured resin material W11 (first stage) formed by unexposed, (4-1) XPS analysis of the surface of the cured resin material was performed, and the obtained F The elemental concentrations (atom%) of atoms and Si atoms are shown in Table 3. The C1s spectrum 31 of the surface of the cured resin W5 (second stage) formed by half exposure is shown in FIG. 12. Additionally, (5) the durability evaluation results are shown in Table 3.

The XPS analysis result of the surface of the cured resin W11 (second stage) formed by half exposure was a result that satisfied characteristic (v). The surface of the cured resin W11 (second stage) formed by half exposure is lyophilic, and (5) in the evaluation of durability, as shown in FIG. 2, the first electrode 8 patterned on the substrate and the resin The functional ink (11) was able to be continuously dripped onto the second stage (10) of the cured product without white spots.

Example 17

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 cured resin (4-1) in the first and second stages, and the obtained element concentrations (atom%) of F atoms and Si atoms are shown in Table 3. Additionally, the C1s spectrum 32 of the surface of the second stage cured resin W10 is shown in FIG. 13. Additionally, (5) the durability evaluation results are shown in Table 3.

The XPS analysis results of the surface of the cured resin W10 (second stage) were results that satisfied characteristic (v). The surface of the cured resin W10 (second stage) is lyophilic, and (5) in the evaluation of durability, as shown in FIG. 3, the first electrode 8 patterned on the substrate and the second stage of the cured resin (9) The functional ink (11) was able to be continuously dripped onto the surface without leaving white spots.

Compared to Example 13, Example 17 showed a reduction in the light emitting area in the durability evaluation of the display device. In the photosensitive resin composition W12 used in the first stage, it is assumed that the emission area was reduced because the concentration of F atoms was 0 atom%, based on analysis of the inside of the cured resin material by XPS in Comparative Example 8.

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

Claims (10)

A laminate in which a substrate, a first electrode patterned on the substrate, and a cured resin are laminated in that order, and at least a portion of the cured resin on the first electrode is open,
A laminate wherein analysis of the cured resin by X-ray photoelectron spectroscopy (XPS) satisfies properties (i) and (ii).
(i) the F atom concentration of the cured resin measured from at least a portion of the surface opposite to the interface where the first electrode and the cured resin are in contact is 8.1 atom% or more and 30.0 atom% or less and the Si atom concentration is 1.0 atom % or more and 6.0 atom% or less
(ii) perpendicular to the interface where the first electrode and the cured resin are in contact, and in the direction of the cured resin from the substrate, and of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. The concentration of F atoms in the cured resin as measured within the range is 0.1 atom% or more and 8.0 atom% or less. The laminate according to claim 1, wherein the concentration of F atoms in characteristic (ii) is 4.0 atom% or more and 7.5 atom% or less. The method of claim 1 or 2, wherein in the analysis of the cured resin material by X-ray photoelectron spectroscopy (XPS),
C1s spectrum [A] of the cured resin measured from at least a portion of the surface opposite to the interface where the first electrode and the cured resin are in contact,
Perpendicular to the interface where the first electrode and the cured resin are in contact, and in the direction of the cured resin from the substrate, within a range of 100 to 200 nm starting from the interface where the first electrode and the cured resin are in contact. The C1s spectrum [B] of the cured resin to be measured is,
A laminate satisfying properties (iii) and (iv).
(iii) The same peak height in the C1s spectrum [A] is higher than the peak height of the peak derived from the CF ₂ group with a peak top within the range of binding energy 290 to 292 eV in the C1s spectrum [B].
(iv) The peak height of the same peak in the C1s spectrum [B] is higher than the peak height of the peak derived from the CF ₃ group with a peak top within the range of binding energy 292 to 294 eV in the C1s spectrum [A]. The laminate according to any one of claims 1 to 3, wherein the resin cured product contains a compound having an imide ring structure. The laminate according to any one of claims 1 to 4, wherein the cured resin contains a compound having an indene structure. The method according to any one of claims 1 to 5, wherein the cured resin has a first stage having a thickness of 0.8 ㎛ to 10.0 ㎛ starting from an interface where the first electrode and the cured resin are in contact, and It is a stepped resin cured material having a second stage with a thickness of 0.1 ㎛ to 0.7 ㎛ starting from the interface where the first electrode and the cured resin are in contact, and the cured resin is measured by X-ray photoelectron spectroscopy (XPS). In the analysis, the first stage of the cured resin satisfies the characteristic (i), and the second stage of the cured resin satisfies the characteristic (v).
(v) The concentration of F atoms measured from at least a portion of the surface opposite to the interface where the first electrode and the cured resin are in contact is 0.1 atom% or more and 20.0 atom% or less, and the concentration of Si atoms is 0.1 atom% or more and 0.9 atoms. % or less, and the peak with the maximum peak height measured in the range of 290 to 295 eV of binding energy in the C1s spectrum is the peak derived from the CF ₃ group with the peak top in the range of 292 to 294 eV. The laminate according to claim 6, wherein the concentration of F atoms in the characteristic (v) is 8.0 atom% or more and 18.0 atom% or less. A display device comprising the laminate according to any one of claims 1 to 7. A method for manufacturing a display device, comprising steps (5) and (6) in this order.
(5) In the laminate according to any one of claims 1 to 7, a step of forming a functional layer by applying a functional ink to the first electrode by inkjet.
(6) Process of forming a second electrode on the functional layer A method for manufacturing a display device, comprising steps (7) and (8) in this order.
(7) In the laminate according to claim 6 or 7, a step of forming a functional layer by applying a functional ink on the first electrode and on the second stage of the cured resin by inkjet.
(8) Process of forming a second electrode on the functional layer

Images