KR102632744B1 - Light-emitting devices and organic EL devices, and methods for manufacturing them - Google Patents

Abstract

(Problem) To provide a light-emitting device with better flexibility by eliminating the need for a support substrate for a touch panel on a light-emitting device such as an organic EL device and reducing the overall thickness of the light-emitting device, and to provide a patterned cured resin layer with high chemical resistance. Provides a light emitting device having a.
(Solution) A light-emitting device having a substrate, a light-emitting element on the substrate, and a cured resin portion on the light-emitting element, wherein the cured resin portion includes a patterned cured resin layer, and the patterned cured resin layer , when immersed in a 70% by mass 2-aminoethanol aqueous solution at 60°C for 5 minutes, the film thickness after immersion is 80 to 120 when the film thickness before immersion is 100, and the light emitting device includes the cured resin portion and A light-emitting device characterized by not having a glass substrate or a support made of polyethylene terephthalate or the like between the light-emitting elements.

Description

Light-emitting devices and organic EL devices, and methods for manufacturing them

The present invention relates to light emitting devices and organic EL devices, and methods for manufacturing them.

As one of the light-emitting devices under recent development, an organic electroluminescence (EL) device having a layered structure including an anode, an organic light-emitting layer, and a cathode is known. The organic EL device has the organic EL element described above. Here, an organic EL device with a touch panel that has a touch panel member on the entire surface of the device is known (for example, see Patent Document 1).

In the organic EL device with a touch panel, for example, after manufacturing a touch panel by forming a touch panel member on a support substrate for a touch panel, the support substrate for a touch panel is connected to the organic EL element through an adhesive layer or adhesive layer. It is manufactured by bonding to a formed substrate.

Japanese Patent Publication No. 2015-161806

When a support substrate for a touch panel is bonded to a substrate on which an organic EL element is formed through an adhesive layer or an adhesive layer, the overall thickness of the organic EL device increases, and when the organic EL device is bent, damage or functional deterioration of the device occurs. There are cases.

Rather than bonding a support substrate for a touch panel to a substrate on which an organic EL element is formed through an adhesive layer or an adhesive layer, a touch panel is produced directly on the organic EL element using techniques such as lithography and etching, thereby significantly increasing the production of organic EL devices. The overall thickness of the light emitting device, such as the like, can be reduced. However, in the conventional method, baking at a temperature exceeding 100°C is required to form the patterning resin insulating film in the touch panel, and when the patterning cured resin layer is formed directly on the organic EL element, it has the disadvantage of causing deterioration of the EL emitting layer. There was. Additionally, when the patterned cured resin layer was formed using conventional materials at a low temperature of 100°C or lower, the patterned cured resin layer could not withstand the etching chemical solution for forming wiring, making it impossible to manufacture a touch panel structure.

The present invention provides a light-emitting device with better flexibility by eliminating the need for a support substrate for a touch panel on a light-emitting device such as an organic EL device and reducing the overall thickness of the light-emitting device, and also provides a pattern with high chemical resistance. The object is to provide a light-emitting device having a cured resin layer.

The present inventors conducted intensive studies to solve the above problems. As a result, by forming a patterned cured resin layer with high chemical resistance at a temperature of 100°C or lower directly on the light emitting element, a support substrate for a touch panel is eliminated, and the overall thickness of the light emitting device such as an organic EL device can be reduced. It was discovered that a light-emitting device with good flexibility could be obtained, and the present invention was completed. The present invention relates to, for example, the following [1] to [13].

[1] A light-emitting device having a substrate, a light-emitting element on the substrate, and a cured resin portion on the light-emitting element, wherein the cured resin portion includes a patterned cured resin layer, and the patterned cured resin layer includes, When immersed in a 70% by mass 2-aminoethanol aqueous solution at 60°C for 5 minutes, the film thickness after immersion is 80 to 120 when the film thickness before immersion is 100, and the light emitting device includes the cured resin portion and the Between the light emitting elements, a glass substrate or polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, and allyl diglycol carbonate resin. , polyamide, polyimide, polyamidoimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, polynorbornene, and triacetylcellulose resin, and has a thickness of A light emitting device characterized by not having a support exceeding 50 μm.

[2] The light-emitting device according to [1], wherein the light-emitting device is an organic EL device and the light-emitting device is an organic EL device.

[3] The light emitting device according to [1] or [2] above, wherein the patterned cured resin layer is a layer formed of a radiation-sensitive resin composition.

[4] The cured resin portion is formed on an encapsulation layer that encapsulates the light emitting element, and the light emitting device does not have the glass substrate or support between the cured resin portion and the encapsulation layer. The light emitting device according to any one of [1] to [3].

[5] The light-emitting device according to any one of [1] to [4] above, wherein the cured resin portion is in direct contact with the light-emitting element or its encapsulation layer.

[6] The light emitting device according to any one of [1] to [5] above, wherein the cured resin portion is not bonded to the substrate and the element substrate having the light emitting element through an adhesive layer or adhesive layer.

[7] The light-emitting device according to any one of [1] to [6], wherein the cured resin portion further includes a cured layer as a wiring base layer on the light-emitting element side of the patterned cured resin layer.

[8] An organic EL device with a touch panel having a substrate, an organic EL element on the substrate, and a touch panel member on the organic EL element, wherein the touch panel member includes a patterned cured resin layer, and When the patterned cured resin layer is immersed in a 70% by mass 2-aminoethanol aqueous solution at 60°C for 5 minutes, the film thickness after immersion is 80 to 120 when the film thickness before immersion is set to 100, and the touch An organic EL device with a touch panel, wherein a support substrate for a touch panel is not disposed on the surface of the panel member on the organic EL element side.

[9] The touch panel member is formed between (1) a first metal wiring layer, (2) a second metal wiring layer, and (3) the first and second metal wiring layers, and the first and second metal wiring layers a patterned cured resin layer that partially insulates the metal wiring layer and has a contact hole in which wiring is formed to conduct the first and second metal wiring layers; (4) a cured resin layer that covers the second metal wiring layer; The organic EL device with a touch panel according to [8] above.

[10] A method of manufacturing a light-emitting device comprising a substrate, a light-emitting element on the substrate, and a cured resin portion on the light-emitting element, wherein the cured resin portion includes a patterned cured resin layer, (1 ) A process of forming a coating film of a radiation-sensitive resin composition, (2) a process of irradiating a first radiation to the coating film through a mask, (3) a process of developing the coating film after radiation irradiation, (4) ) A step of irradiating a second radiation to the coated film after development to form the patterned cured resin layer (however, step (4) is performed at 100° C. or lower, and the first radiation and the second radiation may be the same or different. Good), a method of manufacturing a light-emitting device.

[11] The step (4) includes (4-i) heating the coating film at 100°C or lower and then irradiating it with second radiation; or (4-ii) the method of manufacturing a light-emitting device according to [10] above, which is a step of irradiating the coating film with second radiation and then heating it at 100° C. or lower.

[12] The light emitting device is an organic EL device with a touch panel having a substrate, an organic EL element on the substrate, and a touch panel member on the organic EL element, and the touch panel member is a patterned cured resin layer. The light emitting device according to [10] or [11] above, wherein the organic EL device is an organic EL device with a touch panel that does not have a support substrate for a touch panel between the organic EL element and the touch panel member. Method of manufacturing the device.

[13] The method for producing a light-emitting device according to any one of [10] to [12], wherein the radiation-sensitive resin composition contains a polymer represented by the following formula (1) and a radiation-sensitive polymerization initiator.

[In formula (1), n and m each independently represent an integer of 1 to 30.]

According to the present invention, the overall thickness of a light-emitting device such as an organic EL device can be reduced by forming a patterned cured resin layer with high chemical resistance at a temperature of 100 ° C. or lower directly on the light-emitting element, thereby making it possible to bend the light-emitting device. A light-emitting device is provided that can prevent damage or deterioration of function of the device in case of damage.

Figure 1 shows a cross-sectional view of one embodiment of the light-emitting device of the present invention.
Figure 2 shows a cross-sectional view of one embodiment of a conventional light emitting device.

(Form for carrying out the invention)

Hereinafter, modes for carrying out the present invention will be described in detail including suitable aspects. Unless otherwise specified, each component exemplified in this specification may be used individually or in combination of two or more types. In addition, compounds described in each patent publication cited in this specification, etc. are assumed to be described in this specification.

[Light-emitting device]

The light emitting device of the present invention has a substrate, a light emitting element on the substrate, and a cured resin portion on the light emitting element, and the cured resin portion includes a patterned cured resin layer.

However, the light emitting device of the present invention has a glass substrate or polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, or a glass substrate between the cured resin portion and the light emitting element. Polyethersulfone, polyarylate, allyldiglycolcarbonate resin, polyamide, polyimide, polyamidoimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, polynorbornene, and triacetylcellulose resin. It consists of at least one type selected from the group, and does not have a support exceeding 50 μm in thickness. Hereinafter, these glass substrates and the support made of the resin are collectively referred to as “support substrate.” Additionally, the substrate on which the light-emitting device is formed is also called an “element substrate.”

In this aspect, it is possible to significantly reduce the thickness of the light emitting device compared to a light emitting device in which the support substrate on which the cured resin portion is formed is bonded to the element substrate through an adhesive layer or adhesive layer and the cured resin portion is disposed on the light emitting element. do.

In this specification, in the expressions “BB on AA”, “BB disposed on AA”, or “forming BB on AA”, AA and BB may be in contact, and AA and BB may not be in contact, For example, another layer may exist between AA and BB.

The light-emitting device is, for example, a device with a laminated structure including an organic layer such as an organic light-emitting layer and an organic semiconductor thin film, and specific examples include an organic electroluminescence (EL) device and an organic transistor, and organic EL devices are preferred. Examples of organic EL devices include organic EL lighting devices and organic EL display devices. These light emitting devices have a patterning structure (eg, a touch panel member, a light extraction structure, a light scattering structure, a lens structure) including a patterned cured resin layer on the front surface of the device.

<Substrate>

Examples of the substrate include a glass substrate and a resin substrate, and in one embodiment, a transparent substrate with high transmittance to visible light is included. From the viewpoint of flexibility, a resin substrate is preferable. Examples of the constituent materials of the substrate include glass such as alkali-free glass, borosilicate glass, alumino borosilicate glass, quartz glass, synthetic quartz glass, soda lime glass, and white sapphire; Polyesters (e.g. polyethylene terephthalate, polyethylene naphthalate), polyolefins, polystyrene, polyimides, polyamides, polyamidoimides, polyetherimides, polyarylates, polyethersulfone, polysulfone, polyetheretherketone, polycarbonate. , polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, and polyurethane. Other substrates include silicon substrates, silicon nitride substrates, and molybdenum substrates.

The substrate is, for example, a TFT substrate having thin film transistors (TFTs) that drive the light emitting elements, and in one embodiment, the TFTs are arranged in a matrix shape. Additionally, the TFT substrate may have a planarization film covering the TFT.

The thickness of the substrate is usually 10 to 500 μm.

<Light-emitting device>

Light-emitting elements are usually formed on a substrate.

As a light-emitting element, an organic EL element is preferable.

Although a detailed description of its structure will be omitted, the organic EL element may have a structure in which an organic light-emitting layer containing a light-emitting material is sandwiched between a pair of opposing electrodes, that is, the organic light-emitting layer may have an anode and a cathode facing each other. It may have a structure sandwiched between, for example, a known structure having an anode/organic light-emitting layer/cathode can be taken.

The organic EL element can have, for example, a top emission structure, and the material of each constituent material can be appropriately selected depending on the structure.

The organic light-emitting layer contains a light-emitting material that is an organic material, that is, an organic light-emitting material. The organic light emitting layer is, for example, a layer that emits each color when driving the device, or a layer that emits white light when driving the device. The white light is emitted from the organic EL device as colored light transmitted through a corresponding color filter.

The organic light-emitting material contained in the organic light-emitting layer may be a low-molecular organic light-emitting material or a high-molecular organic light-emitting material. For example, doping quinacridone or coumarin into base materials such as tris(8-quinolinolato)aluminum (Alq ₃ ) and bis(10-hydroxybenzo[h]quinolinate)beryllium (BeBq ₂ ). One material can be used. Examples of polymer organic light-emitting materials include polyphenylene vinylene and its derivatives, polyacetylene and its derivatives, polyphenylene and its derivatives, polyparaphenylene ethylene and its derivatives, and poly3-hexylthiophene and its derivatives. , polyfluorene and its derivatives can be selected and used.

The anode and cathode of the organic EL element are each made of a conductive material. Examples of materials for the anode include oxides such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and tin oxide; Metals such as aluminum (Al), APC (alloy of silver, palladium, and copper), ARA (alloy of silver, rubidium, and gold), MoCr (alloy of molybdenum and chromium), and NiCr (alloy of nickel and chromium). Alternatively, a laminated film of these metals and a highly transparent electrode (e.g. ITO) may be used. Examples of cathode materials include oxides such as ITO, IZO, and tin oxide; Metals such as magnesium (Mg), calcium (Ca), aluminum (Al), silver (Ag), and alloys containing one or two or more of these metals can be used, and these metals can be used with highly transparent electrodes (e.g. A laminated film of ITO may also be used.

Additionally, a hole injection layer and/or a hole transport layer may be disposed between the anode and the organic light emitting layer. When a hole injection layer and a hole transport layer are disposed between the anode and the organic light emitting layer, the hole injection layer is disposed on the anode, the hole transport layer is disposed on the hole injection layer, and the organic light emitting layer is disposed on the hole transport layer. . Additionally, as long as holes can be efficiently transported from the anode to the organic light-emitting layer, the hole injection layer and the hole transport layer may be omitted. Additionally, an electron transport layer and/or an electron injection layer may be disposed between the cathode and the organic light emitting layer.

Additionally, the anode may be separated for each pixel, or a partition (pixel defining layer) may be formed to cover the end of the anode. The partition wall determines the light emitting area by covering the ends of the anodes separated for each pixel. Pixels can be arranged to correspond to color filters, for example.

The thickness of the light emitting element is usually 3 to 10 μm.

<Bag layer>

The light-emitting device preferably has an encapsulation layer that seals the light-emitting element. By sealing the light-emitting element, it is possible to reduce moisture entering the element. For this reason, the light-emitting device can suppress the occurrence of dark spots and a decrease in light-emitting characteristics such as luminance and luminous efficiency due to moisture.

The encapsulation layer is preferably a thin film encapsulation layer. The thickness of the thin film encapsulation layer is usually 50 μm or less, preferably 1 to 50 μm, and more preferably 1 to 20 μm.

Examples of the sealing layer include (1) an organic sealing layer, (2) an inorganic sealing layer, and (3) an organic-inorganic sealing layer having an organic sealing layer and an inorganic sealing layer alternately. For example, an organic-inorganic encapsulating layer having an organic encapsulating layer between two inorganic encapsulating layers may be used, or an organic-inorganic encapsulating layer having a total of four or more layers of inorganic encapsulating layers and organic encapsulating layers alternately may be used. The total number of layers in the organic-inorganic sealing layer is, for example, 3 or more layers, and preferably 3 to 9 layers. Here, it is preferable that the outermost layer of the encapsulation layer is an inorganic encapsulation layer.

Examples of the inorganic encapsulating layer include layers described in Japanese Patent Application Laid-Open No. 2010-160906, Japanese Patent Application Laid-Open No. 2016-012433, and Japanese Patent Application Laid-Open No. 2016-143605, etc., specifically, a silicon nitride layer or a silicon oxynitride layer. Examples of these formation methods include the methods described in the above publication, specifically the sputtering method and the chemical vapor growth method. The thickness of one layer of the inorganic encapsulation layer is usually 10 nm to 2 μm.

Examples of the organic sealing layer include a layer formed from a curable composition. The thickness of one layer of the organic encapsulation layer is usually 1 to 50 μm, preferably 1 to 20 μm, and more preferably 1 to 15 μm.

The curable composition is, for example, a composition containing a polymerizable compound and a polymerization initiator.

The polymerizable compound is preferably a compound having two or more polymerizable groups. Examples of the polymerizable group include ethylenically unsaturated group, oxiranyl group (epoxy group), oxetanyl group, and N-alkoxymethylamino group. As the polymerizable compound, cyclic ether compounds such as epoxy compounds and oxetane compounds, compounds having two or more (meth)acryloyl groups, or compounds having two or more N-alkoxymethylamino groups are preferable.

Examples of the polymerization initiator include cationic or radical polymerization initiators. The content of the polymerization initiator in the curable composition is usually 0.01 to 20.0 parts by mass, preferably 0.1 to 5.0 parts by mass, based on 100 parts by mass of the polymerizable compound.

The curable composition may be applied to the entire object or to a part of the object. As a method of applying the curable composition, a known method can be adopted. Examples include spray method, roll coating method, spin coating method, slit die coating method, bar coating method, and inkjet method.

When the curable composition is a radiation-curable material, for example, ultraviolet rays and/or visible rays are used for radiation irradiation for curing, and ultraviolet rays and/or visible rays with a wavelength of 300 to 450 nm are more preferable. The irradiation amount is preferably 100 to 2000 mJ/cm2, more preferably 500 to 1500 mJ/cm2. The wavelength and irradiation amount can be appropriately determined considering the influence on the organic EL element. Examples of the light source include those described in <Step (2)> described later.

Additionally, in order to accelerate curing of the radiation-curable composition, heating may be performed simultaneously with or after radiation irradiation. Additionally, the thermosetting type curable composition is cured by heating. For example, these heating temperatures are preferably 80 to 150°C, more preferably 80 to 100°C; The heating time is preferably 1 to 120 minutes, more preferably 1 to 60 minutes.

The formation of the sealing layer is preferably performed in an environment excluding oxygen and moisture, for example, in an inert gas atmosphere such as an N ₂ atmosphere or in a vacuum.

<Cured resin part>

The cured resin portion includes a patterned cured resin layer. The patterned cured resin layer is a cured resin layer with a pattern, and is preferably a layer formed of a radiation-sensitive resin composition. Specifically, it is preferably a layer formed directly by a photolithography method using a radiation-sensitive resin composition.

The shape of the pattern is not particularly limited, but for example, the shape of the non-existent portion of the cured resin layer may be a hole shape such as a circular shape, an elliptical shape, or a polygonal shape, or a line shape. Among these, hole patterns are preferable.

The radiation-sensitive resin composition is not particularly limited as long as it contains an alkali-soluble resin, a polymerizable compound, and a radiation-sensitive polymerization initiator, and a known composition can be used. Additionally, as the radiation-sensitive resin composition, a radiation-sensitive resin composition containing an alkali-soluble resin having an ethylenically unsaturated group and a radiation-sensitive polymerization initiator may be used, and this radiation-sensitive resin composition contains an alkali-soluble resin having an ethylenically unsaturated group. It may additionally contain polymerizable compounds other than alkali-soluble resin. From the viewpoint of low-temperature curing, the composition described below in the <radiation-sensitive resin composition> described later is preferable. The composition can be mixed with a solvent and used as a liquid composition.

The cured resin portion usually has two or more metal wiring layers. These metal wiring layers are insulated from each other by the patterned cured resin layer, and are electrically connected to necessary portions by wiring formed in contact holes formed in the patterned cured resin layer.

The thickness of the patterned cured resin layer is usually 1 to 5 μm, preferably 1 to 3 μm, and more preferably 1.3 to 2 μm. The thickness of the metal wiring layer is usually 100 to 1000 nm, preferably 200 to 600 nm, and more preferably 200 to 400 nm.

The hole diameter of the contact hole is usually 1 to 20 μm, preferably 2 to 10 μm, and more preferably 3 to 6 μm.

The change in film thickness when the patterned cured resin layer is immersed in an aqueous solution containing 70% by mass of 2-aminoethanol at 60°C for 5 minutes is 80% when the film thickness before immersion is 100%. It is preferable that it is -120, and it is more preferable that it is 95-105. Details of the measurement conditions for film thickness change are described in the Examples. Additionally, the film thickness change is measured at the non-patterned portion of the patterned cured resin layer.

Such a patterned cured resin layer with high chemical resistance has high absorption of radiation used in post-exposure, where the crosslinking density is increased by using, for example, a polymerizable compound with many polymerizable groups or an alkali-soluble resin with an ethylenically unsaturated group. Use a radiation-sensitive polymerization initiator with excellent polymerization initiation efficiency (e.g., a combination of radiation-sensitive polymerization initiators with high absorption of radiation including g-ray, h-ray, i-ray, and j-ray and excellent polymerization initiation efficiency) By doing this, you can get it.

The cured resin portion may further include a cured layer as a wiring base layer on the light-emitting element side of the patterned cured resin layer, and/or on the side opposite to the light-emitting element of the patterned cured resin layer for upper layer protection. You may additionally include a hardened layer as a layer. The cured layer may be a non-patterned layer and acts as a wiring base layer or an upper protective layer of the metal wiring layer. The cured layer is made of, for example, an inorganic film, and may be a layer formed by a sputtering method or a chemical vapor growth method, but is preferably a cured resin layer formed of a radiation-sensitive resin composition or a thermosetting resin composition, and is preferably a radiation-sensitive layer. It is more preferable that it is a cured resin layer formed from a resin composition.

The thickness of the wiring base layer and the upper protective layer are each independently usually 0.5 to 10 μm, preferably 0.5 to 5 μm, and more preferably 0.5 to 3 μm.

The overall thickness of the cured resin portion is preferably 15 μm or less, more preferably 9 μm or less, and even more preferably 6 μm or less.

The average roughness Ra on the surface of the hardened layer as the wiring base layer is preferably 3 nm or less, more preferably 1 nm or less, and still more preferably 0.6 nm or less. Ra can be measured using an AFM device or the like.

As shown in FIG. 1, one embodiment of the cured resin portion 40 includes a wiring base layer 41, a first metal wiring layer 1a formed on the wiring base layer 41, and a first metal wiring layer ( A patterned cured resin layer 42 partially covering 1a), and a wiring 3' formed on the patterned cured resin layer 42 and in the contact hole 3 of the patterned cured resin layer 42. ) is formed on the second metal wiring layer (2a) electrically connected to the first metal wiring layer (1a), the patterned cured resin layer 42, and the second metal wiring layer (2a), and the second metal wiring layer ( It has an upper protective layer 43 covering 2a). The wiring base layer 41 may be omitted. In FIG. 1, the cured resin portion 40 is formed in direct contact with the encapsulation layer 30 in the device substrate composed of the substrate 10, the light emitting element 20, and the encapsulation layer 30.

Since the first and second metal wiring layers are electrically connected to each other by wiring formed in the contact hole of the patterned cured resin layer, for example, the sensitivity of the touch panel increases and it can be driven with low power consumption.

The cured resin portion is preferably a touch panel member.

The cured resin portion is formed on the light emitting element or its encapsulation layer (if formed). In the light-emitting device of the present invention, the above-mentioned support substrate is not disposed between the cured resin portion and the light-emitting element or its encapsulation layer (if formed).

If the above-described support substrate does not exist between the cured resin portion and the light emitting element, the cured resin portion may be bonded to the device substrate through an adhesive layer or adhesive layer. However, the cured resin portion may be bonded to the device substrate through an adhesive layer or adhesive layer. It is preferable that it is not bonded to the device substrate. It is preferable that the light emitting device is sealed with an encapsulation layer.

“The cured resin portion is not bonded to the device substrate through an adhesive layer or adhesive layer” means that the light emitting device of the present invention has a cured resin portion on the support substrate 70 (1), as shown in FIG. 2 . (40) is formed, (2) an adhesive layer or adhesive layer 60 is formed on the surface of the support substrate 70 opposite to the cured resin portion 40, or the substrate 10 and the light emitting element 20 are formed. This means that it is not obtained by forming an adhesive layer or adhesive layer 60 on the device substrate and then (3) bonding the support substrate 70 to the device substrate through the adhesive layer or adhesive layer 60. In Figure 2, the device substrate additionally has an encapsulation layer 30.

That is, the cured resin portion is preferably formed in direct contact with the light emitting element or its encapsulation layer (if formed). In this aspect, compared to the case where the support substrate on which the cured resin portion is formed is bonded to the device substrate through an adhesive layer or an adhesive layer and the cured resin portion is disposed on the light emitting device, it is possible to significantly reduce the thickness of the light emitting device. , which has the excellent advantage of preventing damage and deterioration of function of the light-emitting device when it is bent.

Hereinafter, the radiation-sensitive resin composition will be described.

<Radiation-sensitive resin composition>

〈Alkali-soluble resin〉

As the alkali-soluble resin, a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group is preferable, and a carboxyl group-containing polymer is more preferable. Examples of alkali-soluble resins include acid-modified epoxy (meth)acrylate resins, novolac resins, polyamic acid and its partial imidates as polyimide precursors, polyhydroxyamide as a polybenzoxazole precursor, and phenol- Xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, monomer or copolymer of monomers having phenolic hydroxyl groups such as hydroxystyrene and isopropenylphenol, and one or more carboxyl groups A copolymer of an ethylenically unsaturated monomer having an ethylenically unsaturated monomer and another copolymerizable ethylenically unsaturated monomer may be mentioned.

Alkali-soluble resin may have an ethylenically unsaturated group. As the alkali-soluble resin, acid-modified epoxy (meth)acrylate resin, which is a resin having a carboxyl group and an ethylenically unsaturated group, is preferred because it can achieve both alkali solubility and cured film physical properties at a high level, for example, Cresol novolak-type epoxy (meth)acrylate resin, phenol novolak-type epoxy (meth)acrylate resin, bisphenol A-type epoxy (meth)acrylate resin, and bisphenol F-type epoxy (meth)acrylate resin, respectively, acid-modified. , biphenyl type epoxy (meth)acrylate resin, and trisphenolmethane type epoxy (meth)acrylate resin.

Examples of the acid-modified cresol novolak-type epoxy (meth)acrylate resin include a polymer represented by the following formula (1). The acid-modified cresol novolak-type epoxy (meth)acrylate resin is, for example, an epoxy (meth)acrylate resin obtained by reacting a cresol novolak-type epoxy resin with (meth)acrylic acid, and phthalic anhydride for alkali solubility. It is obtained by reacting acid anhydrides such as 1,2,3,6-tetrahydrophthalic anhydride.

The acid-modified cresol novolak-type epoxy (meth)acrylate resin has the rigid main chain skeleton of the cresol novolak-type epoxy resin, an ethylenically unsaturated group, and a carboxyl group, so that it is solvent-resistant despite curing and firing at low temperatures. , it becomes possible to form a cured film with excellent heat resistance.

In formula (1), n and m each independently represent an integer of 1 to 30.

As specific examples of acid-modified cresol novolak-type epoxy (meth)acrylate resin, CCR-1171H, CCR-1291H, CCR-1307H, and CCR-1309H (manufactured by Nippon Kayaku Co., Ltd.) can be used.

The acid value of the alkali-soluble resin is, for example, 10 to 200 mgKOH/g, preferably 30 to 270 mgKOH/g, and more preferably 50 to 250 mgKOH/g. The acid value represents the number of mg of KOH required to neutralize 1 g of solid content of the alkali-soluble resin.

The alkali-soluble resin usually has a weight average molecular weight (Mw) of 1,000 to 100,000, preferably 3,000 to 50,000. Mw refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (elution solvent: tetrahydrofuran).

The content of alkali-soluble resin in the radiation-sensitive resin composition is usually 30% by mass or more, preferably 40% by mass or more, based on 100% by mass of solid content of the composition, and the upper limit of the content of alkali-soluble resin is Of 100% by mass of solid content of the composition, it is usually 90% by mass, and in one embodiment, it is 70% by mass or 60% by mass.

By adopting this aspect, in addition to further improvement in brightness, alkali developability, storage stability of the composition, pattern shape, and chromaticity characteristics can be improved. In addition, solid content is all components other than the solvent.

<Polymerizable compound>

The polymerizable compound is a polymerizable compound other than the alkali-soluble resin having an ethylenically unsaturated group described above, and the polymerizable compound is preferably a compound having two or more polymerizable groups. Examples of the polymerizable group include ethylenically unsaturated group, oxiranyl group (epoxy group), oxetanyl group, and N-alkoxymethylamino group. As the polymerizable compound, a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

Examples of compounds having two or more (meth)acryloyl groups include the reaction product of an aliphatic polyhydroxy compound and (meth)acrylic acid [polyfunctional (meth)acrylate], and caprolactone-modified polyfunctional (meth)acrylate. Rate, polyfunctional (meth)acrylate modified with alkylene oxide, reaction product of (meth)acrylate with hydroxyl group and polyfunctional isocyanate [polyfunctional urethane (meth)acrylate], (meth)acrylate with hydroxyl group and acid An anhydride reactant [polyfunctional (meth)acrylate having a carboxyl group] can be mentioned. Specific examples of aliphatic polyhydroxy compounds, (meth)acrylates having hydroxyl groups, polyfunctional isocyanates, and acid anhydrides include compounds described in paragraph [0065] of Japanese Patent Application Laid-Open No. 2015-232694, and caprolactone-modified compounds. Examples of functional (meth)acrylates and alkylene oxide-modified polyfunctional (meth)acrylates include the compounds described in paragraph [0066] of the same publication.

Specific examples include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and succinic acid. Modified pentaerythritol tri(meth)acrylate can be mentioned.

Examples of compounds having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure, and specific examples thereof include those described in Japanese Patent Application Laid-Open No. 2015-232694, paragraph [ 0067].

When the radiation-sensitive resin composition contains a polymerizable compound, the content of the polymerizable compound is usually 30 to 200 parts by mass, preferably 30 to 100 parts by mass, based on 100 parts by mass of the alkali-soluble resin. Preferably it is 45 to 100 parts by mass. By using this aspect, curability and developability can be further improved, and brightness can be further improved.

<Radiation-sensitive polymerization initiator>

The radiation-sensitive polymerization initiator carries out a curing reaction of the alkali-soluble resin and the polymerizable compound having an ethylenically unsaturated group by exposure to radiation such as visible light, ultraviolet ray, electron beam, or X-ray, preferably visible light and/or ultraviolet ray. It is a compound that generates active species that can initiate. As a radiation-sensitive polymerization initiator, for example, thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based compounds, onium salt-based compounds, benzoin-based compounds, and benzophenone-based compounds. , α-diketone-based compounds, polynuclear quinone-based compounds, diazo-based compounds, and imide sulfonate-based compounds. Specific examples of these include the compounds described in paragraphs [0073] to [0078] of Japanese Patent Application Laid-Open No. 2015-232694.

When the radiation-sensitive resin composition contains a polymerizable compound, the content of the radiation-sensitive polymerization initiator is usually 0.01 to 120 parts by mass, preferably 1 to 100 parts by mass, per 100 parts by mass of the polymerizable compound. am. In one embodiment, the content of the radiation-sensitive polymerization initiator is 11 parts by mass or more or 13 parts by mass or more with respect to 100 parts by mass of the polymerizable compound. By adopting this aspect, curability and film properties can be further improved, and brightness can be further improved.

In one embodiment, the content of the radiation-sensitive polymerization initiator in the radiation-sensitive resin composition is usually 1 to 20 parts by mass, preferably 5 to 5 parts by mass, based on 100 parts by mass of the alkali-soluble resin having an ethylenically unsaturated group. It is 15 parts by mass.

<additive>

The radiation-sensitive resin composition may contain various additives as needed. Examples of additives include sensitizers, dispersants, fillers, polymer compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, residue improvers, and developability improvers.

In particular, as an adhesion promoter, the coupling agent described in International Publication No. 2017/094831 can be used. As the ultraviolet absorber, the ultraviolet absorber described in Japanese Patent Application Laid-Open No. 2004-190006, etc. can be used. As an antioxidant, the antioxidant described in International Publication No. 2011/046230 can be used.

<Preparation of radiation-sensitive resin composition>

The radiation-sensitive resin composition can be prepared by an appropriate method. For example, it can be prepared by mixing each component such as alkali-soluble resin, polymerizable compound, and radiation-sensitive polymerization initiator with a solvent and optionally added additives.

Solvents include, for example, (poly)alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (cyclo)alkyl alcohols, keto alcohols, (poly)alkylene glycol monoalkyl ether acetates, other ethers, Ketones, diacetates, alkoxycarboxylic acid esters, other esters, aromatic hydrocarbons, amides or lactams can be mentioned, and specific examples thereof include paragraphs [0082] to [0085] of Japanese Patent Application Laid-Open No. 2015-232694. The solvent described in is mentioned.

The content of the solvent is not particularly limited, but the solid content concentration in the radiation-sensitive resin composition is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.

In one embodiment, the cured resin layer formed from the radiation-sensitive resin composition is transparent to the naked eye. With this aspect, a light-emitting device with good optical characteristics can be obtained.

<Absence of touch panel>

An organic EL device, which is an example of the light emitting device of the present invention, has a touch panel member as a cured resin portion in one embodiment. The organic EL device with a touch panel of the present invention has a substrate, an organic EL element on the substrate, and a touch panel member on the organic EL element, and the touch panel member includes a patterned cured resin layer. However, in the above device, the support substrate for the touch panel is not disposed on the surface of the touch panel member on the organic EL element side. The organic EL device preferably has an encapsulation layer that seals the organic EL element.

The touch panel member is, for example, formed between (1) a first metal wiring layer, (2) a second metal wiring layer, and (3) the first and second metal wiring layers, and a patterned cured resin layer that partially insulates the metal wiring layer and has a contact hole in which a wiring connecting the first and second metal wiring layers is formed; (4) a cured resin layer that covers the second metal wiring layer ( It has an upper protective layer). The touch panel member may further have (5) a cured resin layer (wiring base layer) under the first metal wiring layer.

In the present invention, since the first and second metal wiring layers are electrically connected to each other by wiring formed in the contact hole of the patterned cured resin layer, the sensitivity of the touch panel increases and it can be driven with low power consumption. .

The support substrate for the touch panel is, for example, a glass substrate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, At least one selected from the group of allyl diglycol carbonate resin, polyamide, polyimide, polyamidoimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, polynorbornene, and triacetylcellulose resin. It is a support that is made of and has a thickness exceeding 50㎛.

The substrate, organic EL element, encapsulation layer, patterned cured resin layer, first and second metal wiring layers, upper protective layer, and wiring base layer were described above.

The touch panel is preferably a capacitive type, and more preferably a projection type capacitance type.

In the metal wiring layer, the touch panel member has, for example, a capacitive pad made of a patterned metal film that detects the approach of a finger, a touch panel pen, or the like by changing electrical capacity. One group of capacitive pads is connected by wiring in the plane X-axis direction (horizontal direction), and another group of capacitive pads is connected by wiring in the plane Y-axis direction (vertical direction), It is led out to the outside of the panel by wiring and is connected to the touch panel driving or touch detection circuit. Additionally, the arrangement configuration of the capacitive pad is not limited to these, and conventionally known configurations can be adopted. The wiring that extends to the outside of the panel is connected to the touch panel driving circuit and detection circuit by additional wiring in the peripheral area.

In the present invention, after separately manufacturing the touch panel member, the touch panel member can be formed directly on the organic EL element, rather than bonding the touch panel member to the organic EL element through an adhesive layer or adhesive layer. For this reason, the organic EL device of the present invention can have a configuration in which the touch panel support substrate used when separately manufacturing the touch panel member is not provided between the organic EL element and the touch panel member, and thus the touch panel member Compared to the case where the touch panel member is placed on the organic EL element by bonding the formed support substrate to the device substrate through an adhesive layer or adhesive layer, it becomes possible to significantly reduce the thickness of the organic EL device, thereby making it possible to significantly reduce the thickness of the organic EL device. It has the excellent advantage of being able to prevent damage and deterioration of function of the EL device when it is bent.

[Method of manufacturing light emitting device]

The manufacturing method of the light-emitting device of the present invention includes (1) forming a coating film of a radiation-sensitive resin composition, (2) irradiating the coating film with first radiation through a mask, and (3) radiation A step of developing the coating film after irradiation, and (4) irradiating a second radiation to the coating film after development to form the patterned cured resin layer (however, step (4) is performed at 100° C. or lower, and , the first radiation and the second radiation may be the same or different). Through steps (1) to (4), the patterned cured resin layer in the above-described light emitting device and organic EL device with a touch panel is formed.

<Process (1)>

Step (1) is a step of forming a coating film of the radiation-sensitive resin composition described above. In step (1), it is preferable to form a coating film of a radiation-sensitive resin composition on a substrate and an element substrate having a light-emitting element on the substrate. The device substrate may have an encapsulation layer on the light emitting device. As described later, a patterned cured resin layer is formed directly on the device substrate using a radiation-sensitive resin composition, but since low-temperature curing is possible in the present invention, deterioration of light-emitting devices such as organic EL devices can be prevented. there is.

As a method of applying the radiation-sensitive resin composition, a known method can be adopted. Examples include spray method, roll coating method, spin coating method, slit die coating method, and bar coating method. Additionally, a lamination method may be used in which a dry film having a radiation-sensitive resin composition layer formed on a base material is used to transfer the composition layer onto the light-emitting element or its encapsulation layer. Among these, the spin coating method and the slit die coating method are preferable because a coating film with a uniform film thickness can be obtained.

When forming a coating film of the composition, prebaking can be performed. Prebaking can be performed by combining reduced pressure drying and heat drying. Reduced pressure drying is usually performed at a temperature of 70 to 110°C for 1 to 20 minutes, and is preferably performed at a temperature of 75 to 100°C for 1 to 15 minutes. In addition, the thickness of the coating film is usually 1.5 to 8 μm, preferably 1.5 to 5 μm, as the film thickness after drying.

<Process (2)>

Step (2) is a step of irradiating the coating film obtained in step (1) with the first radiation, that is, performing pre-exposure. At least part of the coating film may be exposed through a mask having a predetermined pattern, or scanning exposure may be performed.

Examples of the first radiation include visible rays such as g-rays, h-rays, i-rays, and j-rays, and ultraviolet rays. Among these, from the viewpoint of solvent resistance and improvement of adhesion to the object to be formed, radiation containing at least one or all of the g-line, h-line, and i-line is preferable, and the g-line, h-line, i-line, and j-line are preferred. Radiation containing at least one or all of these is more preferable. Additionally, in the spectral distribution, the peak at 436 nm is the g line, the peak at 405 nm is the h line, the peak at 365 nm is the i line, and the peak at 313 nm is the j line. The exposure amount is usually 1 to 1000 mJ/cm2, preferably 5 to 500 mJ/cm2, and more preferably 10 to 100 mJ/cm2.

Examples of light sources include ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, halogen lamps, metal halide lamps, LED lamps, and various visible and ultraviolet lasers.

<Process (3)>

Step (3) is a step of developing the coating film obtained in step (2).

For development, the non-hardened portion (unexposed portion in the case of negative type) after exposure is dissolved and removed using a developing solution. Any developer can be used as long as it dissolves the non-cured part and does not dissolve the cured part. For example, a combination of various organic solvents or an aqueous alkaline solution can be used. Among these, alkaline aqueous solution is preferable. Examples of aqueous alkaline solutions include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-dia. and aqueous solutions of zabicyclo-[4.3.0]-5-nonene and the like. For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, an antifoaming agent, or a surfactant may be added to the developer.

As a developing method, for example, shower developing method, spray developing method, dip developing method, puddle developing method, etc. can be applied. Development conditions can be, for example, 5 to 300 seconds at room temperature.

In addition, when an aqueous alkaline solution is used as a developing solution, the coating film is usually washed with water after development. Additionally, after cleaning, the coating film can be air-dried using, for example, compressed air or compressed nitrogen.

<Process (4)>

Step (4) is a step of irradiating the second radiation to the coating film obtained in step (3),

Preferably,

(4-i) a step of heating the coating film at 100° C. or lower and then irradiating the coating film with second radiation; or

(4-ii) A process of irradiating the coating film with second radiation and then heating it at 100°C or lower.

am.

In step (4), post-baking and post-exposure can be performed in any order.

Post-baking heats the patterned coating film at 100°C or lower, but from the viewpoint of improving curability, solvent resistance, and adhesion to the object to be formed, and protecting the substrate, the temperature is preferably 70 to 100°C, more preferably 80 to 90°C. It is ℃. If the post-baking temperature is within this range, the coating film can be sufficiently cured to form a cured film with excellent solvent resistance, and damage to the light-emitting element can be prevented, and shrinkage and deformation of the substrate are reduced, which is preferable. The heating time can be set appropriately depending on the heating temperature, but is usually 5 to 120 minutes, preferably 10 to 100 minutes, and more preferably 15 to 60 minutes.

The exposure amount of post exposure is preferably 200 mJ/cm 2 or more, and more preferably 500 mJ/cm 2 or more from the viewpoints of improving curability, solvent resistance, and adhesion to the object to be formed, and protecting the substrate. In addition, the exposure amount is preferably 10000 mJ/cm 2 or less, more preferably 8000 mJ/cm 2 or less, and even more preferably 6000 mJ/cm 2 or less from the viewpoint of suppressing light deterioration of the color material. Light sources used for post-exposure include the same light sources as those for pre-exposure. By performing pre-exposure and post-exposure separately, high-definition pixels and contact holes can be formed.

The second radiation may be the same as or different from the first radiation used in pre-exposure, for example, radiation containing at least one or all of the g-line, h-line, and i-line as in the pre-exposure, or Radiation containing at least one or all of g-rays, h-rays, i-rays, and j-rays can be applied.

<Regarding the manufacturing method of the touch panel member>

In detail, the method of manufacturing an organic EL device with a touch panel of the present invention includes forming a touch panel member by forming a patterned cured resin layer of a radiation-sensitive resin composition through the above-described steps (1) to (4). It has a process for forming.

An example of a method for manufacturing a touch panel member is described below.

A coating film of a radiation-sensitive resin composition or a thermosetting resin composition is formed on the organic EL element or its encapsulation layer, and is cured by exposure or heat to form a wiring base layer. Curing by exposure is less likely to cause deterioration of the organic EL element than the effect of heating. It is not necessary to form a wiring base layer.

Next, a metal thin film is formed by sputtering, a resist pattern is formed by photolithography, wiring is formed by etching, and the wiring is exposed by resist peeling to form the first metal wiring layer of the touch panel member.

Next, using the radiation-sensitive resin composition, a patterned cured resin layer having a patterned shape including contact holes is formed on the wiring base layer and the first metal wiring layer according to each of the above steps (1) to (4). form

Next, on the patterned cured resin layer, the second metal wiring layer of the touch panel member and the wiring that connects the first and second metal wiring layers are formed by sputtering, photolithography, etching, and resist, as in the formation of the first metal wiring layer. Formed by exfoliation.

Next, if necessary, a coating film of the radiation-sensitive resin composition or thermosetting resin composition is formed on the patterned cured resin layer and the second metal wiring layer, and is cured by exposure or heat to form an upper protective film.

As described above, a touch panel member including a cured resin layer as a wiring base layer, a first metal wiring layer, a patterned cured resin layer as an inter-wiring insulating layer, a second metal wiring layer, and a cured resin layer as an upper protective layer is an element. An organic EL device disposed on a substrate is obtained.

The thickness of the patterned cured resin layer is usually 1 to 5 μm, preferably 1 to 3 μm, and more preferably 1.3 to 2 μm. The thickness of the wiring base layer and the upper protective layer are each independently usually 0.5 to 10 μm, preferably 0.5 to 5 μm, and more preferably 0.5 to 3 μm. The hardened layer has good solvent resistance and good adhesion to the object to be formed, and can effectively suppress peeling. In addition, even if the composition is coated on each layer, there is no erosion of the lower layer due to solvent, and each layer is resistant to various processes such as resist pattern formation during wiring formation, etching process, and resist peeling process.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In descriptions such as the examples below, unless otherwise specified, “part” refers to “part by mass.”

In addition, in the following examples, the thickness of each layer (film thickness) was measured by cross-sectional observation using a stylus level gauge or an electron microscope.

[Preparation example 1]

50 parts of CCR-1291H (manufactured by Nippon Kayaku Co., Ltd.), 15 parts of dipentaerythritol hexaacrylate, 15 parts of succinic acid-modified pentaerythritol triacrylate, and ethanone, 1-[9-ethyl-6-(2) -methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) 3 parts, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane 2 parts of -1-one, 15 parts of 3-(triethoxysilyl)propyl isocyanate, and an amount of propylene glycol monomethyl ether acetate to have a solid content concentration of 30% by mass were added, stirred, and filtered through a 0.2㎛ membrane filter. Thus, a radiation-sensitive resin composition was prepared.

[Preparation Examples 2 to 13]

The radiation-sensitive resin compositions of Preparation Examples 2 to 13 were prepared in the same manner as Preparation Example 1, except that the raw materials and composition ratios shown in Table 1 were mixed.

The raw materials in Table 1 are as follows.

Alkali-soluble resin A1: CCR-1291H (manufactured by Nippongayaku Co., Ltd.)

Alkali-soluble resin A2: Resin included in formula (1) above:

CCR-1309H (manufactured by Nippongayaku Corporation)

Polymerizable Compound B1: Dipentaerythritol hexaacrylate

Polymerizable compound B2: Succinic acid modified pentaerythritol triacrylate

Radiation sensitive polymerization initiator C1: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime)

Radiation sensitive polymerization initiator C2: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one

Radiation-sensitive polymerization initiator C3: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime)]

Additive D1: 3-methacryloxypropyltrimethoxysilane

Additive D2: 3-(triethoxysilyl)propyl isocyanate

Additive D3: 3-Trimethoxysilylpropylsulfanyltriethoxysilane

《Physical property evaluation》

<Resolution evaluation>

On the silicon substrate, the solution of the radiation-sensitive resin composition prepared above was applied using a spinner, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film. Next, the obtained coating film is irradiated with radiation using a high-pressure mercury lamp through a photomask having a plurality of square-shaped residual patterns of different sizes ranging from 3 to 6 μm in diameter, with the exposure amount varying in the range of 30 to 300 mJ/cm2. was done. After that, development was performed by the puddle method at 23°C using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, with the development time being variable, followed by washing with pure water for 1 minute. Next, post-exposure at 600 mJ/cm2 was performed using a high-pressure mercury lamp, and a patterned cured resin layer was formed by further post-baking at 90°C or 150°C in an oven for 60 minutes. The film thickness at this time was 2 μm. In addition, in the above photomask, if the hole-shaped pattern is formed with no residues in the holes, the resolution can be said to be good, and this case was set as AA. In a photomask of 6 μm or less, a hole-shaped pattern was formed, but a case in which light residue was visible within the hole was designated as BB. In a photomask of 6 μm or less, if a hole-shaped pattern is not formed or if residue is visible in the hole and is not resolved, the resolution can be judged to be poor, and this case was designated as CC.

<Chemical resistance evaluation>

The patterned cured resin layer formed into a film in the above resolution evaluation was immersed in an aqueous solution containing 70% by mass of 2-aminoethanol (70% by mass 2-aminoethanol aqueous solution) at 60°C for 5 minutes. Afterwards, the rate of change in each film thickness when heat treated at 90°C for 1 hour was measured. When the film thickness before immersion is set to 100, the film thickness after immersion is taken as the residual film rate. If the film thickness change is within the range of ±5% or less with respect to 100, AA, the film thickness change exceeds ±5% with respect to 100. If it was within the range of ±20% or less, it was evaluated as BB, and if the film thickness change exceeded ±20% of 100 or peeling occurred in the film, it was evaluated as CC.

<Adhesion evaluation>

Films were formed on glass substrates, SiNx substrates, and Mo substrates in the same manner as the resolution evaluation above, and measurements were made based on JIS K5400-8.5 (JIS D0202).

<Measurement of transmittance>

A film was formed on a glass substrate in the same manner as the resolution evaluation above, and the transmittance at a wavelength of 400 nm was measured using a UV-vis spectrometer V-670 manufactured by Nippon Bunko Co., Ltd.

《Device Evaluation》

<Production of organic EL device substrate>

An array substrate having a glass substrate (“OA-10” manufactured by Nippon Denki Glass Co., Ltd.) on which ITO transparent electrodes are formed in an array shape, and a planarization layer with a film thickness of 3 μm having a contact hole in which only a portion of the ITO transparent electrode is exposed. I prepared for revenge.

An Al film with a film thickness of 100 nm was formed on the planarization layer by DC sputtering using an Al target through a metal mask with a predetermined pattern. An ITO film with a film thickness of 20 nm was formed on the Al film by RF sputtering using an ITO target. In this way, an anode layer consisting of an Al film and an ITO film was formed.

A resist material (“Optimer NN803” manufactured by JSR) is used to form a coating film on the anode layer, and a series of treatments including i-ray (wavelength 365 nm) irradiation, development, running water cleaning, air drying, and heat treatment are performed. A pixel defining layer was formed having a part of the anode layer as an opening area.

The substrate on which the anode and the pixel defining layer are formed is moved to a vacuum deposition chamber, the deposition chamber is evacuated to 1E-4Pa, and then molybdenum oxide (MoOx) having hole injection properties is deposited on the substrate using a deposition mask of a predetermined pattern. ) was deposited into a film using a resistance heating deposition method under conditions of a film formation speed of 0.004 to 0.005 nm/sec to form a hole injection layer with a film thickness of 1 nm.

On the hole injection layer, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD) having hole transport properties was applied using a deposition mask with a predetermined pattern. It was formed into a film using a heated vapor deposition method under the same exhaust conditions as that of the hole injection layer, thereby forming a hole transport layer with a film thickness of 35 nm. The film formation speed was under the condition of 0.2 to 0.3 nm/sec.

On the hole transport layer, using a deposition mask with a predetermined pattern, tris(8-quinolinolato)aluminum, an alkylate complex, as a green light-emitting material is deposited by resistance heating deposition under the same film formation conditions as the hole transport layer. , a light emitting layer with a film thickness of 35 nm was formed. The film formation speed was under the condition of 0.5 nm/sec or less.

On the light-emitting layer, using a deposition mask with a predetermined pattern, lithium fluoride was formed into a film by resistance heating evaporation under the same exhaust conditions as the hole injection layer, to form an electron injection layer with a film thickness of 0.8 nm. The film formation speed was under the condition of 0.004 nm/sec or less.

Subsequently, on the electron injection layer, using a deposition mask with a predetermined pattern, Mg and Ag are simultaneously deposited by resistance heating deposition under the same exhaust conditions as those for the hole injection layer, to form a first cathode layer with a film thickness of 5 nm. formed. The film formation speed was under the condition of 0.5 nm/sec or less.

Subsequently, the substrate is transferred to another film formation chamber (sputter chamber), and a film with a film thickness of 100 nm is formed on the first cathode layer by RF sputtering using a mask with a predetermined pattern and an ITO target. 2 A cathode layer was formed.

As described above, an organic EL device was formed on the substrate, and an organic EL device substrate was obtained.

<Thin film encapsulation of organic EL devices>

On the organic EL device, a thin film encapsulation layer was formed in the following order.

The device substrate is transferred to a film formation chamber (sputter chamber), and an inorganic encapsulation layer (SiNx film) with a film thickness of 100 nm is formed on the cathode layer by RF sputtering using a mask with a predetermined pattern and a SiNx target. ) was formed. Subsequently, the device substrate is transferred into an N ₂ -substituted glove box, and a curable composition containing an epoxy compound, an oxetane compound, and a polymerization initiator is ejected in a predetermined pattern using a piezo-type inkjet printer, and then Ushioden An exposure amount of 1000 mJ/cm 2 was irradiated using a UniJetE110ZHD 395 nm LED lamp manufactured by KISSA, and the formed curable composition was cured to form an organic encapsulation layer with a film thickness of 10 μm. The device substrate is transferred to a film formation chamber (sputter room), and an inorganic encapsulation layer (SiNx) with a film thickness of 100 nm is formed on the organic encapsulation layer by RF sputtering using a mask with a predetermined pattern and a SiNx target. membrane) was formed.

As described above, an organic EL device substrate with a sealing layer was obtained.

<Production of patterned cured resin layer>

On the organic EL device substrate with an encapsulation layer, a patterned cured resin layer was formed in the following procedure.

The radiation-sensitive resin composition obtained in the preparation example was coated on the encapsulation layer of an organic EL element substrate with an encapsulation layer by spin coating, and prebaking was performed at a temperature of 90°C for 2 minutes to form a coating film. Next, the obtained coating film was irradiated with radiation through a photomask using a high-pressure mercury lamp, varying the exposure amount in the range of 30 to 300 mJ/cm2. After that, development was performed by the puddle method at 23°C using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, with the development time being variable, followed by washing with pure water for 1 minute.

Next, post exposure at 600 mJ/cm 2 was performed on the obtained patterning film using a high-pressure mercury lamp. Next, the patterning film was cured by performing post-baking at 90°C for 60 minutes to form a patterned cured resin layer (Examples 1-1 to 1-10, Comparative Examples 1-1 to 1-2). Alternatively, in addition to UV irradiation under the same conditions as described above, the patterning film was cured by post-baking at 150°C for 60 minutes (Comparative Example 1-3) to form a patterned cured resin layer. The thickness of the obtained patterned cured resin layer was 2 μm.

An organic EL device was obtained as described above. Additionally, in Comparative Example 1-3, when post-baking was performed at 150°C for 60 minutes, the organic EL element deteriorated and ceased to function, and an organic EL device having an organic EL element could not be obtained.

<Lighting evaluation of organic EL device>

The obtained organic EL device with a patterned cured resin layer was subjected to lighting evaluation in the following procedure. Through the organic EL lighting jig, the organic EL element was turned on by flowing a current at a density of 20 mA/cm2 between the anode layer and the cathode layer of the organic EL element using a constant current source. Next, the luminance in the front direction of the organic EL element was measured using a luminance meter.

Lighting of the organic EL element and measurement of the front luminance using a luminance meter were performed for each organic EL element with a patterned cured resin layer and a comparative organic EL element without a patterned cured resin layer. With respect to the front luminance of the EL element, if it lights up at a luminance of 95% or more, it is rated as AA; if it lights up at a luminance of less than 95% or more than 80%, it is rated as BB; if it lights up at a luminance of less than 80% or does not light up normally, it is rated BB. The case was evaluated as CC.

<Production of flexible organic EL device substrate>

On a polyethylene naphthalate (PEN) resin substrate with a thickness of 50 μm, an inorganic encapsulation layer (SiNx film) with a film thickness of 100 nm was formed by RF sputtering using a SiNx target. A curable composition containing an epoxy compound, an oxetane compound, and a polymerization initiator was applied onto the SiNx film by spin coating, followed by irradiation at an exposure dose of 1000 mJ/cm2 using a UniJetE110ZHD 395 nm LED lamp manufactured by Ushio Denki Co., Ltd. to form a film. The curable composition was cured to obtain a planarization layer with a film thickness of 10 μm. Additionally, an inorganic encapsulation layer (SiNx film) with a film thickness of 100 nm was formed on the planarization layer by RF sputtering using a SiNx target. In this way, a flexible resin substrate with barrier properties (barrier resin substrate) was obtained.

On the barrier resin substrate, an ITO film with a film thickness of 20 nm was formed by RF sputtering using an ITO target through a metal mask with a predetermined pattern. In this way, an anode layer made of an ITO film was formed.

The subsequent processes were performed similarly to the above <production of organic EL device substrate> to form a pixel defining layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, a first cathode layer, and a second cathode layer. As described above, an organic EL device was formed on the barrier resin substrate, and an organic EL device substrate was obtained.

On the organic EL element, a thin film encapsulation layer was formed in the same manner as above <Thin film encapsulation of organic EL element>. As described above, an organic EL device substrate with a sealing layer was obtained.

<Production of patterned cured resin layer> (Example 2-1)

On the organic EL device substrate with an encapsulation layer, a patterned cured resin layer was formed in the following procedure. The radiation-sensitive resin composition (Preparation Example 1) obtained in Preparation Example was coated on the encapsulation layer of an organic EL device substrate with an encapsulation layer by spin coating, and prebaked at a temperature of 90°C for 2 minutes to form a coating film. did. Next, the obtained coating film was irradiated with radiation through a photomask using a high-pressure mercury lamp, varying the exposure amount in the range of 30 to 300 mJ/cm2. After that, development was performed by the puddle method at 23°C using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, with the development time being variable, followed by washing with pure water for 1 minute. Next, post exposure at 600 mJ/cm 2 was performed on the obtained patterning film using a high-pressure mercury lamp. Next, post-baking was performed at 90°C for 60 minutes to cure the patterning film and form a patterned cured resin layer. The thickness of the obtained patterned cured resin layer was 2 μm. Subsequently, as a surface protective layer, a 50-μm-thick polyethylene naphthalate (PEN) resin substrate with a 20-μm-thick rubber-based adhesive material on the back side was adhered onto the patterned cured resin layer.

As described above, an organic EL device for evaluating flexibility was obtained.

<Adhesion of resin substrate> (Comparative Example 2-1)

Separately from the procedure of <Production of patterned cured resin layer> above, as a structure imitating an adhesive touch panel with a resin substrate, the <pattern of Example 2-1 is applied to the surface on an organic EL device substrate with an encapsulation layer. A patterned cured resin layer formed in the same manner as the procedure of <Production of cured resin layer> was bonded to a polyethylene terephthalate (PET) resin substrate with a thickness of 60 μm and a rubber-based adhesive material with a thickness of 20 μm on the back side. Subsequently, as a surface protective layer, a 50-μm-thick polyethylene naphthalate (PEN) resin substrate with a 20-μm-thick rubber-based adhesive material on the back side was adhered onto the patterned cured resin layer.

As described above, an organic EL device for evaluating flexibility was obtained.

<Evaluation of flexibility of organic EL device>

The obtained organic EL device for evaluation of flexibility was evaluated for flexibility in the following procedure. First, the surface side of the obtained organic EL device for evaluating flexibility is pressed against a metal cylinder with a diameter of 5 mm and bent 180 degrees as if winding. Afterwards, it is returned from the bent state again to the straight state. The above operation was repeated 1000 times to conduct a flexibility test.

Next, through the organic EL lighting jig, the organic EL element is turned on by flowing a current at a density of 20 mA/cm2 between the anode layer and the cathode layer of the organic EL element using a constant current source, and the lighting status is confirmed with the naked eye. did.

The case where the organic EL element lights up normally is taken as AA (positive),

The case where the organic EL element did not light up normally was set as BB (impossible).

As a result of performing the above flexibility evaluation on the organic EL device for flexibility evaluation obtained in Example 2-1 and Comparative Example 2-1, normal lighting of the organic EL device was obtained in Example 2-1 (evaluation: AA), and comparison In Example 2-1, normal lighting of the organic EL element was not obtained due to disconnection of the electrode (evaluation: BB).

10: substrate
20: light emitting element
30: Encapsulation layer
40: cured resin portion
41: Wiring base layer
42: Patterned cured resin layer
43: upper protective layer
60: Adhesive layer or adhesive layer
70: Support substrate for touch panel
1a: first metal wiring layer
2a: second metal wiring layer
3: Contact hole
3': Wiring

Claims (16)

substrate,
A light emitting element on the substrate,
Cured resin portion on the light emitting element
It is a light emitting device having,
The cured resin portion is formed on an encapsulation layer that encapsulates the light emitting element and is in direct contact with the encapsulation layer,
The cured resin portion includes a patterned cured resin layer,
The patterned cured resin layer is a layer formed of a radiation-sensitive resin composition, and is immersed in a 70% by mass 2-aminoethanol aqueous solution at 60°C for 5 minutes, and the film thickness before immersion is set to 100. The thickness is 80 to 120,
The radiation-sensitive resin composition contains a polymer represented by the following formula (1) and a radiation-sensitive polymerization initiator,
The light-emitting device is provided between the cured resin portion and the light-emitting element, using a glass substrate or polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, or polyether. Group of sulfone, polyarylate, allyldiglycolcarbonate resin, polyamide, polyimide, polyamidoimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, polynorbornene and triacetylcellulose resin. It consists of at least one type selected from and does not have a support exceeding 50㎛ in thickness.
A light emitting device characterized by:

[In formula (1), n and m each independently represent an integer of 1 to 30]. According to paragraph 1,
A light-emitting device wherein the light-emitting device is an organic EL device, and the light-emitting device is an organic EL device. delete delete substrate,
A light emitting element on the substrate,
Cured resin portion on the light emitting element
It is a light emitting device having,
The cured resin portion is formed on an encapsulation layer that encapsulates the light emitting element and is in direct contact with the encapsulation layer,
The cured resin portion includes a patterned cured resin layer,
The patterned cured resin layer is a layer formed of a radiation-sensitive resin composition, and is immersed in a 70% by mass 2-aminoethanol aqueous solution at 60°C for 5 minutes, and the film thickness before immersion is set to 100. The thickness is 80 to 120,
The radiation-sensitive resin composition contains a polymer represented by the following formula (1) and a radiation-sensitive polymerization initiator,
The encapsulation layer is an organic encapsulation layer, an inorganic encapsulation layer, or an organic-inorganic encapsulation layer,
The organic encapsulation layer is formed of a curable composition containing a polymerizable compound having two or more polymerizable groups and a polymerization initiator,
The inorganic encapsulation layer is a silicon nitride layer or a silicon oxynitride layer,
The organic-inorganic encapsulation layer alternately includes the organic encapsulation layer and the inorganic encapsulation layer,
The light-emitting device is provided between the cured resin portion and the light-emitting element, using a glass substrate or polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, or polyether. Group of sulfone, polyarylate, allyldiglycolcarbonate resin, polyamide, polyimide, polyamidoimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, polynorbornene and triacetylcellulose resin. It consists of at least one type selected from and does not have a support exceeding 50㎛ in thickness.
A light emitting device characterized by:

[In formula (1), n and m each independently represent an integer of 1 to 30]. According to claim 1 or 2,
A light-emitting device in which the cured resin portion is not bonded to the substrate and an element substrate having the light-emitting element through an adhesive layer or adhesive layer. According to claim 1 or 2,
A light emitting device wherein the cured resin portion further includes a cured layer as a wiring base layer on the light emitting element side of the patterned cured resin layer. substrate,
An organic EL device on the substrate,
A touch panel member on the organic EL element
It is an organic EL device with a touch panel having,
The touch panel member is formed on an encapsulation layer that encapsulates the organic EL element and is in direct contact with the encapsulation layer,
When the touch panel member includes a patterned cured resin layer, and the patterned cured resin layer is a layer formed of a radiation-sensitive resin composition, and is immersed in a 70% by mass 2-aminoethanol aqueous solution at 60°C for 5 minutes. The film thickness after immersion is 80 to 120 when the film thickness before immersion is 100, and the radiation-sensitive resin composition contains a polymer represented by the following formula (1) and a radiation-sensitive polymerization initiator,
An organic EL device with a touch panel, wherein a support substrate for a touch panel is not disposed on the surface of the touch panel member on the organic EL element side:

[In formula (1), n and m each independently represent an integer of 1 to 30]. According to clause 8,
The touch panel member is formed between (1) a first metal wiring layer, (2) a second metal wiring layer, and (3) the first and second metal wiring layers, and includes the first and second metal wiring layers. a patterned cured resin layer that partially insulates and has a contact hole formed with a wiring that conducts the first and second metal wiring layers, and (4) a cured resin layer that covers the second metal wiring layer. Panel-mounted organic EL device. delete substrate,
An organic EL device on the substrate,
A touch panel member on the organic EL element
It is an organic EL device with a touch panel having,
The touch panel member is formed on an encapsulation layer that encapsulates the organic EL element and is in direct contact with the encapsulation layer,
The encapsulation layer is an organic encapsulation layer, an inorganic encapsulation layer, or an organic-inorganic encapsulation layer,
The organic encapsulation layer is formed of a curable composition containing a polymerizable compound having two or more polymerizable groups and a polymerization initiator,
The inorganic encapsulation layer is a silicon nitride layer or a silicon oxynitride layer,
The organic-inorganic encapsulation layer alternately includes the organic encapsulation layer and the inorganic encapsulation layer,
When the touch panel member includes a patterned cured resin layer, and the patterned cured resin layer is a layer formed of a radiation-sensitive resin composition, and is immersed in a 70% by mass 2-aminoethanol aqueous solution at 60°C for 5 minutes. The film thickness after immersion is 80 to 120 when the film thickness before immersion is 100, and the radiation-sensitive resin composition contains a polymer represented by the following formula (1) and a radiation-sensitive polymerization initiator,
An organic EL device with a touch panel, wherein a support substrate for a touch panel is not disposed on the surface of the touch panel member on the organic EL element side:

[In formula (1), n and m each independently represent an integer of 1 to 30]. A light emitting device having a substrate, a light emitting element on the substrate, and a cured resin portion on the light emitting element, wherein the cured resin portion is formed on an encapsulation layer that encapsulates the light emitting element, and is in direct contact with the encapsulation layer. A method of manufacturing a light emitting device wherein the cured resin portion includes a patterned cured resin layer,
(1) forming a coating film of a radiation-sensitive resin composition, (2) irradiating the coating film with first radiation through a mask, (3) developing the coating film after irradiation with radiation, (4) A step of forming the patterned cured resin layer by irradiating a second radiation to the developed coating film (however, step (4) is performed at 100° C. or lower, and the first radiation and the second radiation may be the same. (may be different)
With
A method for producing a light-emitting device, wherein the radiation-sensitive resin composition contains a polymer represented by the following formula (1) and a radiation-sensitive polymerization initiator:

[In formula (1), n and m each independently represent an integer of 1 to 30]. According to clause 12,
The above process (4) is,
(4-i) a step of heating the coating film at 100° C. or lower and then irradiating the coating film with second radiation; or
(4-ii) A process of irradiating the coating film with second radiation and then heating it at 100°C or lower.
Phosphorus, method of manufacturing a light-emitting device. According to clause 12,
The light emitting device is an organic EL device with a touch panel having a substrate, an organic EL element on the substrate, and a touch panel member on the organic EL element, and the touch panel member is a seal that seals the organic EL element. It is formed on a layer and is in direct contact with the sealing layer, the touch panel member includes a patterned cured resin layer, and the organic EL device is between the organic EL element and the touch panel member, a touch panel A method of manufacturing a light-emitting device, which is an organic EL device with a touch panel without a support substrate. A method of manufacturing a light emitting device comprising a substrate, a light emitting element on the substrate, and a cured resin portion on the light emitting element, wherein the cured resin portion includes a patterned cured resin layer,
(1) forming a coating film of a radiation-sensitive resin composition, (2) irradiating the coating film with first radiation through a mask, (3) developing the coating film after irradiation with radiation, (4) A step of forming the patterned cured resin layer by irradiating a second radiation to the developed coating film (however, step (4) is performed at 100° C. or lower, and the first radiation and the second radiation may be the same. (may be different)
With
A method for producing a light-emitting device in which the radiation-sensitive resin composition contains a polymer represented by the following formula (1) and a radiation-sensitive polymerization initiator:

[In formula (1), n and m each independently represent an integer of 1 to 30]. According to any one of claims 12 to 14,
The encapsulation layer is an organic encapsulation layer, an inorganic encapsulation layer, or an organic-inorganic encapsulation layer,
The organic encapsulation layer is formed of a curable composition containing a polymerizable compound having two or more polymerizable groups and a polymerization initiator,
The inorganic encapsulation layer is a silicon nitride layer or a silicon oxynitride layer,
A method of manufacturing a light-emitting device, wherein the organic-inorganic encapsulation layer alternately includes the organic encapsulation layer and the inorganic encapsulation layer.