WO2019009360A1 - Light emission device, organic electroluminescence device and method for manufacturing light emission device and organic electroluminescence device - Google Patents

Abstract

[Problem] To provide a light emission device, such as an organic electroluminescence device, in which the need for a touch panel support substrate on the light emission device is obviated, and the overall thickness of the light emission device is reduced, whereby flexibility is improved; and to further provide a light emission device having a patterned cured resin layer having a high chemical resistance. [Solution] A light emission device having a substrate, a light-emitting element provided on the substrate, and a cured resin part provided on the light-emitting element, the light emission device being characterized in that: the cured resin part has a patterned cured resin layer; the film thickness of the patterned cured resin layer when the patterned cured resin layer has been immersed in a 70 mass% 2-aminoethanol aqueous solution for 5 minutes at 60°C is 80-120, where 100 represents the film thickness before the immersion; and the light emission device does not have a support body comprising polyethylene terephthalate, etc., or a glass substrate between the cured resin part and the light-emitting element.

Description

Light emitting device, organic EL device, and manufacturing method thereof

The present invention relates to a light emitting device and an organic EL device, and a method of manufacturing them.

An organic electroluminescent (EL) element having a laminated structure including an anode, an organic light emitting layer, and a cathode is known as one of light emitting elements which have been developed in recent years. The organic EL device has the organic EL element. Here, an organic EL device with a touch panel having a touch panel member on the entire surface of the device is known (see, for example, Patent Document 1).

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

JP, 2015-161806, A

In the case where the support substrate for a touch panel is attached to the substrate on which the organic EL element is formed through the adhesive layer or the adhesive layer, the thickness of the whole organic EL device is increased and the organic EL device is bent. Damage or loss of function may occur.

Instead of bonding the support substrate for a touch panel to the substrate on which the organic EL element is formed via the adhesive layer or adhesive layer, the touch panel is manufactured directly on the organic EL element by a method such as lithography and etching. The thickness of the entire light emitting device such as the organic EL device can be reduced. However, in the conventional method, baking at a temperature of over 100 ° C. is required to form the patterning resin insulating film in the touch panel, and when the patterned cured resin layer is formed directly on the organic EL element, the EL light emitting layer There was a bad effect that it caused the deterioration of the Further, when the patterned cured resin layer is formed of a conventional material at a low temperature of 100 ° C. or less, the patterned cured resin layer can not withstand the etching chemical solution for wiring formation, making it impossible to produce a touch panel structure .

The present invention eliminates the need for a touch panel support substrate on a light emitting device such as an organic EL device, and reduces the thickness of the entire light emitting device to provide a light emitting device with more flexibility, and a pattern having high chemical resistance. It is an object of the present invention to provide a light emitting device having a chemical curing resin layer.

The present inventors diligently studied to solve the above problems. As a result, by directly forming a patterned cured resin layer having high chemical resistance at a temperature of 100 ° C. or less on the light emitting element, the touch panel supporting substrate is unnecessary, and the thickness of the entire light emitting device such as an organic EL device is small. It has been found that it is possible to obtain a light-emitting device with good flexibility, and thus complete the present invention. The present invention relates to, for example, the following [1] to [13].

[1] A light emitting device comprising a substrate, a light emitting element on the substrate, and a cured resin portion on the light emitting element, the cured resin portion including a patterned cured resin layer, the patterned cured resin layer The film thickness after immersion is 80 to 120 when the film thickness before immersion is 100 when immersed in a 70% by mass aqueous solution of 2-aminoethanol at 60 ° C. for 5 minutes, and the light emitting device Between the cured resin portion and the light emitting element, a glass substrate, or polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate Resin, polyamide, polyimide, polyamide imide, polyether imide, poly Nzuazoru, polyphenylene sulfide, polycycloolefin, consists of at least one selected from the group consisting of polynorbornene and triacetyl cellulose resin, a light-emitting device, characterized in that no support in excess of thickness 50 [mu] m.

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

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

[4] The cured resin portion is formed on a sealing layer sealing the light emitting element, and the light emitting device is the glass substrate between the cured resin portion and the sealing layer Alternatively, the light emitting device according to any one of the above [1] to [3] which does not have a support.

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

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

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

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

[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, (4) A patterned cured resin layer having a contact hole in which a wiring which partially insulates the first and second metal wiring layers and which conducts the first and second metal wiring layers is formed; The organic EL device with a touch panel according to the above [8], having a cured resin layer covering the second metal wiring layer.

[10] 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. (1) forming a coating of the radiation sensitive resin composition, (2) irradiating the coating with the first radiation through the mask, and (3) after the radiation irradiation. The step of developing the coating film, and (4) the step of irradiating the coating film after development with a second radiation to form the patterned cured resin layer (however, the step (4) is 100 ° C. or less) And the first radiation and the second radiation may be the same or different).

[11] A step of irradiating a second radiation after the step (4) heats the coating film at a temperature of 100 ° C. or less (4-i); or (4-ii) a second radiation on the film The method of manufacturing the light-emitting device according to the above [10], which is a step of heating at 100 ° C. or less after irradiation with

[12] The light emitting device is an organic EL device with a touch panel including 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 [10] or [11], wherein the organic EL device is an organic EL device with a touch panel that does not have a touch panel supporting substrate between the organic EL element and the touch panel member. Manufacturing method.

[13] The light emission according to any one of the above [10] to [12], wherein the radiation sensitive resin composition contains a polymer represented by the following formula (1) and a radiation sensitive polymerization initiator Device manufacturing method.

［式（１）中、ｎおよびｍは、それぞれ独立に１～３０の整数を示す。］

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

According to the present invention, the thickness of the entire light emitting device such as an organic EL device can be reduced by directly forming a patterned cured resin layer having high chemical resistance at a temperature of 100 ° C. or less on the light emitting element. Thus, when the light emitting device is bent, a light emitting device capable of preventing damage or deterioration of the device is provided.

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

Hereinafter, modes for carrying out the present invention will be described in detail including preferred modes. Each component exemplified in the present specification may be used alone or in combination of two or more unless otherwise stated. In addition, compounds and the like described in each patent publication cited in the present specification shall be described in the present specification.

[Light Emitting Device]
The light emitting device of the present invention includes 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, in the light emitting device of the present invention, a glass substrate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, or the like is provided between the cured resin portion and the light emitting element. Polyarylate, allyldiglycol carbonate resin, polyamide, polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, polycycloolefin, polynorbornene and triacetylcellulose resin There is no support over 50 μm. Hereinafter, the support body which consists of these glass substrates and the said resin is named generically, and it is also called a "support substrate." In addition, a substrate on which a light emitting element is formed is also referred to as an “element substrate”.

In such an embodiment, the support substrate on which the cured resin portion is formed is bonded to the element substrate via the adhesive layer or the adhesive layer, and this is compared to the light emitting device in which the cured resin portion is disposed on the light emitting element. It is possible to significantly reduce the thickness of the light emitting device.

In the present specification, in the expressions “BB on AA”, “BB arranged on AA”, and “form BB on AA”, AA and BB may be in contact, and AA and BB are in contact with each other. For example, another layer may be present between AA and BB.

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

<Board>
Examples of the substrate include a glass substrate and a resin substrate, and in one embodiment, a transparent substrate having a high transmittance to visible light. A resin substrate is preferable from the viewpoint of flexibility. As a constituent material of the substrate, for example, alkali-free glass, borosilicate glass, aluminoborosilicate glass, quartz glass, synthetic quartz glass, soda lime glass, glass such as white sapphire; polyester (eg, polyethylene terephthalate, polyethylene naphthalate), Resins such as polyolefin, polystyrene, polyimide, polyamide, polyamide imide, polyether imide, polyarylate, polyether sulfone, polysulfone, polyether ether ketone, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyurethane etc. Be In addition, as a substrate, a silicon substrate, a silicon nitride substrate, a molybdenum substrate may be mentioned.

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

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

<Light emitting element>
The light emitting element is usually formed on a substrate.

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

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 electrodes facing each other, that is, the organic light emitting layers are mutually omitted. It may have a structure in which it is held between the facing anode and the cathode, and, for example, a known structure having an anode / organic light emitting layer / cathode can be adopted.

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

The organic light emitting layer contains a light emitting material which 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 the device is driven, or a layer that emits white light when the device is driven. The white light is emitted from the organic EL device as color light which is selected to be transmitted by the corresponding color filter.

The organic light emitting material contained in the organic light emitting layer may be a low molecular weight organic light emitting material or a high molecular weight organic light emitting material. For example, a base material such as tris (8-quinolinolato) aluminum (Alq ₃ ), bis (10-hydroxybenzo [h] quinolinate) beryllium (BeBq ₂ ) or the like can be used as a base material doped with quinacridone or coumarin. As high molecular weight organic light emitting materials, for example, polyphenylene vinylene and its derivatives, polyacetylene and its derivatives, polyphenylene and its derivatives, polyparaphenylene ethylene and its derivatives, poly 3-hexylthiophene and its derivatives, polyfluorene and its derivatives, etc. It can be selected and used.

The anode and the cathode of the organic EL element are each made of a conductive material. Examples of the material of the anode include oxides such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO) and tin oxide; aluminum (Al), APC (silver, palladium, alloy of copper), ARA (silver, rubidium) Metals such as gold alloy), MoCr (alloy of molybdenum and chromium), NiCr (alloy of nickel and chromium), etc., and even laminated films of these metals and highly transparent electrodes (eg, ITO) Good. Examples of the material of the cathode include oxides such as ITO, IZO and tin oxide; magnesium (Mg), calcium (Ca), aluminum (Al), silver (Ag), and an alloy containing one or more of these. And metals, and may be a laminated film of these metals and a highly transparent electrode (eg, ITO).

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

The anode may be separated for each pixel, or a partition (pixel defining layer) covering the end of the anode may be formed. The partition covers the end of the anode separated for each pixel to define a light emitting area. The pixels can be arranged, for example, to correspond to the color filters.

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

<Sealing layer>
The light emitting device preferably has a sealing layer for sealing the light emitting element. By sealing the light emitting element, entry of moisture into the element can be reduced. Therefore, the light emitting device can suppress the generation of dark spots and the decrease in light emission characteristics such as luminance and light emission efficiency, which are caused by water.

The sealing layer is preferably a thin film sealing layer. The thickness of the thin film sealing layer is usually 50 μm or less, preferably 1 to 50 μm, 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, it may be an organic-inorganic sealing layer having an organic sealing layer between two inorganic sealing layers, and an organic-inorganic sealing having an inorganic sealing layer and an organic sealing layer alternately in total of four or more layers. It may be a barrier layer. The total number of layers in the organic / inorganic sealing layer is, for example, three or more layers, preferably 3 to 9 layers. Here, the outermost layer of the sealing layer is preferably an inorganic sealing layer.

As the inorganic sealing layer, for example, layers described in JP-A-2010-160906, JP-A-2016-012433, JP-A-2016-143605, etc., specifically, a silicon nitride layer or a silicon oxynitride layer As the method of forming them, the methods described in the above-mentioned publication, specifically the sputtering method and the chemical vapor deposition method can be mentioned. The thickness of the inorganic sealing layer is usually 10 nm to 2 μm.

As an organic sealing layer, the layer formed from the curable composition is mentioned, for example. The thickness of one layer of the organic sealing layer is usually 1 to 50 μm, preferably 1 to 20 μm, 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 an ethylenically unsaturated group, an oxiranyl group (epoxy group), an oxetanyl group, and an N-alkoxymethylamino group. The polymerizable compound is preferably a cyclic ether compound such as an epoxy compound and an oxetane compound, a compound having two or more (meth) acryloyl groups, or a compound having two or more N-alkoxymethylamino groups.

As a polymerization initiator, a cation or radical polymerization initiator is mentioned, for example. 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, with respect to 100 parts by mass of the polymerizable compound.

The curable composition may be applied to the entire surface of the object or may be applied to part of the object. A publicly known method can be adopted as a method of applying the curable composition. For example, a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an inkjet method can be mentioned.

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

Also, in order to accelerate the curing of the radiation curable curable composition, heating may be performed simultaneously with or after the radiation irradiation. In addition, the thermosetting curable composition is cured by heating. For example, the heating temperature is 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 atmosphere from which oxygen and moisture have been removed, for example, in an inert gas atmosphere such as N ₂ atmosphere or in vacuum.

<Cured resin part>
The cured resin portion includes a patterned cured resin layer. The patterned cured resin layer is a cured resin layer having a pattern, and is preferably a layer formed of a radiation sensitive resin composition. Specifically, a photolithographic method using a radiation sensitive resin composition It is preferable that it is a layer directly formed by

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

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 known ones can be used. In addition, 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 can also be used, and this radiation sensitive resin composition The composition can further contain a polymerizable compound other than the alkali-soluble resin having an ethylenically unsaturated group. From the viewpoint of low temperature curing, the composition described in <radiation sensitive resin composition> described later is preferable. The composition can be used as a liquid composition by blending a solvent.

The cured resin portion usually has two or more metal wiring layers. These metal wiring layers are mutually insulated by the patterned cured resin layer, and the necessary portions are electrically connected by the wirings formed in the 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, 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, more preferably 200 to 400 nm.

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

The film thickness change 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 a film after immersion when the film thickness before immersion is 100. The thickness is preferably 80 to 120, and more preferably 95 to 105. Details of the measurement conditions of the film thickness change are described in the examples. In addition, a film thickness change is measured in the non-pattern formation part in a patterning cured resin layer.

Such a patterned cured resin layer having high chemical resistance is, for example, a radiation used in post exposure to increase the crosslink density by using a polymerizable compound having a large number of polymerizable groups or an alkali-soluble resin having an ethylenically unsaturated group. Radiation-sensitive polymerization initiators that are highly absorbable to radiation and excellent in polymerization initiation efficiency (for example, radiation-sensitive polymerization initiators that are highly absorbable to radiation including g-line, h-line, i-line and j-line) and are excellent in polymerization initiation efficiency It can be obtained by using the combination).

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 an upper layer on the opposite side of the patterned cured resin layer to the light emitting element. It may further include a cured layer as a protective layer. The hardened layer may be an unpatterned layer and serves as a wiring underlayer or upper protective layer of a metal wiring layer. The cured layer is, for example, an inorganic film, and may be a layer formed by a sputtering method or a chemical vapor deposition method, but a cured resin layer formed from a radiation sensitive resin composition or a thermosetting resin composition. It is more preferable that it is a cured resin layer formed from a radiation sensitive resin composition.

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

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

The average roughness Ra of the surface of the cured layer as the wiring underlayer 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 by 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 1a. The first metal wiring layer 1a is electrically formed by the patterned cured resin layer 42 to be covered and the wires 3 'formed on the patterned cured resin layer 42 and formed in the contact holes 3 of the patterned cured resin layer 42. And an upper protection layer 43 formed on the pattern cured resin layer 42 and the second metal wiring layer 2a and covering the second metal wiring layer 2a. The wiring base layer 41 may not be present. In FIG. 1, the cured resin portion 40 is formed in direct contact with the sealing layer 30 in the element substrate including the substrate 10, the light emitting element 20, and the sealing layer 30.

Since the first and second metal wiring layers are electrically connected to each other by the wirings formed in the contact holes of the patterned cured resin layer, for example, the sensitivity of the touch panel is increased, and the driving is performed with low power consumption. It can be done.

The cured resin portion is preferably a touch panel member.

The cured resin portion is formed on the light emitting element or the sealing layer (if formed). In the light emitting device of the present invention, the supporting substrate described above is not disposed between the cured resin portion and the light emitting element or the sealing layer (if formed) of the light emitting element.

If the supporting substrate described above does not exist between the cured resin portion and the light emitting element, the cured resin portion may be bonded to the element substrate via the adhesive layer or the adhesive layer, but the cured resin portion may be cured. It is preferable that the resin portion is not attached to the element substrate via the adhesive layer or the adhesive layer. The light emitting element is preferably sealed by a sealing layer.

“The cured resin portion is not attached to the element substrate via the adhesive layer or adhesive layer” means that the light emitting device of the present invention is (1) on the support substrate 70 as shown in FIG. (2) form an adhesive layer or an adhesive layer 60 on the surface of the support substrate 70 opposite to the cured resin portion 40, or on an element substrate comprising the substrate 10 and the light emitting element 20. It means that the adhesive layer or the adhesive layer 60 is not formed, and subsequently (3) it is not obtained by bonding the supporting substrate 70 to the element substrate via the adhesive layer or the adhesive layer 60. In FIG. 2, the element substrate further includes a sealing layer 30.

That is, the cured resin portion is preferably formed in direct contact with the light emitting element or the sealing layer (if formed). In such an embodiment, the light emitting device is compared to the case where the supporting substrate on which the cured resin portion is formed is bonded to the element substrate via the adhesive layer or the adhesive layer and the cured resin portion is disposed on the light emitting element. The thickness of the light emitting device can be significantly reduced, which has the excellent advantage that the device can be prevented from being damaged or degraded when the light emitting device is bent.

Hereinafter, the radiation sensitive resin composition will be described.

Radiation-sensitive resin composition
<Alkali-soluble resin>
The alkali-soluble resin is preferably a resin having an acidic functional group such as a carboxy group or a phenolic hydroxyl group, and more preferably a carboxy group-containing polymer. Examples of the alkali-soluble resin include acid-modified epoxy (meth) acrylate resin, novolak resin, polyamic acid which is a polyimide precursor and a partial imidate thereof, polyhydroxyamide which is a polybenzoxazole precursor, and phenol-xylylene glycol condensation. Resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, homopolymer or copolymer of monomers having a phenolic hydroxyl group such as hydroxystyrene and isopropenyl phenol, ethylene having one or more carboxy groups Copolymers of a polyunsaturated monomer and another copolymerizable ethylenically unsaturated monomer can be mentioned.

The alkali soluble resin can have an ethylenically unsaturated group. As the alkali-soluble resin, an acid-modified epoxy (meth) acrylate resin which is a resin having a carboxy group and an ethylenically unsaturated group is preferable, from the viewpoint of achieving both alkali solubility and cured film physical properties at a high level. Acid-modified cresol novolac epoxy (meth) acrylate resin, phenol novolac epoxy (meth) acrylate resin, bisphenol A epoxy (meth) acrylate resin, bisphenol F epoxy (meth) acrylate resin, biphenyl epoxy (meta) Acrylate resin and trisphenolmethane type epoxy (meth) acrylate resin can be mentioned.

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

The acid-modified cresol novolac epoxy (meth) acrylate resin has a rigid main chain skeleton of cresol novolac epoxy resin, an ethylenically unsaturated group, and a carboxy group, so that curing and baking at low temperatures is possible. Regardless, it becomes possible to form a cured film excellent in solvent resistance and heat resistance.

　式（１）中、ｎおよびｍは、それぞれ独立に１～３０の整数を示す。

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

As a specific example of the acid-modified cresol novolac epoxy (meth) acrylate resin, CCR-1171H, CCR-1291H, CCR-1307H, 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 mg KOH / g, preferably 30 to 270 mg KOH / g, and more preferably 50 to 250 mg KOH / g. The acid value represents the number of mg of KOH necessary to neutralize 1 g of solid content of the alkali-soluble resin.

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

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

By adopting such an embodiment, in addition to the further improvement of the luminance, the alkali developability, the storage stability of the composition, the pattern shape, and the chromaticity characteristics can be enhanced. In addition, solid content is all components other than a solvent.

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

As a compound having two or more (meth) acryloyl groups, for example, a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid [polyfunctional (meth) acrylate], caprolactone-modified polyfunctional (meth) Acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, reaction product of hydroxyl group-containing (meth) acrylate and polyfunctional isocyanate [polyfunctional urethane (meth) acrylate], hydroxyl group-containing (meth) acrylate and acid anhydride And a reaction product thereof (polyfunctional (meth) acrylate having a carboxy group). Specific examples of the aliphatic polyhydroxy compound, (meth) acrylate having a hydroxyl group, polyfunctional isocyanate and acid anhydride include compounds described in paragraph [0065] of JP-A-2015-232694, and caprolactone modified Examples of the polyfunctional (meth) acrylate and the alkylene oxide-modified polyfunctional (meth) acrylate which may be mentioned include the compounds described in paragraph [0066] of the same publication.

Specific examples thereof include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid-modified pentaerythritol tri (meth) ) Acrylates.

Examples of the compound 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 the paragraph [Japanese Patent Laid-Open No. 2015-232694]. And the like.

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, per 100 parts by mass of the alkali-soluble resin. Preferably, it is 45 to 100 parts by mass. With such an embodiment, the curability and the developability can be further enhanced, and the luminance can be further enhanced.

Radiation-sensitive polymerization initiator
The radiation sensitive polymerization initiator may be an alkali soluble resin having an ethylenically unsaturated group and curing of a polymerizable compound by exposure to radiation such as visible light, ultraviolet light, electron beam, X-ray, preferably visible light and / or ultraviolet light. It is a compound that generates an active species capable of initiating a reaction. Examples of the radiation sensitive polymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α- Examples include diketone compounds, polynuclear quinone compounds, diazo compounds, and imidosulfonate compounds. Specific examples thereof include compounds described in paragraphs [0073] to [0078] of JP-A-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 10 parts by mass with respect to 100 parts by mass of the polymerizable compound. 100 parts by mass. In one embodiment, the content of the radiation sensitive polymerization initiator is at least 11 parts by mass or at least 13 parts by mass with respect to 100 parts by mass of the polymerizable compound. With such an embodiment, the curability and the film properties can be further enhanced, and the luminance can be further enhanced.

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 100 parts by mass with respect to the alkali-soluble resin having an ethylenically unsaturated group. 5 to 15 parts by mass.

<Additive>
The radiation sensitive resin composition can also contain various additives, if necessary. Additives include, for example, sensitizers, dispersants, fillers, polymer compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, residue improvers, and developability improvers. It can be mentioned.

In particular, as the adhesion promoter, the coupling agent described in WO 2017/094831 can be used. As the ultraviolet absorber, the ultraviolet absorber described in JP-A-2004-190006 can be used. As the antioxidant, the antioxidant described in WO 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 an alkali soluble resin, a polymerizable compound, and a radiation sensitive polymerization initiator together with a solvent and optionally added additives.

As the solvent, 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, and specific examples thereof are described in paragraph [0082] of JP-A-2015-232694 Solvents described in [0085] can be mentioned.

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

In one embodiment, the cured resin layer formed of the radiation sensitive resin composition is visually clear. With such an embodiment, a light emitting device having good optical characteristics can be obtained.

<Touch panel member>
The organic electroluminescent apparatus which is an example of the light-emitting device of this invention has a touch-panel member as a hardening resin part 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 device, the touch panel supporting substrate is not disposed on the surface on the organic EL element side of the touch panel member. The organic EL device preferably has a sealing layer for sealing the organic EL element.

The touch panel member is formed, for example, between (1) the first metal wiring layer, (2) the second metal wiring layer, and (3) the first and second metal wiring layers. And a patterned cured resin layer having a contact hole in which a wire for partially insulating the second metal wiring layer and for conducting the first and second metal wiring layers is formed; And a cured resin layer (upper protective layer) covering the two metal wiring layers. The touch panel member may further include (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 the wirings formed in the contact holes of the patterned cured resin layer, the sensitivity of the touch panel is increased, and the consumption is reduced. It can be driven by electric power.

The support substrate for a touch panel is, for example, a glass substrate, or polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate resin, polyamide, polyimide And a support having a thickness of more than 50 μm comprising at least one member selected from the group consisting of polyamideimides, polyetherimides, polybenzazoles, polyphenylene sulfides, polycycloolefins, polynorbornenes and triacetylcellulose resins.

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

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

The touch panel member has, in the metal wiring layer, for example, a capacitive pad which is formed of a patterned metal film and detects an approach of a finger / touch panel pen or the like by an electrical capacitance change. A plurality of capacitive pads in a group are connected by wiring in a plane X-axis direction (lateral direction), and a plurality of other capacitive pads in a group are connected by wiring in a planar Y-axis direction (longitudinal direction) It is drawn out and connected to a touch panel drive or touch detection circuit. The arrangement configuration of the capacitor pads is not limited to these, and a conventionally known configuration can be adopted. The wiring drawn out of the panel is further connected to the touch panel drive circuit / detection circuit by the wiring of the peripheral part.

In the present invention, after the touch panel member is separately manufactured, the touch panel member can be formed directly on the organic EL element, instead of bonding the touch panel member on the organic EL element via the adhesive layer or the adhesive layer. For this reason, the organic EL device of the present invention can have a configuration in which the touch panel supporting substrate used when separately manufacturing the touch panel member is not provided between the organic EL element and the touch panel member. To significantly reduce the thickness of the organic EL device as compared with the case where the touch panel member is disposed on the organic EL element by bonding the support substrate on which the device is formed to the element substrate through the adhesive layer or the adhesive layer. It has the excellent advantage of being able to prevent breakage and deterioration of the organic EL device when it is bent.

[Method of manufacturing light emitting device]
The method for producing a light emitting device of the present invention comprises the steps of (1) forming a coating of a radiation sensitive resin composition, and (2) irradiating the coating with a first radiation through a mask. (3) developing the coating after radiation irradiation, and (4) irradiating the coating after development with a second radiation to form the patterned cured resin layer (however, Step (4) is performed at 100 ° C. or less, and the first radiation and the second radiation may be the same or different. By the steps (1) to (4), the patterned cured resin layer in the light emitting device and the organic EL device with a touch panel described above is formed.

<Step (1)>
A process (1) is a process of forming the coating film of the radiation sensitive resin composition mentioned above. In the 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 element substrate may have a sealing layer on the light emitting element. As described later, a radiation curable resin composition is directly formed on the element substrate to form a patterned cured resin layer, but in the present invention, since low temperature curing is possible, deterioration of light emitting elements such as organic EL elements is It can be prevented.

A well-known method is employable as an application method of a radiation sensitive resin composition. For example, a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method may be mentioned. Moreover, you may use the lamination method which transcribe | transfers a composition layer on a light emitting element or its sealing layer using the dry film by which the radiation sensitive resin composition layer was formed on the base material. Among these, a spin coating method and a slit die coating method are preferable from the viewpoint that a coating film having a uniform film thickness can be obtained.

At the time of film formation of the composition, prebaking can be performed. Pre-baking can be performed by combining drying under reduced pressure and drying under heating. Drying under reduced pressure is usually at a temperature of 70 to 110 ° C. for about 1 to 20 minutes, preferably at a temperature of 75 to 100 ° C. for 1 to 15 minutes. 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.

<Step (2)>
The step (2) is a step of irradiating the coating obtained in the step (1) with the first radiation, ie, pre-exposure. At least a 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 light and ultraviolet light such as g-rays, h-rays, i-rays, and j-rays. Among them, radiation containing at least one or all of g-line, h-line and i-line is preferable from the viewpoint of improvement of solvent resistance and adhesion to the object to be formed, g-line, h-line, i-line and j-line More preferred is radiation comprising at least one or all of the lines. 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 dose is usually 1 to 1000 mJ / cm ² , preferably 5 to 500 mJ / cm ² , and more preferably 10 to 100 mJ / cm ² .

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.

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

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

As a development method, for example, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions can be, for example, 5 to 300 seconds at normal temperature.

When an alkaline aqueous solution is used as a developer, the coating is usually washed with water after development. In addition, after washing, for example, the coating film can be air-dried with compressed air, compressed nitrogen or the like.

<Step (4)>
The step (4) is a step of irradiating the coating obtained in the step (3) with a second radiation,
Preferably,
(4-i) a step of irradiating the second coating after heating the coating at 100 ° C. or lower; or (4-ii) heating the coating at a second temperature after heating the second coating. Process.

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

Post-baking heats the patterned coating film at 100 ° C. or less, preferably from 70 to 100 ° C., more preferably from the viewpoint of improving the curability, solvent resistance and adhesion to the object to be formed, and protecting the substrate. Is 80-90.degree. If the post-baking temperature is in this range, the coating film can be sufficiently cured to form a cured film having excellent solvent resistance, and damage to the light emitting element can be prevented, and shrinkage and deformation of the substrate can be reduced. preferable. The heating time can be appropriately set 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 amount of exposure for post exposure is preferably 200 mJ / cm ² or more, more preferably 500 mJ / cm ² or more, from the viewpoints of curability, improvement of solvent resistance, adhesion to a formation target, and substrate protection. The exposure amount is from the viewpoint of light suppressing deterioration of the colorant is preferably 10000 mJ / cm ² or less, more preferably 8000 mJ / cm ² or less, more preferably 6000 mJ / cm ² or less. As a light source used for post exposure, the thing similar to pre-exposure is mentioned. 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, and includes, for example, at least one or all of g-ray, h-ray and i-ray as in pre-exposure Radiation, or radiation including at least one or all of g-ray, h-ray, i-ray and j-ray can be applied.

<Regarding Method of Manufacturing Touch Panel Member>
More specifically, in the method of manufacturing an organic EL device with a touch panel according to the present invention, the step of forming the touch panel member is performed by forming the patterned cured resin layer of the radiation sensitive resin composition by the steps (1) to (4) described above. Process.

An example of the manufacturing method of 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 the sealing layer thereof, and cured by exposure or heat to form a wiring underlayer. Curing by exposure is less likely to cause deterioration of the organic EL element than the effect by heating. The wiring underlayer may not be formed.

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

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

Then, on the patterned cured resin layer, sputtering is performed on the second metal wiring layer of the touch panel member and the wiring that conducts the first and second metal wiring layers, similarly to the formation of the first metal wiring layer. , Photolithography, etching, and resist stripping.

Then, if necessary, a coating film of a radiation sensitive resin composition or a thermosetting resin composition is formed on the patterned cured resin layer and the second metal wiring layer, cured by exposure or heat, and upper layer protection Form a film.

As described above, the cured resin layer as the wiring underlayer, the first metal wiring layer, the patterned cured resin layer as the interwiring insulating layer, the second metal wiring layer, and the cured resin layer as the upper protective layer An organic EL device is obtained in which the touch panel member including the above is disposed on the element substrate.

The thickness of the patterned cured resin layer is usually 1 to 5 μm, preferably 1 to 3 μm, more preferably 1.3 to 2 μm. The thicknesses of the wiring underlayer and the upper protective layer are each independently usually 0.5 to 10 μm, preferably 0.5 to 5 μm, more preferably 0.5 to 3 μm. The cured layer is excellent in solvent resistance and adhesion to the object to be formed, and peeling can be effectively suppressed. In addition, even if the composition is overcoated on each layer, there is no erosion of the lower layer by the solvent, and each layer is resistant to each process such as resist pattern formation at the time of wiring formation, etching process and resist peeling process. .

Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In the description of the following examples etc., unless otherwise stated, "part" shows a "mass part".

In the following examples, the thickness (film thickness) of each layer was measured by cross-sectional observation with a stylus profilometer 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 and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2 parts And 15 parts of 3- (triethoxysilyl) propyl isocyanate and propylene glycol monomethyl ether acetate in an amount to give a solid concentration of 30% by mass, and the mixture is stirred and filtered with a 0.2 μm membrane filter to obtain radiation. 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 in Preparation Example 1 except that the raw materials of the types shown in Table 1 and the composition ratio were mixed.

The raw materials in Table 1 are as follows.

Alkali-soluble resin A1: CCR-1291H (manufactured by Nippon Kayaku Co., Ltd.)
Alkali-soluble resin A2: Resin included in the above formula (1):
CCR-1309H (manufactured by Nippon Kayaku Co., Ltd.)
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>
After applying the solution of the radiation sensitive resin composition prepared above on a silicon substrate with a spinner, respectively, a coating film was formed by prebaking on a 90 ° C. hot plate for 2 minutes. Next, the obtained coating film is exposed to a light exposure of 30 to 300 mJ / cm ² using a high-pressure mercury lamp through a photomask having a plurality of square-shaped remaining patterns of different sizes ranging from 3 to 6 μm in diameter. Irradiation was performed at a variable range. Thereafter, development was carried out using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. with the development time as a variable, followed by washing with pure water for 1 minute. Then, a patterned cured resin layer was formed by post-exposure at 600 mJ / cm ^{2 with} a high pressure mercury lamp and further post-baking in an oven at 90 ° C. or 150 ° C. for 60 minutes. The film thickness at this time was 2 μm. Further, in the above-mentioned photomask, if a hole-like pattern is formed in a state without residue or the like in the hole, it can be said that the resolution is good, and that case is referred to as AA. In the photomask of 6 μm or less, a hole-like pattern was formed, but a case where a slight residue was observed in the hole was taken as BB. In a photomask of 6 μm or less, when no hole-like pattern is formed or a residue is found in the hole and is not resolved, it can be determined that the resolution is poor, and that case is referred to as CC.

<Chemical resistance evaluation>
The patterned cured resin layer formed into a film by 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. Then, each film thickness change rate at the time of heat-processing at 90 degreeC for 1 hour was measured. Assuming that the film thickness before immersion is 100, the film thickness after immersion is the residual film ratio, and if the film thickness change is within the range of ± 5% or less with respect to 100, the film thickness change is ± 5 with respect to 100 In the range of more than% ± 20% or less, BB was evaluated as CC when the change in film thickness was more than ± 20% with respect to 100 or peeling occurred in the film.

<Evaluation of adhesion>
A film was formed on a glass substrate, a SiNx substrate, and a Mo substrate by the same method as the above evaluation of resolution, and the film was measured according to JIS K5400-8.5 (JIS D0202).

<Transmittance measurement>
A film was formed on a glass substrate in the same manner as in the above resolution evaluation, and the transmittance at a wavelength of 400 nm was measured using a UV-vis spectrometer V-670 manufactured by JASCO Corporation.

Element evaluation
<Preparation of organic EL element substrate>
A 3 μm-thick planarizing layer having a glass substrate (“OA-10” manufactured by Nippon Electric Glass Co., Ltd.) in which ITO transparent electrodes are formed in an array and a contact hole in which only a part of the ITO transparent electrode is exposed. And a plurality of array substrates having

An Al film having a thickness of 100 nm was formed on the planarized layer by DC sputtering using an Al target through a metal mask of a predetermined pattern. An ITO film having a thickness of 20 nm was formed on an Al film by an RF sputtering method using an ITO target. Thus, an anode layer comprising an Al film and an ITO film was formed.

A coating film is formed on the anode layer using a resist material ("Optomer NN 803" manufactured by JSR), and a series of treatments including i-ray (wavelength 365 nm) irradiation, development, washing with flowing water, air drying and heat treatment are performed. A pixel defining layer having a part of the opening as an opening area was formed.

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-4 Pa, and then a hole injection property is formed on the substrate using a deposition mask of a predetermined pattern. A molybdenum oxide (MoOx) film having a thickness of 10 nm was formed by resistance heating evaporation under the conditions of a film forming speed of 0.004 to 0.005 nm / sec to form a hole injection layer with a thickness of 1 nm.

4,4′-Bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) having hole transportability is formed on the hole injection layer using a deposition mask of a predetermined pattern. A film was formed by resistance heating evaporation under the same exhaust conditions as the hole injection layer to form a hole transport layer having a thickness of 35 nm. The deposition rate was 0.2 to 0.3 nm / sec.

On the hole transport layer, tris (8-quinolinolato) aluminum which is an alkylate complex as a green light emitting material using a deposition mask of a predetermined pattern by the resistance heating deposition method, and the same film forming conditions as the hole transport layer The light emitting layer was formed to a thickness of 35 nm. The deposition rate was 0.5 nm / sec or less.

Lithium fluoride was deposited on the light emitting layer using a deposition mask of a predetermined pattern by resistance heating deposition under the same exhaust conditions as the hole injection layer to form an electron injection layer with a thickness of 0.8 nm. . The deposition rate was 0.004 nm / sec or less.

Subsequently, on the electron injection layer, Mg and Ag are simultaneously formed under the same exhaust conditions as the hole injection layer by resistance heating evaporation using a deposition mask of a predetermined pattern, and a first cathode layer with a thickness of 5 nm Formed. The deposition rate was 0.5 nm / sec or less.

Subsequently, the substrate is transferred to another film forming chamber (sputtering chamber), and a 100 nm-thick film is formed on the first cathode layer by an RF sputtering method using an ITO target using a mask of a predetermined pattern. Two cathode layers were formed.

As described above, the organic EL element was formed on the substrate to obtain an organic EL element substrate.

<Thin film sealing of organic EL element>
A thin film sealing layer was formed on the organic EL element according to the following procedure.

The element substrate is transferred to a film forming chamber (sputtering chamber), and a 100 nm-thick inorganic sealing layer (SiNx film) is formed on the cathode layer by an RF sputtering method using a SiNx target using a mask of a predetermined pattern. Formed. Subsequently, the element substrate is transferred into a N ₂ -substituted glove box, and a curable composition containing an epoxy compound, an oxetane compound and a polymerization initiator is discharged in a predetermined pattern by a piezo inkjet printer, and then, Using a UniJet E110 ZHD 395 nm LED lamp manufactured by Ushio Inc., an exposure dose of 1000 mJ / cm ² was irradiated to cure the formed curable composition, thereby forming an organic sealing layer having a film thickness of 10 μm. The element substrate is transferred to a film forming chamber (sputtering chamber), and an inorganic sealing layer with a film thickness of 100 nm is formed on the organic sealing layer using a mask of a predetermined pattern and a SiNx target by RF sputtering. A SiNx film was formed.

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

<Preparation of a patterned cured resin layer>
A patterned cured resin layer was formed on the sealing layer-provided organic EL element substrate according to the following procedure.

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

Next, post-exposure of 600 mJ / cm ² was performed on the obtained patterned film using a high pressure mercury lamp. Then, the patterned film was cured by 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 the UV irradiation under the same conditions, the patterned 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. In the case where post-baking was performed at 220 ° C. for 60 minutes in Comparative Example 1-3, the organic EL element was deteriorated and ceased to function, and an organic EL device having an organic EL element could not be obtained.

<Lighting evaluation of organic EL element>
The lighting evaluation was performed on the obtained organic EL element with a patterned cured resin layer according to the following procedure. Through the organic EL lighting jig, a current was supplied at a density of 20 mA / cm ² between the anode layer and the cathode layer of the organic EL element by a constant current source to light the organic EL element. Next, the luminance in the front direction of the organic EL element was measured by a luminance meter.

The lighting of the organic EL element and the front luminance measurement by the luminance meter are performed on each of the organic EL element with the patterned cured resin layer and the organic EL element for comparison for which the patterned cured resin layer was not formed. When lighting at a luminance of 95% or more with respect to the front luminance of the organic EL element, the evaluation is AA, when lighting at a luminance of less than 95% and 80% or more, evaluation BB, when lighting at a luminance of less than 80% or Evaluation was made into CC about the case where it did not light normally.

　＜屈曲性有機ＥＬ素子基板の作製＞
　厚さ５０μｍのポリエチレンナフタレート（ＰＥＮ）樹脂基材上に、ＳｉＮｘターゲットを用いたＲＦスパッタリング法により、膜厚１００ｎｍの無機封止層（ＳｉＮｘ膜）を形成した。スピンコート法によってエポキシ化合物及びオキセタン化合物と重合開始剤とを含む硬化性組成物をＳｉＮｘ膜上に塗布し、続いてウシオ電機社製ＵｎｉＪｅｔＥ１１０ＺＨＤ　３９５ｎｍ　ＬＥＤランプを用いて露光量１０００ｍＪ／ｃｍ²を照射し、製膜された硬化性組成物を硬化させ、膜厚１０μｍの平坦化層を得た。さらにＳｉＮｘターゲットを用いたＲＦスパッタリング法により、平坦化層上に膜厚１００ｎｍの無機封止層（ＳｉＮｘ膜）を形成した。このようにしてバリア性を持つ屈曲性の樹脂基材（バリア性樹脂基材）を得た。

<Fabrication of flexible organic EL element substrate>
An inorganic sealing layer (SiNx film) having a film thickness of 100 nm was formed on a 50 μm-thick polyethylene naphthalate (PEN) resin base material by RF sputtering using a SiNx target. A curable composition containing an epoxy compound and an oxetane compound and a polymerization initiator is applied onto a SiNx film by spin coating, and subsequently an exposure dose of 1000 mJ / cm ² is irradiated using a UniJet E110 ZHD 395 nm LED lamp manufactured by Ushio Inc. Then, the formed curable composition was cured to obtain a planarized layer having a thickness of 10 μm. Further, an inorganic sealing layer (SiNx film) having a thickness of 100 nm was formed on the planarizing layer by RF sputtering using a SiNx target. Thus, a flexible resin substrate (barrier resin substrate) having a barrier property was obtained.

An ITO film with a film thickness of 20 nm was formed on the barrier resin base material by an RF sputtering method using an ITO target through a metal mask of a predetermined pattern. Thus, an anode layer made of an ITO film was formed.

The subsequent steps are performed in the same manner as in the above-mentioned <Production of organic EL element 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. did. As described above, an organic EL element was formed on the barrier resin substrate to obtain an organic EL element substrate.

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

<Preparation of Patterned Cured Resin Layer> (Example 2-1)
A patterned cured resin layer was formed on the sealing layer-provided organic EL element substrate according to the following procedure. The radiation sensitive resin composition (Preparation Example 1) obtained in Preparation Example is coated on the sealing layer of the organic EL element substrate with a sealing layer by spin coating, and prebaked at a temperature of 90 ° C. for 2 minutes. A coating was formed. Next, the obtained coating film was irradiated with radiation by varying the exposure amount in the range of 30 to 300 mJ / cm ² using a high pressure mercury lamp through a photomask. Thereafter, development was carried out using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. with the development time as a variable, followed by washing with pure water for 1 minute. Next, post-exposure of 600 mJ / cm ² was performed on the obtained patterned film using a high pressure mercury lamp. Then, the patterned film was cured by post-baking at 90 ° C. for 60 minutes to form a patterned cured resin layer. The thickness of the obtained patterned cured resin layer was 2 μm. Subsequently, a 50 μm-thick polyethylene naphthalate (PEN) resin base material having a 20 μm-thick rubber-based adhesive material on the back surface as a surface protective layer was attached onto the patterned cured resin layer.

The organic EL device for flexibility evaluation was obtained as described above.

Bonding of Resin Base (Comparative Example 2-1)
Aside from the procedure of the above <Production of patterned cured resin layer>, a structure resembling a bonding-type touch panel having a resin base material is formed on the surface of the organic EL element substrate with a sealing layer on the surface of Example 2-1. 60 μm thick polyethylene terephthalate (PET) resin base material having a patterned cured resin layer formed in the same manner as the above-mentioned <preparation of patterned cured resin layer>, and a rubber adhesive of 20 μm thickness on the back surface Pasted. Subsequently, a 50 μm-thick polyethylene naphthalate (PEN) resin base material having a 20 μm-thick rubber-based adhesive material on the back surface as a surface protective layer was attached onto the patterned cured resin layer.

The organic EL device for flexibility evaluation was obtained as described above.

<Flexibility evaluation of organic EL device>
With respect to the obtained organic EL device for evaluating flexibility, the flexibility was evaluated in the following procedure. First, the surface side of the obtained organic EL device for evaluating flexibility is pressed against a metal cylinder having a diameter of 5 mm, and is bent 180 degrees so as to be wound. After that, the folded state is returned to the linear state again. The above operation was repeated 1000 times to make a flexibility test.

Next, current flows at a density of 20 mA / cm ² between the anode layer and the cathode layer of the organic EL element by a constant current source through the organic EL lighting jig to turn on the organic EL element, and the lighting state by visual observation It was confirmed.

AA (good) when the organic EL element lights up normally,
The case where the organic EL element did not light normally was regarded as BB (impossible).

When the above-mentioned flexibility evaluation was carried out to the organic EL device for flexibility evaluation obtained in Example 2-1 and Comparative Example 2-1, in Example 2-1 normal lighting of the organic EL element was obtained (Evaluation: AA) In Comparative Example 2-1, normal lighting of the organic EL element was not obtained due to the disconnection of the electrode (Evaluation: BB).

DESCRIPTION OF SYMBOLS 10 ... board | substrate 20 light emitting element 30 sealing layer 40 cured resin part 41 wiring base layer 42 patterned cured resin layer 43 upper layer 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 (13)

A substrate,
A light emitting element on the substrate;
A light emitting device having a cured resin portion on the light emitting element,
The cured resin portion includes a patterned cured resin layer,
The film thickness after immersion is 80 to 120 when the film thickness before immersion is 100, when the patterned cured resin layer is immersed in a 70% by mass aqueous solution of 2-aminoethanol at 60 ° C. for 5 minutes. ,
The light emitting device is a glass substrate, or polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, between the cured resin portion and the light emitting element. And at least one member selected from the group consisting of allyl diglycol carbonate resin, polyamide, polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, polynorbornene and triacetylcellulose resin, and having a thickness of 50 μm A light emitting device characterized by not having a support exceeding. The light emitting device according to claim 1, wherein the light emitting element is an organic EL element, and the light emitting device is an organic EL device. The light emitting device according to claim 1, wherein the patterned cured resin layer is a layer formed of a radiation sensitive resin composition. The cured resin portion is formed on a sealing layer for sealing the light emitting element, and the light emitting device is the glass substrate or the support between the cured resin portion and the sealing layer. The light emitting device according to any one of claims 1 to 3, which does not have The light emitting device according to any one of claims 1 to 4, wherein the cured resin portion is in direct contact with the light emitting element or the sealing layer thereof. The light emitting device according to any one of claims 1 to 5, 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 an adhesive layer. The light emitting device according to any one of claims 1 to 6, wherein the cured resin portion further includes a cured layer as a wiring underlayer on the light emitting element side of the patterned cured resin layer. A substrate,
An organic EL element on the substrate;
It is an organic EL device with a touch panel having a touch panel member on the organic EL element,
The film thickness before immersion is 100 when the touch panel member includes a patterned cured resin layer and the patterned cured resin layer is immersed in a 70% by mass aqueous solution of 2-aminoethanol at 60 ° C. for 5 minutes. An organic EL device with a touch panel characterized in that the film thickness after immersion is 80 to 120 and the touch panel supporting substrate is not disposed on the surface of the touch panel member on the organic EL element side. 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. (4) A patterned cured resin layer having a contact hole in which a wire for partially insulating the second metal wiring layer and for conducting the first and second metal wiring layers is formed; The organic EL device with a touch panel according to claim 8, comprising: a cured resin layer covering the metal wiring layer of 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 of a radiation sensitive resin composition, (2) irradiating the coating with a first radiation through a mask, and (3) applying the coating after irradiation. The step of developing the film, and (4) the step of irradiating the coating film after the development with a second radiation to form the patterned cured resin layer (wherein the step (4) is carried out at 100 ° C. or lower) Also, the first radiation and the second radiation may be the same or different.)
A method of manufacturing a light emitting device, comprising: In the step (4),
(4-i) a step of irradiating the second coating after heating the coating at 100 ° C. or lower; or (4-ii) heating the coating at a second temperature after heating the second coating. The method of manufacturing a light emitting device according to claim 10, which is a step of The light emitting device is an organic EL device with a touch panel including 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. The manufacturing method of the light-emitting device according to claim 10, 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. The method for producing a light emitting device according to any one of claims 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 the formula (1), n and m each independently represent an integer of 1 to 30. ]

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