Device structure and method for manufacturing the same

Abstract

The present application provides a device structure, comprising: a multilayer article having a substrate and an element portion provided on the substrate; and a sealing layer sealing the element portion, the sealing layer having a structure in which an organic sealing layer and an inorganic sealing layer are sequentially stacked with respect to the element portion, the inorganic sealing layer containing silicon nitride, the organic sealing layer containing a thermoplastic elastomer, and a residual film rate of the organic sealing layer in a dibutyl ether dissolving test being 90% or more. It is preferable that the sealing layer contain: a first sealing layer provided on the element portion; and two or more second sealing layers and two or more third sealing layers provided on the first sealing layer, the sealing layer having a structure in which the second sealing layers and the third sealing layers are alternately stacked, the second sealing layers being the inorganic sealing layer, and the third sealing layers being the organic sealing layer.

Description

Technical Field

[0001] This invention relates to device structures and their manufacturing methods. Background Technology

[0002] In devices such as organic electroluminescent devices and flexible touch sensors, it is sometimes required to include components that prevent moisture from penetrating the device. For example, an organic electroluminescent device may have a substrate such as a glass plate and an element portion containing an electrode layer and a light-emitting layer disposed on the substrate. The material contained in the element portion may contain materials that deteriorate due to moisture intrusion. Therefore, to prevent moisture from penetrating the element portion, a sealing layer is sometimes formed to seal the element portion.

[0003] In many devices, sealing layers include organic sealing layers formed from organic materials and inorganic sealing layers formed from inorganic materials (Patent Document 1). Conventionally, organic sealing layers are typically formed under atmospheric pressure. Furthermore, inorganic sealing layers are mostly formed in a vacuum environment using methods such as CVD (Chemical Vapor Deposition).

[0004] However, the vacuum environment process described in Patent Document 1 results in high costs due to the large size and complexity of the inorganic sealing layer formation apparatus. In particular, processes such as plasma CVD using plasma generate plasma dust and other particles, which can cause component degradation.

[0005] Against this backdrop, there is a need to develop a technology capable of forming inorganic sealing layers under atmospheric pressure. To address this need, in recent years, methods have been developed for forming inorganic sealing layers containing silicon nitride using polysilazane compounds under atmospheric pressure (Patent Document 2 and Non-Patent Document 1).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2018-147812;

[0009] Patent document 2: Japanese Patent Application Publication No. 2015-202620.

[0010] Non-patent literature

[0011] Non-patent literature 1: Lina Sun, Kaho Uemura, Tatsuhiro Takahashi, Tsukasa Yoshida, Yoshiyuki Suzuri, "Interfacial Engineering in Solution Processing of Silicon-Based Hybrid Multilayer for High Performance Thin Film Encapsulation", ACS Appl. Mater. Interfaces, 11, 43425-43432 (2019). Summary of the Invention

[0012] The problem the invention aims to solve

[0013] There is a need to improve the sealing performance of sealing layers containing both inorganic and organic sealing layers, which are based on silicon nitride, under high temperature and high humidity conditions. This invention was made in view of the above-mentioned realities, and its object is to provide a device structure having a sealing layer containing silicon nitride that exhibits good sealing performance under high temperature and high humidity conditions, as well as a manufacturing method that can easily form the aforementioned device structure.

[0014] Solution for solving the problem

[0015] To address the aforementioned problems, the inventors conducted in-depth research and obtained the following insights. When using liquid compositions containing polysilazane compounds to form inorganic sealing layers, dibutyl ether is one of the suitable solvents due to its minimal impact on the polysilazane compounds. However, it has been found that dibutyl ether readily damages organic sealing layers containing thermoplastic elastomers. To address this problem, the inventors discovered that irradiating the organic sealing layer with vacuum ultraviolet light can improve its dibutyl ether resistance. This invention is based on these insights and comprises the following.

[0016] [1] A device structure comprising: a multilayer having a substrate and an element portion disposed on the substrate; and a sealing layer sealing the element portion, the sealing layer having a structure in which an organic sealing layer and an inorganic sealing layer are sequentially stacked relative to the element portion, the inorganic sealing layer comprising silicon nitride, the organic sealing layer comprising a thermoplastic elastomer, and the residual film rate of the organic sealing layer in a dibutyl ether dissolution test being 90% or more.

[0017] [2] According to the device structure described in [1], the sealing layer includes: a first sealing layer disposed on the element portion; and two or more second sealing layers and two or more third sealing layers disposed on the first sealing layer, wherein the sealing layer has a structure in which the second sealing layer and the third sealing layer are alternately stacked, the second sealing layer is the inorganic sealing layer, and the third sealing layer is the organic sealing layer.

[0018] [3] According to the device structure described in [1] or [2], wherein the first sealing layer is the organic sealing layer or an organic silicon sealing layer containing organic silicon.

[0019] [4] The device structure according to any one of [1] to [3], wherein the thermoplastic elastomer is one or more of the modified products based on silicon-containing polar groups selected from hydrogenated aromatic vinyl compounds-conjugated diene block copolymers and hydrogenated aromatic vinyl compounds-conjugated diene block copolymers.

[0020] [5] According to the device structure described in [4], the hydrogenated aromatic vinyl compound-conjugated diene block copolymer has a structure in which both non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds are hydrogenated.

[0021] [6] The device structure according to any one of [1] to [5], wherein the organic sealing layer comprises one or more selected from moisture adsorbents and ultraviolet absorbers.

[0022] [7] The device structure according to any one of [1] to [6], wherein the thickness of each constituent layer included in the sealing layer is 300 nm or less.

[0023] [8] The device structure according to any one of [1] to [7], wherein the above-mentioned element part is an organic electroluminescent element part.

[0024] [9] A method for manufacturing a device structure includes the following steps: step (a), preparing a multilayer having a substrate and an element portion disposed on the substrate; and step (b), forming a sealing layer that seals the element portion, wherein step (b) of forming the sealing layer includes step (b1) of forming an organic sealing layer and step (b2) of forming an inorganic sealing layer after step (b1), wherein step (b1) includes step (b1-1) of forming an organic intermediate layer comprising a thermoplastic elastomer and step (b1-2) of obtaining the organic sealing layer by irradiating the organic intermediate layer with vacuum ultraviolet light, wherein step (b2) includes step (b2-1) of forming an intermediate layer using a liquid composition comprising a polysilazane compound and a solvent and step (b2-2) of obtaining an inorganic sealing layer comprising silicon nitride by irradiating the intermediate layer with ultraviolet light.

[0025]

[10] The method for manufacturing the device structure according to [9], wherein the liquid composition of step (b) contains dibutyl ether as the solvent.

[0026]

[11] The manufacturing method of the device structure according to [9] or

[10] , wherein the above-mentioned step (b1-2) includes a step (b1-2-1) of irradiating the above-mentioned organic intermediate layer with vacuum ultraviolet light in an inactive gas atmosphere and a step (b1-2-2) of irradiating the above-mentioned organic intermediate layer after the above-mentioned step (b1-2-1) with vacuum ultraviolet light in a mixed atmosphere of inactive gas and oxygen.

[0027]

[12] The method for manufacturing a device structure according to any one of [9] to

[11] , wherein the above-mentioned step (b) includes a step (b3) of forming a first sealing layer, a step (b4) of forming a second sealing layer disposed on the first sealing layer as the inorganic sealing layer, and a step (b5) of forming a third sealing layer disposed on the second sealing layer as the organic sealing layer, wherein the above-mentioned step (b) includes a step of alternately performing the above-mentioned step (b4) and the above-mentioned step (b5) at least twice, wherein the above-mentioned step (b4) is the above-mentioned step (b2), and the above-mentioned step (b5) is the above-mentioned step (b1).

[0028]

[13] According to the manufacturing method of the device structure described in

[12] , the above-mentioned step (b3) is the above-mentioned step (b1), and the above-mentioned step (b3) is the step of forming the above-mentioned first sealing layer as the above-mentioned organic sealing layer.

[0029] Invention Effects

[0030] According to the present invention, a device structure having a sealing layer comprising silicon nitride and having good sealing performance in high temperature and high humidity environments can be provided, as well as a manufacturing method that can easily form the above-mentioned device structure. Attached Figure Description

[0031] Figure 1 This is a schematic cross-sectional view illustrating a device structure according to one embodiment of the present invention.

[0032] Figure 2 This is a cross-sectional view schematically illustrating a step (a) of a method for manufacturing a device structure according to an embodiment of the present invention, showing a multilayer material prepared in step (a).

[0033] Figure 3 This is a cross-sectional view schematically showing a case in step (b) of a method for manufacturing a device structure according to one embodiment of the present invention, in which a first sealing layer for sealing a component portion is formed on a multilayer.

[0034] Figure 4 This is a schematic cross-sectional view showing a case in step (b) of a method for manufacturing a device structure according to one embodiment of the present invention, in which a second sealing layer as an inorganic sealing layer is formed on a multilayer.

[0035] Figure 5 This is a cross-sectional view schematically showing a case in step (b) of a method for manufacturing a device structure according to one embodiment of the present invention, in which a third sealing layer as an organic sealing layer is formed on a multilayer.

[0036] Figure 6 This is a cross-sectional view schematically showing a case in step (b) of a method for manufacturing a device structure according to one embodiment of the present invention, in which a second sealing layer as an inorganic sealing layer and a third sealing layer as an organic sealing layer are alternately formed on a multilayer.

[0037] Figure 7 This is a graph showing the results of microscopic observations of the embodiments and comparative examples.

[0038] Figure 8 This is a graph showing the changes in shrinkage between the examples and comparative examples. Detailed Implementation

[0039] The present invention will now be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented in any way without departing from the scope of the claims of this application and their equivalents.

[0040] Unless otherwise specified, in the following description, "(meth)acrylic acid" is a term that includes "acrylic acid", "methacrylic acid", and combinations thereof. For example, "(meth)acrylate alkyl ester" includes alkyl acrylate, alkyl methacrylate, or mixtures thereof.

[0041] In the following description, for ease of explanation, the term "solvent" refers not only to the medium in the solution but also to the dispersion medium in which the solid is dispersed.

[0042] [I. Device Structure]

[0043] One embodiment of the present invention provides a device structure comprising: a multilayer having a substrate and an element portion disposed on the substrate; and a sealing layer sealing the element portion, the sealing layer having a structure in which an organic sealing layer and an inorganic sealing layer are sequentially stacked relative to the element portion, the inorganic sealing layer comprising silicon nitride, the organic sealing layer comprising a thermoplastic elastomer, and the residual film rate of the organic sealing layer in a dibutyl ether dissolution test being 90% or more.

[0044] Figure 1 This is a schematic cross-sectional view illustrating a device structure according to one embodiment of the present invention. The device structure 10 includes: a multilayer 100 having a substrate 110 and an element portion 120 disposed on the substrate 110; and a sealing layer 200 sealing the element portion 120. The sealing layer 200 has a structure in which an organic sealing layer 210 and an inorganic sealing layer 220 are sequentially stacked relative to the element portion 120. The inorganic sealing layer 220 comprises silicon nitride. The organic sealing layer 210 comprises a thermoplastic elastomer, and the residual film rate of the organic sealing layer 210 in a dissolution test relative to dibutyl ether is 90% or more.

[0045] exist Figure 1 In the device structure 10 shown, an example is illustrated where the sealing layer 200 includes: a first sealing layer 201 disposed on the component portion 120; and three second sealing layers 202 and three third sealing layers 203 disposed on the first sealing layer 201. The sealing layer 200 has a structure in which the second sealing layers 202 and the third sealing layers 203 are alternately stacked, wherein the second sealing layer 202 is an inorganic sealing layer 220 and the third sealing layer 203 is an organic sealing layer 210. Furthermore, an example is shown where the first sealing layer 201 is an organosilicon sealing layer 230.

[0046] Here, dibutyl ether is a preferred solvent for polysilazane compounds because it has low reactivity with polysilazane compounds in the method for forming inorganic sealing layers using polysilazane compounds. On the other hand, dibutyl ether can sometimes dissolve thermoplastic elastomers. Therefore, when an inorganic sealing layer is formed by laminating an organic sealing layer onto an organic sealing layer, the organic sealing layer may sometimes deteriorate due to dibutyl ether when a liquid composition containing a polysilazane compound and dibutyl ether is applied to the organic sealing layer, resulting in insufficient sealing performance as a whole. In contrast, the device structure of this embodiment has a high residual film rate of the organic sealing layer relative to the dibutyl ether dissolution test, thus exhibiting high dibutyl ether resistance in the organic sealing layer. Therefore, even when the above-mentioned liquid composition is applied to the organic sealing layer, deterioration of the organic sealing layer due to dibutyl ether can be suppressed. Therefore, a sealing layer in which the organic and inorganic sealing layers are laminated in a good state can be formed, thus enabling good sealing performance under high temperature and high humidity environments.

[0047] [1. Multilayer structures]

[0048] The multilayer 100 includes a substrate and element portions formed on the substrate.

[0049] As the substrate 110, a substrate capable of constituting a device structure can be appropriately used. Examples of substrate 110 include glass plates, resin plates, and resin films. The substrate may have only one layer or multiple layers. For example, a substrate 110 containing a resin film and a barrier layer disposed on its surface can be used.

[0050] As the component section 120, a component section capable of constituting a device structure can be appropriately employed. Typically, the component section 120 includes one or more conductive layers. The layers referred to by the term "conductive layer" include various layers whose function is manifested through the movement of electrons within the layer. Therefore, the term "conductive layer" can include not only highly conductive layers such as metals, but also thin organic layers with lower conductivity, such as light-emitting layers. In the device structure of this embodiment, a sealing layer is typically formed to suppress deterioration caused by moisture in the conductive layer.

[0051] Examples of conductor layers include electrode layers, light-emitting layers, and combinations thereof constituting organic electroluminescent elements; and patterned wiring constituting a touch panel. The conductor layer can occupy a large area on the substrate 110. Furthermore, the conductor layer can also be provided with any surface shape, such as a strip, a thin line, a rectangle, or a dot, similar to the wiring and other structures on the substrate 110.

[0052] The element section 120 may have one or more conductor layers. When the element section 120 has two or more layers, these layers may be arranged without overlapping, or they may partially or completely overlap.

[0053] The element section 120 may contain components other than the conductor layer inside or on its surface. Examples of such components include, for instance, components that maintain the mechanical structure of the element section 120. Specific examples of such components include components of display elements such as liquid crystal cells and organic light-emitting elements.

[0054] exist Figure 1 In this description, the element section 120 is exemplified by an organic electroluminescent element having a first electrode layer 121, a light-emitting layer 122, and a second electrode layer 123 sequentially in the thickness direction. The first electrode layer 121, the light-emitting layer 122, and the second electrode layer 123 are all conductive layers. Typically, by applying a voltage to the first electrode layer 121 and the second electrode layer 123, the light-emitting layer 122 can generate light. Examples of materials for the light-emitting layer 122 include poly(paraphenylene vinylene) based materials, polyfluorene based materials, and polyvinylcarbazole based materials. Furthermore, the light-emitting layer 122 may also be a laminate of multiple layers with different emission colors or a mixed layer in which different pigments are doped into a layer of a certain pigment. Furthermore, the element section 120 may also have functional layers (not shown) such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an equipotential surface formation layer, and a charge generation layer.

[0055] The multilayer 100 can be manufactured by a manufacturing method that includes, for example, forming a component portion 120 on a substrate 110. Examples of methods for forming the component portion 120 include forming a conductor layer on the substrate 110 by methods such as sputtering or vapor deposition.

[0056] [2. Sealing layer]

[0057] The sealing layer 200 has a structure in which an organic sealing layer 210 and an inorganic sealing layer 220 are sequentially stacked relative to the element portion 120. The sealing layer 200 is a layer provided in a manner that seals at least a portion of the element portion 120, preferably in a manner that seals all or most of the element portion 120. In this embodiment, an example in which a sealing portion is formed in a manner that seals the entire portion that is not in contact with the surface of the substrate 110 of the element portion will be shown for explanation.

[0058] [2.1. Layer structure of the sealing layer]

[0059] In the sealing layer, the organic sealing layer and the inorganic sealing layer are typically directly stacked without any other layers between them. In the case of a multilayer structure where the sealing layer consists of two or more alternating layers of organic sealing layer and two or more layers of inorganic sealing layer, the multilayer structure includes at least one layer of organic sealing layer and one layer of inorganic sealing layer directly stacked. In this embodiment, it is preferable that the organic sealing layer and the inorganic sealing layer in the multilayer structure are each directly stacked.

[0060] In the case of a multilayer structure in which two or more organic sealing layers and two or more inorganic sealing layers are alternately stacked, the number of organic sealing layers and inorganic sealing layers can be the same. Although not illustrated, there can be one more organic sealing layer than inorganic sealing layer, or one less organic sealing layer than inorganic sealing layer. The number of organic sealing layers is, for example, two or more, preferably three or more, and preferably ten or less. The number of inorganic sealing layers is, for example, two or more, preferably three or more, and preferably ten or less.

[0061] The specific layer structure of the sealing layer can be appropriately selected based on the device structure. For example, such as Figure 1 As shown, the sealing layer 200 can have a structure in which a first sealing layer 201, a second sealing layer 202, and a third sealing layer 203 are sequentially stacked relative to the element portion 120. In this case, the sealing layer 200 can have, for example, a second sealing layer 202 as an inorganic sealing layer 220 and a third sealing layer 203 as an organic sealing layer 210. When having a second sealing layer 202 as an inorganic sealing layer 220 and a third sealing layer 203 as an organic sealing layer 210, it is preferable to have two or more layers of second sealing layer 202 and two or more layers of third sealing layer 203, and to have a structure in which the second sealing layer 202 and the third sealing layer 203 are alternately stacked. This is because the sealing performance of the sealing layer 200 can be improved.

[0062] like Figure 1 As shown, when the sealing layer has a structure in which a first sealing layer, a second sealing layer, and a third sealing layer are sequentially stacked relative to the component portion, the first sealing layer can be, for example, an organic sealing layer. Furthermore, the first sealing layer can be, for example, an organosilicon sealing layer. Inorganic sealing layers containing silicon nitride tend to experience increased stress under high temperature and high humidity environments, thus easily leading to cracking. Therefore, when the second sealing layer is an inorganic sealing layer, using an organic or organosilicon sealing layer as the first sealing layer can absorb the stress of the inorganic sealing layer and suppress crack formation. The first sealing layer can directly seal the component portion; therefore, it is preferable to select the material based on the type of component portion and considering the impact on the component portion during the formation of the first sealing layer.

[0063] In addition to the layer structures mentioned above, other possible layer structures for sealing layers include, for example, a two-layer structure in which an organic sealing layer and an inorganic sealing layer are stacked sequentially relative to the component portion, and a three-layer structure in which an organic sealing layer, an inorganic sealing layer, and an organic sealing layer are stacked sequentially relative to the component portion.

[0064] [2.2. Organic sealing layer]

[0065] The organic sealing layer is a layer containing a thermoplastic elastomer. Furthermore, the residual film rate of the organic sealing layer in the dissolution test relative to dibutyl ether is over 90%.

[0066] The residual film rate of the organic sealing layer in the dibutyl ether dissolution test was obtained by the following determination method. First, the organic sealing layer was exposed on the surface of the device structure and immersed in dibutyl ether for 60 seconds. Then, it was allowed to air dry. The thickness of the organic sealing layer before immersion in dibutyl ether was defined as T1, and the thickness of the organic sealing layer after immersion in dibutyl ether and air drying was defined as T2. The ratio of thickness T2 to thickness T1 was taken as the residual film rate.

[0067] The residual film rate of the organic sealing layer is 90% or more, preferably 95% or more, more preferably 98% or more, and ideally 100%.

[0068] The organic sealing layer is formed on the component side compared to the inorganic sealing layer. Because the organic sealing layer has higher resistance to dibutyl ether, it can suppress damage to the organic sealing layer when an inorganic sealing layer is formed using a liquid composition containing a polysilazane compound and dibutyl ether. Furthermore, the organic sealing layer can be formed directly on the surface of the component or in between other layers. When the organic sealing layer is formed directly on the surface of the component, it can directly seal the component. Here, "direct" sealing of the component using a layer means that there are no other layers between the layer and the component.

[0069] [2.2.1. Materials of the Organic Sealing Layer]

[0070] (Thermoplastic elastomer)

[0071] Thermoplastic elastomers are materials that exhibit rubber-like properties at room temperature but are plasticized and moldable at high temperatures. Such thermoplastic elastomers are characterized by their resistance to stretching and fracture under low-force loads. Specifically, thermoplastic elastomers at 23°C exhibit a Young's modulus of 0.001–1 GPa and an elongation at break of 100–1000%. Furthermore, in a high temperature range above 40°C and below 200°C, the storage modulus of thermoplastic elastomers decreases sharply, and the loss tangent tanδ (loss modulus / storage modulus) shows a peak or a value greater than 1, indicating softening. Young's modulus and elongation at break can be measured according to JIS K7113. Additionally, the loss tangent tanδ can be measured using a commercially available dynamic viscoelasticity measuring device.

[0072] Thermoplastic elastomers typically contain no residual solvents, or if they do, the amount is minimal. Therefore, thermoplastic elastomers offer the advantages of low outgassing and the ability to be sealed using simple processes that do not involve cross-linking.

[0073] Polymers can be used as thermoplastic elastomers. Examples of polymers that can be used as thermoplastic elastomers include: ethylene-α-olefin copolymers such as ethylene-propylene copolymers; ethylene-α-olefin-polyene copolymers; copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-methyl methacrylate copolymers and ethylene-butyl acrylate copolymers; copolymers of ethylene and fatty acid vinyl esters such as ethylene-vinyl acetate copolymers; polymers of alkyl acrylates such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate; and diene copolymers such as polybutadiene, polyisoprene, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, butadiene-(meth)alkyl acrylate copolymers, butadiene-(meth)alkyl acrylate-acrylonitrile copolymers, and butadiene-(meth)alkyl acrylate-acrylonitrile copolymers. Butene-isoprene copolymers; styrene-butadiene random copolymers, styrene-isoprene random copolymers, styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene block copolymers, styrene-isoprene-styrene block copolymers, and other aromatic vinyl compound-conjugated diene copolymers; hydrogenated styrene-butadiene random copolymers, hydrogenated styrene-isoprene random copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, and other hydrogenated aromatic vinyl compound-conjugated diene copolymers; low-crystallinity polybutadiene; styrene-grafted ethylene-propylene elastomers; thermoplastic polyester elastomers; ethylene-based ionomers. Thermoplastic elastomers can be used alone or in combination of two or more in any ratio.

[0074] To achieve the desired effects of the present invention, hydrogenated aromatic vinyl compound-conjugated diene block copolymers are preferred as thermoplastic elastomers. Hydrogenated aromatic vinyl compound-conjugated diene block copolymers refer to hydrogenated forms of aromatic vinyl compound-conjugated diene block copolymers. That is, hydrogenated aromatic vinyl compound-conjugated diene block copolymers represent polymers having a structure obtained by hydrogenating some or all of the non-aromatic carbon-carbon unsaturated bonds, aromatic carbon-carbon bonds, or both of the aromatic vinyl compound-conjugated diene block copolymer. However, the aforementioned hydrides are not limited to their manufacturing method.

[0075] As aromatic vinyl compounds, styrene and its derivatives, and vinylnaphthalene and its derivatives are preferred. Styrene is particularly preferred from the perspective of industrial availability. On the other hand, as conjugated dienes, chain-like conjugated dienes (straight-chain conjugated dienes, branched-chain conjugated dienes) are preferred. Preferred examples of conjugated dienes include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Among these, 1,3-butadiene and isoprene are particularly preferred from the perspective of industrial availability.

[0076] When the mass fraction of all aromatic vinyl monomer units in the total aromatic vinyl compound-conjugated diene block copolymer is defined as wA, and the mass fraction of all conjugated diene monomer units in the total aromatic vinyl compound-conjugated diene block copolymer is defined as wB, the ratio of wA to wB (wA / wB) is preferably within a specific range. Specifically, the ratio (wA / wB) is preferably 20 / 80 or more, more preferably 30 / 70 or more, more preferably 60 / 40 or less, and more preferably 55 / 45 or less. When the ratio wA / wB is above the lower limit of the above range, the heat resistance of the organic sealing layer can be improved. Furthermore, when the ratio wA / wB is below the upper limit of the above range, the flexibility of the organic sealing layer can be improved. In addition, when the ratio (wA / wB) is within the above range, the temperature range in which the organic sealing layer has rubber elasticity can be expanded, thus expanding the temperature range in which the device structure has flexibility.

[0077] As aromatic vinyl compound-conjugated diene block copolymers, polymers selected from styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene block copolymers, styrene-isoprene-styrene block copolymers, and mixtures thereof are preferred. More specific examples include aromatic vinyl compound-conjugated diene block copolymers described in Japanese Patent Application Publication Nos. 2-133406, 2-305814, 3-72512, 3-74409, and International Publication No. 2015 / 099079.

[0078] The hydrogenation rate of the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferably 90% or more, more preferably 97% or more, and particularly preferably 99% or more. A higher hydrogenation rate results in better heat resistance and light resistance of the organic sealing layer. The hydrogenation rate of the hydride can be determined by measurement using 1H-NMR.

[0079] The hydrogenation rate of the non-aromatic carbon-carbon unsaturated bonds in the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferably 95% or more, more preferably 99% or more. A high hydrogenation rate of the non-aromatic carbon-carbon unsaturated bonds further improves the lightfastness and oxidation resistance of the organic sealing layer.

[0080] The hydrogenation rate of the aromatic carbon-carbon unsaturated bonds in the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more. A high hydrogenation rate of the aromatic carbon-carbon unsaturated bonds results in a higher glass transition temperature of the hydride, thus effectively improving the heat resistance of the organic sealing layer. Furthermore, it can reduce the photoelasticity of the organic sealing layer, minimizing delayed manifestation.

[0081] Hydrogenated aromatic vinyl compounds-conjugated diene block copolymers are particularly preferred to have a structure in which both non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds are hydrogenated.

[0082] Particularly preferred block configurations for hydrogenated aromatic vinyl compounds-conjugated diene block copolymers are: triblock copolymers in which blocks [B] of aromatic vinyl polymer hydrides are bonded to both ends of blocks [B] of conjugated diene polymer hydrides; and pentablock copolymers in which polymer blocks [B] are bonded to both ends of polymer blocks [A], and further, polymer blocks [A] are bonded to the other ends of each of the two polymer blocks [B]. In particular, triblock copolymers of [A]-[B]-[A] are particularly preferred because they are easy to manufacture and allow the properties of the thermoplastic elastomer to be within the desired range.

[0083] Hydrogenated aromatic vinyl compounds-conjugated diene block copolymers can be manufactured by methods described, for example, those specified in International Publication No. 2015 / 099079 and Japanese Patent Application Publication No. 2016-204217.

[0084] Furthermore, polymers having silicon-containing polar groups can also be used as thermoplastic elastomers. Examples of such polymers include, for instance, modified versions of polymers with silicon-containing polar groups that can be used as thermoplastic elastomers. When using polymers with silicon-containing polar groups as thermoplastic elastomers, the adhesion between the organic sealing layer and other components can be improved.

[0085] Hereinafter, the polymer used in the reaction to obtain the above-described modified product will sometimes be referred to as the "pre-reaction polymer". The modified product can have a structure, for example, obtained by graft polymerization of the pre-reaction polymer with a compound having a silicon-containing polar group as a monomer. However, the modified product is not limited by its manufacturing method.

[0086] Alkoxysilane is preferred as the silicon-containing polar group. Examples of compounds having alkoxysilane as the silicon-containing polar group include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and 2-norbornen-5-yltrimethoxysilane, etc., which are olefinic unsaturated silane compounds.

[0087] By reacting a polymer prior to reaction with a compound having a silicon-containing polar group, a silicon-containing polar group can be introduced into the polymer prior to reaction, resulting in a modified product having a silicon-containing polar group. When alkoxysilyl groups are introduced as silicon-containing polar groups, the amount of alkoxysilyl group introduced relative to 100 parts by weight of the polymer prior to reaction is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, even more preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and even more preferably 3 parts by weight or less. When the amount of alkoxysilyl group introduced is controlled within the above range, it is possible to prevent the degree of crosslinking between alkoxysilyl groups after decomposition by water from becoming excessively high, thus maintaining high adhesion. Examples of substances containing alkoxysilyl groups for introducing alkoxysilyl groups and modification methods include the substance containing alkoxysilyl groups and modification method described in International Publication No. 2015 / 099079.

[0088] The amount of polar groups introduced can be measured by 1H-NMR spectroscopy. Furthermore, when measuring the amount of polar groups introduced, the number of cumulative measurements can be increased when the amount introduced is low.

[0089] In the aforementioned thermoplastic elastomers, from the viewpoint of significantly achieving the desired effects of the present invention, one or more selected from hydrogenated aromatic vinyl compound-conjugated diene block copolymers and silicon-containing polar group-based modifiers of hydrogenated aromatic vinyl compound-conjugated diene block copolymers are preferred. Silicon-containing polar group-based modifiers of hydrogenated aromatic vinyl compound-conjugated diene block copolymers are particularly preferred.

[0090] In modifications of hydrogenated aromatic vinyl compound-conjugated diene block copolymers based on silicon-containing polar groups, it is preferable to introduce alkoxysilane groups as silicon-containing polar groups. Generally, introducing alkoxysilane groups as polar groups into pre-reaction polymers such as hydrogenated aromatic vinyl compound-conjugated diene block copolymers is sometimes referred to as silane modification. During silane modification, the alkoxysilane group can be directly bonded to the pre-reaction polymer, or it can be bonded via a divalent organic group such as an alkylene group. Hereinafter, polymers obtained by silane modification of pre-reaction polymers will also be referred to as "silane-modified products".

[0091] Therefore, as a modification of hydrogenated aromatic vinyl compound-conjugated diene block copolymers based on silicon-containing polar groups, silane-modified hydrogenated aromatic vinyl compound-conjugated diene block copolymers are preferred. Particularly preferred are silane-modified styrene-butadiene block copolymers, silane-modified styrene-butadiene-styrene block copolymers, silane-modified styrene-isoprene block copolymers, and silane-modified styrene-isoprene-styrene block copolymers of one or more selected from these categories.

[0092] The weight-average molecular weight (Mw) of the thermoplastic elastomer is not particularly limited, but is preferably 20,000 or more, more preferably 30,000 or more, even more preferably 35,000 or more, preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 70,000 or less. The weight-average molecular weight of the thermoplastic elastomer can be determined by gel permeation chromatography using tetrahydrofuran as a solvent, with values ​​converted to polystyrene. Furthermore, the molecular weight distribution (Mw / Mn) of the thermoplastic elastomer is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and preferably 1 or more. When the weight-average molecular weight Mw and the molecular weight distribution Mw / Mn of the thermoplastic elastomer are within the above ranges, the mechanical strength and heat resistance of the organic sealing layer can be improved.

[0093] The glass transition temperature of the thermoplastic elastomer is not particularly limited, but is preferably 40°C or higher, more preferably 70°C or higher, more preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 160°C or lower. Furthermore, when using a substance containing block copolymers as the thermoplastic elastomer, the glass transition temperature can be adjusted by changing the weight ratio of the respective polymer blocks, thereby achieving a balance between the adhesiveness and flexibility of the organic sealing layer. The glass transition temperature of the resin can be measured using a differential scanning calorimeter (DSC) with a heating rate of 10°C / min.

[0094] (Any ingredients)

[0095] In addition to thermoplastic elastomers, organic sealing layers can also contain any other components. Examples of such components include hygroscopic particles and ultraviolet absorbers.

[0096] Hygroscopic particles refer to particles with a high rate of weight change after standing at 20°C and 90% RH for 24 hours. The specific range of this weight change rate is typically 3% or more, preferably 10% or more, and more preferably 15% or more. There is no particular upper limit to the weight change rate, and it can be, for example, below 100%. Hygroscopic particles with such high hygroscopicity can absorb a large amount of moisture in a small amount, thus effectively inhibiting moisture permeation through the sealing layer. As a result, it does not impede the rubber-like properties of the thermoplastic elastomer, which is advantageous.

[0097] The weight change rate of hygroscopic particles can be calculated using the following formula (K1). In the following formula (K1), W1 represents the weight of the particles before standing in an environment of 20°C and 90% Rh, and W2 represents the weight of the particles after standing in an environment of 20°C and 90% Rh for 24 hours.

[0098] Weight change rate (%) = ((W2-W1) / W1) × 100 (K1)

[0099] Examples of materials contained in hygroscopic particles include alkaline hygroscopic materials and acidic hygroscopic materials. Examples of alkaline hygroscopic materials include: compounds containing alkali metals, alkaline earth metals, and aluminum (oxides, hydroxides, salts, etc.) and not containing silicon (e.g., barium oxide, magnesium oxide, calcium oxide, strontium oxide, aluminum hydroxide, hydrotalcite, etc.); organometallic compounds as described in Japanese Patent Application Publication No. 2005-298598; and clays containing metal oxides. Furthermore, examples of acidic hygroscopic materials include: inorganic compounds containing silicon (e.g., silica gel, nanoporous silica, zeolite).

[0100] The preferred material for the hygroscopic particles is selected from one or more substances chosen from zeolite and hydrotalcite. Zeolite, in particular, typically exhibits exceptionally high hygroscopic capacity. Specifically, zeolite can readily achieve a high weight change rate of 10% to 30% after standing at 20°C and 90% RH for 24 hours. Furthermore, zeolite releases water upon drying, thus enabling its reuse. The hygroscopic particles can be made from a single material or by combining two or more materials in any ratio.

[0101] The primary particle size of the hygroscopic particles is preferably 30 nm or more, more preferably 40 nm or more, more preferably 150 nm or less, and more preferably 80 nm or less. The primary particle size of the hygroscopic particles represents the number-average particle size of the primary particles. The primary particle size of the hygroscopic particles can be measured using a particle size measuring device employing dynamic light scattering in a dispersion dispersed in a solvent. If the primary particle size of the hygroscopic particles cannot be measured using dynamic light scattering, it can also be measured by observation using an electron microscope. Specifically, the measurement can be performed by the following method: By observing 50 primary particles, the sum of the minor axis and major axis of each particle is calculated, and the sum is divided by 2 to determine the particle size of each particle. The arithmetic mean of the particle sizes of the 50 primary particles measured in this way can be taken as the primary particle size. When the primary particle size is determined by observation using an electron microscope, the particles in the cross-section of the organic sealing layer can be observed.

[0102] The refractive index of the hygroscopic particles at a measurement wavelength of 589 nm is preferably 1.2 or higher and 3.0 or lower. Using hygroscopic particles with such a refractive index reduces the haze of the organic sealing layer, resulting in a sealing layer with excellent transparency.

[0103] The proportion of hygroscopic particles in the organic sealing layer is not particularly limited and can be adjusted to a range that yields the desired properties. Specifically, the proportion of hygroscopic particles in the organic sealing layer is preferably 5% by weight or more, more preferably 10% by weight or more, more preferably 60% by weight or less, more preferably 40% by weight or less, and more preferably 30% by weight or less. By setting the proportion of hygroscopic particles to the lower limit or above mentioned above, the moisture intrusion inhibition effect of the organic sealing layer can be improved. Furthermore, by setting the proportion of hygroscopic particles to the upper limit or below mentioned above, the transparency of the organic sealing layer can be improved.

[0104] Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, acrylonitrile-based ultraviolet absorbers, salicylates-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, azobenzene-based ultraviolet absorbers, indole-based ultraviolet absorbers, naphthalenedicarboximide-based ultraviolet absorbers, and phthalocyanine-based ultraviolet absorbers. In this embodiment, it is particularly preferred to include one or more ultraviolet absorbers selected from benzotriazole-based and triazine-based ultraviolet absorbers.

[0105] Benzotriazole-based UV absorbers contain a benzotriazole structure within their molecules. Examples of benzotriazole-based UV absorbers include 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-p-cresol, and 2-(5-chloro-2H-benzotriazole-2-yl)-6-tert-butyl-4-methylphenol. Examples of commercially available benzotriazole-based UV absorbers include ADK STABLA-31, ADK STAB LA-32, and ADK STAB LA-36 manufactured by Adicon Ltd.

[0106] Triazine-based UV absorbers contain a triazine structure within their molecules. Preferably, compounds containing a 1,3,5-triazine structure within their molecules are triazine-based UV absorbers. Examples of triazine-based UV absorbers include 2,4,6-tris(2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol, and 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine. Examples of commercially available triazine-based UV absorbers include ADK STAB LA-F70 and ADK STAB LA-46 manufactured by Adicon Inc., and Tinuvin 1577 manufactured by BASF Japan. Other specific examples of ultraviolet absorbers include the ultraviolet absorber described in Japanese Patent Application Publication No. 2017-154401.

[0107] In addition to the aforementioned hygroscopic particles and ultraviolet absorbers, other possible components that can be included in the resin composition include, for example, dispersants, plasticizers, light stabilizers, antioxidants, lubricants, and inorganic fillers. The types, properties, and amounts of these components can be, for example, those described in International Publication No. 2019 / 220896.

[0108] Any ingredient may be used alone or in combination of two or more ingredients in any ratio.

[0109] [2.2.2. Properties of Organic Sealing Layers]

[0110] The thickness of the organic sealing layer is preferably 1 nm or more, more preferably 10 nm or more, even more preferably 80 nm or more, preferably 300 nm or less, more preferably 200 μm or less, and particularly preferably 150 μm or less. When the thickness of the organic sealing layer is at or above the aforementioned lower limit, moisture intrusion can be effectively suppressed. Furthermore, when the thickness of the organic sealing layer is at or below the aforementioned upper limit, the thickness of the device structure can be reduced. Here, the thickness of the organic sealing layer refers to the thickness of each individual layer of the organic sealing layer.

[0111] The haze of the organic sealing layer is preferably 0.5% or less, more preferably 0.15% or less, and particularly preferably 0.05% or less. When the haze is below the above range, the transparency of the organic sealing layer can be improved, thus making it suitable for applications in device structures such as organic electroluminescent devices and flexible touch sensors where light transmission is required. The haze can be measured using a turbidimeter.

[0112] [2.3. Inorganic sealing layer]

[0113] The inorganic sealing layer is a layer containing silicon nitride. In addition to silicon nitride, the inorganic sealing layer may also contain, for example, silicon oxide and silicon oxynitride.

[0114] Such an inorganic sealing layer can be formed using a polysilazane compound. More specifically, it can be formed using the formation method described in the section on [II. Manufacturing Method of Device Structure], which is described later.

[0115] The thickness of the inorganic sealing layer is preferably 1 nm or more, more preferably 10 nm or more, more preferably 300 nm or less, more preferably 200 nm or less, and particularly preferably 150 nm or less. When the thickness of the inorganic sealing layer is at or above the aforementioned lower limit, moisture intrusion can be effectively suppressed. Furthermore, when the thickness of the inorganic sealing layer is at or below the aforementioned upper limit, the thickness of the device structure can be reduced. Here, the thickness of the inorganic sealing layer refers to the thickness of each layer of the inorganic sealing layer.

[0116] [2.4. Silicone Sealing Layer]

[0117] In addition to the organic and inorganic sealing layers described above, the sealing layer of this embodiment may also include, for example, an organosilicon sealing layer. The organosilicon sealing layer comprises, for example, a siloxane compound whose main skeleton is composed of highly bond-energy Si-O bonds; more specifically, the organosilicon sealing layer comprises an organopolysiloxane. Examples of organopolysiloxanes include, for instance, dimethylpolysiloxane. Furthermore, the organosilicon sealing layer is preferably an organosilicon rubber (organosilicon elastomer). The thickness of the organosilicon sealing layer is preferably 1 nm or more, more preferably 10 nm or more, further preferably 80 nm or more, preferably 300 nm or less, and more preferably 200 nm or less.

[0118] [2.5. Sealing layer]

[0119] The overall thickness of the sealing layer can be appropriately adjusted within a range that allows it to perform the desired sealing performance as a sealing layer in the device structure. The overall thickness of the sealing layer is preferably 0.7 μm or more, more preferably 1 μm or more, more preferably 10 μm or less, and more preferably 5 μm or less. The sealing layer of this embodiment, by having a structure in which the above-described organic and inorganic sealing layers are stacked, can achieve good sealing performance with a thin thickness.

[0120] The thickness of each constituent layer constituting the sealing layer is preferably 300 nm or less, more preferably 200 nm or less. Furthermore, the lower limit of the thickness of each constituent layer can be, for example, 1 nm or more.

[0121] [3. Device Structure]

[0122] As described in the above embodiment, the device structure 10, which has an organic electroluminescent element portion as the element portion 120, can be used as a device such as a display device or a lighting device. However, the device structure is not limited to these devices. The device structure can include a wide range of devices with element portions and components that form part of the device. In particular, since the sealing layer of the device structure has excellent transparency, various optical devices and components that form part of the optical devices are preferred as the device structure. Examples of optical devices include liquid crystal display devices, touch panels, and organic electroluminescent devices that serve as both display devices and light source devices. In particular, by effectively utilizing the excellent properties of the flexible organic electroluminescent element portion, the device structure is preferably used as a flexible optical device.

[0123] [II. Manufacturing Method of Device Structure]

[0124] A method for manufacturing a device structure according to one embodiment of the present invention includes: a step (a) of preparing a multilayer having a substrate and an element portion disposed on the substrate; and a step (b) of forming a sealing layer that seals the element portion. The step (b) of forming the sealing layer includes a step (b1) of forming an organic sealing layer and a step (b2) of forming an inorganic sealing layer after step (b1). The step (b1) includes a step (b1-1) of forming an organic intermediate layer comprising a thermoplastic elastomer and a step (b1-2) of obtaining the organic sealing layer by irradiating the organic intermediate layer with vacuum ultraviolet light. The step (b2) includes a step (b2-1) of forming an intermediate layer using a liquid composition comprising a polysilazane compound and a solvent and a step (b2-2) of obtaining an inorganic sealing layer comprising silicon nitride by irradiating the intermediate layer with ultraviolet light.

[0125] Figures 2-6This is a cross-sectional view illustrating a method for manufacturing a device structure according to one embodiment of the present invention. Figures 2-6 The example shown illustrates a sealing layer 200 formed in step (b) of forming the sealing layer 200, in which a first sealing layer 201, a second sealing layer 202, a third sealing layer 203, and a second sealing layer 202 and a third sealing layer 203 are sequentially stacked relative to the component portion 120. In the manufacturing method of the device structure 10 in this example, as... Figure 2 As shown, a multilayer 100 having a substrate 110 and element portions 120 disposed on the substrate 110 is prepared (step (a)). Next, as... Figure 3 As shown, a first sealing layer 201 is formed relative to the component portion 120 (step (b3)). In Figure 3 The example shown is an example of forming an organosilicon sealing layer 230 as a first sealing layer 201. Next, as... Figure 4 As shown, a second sealing layer 202, serving as an inorganic sealing layer 220, is formed on the first sealing layer 201 (step (b4)). Next, as... Figure 5 As shown, a third sealing layer 203, serving as an organic sealing layer 210, is formed on the second sealing layer 202 (step (b5)). Next, as... Figure 6 As shown, by further repeating the above steps (b4) and (b5), a sealing layer 200 is formed.

[0126] The manufacturing method of the device structure in this embodiment improves the resistance of the organic sealing layer to solvents containing polysilazane compounds by irradiating the organic intermediate layer with vacuum ultraviolet light in step (b1). Therefore, when an inorganic sealing layer is formed on the organic sealing layer, the degradation of the organic sealing layer caused by the solvent of the polysilazane compound can be suppressed, and a sealing layer with good sealing performance can be formed.

[0127] The inventors speculate, as follows, that irradiating the organic sealing layer with vacuum ultraviolet light can improve its resistance to solvents containing polysilazane compounds. However, the scope of the present invention is not limited to the mechanism described below.

[0128] It is speculated that when a liquid composition containing a polysilazane compound and a solvent is applied to an organic sealant layer, the solvent penetrates into the organic sealant layer, thereby causing damage. In contrast, it is speculated that by irradiating the organic sealant layer with vacuum ultraviolet light, the surface of the organic sealant layer becomes denser, making it less susceptible to solvent penetration, and thus the damage is suppressed.

[0129] [1. Process (a): Preparation of multi-layered materials]

[0130] Step (a) is the step of preparing multilayer objects. Multilayer objects can be prepared by manufacturing them in-house or by purchasing them from others. For multilayer objects, the same content as described in the above item [I. Device Structure 1. Multilayer Objects].

[0131] [2. Process (b): Formation of the sealing layer]

[0132] Step (b) of forming the sealing layer includes step (b1) of forming an organic sealing layer and step (b2) of forming an inorganic sealing layer after step (b1). Step (b) includes at least the steps of performing steps (b1) and (b2) sequentially. The sealing layer preferably has a structure in which two or more organic sealing layers and two or more inorganic sealing layers are alternately stacked, so steps (b1) and (b2) are preferably repeated more than twice. In this case, steps (b1) and (b2) can be repeated in sequence, or steps (b2) and (b1) can be repeated in sequence.

[0133] [2.1. Process (b1): Formation of the organic sealing layer]

[0134] The process of forming the organic sealing layer includes a process of forming an organic intermediate layer containing a thermoplastic elastomer (b1-1) and a process of obtaining the organic sealing layer by irradiating the organic intermediate layer with vacuum ultraviolet light (b1-2).

[0135] [2.1.1. Process (b1-1): Formation of the organic intermediate layer]

[0136] Step (b1-1) is the step of forming an organic intermediate layer containing a thermoplastic elastomer. The organic intermediate layer is a layer of resin composition containing a thermoplastic elastomer, which is a layer obtained in the pre-stage of irradiation with vacuum ultraviolet light.

[0137] The preferred method for forming the organic intermediate layer is as follows: after forming a layer of a resin composition comprising a thermoplastic elastomer and a solvent, the layer of the resin composition is dried to obtain the organic intermediate layer. Hereinafter, in order to distinguish it from the solvent used in forming the inorganic sealing layer, the solvent contained in the resin composition is sometimes referred to as the "first solvent".

[0138] The resin composition comprises a thermoplastic elastomer and a first solvent. The resin composition preferably comprises any components. The thermoplastic elastomer and any components are the same as those described in the items above [I. Device Structure 2. Sealing Layer 2.2. Organic Sealing Layer].

[0139] As the first solvent, a solvent capable of dissolving or dispersing the thermoplastic elastomer can be used. Furthermore, a single first solvent can be used, or two or more can be used in combination. Especially since the component part to be sealed generally has poor resistance to moisture, a non-aqueous solvent is preferred as the first solvent. Furthermore, from the viewpoint of suppressing damage to the component part and effectively suppressing moisture infiltration, a non-polar solvent is preferred as the first solvent.

[0140] Examples of nonpolar solvents include cyclohexane, methylcyclohexane, ethylcyclohexane, hexane, toluene, benzene, xylene, decahydronaphthalene, tetrahydronaphthalene, trimethylbenzene, cyclooctane, cyclodecane, octane (e.g., n-octane), dodecane, tridecaane, tetradecaane, and cyclododecane.

[0141] The amount of nonpolar solvent relative to the total amount of 100% by weight of the first solvent is preferably 95% by weight or more, more preferably 99% by weight or more, even more preferably 99.9% by weight or more, and ideally 100% by weight.

[0142] The first solvent preferably contains a high-boiling-point solvent. The high-boiling-point solvent has a boiling point of 1 atm (1.01325 × 10⁻⁶). 5 The boiling point at 1 atm is preferably 90°C or higher, more preferably 100°C or higher, even more preferably 125°C or higher, even more preferably 150°C or higher, and particularly preferably 175°C or higher. When the first solvent contains a high-boiling-point solvent, uneven surface formation of the organic sealing layer obtained by drying the organic intermediate layer, which is a layer of resin composition containing the first solvent, can be suppressed, resulting in a smooth surface. Furthermore, nozzle clogging when applying the resin composition using inkjet printing is generally suppressed. The upper limit of the boiling point of the high-boiling-point solvent at 1 atm is preferably 300°C or lower, more preferably 250°C or lower. When the boiling point of the high-boiling-point solvent is below the upper limit of the above range, the drying of the organic intermediate layer can be easily performed.

[0143] The amount of the high-boiling-point solvent relative to the total amount of the first solvent (100% by weight) is preferably 10% by weight or more, more preferably 25% by weight or more, even more preferably 50% by weight or more, even more preferably 70% by weight or more, particularly preferably 80% by weight or more, and usually 100% by weight or less.

[0144] The resin composition is preferably a liquid composition. By using a liquid resin composition, an organic intermediate layer can be easily formed by coating. The viscosity of this liquid resin composition is preferably 1 cP or more, more preferably 2 cP or more, particularly preferably 3 cP or more, preferably 5000 cP or less, more preferably 1000 cP or less, further preferably 500 cP or less, further preferably 50 cP or less, further preferably 30 cP or less, and particularly preferably 20 cP or less. When the viscosity of the resin composition is above or below the lower limit of the above range, the thickness of the organic intermediate layer can be easily adjusted, and an organic sealing layer with a desired thickness can be easily formed. Furthermore, when the viscosity of the resin composition is below or above the upper limit of the above range, the formation of the organic intermediate layer by coating can be easily performed. In particular, when the viscosity is below 50 cP, the organic intermediate layer can be formed by inkjet printing. Viscosity can be measured using a tuning fork vibrating viscometer (such as the tuning fork vibrating viscometer SV-10 manufactured by A&D Co., Ltd.) at a measurement temperature of 25°C ± 2°C.

[0145] The proportion of solid components in the resin composition is not particularly limited, but is preferably appropriately adjusted so that properties such as viscosity are within a desired range. Specifically, the amount of solid components relative to the total amount of 100% by weight of the resin composition is preferably 1% by weight or more, more preferably 3% by weight or more, preferably 40% by weight or less, more preferably 30% by weight or less, and even more preferably 20% by weight or less.

[0146] The organic intermediate layer is preferably formed by a method that includes preparing the above-described resin composition comprising a thermoplastic elastomer and a first solvent and coating the resin composition. This allows for the easy formation of the organic intermediate layer.

[0147] Examples of coating methods include curtain coating, extrusion coating, roller coating, spin coating, dip coating, bar coating, spray coating, glide coating, printing coating, gravure coating, die coating, slot coating, and impregnation. Screen printing and inkjet printing are particularly preferred, with inkjet printing being especially preferred.

[0148] When the resin composition layer contains a first solvent, the first solvent is removed by drying it after the resin composition is applied. Examples of drying methods for the resin composition layer include natural drying, heat drying, vacuum drying, and vacuum-heat drying. If natural drying can be achieved simply by leaving the layer at room temperature for a short time, specific drying operations are unnecessary. However, since the resin composition layer typically contains a large amount of the first solvent, it is preferable to promote drying through operations such as heating or vacuum. By drying the resin composition layer and removing the first solvent from it, an organic intermediate layer formed from the solid components of the resin composition is obtained.

[0149] [2.1.2. Process (b1-2): Vacuum ultraviolet irradiation]

[0150] Step (b1-2) is the process of obtaining the organic sealing layer by irradiating the above-mentioned organic intermediate layer with vacuum ultraviolet light. By performing step (b1-2), the dibutyl ether resistance of the organic sealing layer can be improved.

[0151] As a vacuum ultraviolet light source, light with wavelengths of 100nm to 200nm can be used. Examples of vacuum ultraviolet light sources include rare gas excimer lamps. In particular, Xe excimer lamps have excellent luminous efficiency because they emit ultraviolet light with a short wavelength of 172nm in a single wavelength.

[0152] The irradiation conditions for vacuum ultraviolet light can be appropriately adjusted to a range that yields the desired organic sealing layer. In this embodiment, it is preferable to set irradiation conditions including: step (b1-2-1) of irradiating the aforementioned organic intermediate layer with vacuum ultraviolet light in an inert gas atmosphere; and step (b1-2-2) of irradiating the aforementioned organic intermediate layer after step (b1-2-1) with vacuum ultraviolet light in a mixed atmosphere of inert gas and oxygen. When irradiating with vacuum ultraviolet light in an inert gas atmosphere, solvent resistance can be imparted to the surface of the organic sealing layer; on the other hand, the wettability to solvents tends to decrease, and it tends to easily repel liquid compositions. Therefore, it is preferable to first impart solvent resistance by irradiating with vacuum ultraviolet light in an inert gas atmosphere, and then irradiate with vacuum ultraviolet light in a mixed atmosphere of inert gas and oxygen to modify a portion of the surface of the organic sealing layer and improve its coating properties to solvents.

[0153] The "inactive gas atmosphere" in process (b1-2-1) includes not only an atmosphere containing only inactive gases, but also an atmosphere containing both inactive gases and trace amounts of oxygen. Specifically, the oxygen concentration in the aforementioned inactive gas atmosphere is preferably 500 ppm or more, more preferably 1000 ppm or more, more preferably 10000 ppm or less, and more preferably 5000 ppm or less. The unit "ppm" refers to mass.

[0154] Examples of inert gases include nitrogen, helium, neon, and argon, with nitrogen being particularly preferred. Furthermore, an inert gas can be used alone or in combination of two or more. When using an inert gas, ultraviolet irradiation can be performed, for example, in a treatment chamber that supplies and exhausts the inert gas. In this case, the flow rates of oxygen and inert gas introduced into the treatment chamber can be adjusted to regulate the oxygen concentration in the atmosphere.

[0155] The intensity of vacuum ultraviolet irradiation in a non-reactive gas atmosphere can be appropriately adjusted to a range that yields the desired organic sealing layer. When a specific range is given, the irradiation intensity is preferably 30 mW / cm². 2 The above is preferred, with 40mW / cm being even more desirable. 2 The above is further optimized to 50mW / cm. 2 The above is preferably 100mW / cm 2 The preferred value is 80mW / cm. 2 The following is a further preferred value: 60mW / cm 2 the following.

[0156] The irradiation time of vacuum ultraviolet light in an inactive gas atmosphere can be appropriately adjusted to a range that yields the desired organic sealing layer. When a specific range is shown, the irradiation time is preferably 100 seconds or more, more preferably 150 seconds or more, more preferably 300 seconds or less, and more preferably 250 seconds or less.

[0157] The "mixed atmosphere of inactive gas and oxygen" in process (b1-2-2) refers to an atmosphere containing both inactive gas and oxygen. The oxygen concentration can be adjusted to a degree that changes the wettability of the organic sealing layer surface to the solvent. Specifically, the oxygen concentration is preferably 1% or more, more preferably 3% or more, more preferably 20% or less, and more preferably 10% or less. The unit "%" refers to mass.

[0158] Furthermore, the irradiation intensity of vacuum ultraviolet light in a mixed atmosphere of inert gas and oxygen can be appropriately adjusted to a range that yields the desired organic sealing layer. When a specific range is given, the irradiation intensity is preferably 30 mW / cm². 2 The above is preferred, with 40mW / cm being even more desirable. 2 The above is further optimized to 50mW / cm. 2 The above is preferably 100mW / cm 2 The preferred value is 80mW / cm. 2 The following is a further preferred value: 60mW / cm 2 the following.

[0159] The irradiation time of vacuum ultraviolet light in a mixed atmosphere of inactive gas and oxygen can be appropriately adjusted to a range that yields the desired organic sealing layer. When a specific range is shown, it is preferably 100 seconds or more, more preferably 150 seconds or more, more preferably 300 seconds or less, and more preferably 250 seconds or less.

[0160] The irradiation conditions, such as the intensity and duration of vacuum ultraviolet irradiation in process (b1-2), can be adjusted based on, for example, the reduction in the peak intensity of CH stretching in the FT-IR spectrum of the organic intermediate layer (organic sealing layer) before and after vacuum ultraviolet irradiation. Specifically, when the peak intensity of CH stretching in the FT-IR spectrum of the organic intermediate layer before vacuum ultraviolet irradiation is set to I1, and the peak intensity of CH stretching in the FT-IR spectrum of the organic intermediate layer after vacuum ultraviolet irradiation is set to I2, it is preferable to set the irradiation condition where the ratio of I2 to I1 (I2 / I1) is 50% or less. Furthermore, it is preferable to set the irradiation condition where I2 / I1 is 20% or more. This is because, when I2 / I1 is within the above range, it is easy to obtain an organic sealing layer with good dibutyl ether resistance. For example, at 2960 cm⁻¹... -1 ~2850cm -1 Observe the peaks from CH stretching in the FT-IR spectrum within the range.

[0161] [2.2. Process (b2): Formation of the inorganic sealing layer]

[0162] The step (b2) of forming the inorganic sealing layer includes a step (b2-1) of forming an intermediate layer using a liquid composition containing a polysilazane compound and a solvent, and a step (b2-2) of obtaining an inorganic sealing layer containing silicon nitride by irradiating the intermediate layer with ultraviolet light. Since the inorganic sealing layer is formed on the organic sealing layer, it can indirectly seal the component. In cases where the sealing layer has two or more inorganic sealing layers, the inorganic sealing layer can also be formed directly on the component, for example.

[0163] [2.2.1. Process (b2-1): Formation of the intermediate layer]

[0164] Step (b2) includes step (b2-1) of forming an intermediate layer using a liquid composition comprising a polysilazane compound and a solvent. The intermediate layer is a layer comprising a polysilazane compound.

[0165] The intermediate layer comprising the above-mentioned polysilazane compound is preferably formed by a method including the step of coating a liquid composition comprising the polysilazane compound and a solvent. According to this method, the intermediate layer can be easily formed.

[0166] Polysilazane compounds are polymers containing silicon-nitrogen bonds. Examples of polysilazane compounds include SiO2, Si3N4, and intermediate solid solutions of both, such as SiO2. x N y Polysilazane compounds that can be used as precursors for ceramics.

[0167] Preferred polysilazane compounds include, for example, compounds containing repeating units represented by the following formula (1).

[0168] [Chemical Formula 1]

[0169]

[0170] In equation (1), R 1 R 2 and R 3 Each group independently represents one or more groups selected from hydrogen atoms and monovalent organic groups. Examples of monovalent organic groups include: aliphatic hydrocarbon groups such as alkyl and alkenyl; alicyclic hydrocarbon groups such as cycloalkyl; aromatic hydrocarbon groups such as aryl; alkylsilyl; alkylamino; alkoxy, etc. As the polysilazane compound represented by formula (1), the polysilazane compound described in Japanese Patent Application Publication No. 8-112879 can be used.

[0171] Especially from the perspective of obtaining an inorganic sealing layer with excellent sealing performance, R 1 R 2 and R 3 Hydrogen atoms are preferred. R in repeating units 1 R 2 and R 3 Polysilazane compounds consisting entirely of hydrogen atoms are sometimes called perhydropolysilazanes. The number-average molecular weight (Mn) of perhydropolysilazanes can be, for example, around 600 to 2000 (converted from polystyrene).

[0172] Other preferred polysilazane compounds include, for example, silanolate addition polysilazanes obtained by reacting a silanolate with a polysilazane compound containing a repeating unit represented by formula (1) (Japanese Patent Application Publication No. 5-238827), glycidyl addition polysilazanes obtained by reacting glycidyl with a polysilazane compound containing a repeating unit represented by formula (1) (Japanese Patent Application Publication No. 6-122852), alcohol addition polysilazanes obtained by reacting an alcohol with a polysilazane compound containing a repeating unit represented by formula (1) (Japanese Patent Application Publication No. 6-240208), and metal carboxylates with a polysilazane compound containing formula (1). The invention relates to polysilazanes obtained by reacting a polysilazane compound containing a repeating unit as shown in the invention (Japanese Patent Application Publication No. 6-299118), polysilazanes obtained by reacting a metal-containing acetylacetonato complex with a polysilazane compound containing a repeating unit as shown in formula (1), and polysilazanes with added metal particles obtained by adding metal particles to a polysilazane compound containing a repeating unit as shown in formula (1) (Japanese Patent Application Publication No. 7-196986).

[0173] Polysilazane compounds can be used alone or in combination of two or more. For example, a combination of perhydropolysilazane and organopolysilazane in which a portion of the hydrogen atoms bonded to the Si atom are replaced by organic groups such as alkyl groups can also be used. When perhydropolysilazane and organopolysilazane are used in combination, the toughness of the second sealing layer can be improved, thus suppressing cracking. In particular, when organopolysilazane substituted with methyl groups is used in combination with perhydropolysilazane, toughness is significantly improved.

[0174] Alternatively, only perhydropolysilazane can be used as the polysilazane compound. Inorganic sealing layers formed using only perhydropolysilazane tend to be prone to cracking. In this embodiment, even when forming an inorganic sealing layer that is so prone to cracking, cracking can be suppressed by combining it with an organic sealing layer.

[0175] Polysilazane compounds can typically be in liquid or solid form. Commercially available polysilazane compounds are also available.

[0176] Liquid compositions typically contain a solvent. Hereinafter, to distinguish it from the first solvent used to form the organic intermediate layer, the solvent used to form the intermediate layer is sometimes referred to as the "second solvent." As the second solvent, a solvent containing dibutyl ether is preferred. The content of dibutyl ether in the second solvent is preferably 50% by weight or more, more preferably 70% by weight or more, and even more preferably 90% by weight or more. This is because, in step (b1), the dibutyl ether resistance of the organic sealing layer can be improved by irradiation with vacuum ultraviolet light; therefore, by including dibutyl ether as the second solvent, the effects brought about by this embodiment can be highly utilized.

[0177] Furthermore, as a second solvent, a solvent in which the residual film rate of the organic sealing layer in the dissolution test of the second solvent is 90% or more can also be used. In this embodiment, a step (b2-3) for selecting a second solvent may be included, wherein the second solvent is a solvent in which the residual film rate of the aforementioned organic sealing layer in the dissolution test of the second solvent is 90% or more. In selecting the second solvent, for example, after preparing a sample in which an organic sealing layer is formed on a support substrate such as a silicon substrate under the same conditions as in step (b1) and irradiating it with vacuum ultraviolet light, the sample is immersed in the second solvent under the same conditions as in the dibutyl ether dissolution test and then dried. The residual film rate is calculated from the thickness of the organic sealing layer before and after immersion, and a solvent in which the residual film rate is 90% or more can be selected as the second solvent. The irradiation conditions with vacuum ultraviolet light can be, for example, the following: at a temperature of 23–25°C and a humidity of 50–60%, in an inert gas atmosphere (e.g., in a nitrogen atmosphere) with an illuminance of 30 mW / cm². 2 Irradiate with vacuum ultraviolet light (VUV (172nm)) for 3 minutes.

[0178] Examples of second solvents include: hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons; halogenated hydrocarbon solvents; and ether solvents such as aliphatic ethers and alicyclic ether solvents. Specific examples include: hydrocarbon solvents such as pentane, hexane, cyclohexane, toluene, xylene, solvesses, and turpentine; halogenated hydrocarbon solvents such as dichloromethane and trichloroethane; and dibutyl ether, ... Alkane, tetrahydrofuran, and other ether solvents. The second solvent can be used alone or in combination of two or more in any ratio.

[0179] The amount of the second solvent in the liquid composition is preferably adjusted to control the concentration of the polysilazane compound in the liquid composition within an appropriate range. When a specific range is given, the amount of the polysilazane compound is preferably 0.2% to 35% by weight relative to 100% of the total amount of the liquid composition.

[0180] The liquid composition may contain any component other than the polysilazane compound and the second solvent.

[0181] There are no particular limitations on the coating method for the liquid composition. As an example of a coating method, the same method used for coating resin compositions for forming organic intermediate layers can be used. By such coating, an intermediate layer as a layer of the liquid composition can be formed under atmospheric pressure.

[0182] Since the intermediate layer contains a second solvent, step (b2-1) may include a step (b2-4) of drying the intermediate layer. Drying may be performed simultaneously with step (b2-2), but is preferably performed before step (b2-2). The second solvent can be removed from the intermediate layer by drying.

[0183] The drying of the intermediate layer is preferably carried out in an atmosphere with a low oxygen concentration. Specifically, the oxygen concentration of the atmosphere is preferably 10% or less, more preferably 5% or less. By drying in an atmosphere with such a low oxygen concentration, the absorption of oxygen by the intermediate layer can be suppressed. Therefore, the absorption of ultraviolet light irradiated in step (b2-2) by oxygen can be suppressed, thus enabling the reaction of the polysilazane compound to proceed stably.

[0184] From the viewpoint of drying in an atmosphere with low oxygen concentration, the drying of the intermediate layer is preferably carried out in an atmosphere of inert gas. Examples of inert gases include nitrogen, helium, neon, and argon, with nitrogen being particularly preferred. Furthermore, an inert gas can be used alone or in combination of two or more. When using an inert gas, drying can be carried out, for example, in a drying chamber that supplies and exhausts the inert gas. Additionally, heating can be performed during drying.

[0185] [2.2.2. Process (b2-2): Ultraviolet irradiation of the intermediate layer]

[0186] Step (b2) includes step (b2-2) of irradiating the intermediate layer with ultraviolet light after obtaining the intermediate layer in step (b2-1). By irradiating the intermediate layer with ultraviolet light, the polysilazane compound contained in the intermediate layer reacts to obtain an inorganic sealing layer containing silicon nitride.

[0187] As the ultraviolet light source, light with wavelengths from 1 nm to 380 nm can be used. Vacuum ultraviolet light with wavelengths from 100 nm to 200 nm is particularly preferred. By irradiating with vacuum ultraviolet light, the modification reaction of the polysilazane compound can be carried out in a short time, thus suppressing damage to the component and organic sealing layer caused by ultraviolet light. The source of the vacuum ultraviolet light is the same as that described in the item [2.1.2. Process (b1-2): Irradiation with vacuum ultraviolet light] above.

[0188] The intensity of ultraviolet radiation can be appropriately adjusted to a range that yields the desired inorganic sealing layer. When a specific range is given, the preferred intensity is 10 mW / cm². 2 The above, more preferably 100mW / cm 2 The above is preferably 300mW / cm 2 The following is more preferably 200mW / cm 2 The following, especially process (b2-2), preferably includes one or more steps at 100mW / cm. 2 ~200mW / cm 2 The maximum intensity of ultraviolet irradiation. Based on the ultraviolet irradiation at such intensity, the modification reaction of polysilazane compounds can be carried out in a short time or damage to the component and organic sealing layer caused by ultraviolet radiation can be suppressed.

[0189] The irradiation time of ultraviolet light can be appropriately adjusted to a range that yields the desired inorganic sealing layer. When a specific range is shown, the irradiation time is preferably 0.1 seconds or more, more preferably 0.5 seconds or more, preferably 10 minutes or less, more preferably 3 minutes or less, and even more preferably 1 minute or less. With irradiation of ultraviolet light for such a duration, the modification reaction of the polysilazane compound can be fully carried out, reducing deviations in sealing ability or suppressing damage to the component and organic sealing layer caused by ultraviolet light.

[0190] The ultraviolet irradiation is preferably carried out in an atmosphere with a low oxygen concentration. Specifically, the oxygen concentration of the atmosphere is preferably 500 ppm or more, more preferably 1000 ppm or more, more preferably 10000 ppm or less, and even more preferably 5000 ppm or less. The unit "ppm" refers to mass. When the oxygen concentration of the atmosphere irradiating the ultraviolet light is within the above range, the modification reaction of the polysilazane compound can be effectively promoted, and the resulting inorganic sealing layer can have good sealing ability.

[0191] From the viewpoint of performing ultraviolet irradiation in an atmosphere with low oxygen concentration, ultraviolet irradiation of the intermediate layer is preferably carried out in an inert gas atmosphere. The type of inert gas and the ultraviolet irradiation conditions in the inert gas atmosphere can be the same as those described in the item [2.1.2. Process (b1-2): Vacuum ultraviolet irradiation] above.

[0192] [2.3. Process (c): Formation of the silicone sealing layer]

[0193] In this embodiment, a step of forming an organosilicon sealing layer may also be included. As a method for forming the organosilicon sealing layer, one example is a method of irradiating the layer with ultraviolet light after forming a layer containing a polysilazane compound. The ultraviolet irradiation conditions can, for example, be the same as the ultraviolet irradiation conditions for the intermediate layer described above in [2.2.2. Step (b2-2): Ultraviolet Irradiation of the Intermediate Layer].

[0194] [3. Variations]

[0195] The manufacturing method of the device structure in this embodiment does not limit the number of repetitions and the number of processes (b1 and b2) as long as process (b) is performed sequentially. It can also be appropriately adjusted according to the desired layer structure of the sealing layer.

[0196] As such a process, an example is the following process: the above process (b) includes a process of forming a first sealing layer (b3), a process of forming a second sealing layer disposed on the first sealing layer as the inorganic sealing layer (b4), and a process of forming a third sealing layer disposed on the second sealing layer as the organic sealing layer (b5). The above process (b) includes a process of performing the above process (b4) and the above process (b5) at least twice alternately. The above process (b4) is the above process (b2), and the above process (b5) is the above process (b1).

[0197] When forming two or more organic sealing layers and two or more inorganic sealing layers, process (b1) and process (b2) can be performed the same number of times, process (b1) can be performed more times than process (b2), or process (b1) can be performed less times than process (b2).

[0198] In the above Figures 2-6 The example described is of forming an organosilicon sealing layer as the first sealing layer, but an organic sealing layer can also be formed, for example, as the first sealing layer.

[0199] Furthermore, although not illustrated, a double-layer sealing layer can be formed, for example, by forming an organic sealing layer on the component and then forming an inorganic sealing layer.

[0200] For example, a method for manufacturing a device structure may include a step of forming an arbitrary layer. Therefore, a method for manufacturing a device structure may also include a step of forming an arbitrary layer between the element portion and the sealing layer. Furthermore, a method for manufacturing a device structure may also include a step of forming an arbitrary layer that covers the sealing portion. As a specific example, in the case of a display device having an organic electroluminescent element portion, the method for manufacturing this device structure may also include a step of applying a layer of circular polarizer to the sealing layer via an adhesive as needed.

[0201] The above-described manufacturing method can also be performed under atmospheric pressure, including either step (b1) of forming the organic sealing layer 210 and step (b2) of forming the inorganic sealing layer 220. Therefore, large and complex manufacturing equipment is not required, enabling the device structure 10 to be manufactured at low cost. Furthermore, in particular, when forming the organic intermediate layer and intermediate body layer using a coating method, the layers can be formed using a wet process, thus suppressing the deterioration of the component portion caused by particles such as plasma dust.

[0202] Example

[0203] The present invention will be specifically described below with reference to embodiments. However, the present invention is not limited to the embodiments shown below, and can be implemented in any way without departing from the scope of the claims and their equivalents.

[0204] In the following instructions, unless otherwise specified, "%" and "parts" refer to quantities based on weight. Furthermore, unless otherwise specified, the operations described below are performed under normal temperature and pressure conditions.

[0205] [Evaluation Method]

[0206] [Young's modulus, tensile elongation, and tanδ of the resin]

[0207] The Young's modulus and elongation at 23°C were determined according to JIS K7113. The loss tangent tanδ (loss modulus / storage modulus) of the resin at temperatures above 40°C and below 200°C was measured using a dynamic viscoelasticity measuring device DMS6100 manufactured by Hitachi High Tech Co., Ltd., after the resin was prepared into a film and cut into test pieces with a width of 10 mm and a length of 20 mm.

[0208] [Evaluation of sealing performance under high temperature and high humidity conditions]

[0209] The aforementioned device structure was left to stand in a test environment of 60°C and 90% RH. After 0 hours, 24.5 hours, 138 hours, 210 hours, and 284.5 hours, the emitting surface was observed under a microscope to check for any discoloration. Furthermore, the shrinkage was measured after 0 hours, 24.5 hours, 138 hours, 210 hours, 284.5 hours, and 500 hours. Shrinkage refers to the length of the non-emitting portion measured after a specified time, starting from the end of the initial emitting portion.

[0210] [Manufacturing Example 1: Manufacturing of modified products based on silicon-containing polar groups of hydrogenated aromatic vinyl compounds-conjugated diene block copolymers]

[0211] (P1-1. Preparation of hydrogenated block copolymers)

[0212] Using styrene as an aromatic vinyl compound and isoprene as a chain conjugated diene compound, a hydride (hydrogenated block copolymer) of a block copolymer having a triblock structure with polymer blocks [A] bonded to both ends of polymer blocks [B] is produced by the following steps.

[0213] In a stirred reactor with fully nitrogen-purified interior, 256 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene, and 0.615 parts of dibutyl ether were added. While stirring at 60°C, 1.35 parts of n-butyllithium (15% cyclohexane solution) were added to initiate polymerization. The reaction was further carried out at 60°C for 60 minutes with stirring. The polymerization conversion rate at this point was 99.5% (polymerization conversion rate was determined by gas chromatography; the same applies below).

[0214] Next, 50.0 parts of dehydrated isoprene were added, and the mixture was stirred for another 30 minutes at the same temperature. At this point, the polymerization conversion rate was 99%.

[0215] Then, 25.0 parts of dehydrated styrene were added, and the mixture was stirred at the same temperature for 60 minutes. At this point, the polymerization conversion rate was approximately 100%.

[0216] Next, 0.5 parts of isopropanol were added to the reaction solution to terminate the reaction and obtain a solution (i) containing the block copolymer.

[0217] The block copolymer in the obtained solution (i) had a weight-average molecular weight (Mw) of 44,900 and a molecular weight distribution (Mw / Mn) of 1.03 (determined by gel permeation chromatography with tetrahydrofuran as solvent, converted to polystyrene values. The same applies below).

[0218] Next, solution (i) was transferred to a pressure reactor equipped with a stirrer. 4.0 parts of a silica-alumina supported nickel catalyst (E22U, 60% nickel loading; manufactured by Nichih Chemical Industry Co., Ltd.) and 350 parts of dehydrated cyclohexane were added to solution (i) and mixed. The reactor was purged with hydrogen, and hydrogen was further supplied while stirring the solution. The hydrogenation reaction was carried out for 6 hours at 170°C and 4.5 MPa, thereby hydrogenating the block copolymer to obtain a solution (iii) containing hydride (ii) of the block copolymer. The weight-average molecular weight (Mw) of hydride (ii) in solution (iii) was 45,100, and the molecular weight distribution (Mw / Mn) was 1.04.

[0219] After the hydrogenation reaction is complete, solution (iii) is filtered to remove the hydrogenation catalyst. Then, 1.0 part of a xylene solution containing 0.1 part of 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetratert-butyldibenzo[d,f][1.3.2]dioxaphosphepine (Sumitomo Chemical Co., Ltd., "Sumilizer (registered trademark) GP", hereinafter referred to as "antioxidant A") as a phosphorus-based antioxidant is added to the filtered solution (iii) to dissolve it, thus obtaining solution (iv).

[0220] Next, the solution (iv) was filtered through a ZetaPlus (registered trademark) 30H filter (manufactured by Kunuo Corporation, pore size 0.5μm~1μm), and then further filtered sequentially through another metal fiber filter (pore size 0.4μm, manufactured by NICHIDAI Corporation) to remove minute solid components. Using a cylindrical concentrator (product name "CONTRO", manufactured by Hitachi, Ltd.), cyclohexane, xylene, and other volatile components used as solvents were removed from the filtered solution (iv) at a temperature of 260°C and a pressure below 0.001MPa. Then, the solid components were extruded in a molten state into strands through a die directly connected to the concentrator, cooled, and cut using a granulator to obtain 85 parts of granules (v) containing the hydride of the block copolymer and antioxidant A. The resulting granules (v) contain a hydrogenated block copolymer with a weight-average molecular weight (Mw) of 45,000 and a molecular weight distribution (Mw / Mn) of 1.08. Furthermore, through... 1 The hydrogenation rate, as determined by H-NMR, was 99.9%.

[0221] (P1-2. Preparation of silane-modified hydrogenated block copolymers)

[0222] Relative to 100 parts of the granules (v) obtained in the above process (P1-1), 2.0 parts of vinyltrimethoxysilane and 0.2 parts of di-tert-butyl peroxide were added to obtain a mixture. This mixture was kneaded using a biaxial extruder at a barrel temperature of 210°C and a residence time of 80-90 seconds. The kneaded mixture was extruded and cut using a granulator to obtain granules (vi) of the silane-modified hydrogenated block copolymer. Film-like test pieces were prepared from this granule (vi), and the glass transition temperature Tg was evaluated using a dynamic viscoelasticity measuring device with a tanδ peak value, which was 124°C. Furthermore, the peak value of the tanδ of this granule (vi) was 1.3 at temperatures above 40°C and below 200°C. The Young's modulus of this granule (vi) at 23°C was 0.5 GPa, and the elongation at break was 550%. Furthermore, the refractive index (n1) of this granule (vi), measured by an Abbe refractometer, was 1.50.

[0223] [Manufacturing Example 2: Manufacturing of a Resin Composition for Forming an Organic Sealing Layer]

[0224] (P2-1. Preparation of hygroscopic particulate dispersions)

[0225] 10 g of primary zeolite particles with a number average particle size of 50 nm (refractive index 1.5), 4 g of a dispersant with alkaline adsorption groups (containing hydroxycarboxylic acid ester, trade name "DISPERBYK108", manufactured by BYK Chemical Company), and 46 g of cyclohexane were mixed and dispersed using a bead mill. This process prepared a 17% zeolite dispersion.

[0226] (P2-2. Preparation of polymer solutions)

[0227] 28g of the granules (vi) obtained in Manufacturing Example 1 and 12g of plasticizer (a plasticizer containing an aliphatic hydrocarbon polymer, product name "Nisseki Polybutene LV-100", manufactured by Nippon Oil Co., Ltd., refractive index 1.50, number average molecular weight 500) were mixed with 60g of cyclohexane and dissolved. Through this operation, a polymer solution 1 with a solid content of 40% was prepared.

[0228] (P2-3. Preparation of resin compositions)

[0229] 60g of the zeolite dispersion 1 obtained in step (P2-1) above was mixed with 100g of the polymer solution 1 obtained in step (P2-2) above to obtain resin solution 1 as a resin composition. The viscosity of the obtained resin solution 1 was measured. A tuning fork type vibratory viscometer "SV-10" manufactured by A&D Co., Ltd. was used for the viscosity measurement. The measurement was performed as follows: the container was filled with resin solution 1 until the liquid level reached the baseline of the sample container, and a vibrator was added to the resin solution to the specified position. Furthermore, the measurement was performed at an environment of 25°C ± 2°C. The resulting viscosity of resin solution 1 was 400 cP.

[0230] [Manufacturing Example 3: Manufacturing of a liquid composition for an organosilicon sealing layer (PDMS layer)]

[0231] A solution of Shin-Etsu Chemical's X-34-4184-A, X-34-4184-B, and D5 KF-995 in a weight ratio of X-34-4184-A∶X-34-4184-B∶D5 KF-995 = 1∶1∶16 was mixed to prepare a liquid composition for PDMS layer.

[0232] [Manufacturing Example 4: Preparation of Liquid Composition for Inorganic Sealing Layers]

[0233] A liquid composition was prepared by mixing PHPS X-45-850 (20wt% dibutyl ether solution) manufactured by Shin-Etsu Chemical Co., Ltd. and dibutyl ether (DBE) in a weight ratio of PHPS X-45-850∶DBE=1∶1.

[0234] [Manufacturing Example 5: Manufacturing of a multilayer material having an organic electroluminescent element section]

[0235] Prepare a glass substrate with dimensions of 40mm x 40mm. Sequentially form a transparent electrode layer with a thickness of 100nm, a hole transport layer with a thickness of 10nm, a yellow light-emitting layer with a thickness of 20nm, an electron transport layer with a thickness of 15nm, an electron injection layer with a thickness of 1nm, and a reflective electrode layer with a thickness of 100nm on the glass substrate.

[0236] The hole transport layer and the electron transport layer are all formed of organic materials. The materials forming each layer from the transparent electrode layer to the reflective electrode layer are described below.

[0237] • Transparent electrode layer; tin-doped indium oxide (ITO)

[0238] Hole transport layer; 4,4'-bis[N-(naphthyl)-N-phenylamino]biphenyl (α-NPD)

[0239] • Yellow luminescent layer; α-NPD with 1.5 wt% rubrene added

[0240] • Electron transport layer; o-phenanthroline derivative (BCP)

[0241] • Electron injection layer; Lithium fluoride (LiF)

[0242] • Reflective electrode layer; Al

[0243] The transparent electrode layer is formed using reactive sputtering with an ITO target.

[0244] Furthermore, the formation from the hole transport layer to the reflective electrode layer is carried out in the following manner: a substrate with a transparent electrode layer already formed is placed in a vacuum evaporation apparatus, and materials from the hole transport layer to the reflective electrode layer are sequentially deposited by resistance heating.

[0245] Through the above operations, a multilayer material having a glass substrate and an organic electroluminescent element is obtained. The organic electroluminescent element has, in sequence, a transparent electrode layer, a hole transport layer, a yellow light-emitting layer, an electron transport layer, an electron injection layer, and a reflective electrode layer.

[0246] [Example]

[0247] The liquid composition for the PDMS layer obtained in Manufacturing Example 3 was coated by spin coating (conditions: 1 mL drop volume, 6000 rpm, 30 seconds) to cover the organic electroluminescent element portion of the multilayer material prepared in Manufacturing Example 5, and then dried. The coating was then applied at 12 mW / cm². 2 The PDMS layer was cured by UV irradiation (365nm) for 200 seconds. Then, the PDMS layer was cured in a N2 atmosphere at 55mW / cm². 2 Irradiate with VUV (172nm) for 130 seconds. Through the above steps, a PDMS layer (first sealing layer) with a thickness of approximately 170nm is obtained.

[0248] Next, the liquid composition used to manufacture the inorganic sealing layer of Example 4 was coated by spin coating (conditions: 1 mL drop volume, 6000 rpm, 30 seconds), dried, and then subjected to a nitrogen atmosphere at 55 mW / cm². 2 Irradiate with VUV (172nm) for 220 seconds. Through the above steps, an inorganic sealing layer (second sealing layer) with a thickness of 130nm is obtained. This process is equivalent to process (b2).

[0249] Next, the resin composition obtained in Manufacturing Example 2 was coated by spin coating (conditions: 1 mL drop volume, 6000 rpm, 60 seconds), and allowed to dry to form an organic intermediate layer. Then, the organic intermediate layer was subjected to a nitrogen atmosphere with a spray pressure of 55 mW / cm². 2Irradiate with VUV (172nm) for 220 seconds. Then, introduce oxygen to bring the O2 concentration in the system to 5%, and irradiate in a mixed atmosphere of N2 and O2 at 55mW / cm². 2 Irradiate with VUV (172nm) for 220 seconds. Obtain an organic sealing layer (third sealing layer) with a thickness of 100nm through the following steps. This process is equivalent to process (b1).

[0250] Then, repeat steps (b2) and (b1) to produce a product with... Figure 1 The seven-layer sealing layer is shown. Through the above steps, the device structure is obtained.

[0251] Furthermore, the resin composition obtained in Manufacturing Example 2 was coated onto a silicon substrate to form an organic sealing layer, similar to the third sealing layer. Under a N2 atmosphere, at 23°C–25°C and 50%–60% humidity, and with an illuminance of 30 mW / cm², the mixture was subjected to [further treatment / treatment]. 2 Samples were obtained after irradiation with VUV (172 nm) for 3 minutes. After measuring the thickness T1 of the organic sealing layer in the obtained samples, the samples were immersed in dibutyl ether for 60 seconds and then allowed to air dry. The thickness T2 of the organic sealing layer in the air-dried samples was then measured. The residual film rate of the organic sealing layer in the dissolution test relative to dibutyl ether was calculated from the measured values ​​of T1 and T2, and the result was 97%.

[0252] [Comparative Example]

[0253] Similar to the embodiment, a PDMS layer and an inorganic sealing layer are fabricated on the organic electroluminescent element portion of the multilayer structure. Next, by repeating the same steps as with the first PDMS layer, a third PDMS layer is formed on the second inorganic sealing layer. Then, by repeating the same steps as with the second inorganic sealing layer and the first PDMS layer, the inorganic sealing layer and the PDMS layer are further stacked alternately in pairs to fabricate a sealing layer with a seven-layer structure. The device structure is obtained through these steps.

[0254] [result]

[0255] The photograph of the luminescent surface used in the sealing performance evaluation under high temperature and high humidity conditions is shown. Figure 7 The graph representing the change in shrinkage over time is shown in... Figure 8 .like Figure 7 and 8 As shown, the embodiment including the organic and inorganic sealing layers of this invention showed no discoloration on the luminescent surface even after 284.5 hours, and the change in shrinkage was small, demonstrating good sealing performance. On the other hand, in the comparative example, it was confirmed that the number of discoloration points gradually increased after 138 hours, and the shrinkage also increased.

[0256] [Reference Example]

[0257] The resin composition obtained in Manufacturing Example 2 was coated onto a silicon substrate and heated at 100°C for 1 minute to form an organic layer with a thickness of 120 nm. The layer was then heated in a nitrogen atmosphere with an illuminance of 30 mW / cm². 2 The organic layer was irradiated with VUV (172 nm), and the FT-IR spectra before and after irradiation were measured. The results confirmed that the wavelength at 2925 cm⁻¹ was [missing information]. -1 The peak intensity decreased before and after VUV irradiation. Furthermore, by adjusting the irradiation time, the correlation between the ratio of I2 to I1 (with the peak intensity before VUV irradiation set to I1 and the peak intensity after irradiation set to I2) and the residual film rate in the dibutyl ether dissolution test was studied. The results confirmed that the residual film rate of the organic layer with an I2 / I1 ratio below 50% was above 90%. In the FT-IR spectrum, the peak intensity at 2925 cm⁻¹... -1 The peak is from the stretching vibration of CH.

[0258] In the reference example, the VUV irradiation time and residual film rate are as follows.

[0259] • Irradiation time: 1 minute; residual film rate: 80%

[0260] • Irradiation time: 3 minutes; residual film rate: 97%

[0261] • Irradiation time: 5 minutes; residual film rate: 100%

[0262] Explanation of reference numerals in the attached figures

[0263] 10: Device Structure

[0264] 100: Multi-layered structures

[0265] 110: Substrate

[0266] 120: Components Department

[0267] 121: First electrode layer

[0268] 122: Emissive layer

[0269] 123: Second electrode layer

[0270] 200: Sealing layer

[0271] 201: First sealing layer

[0272] 202: Second sealing layer

[0273] 203: Third sealing layer

[0274] 210: Organic sealing layer

[0275] 220: Inorganic sealing layer

[0276] 230: Silicone sealing layer

Claims

1. A device structure comprising: a multilayer having a substrate and an element portion disposed on the substrate; and a sealing layer for sealing the element portion. The sealing layer has a structure in which an organic sealing layer and an inorganic sealing layer are sequentially stacked relative to the element portion. The inorganic sealing layer comprises silicon nitride. The organic sealing layer comprises a thermoplastic elastomer, and The residual film rate of the organic sealing layer in the dibutyl ether dissolution test was over 90%. The thermoplastic elastomer is a modified product of hydrogenated aromatic vinyl compound-conjugated diene block copolymer based on silicon-containing polar groups.

2. The device structure according to claim 1, wherein, The sealing layer includes: a first sealing layer disposed on the component portion; and two or more second sealing layers and two or more third sealing layers disposed on the first sealing layer, wherein the sealing layer has a structure in which the second sealing layer and the third sealing layer are alternately stacked. The second sealing layer is the inorganic sealing layer, and the third sealing layer is the organic sealing layer.

3. The device structure according to claim 2, wherein, The first sealing layer is the organic sealing layer or an organosilicon sealing layer containing organosilicon.

4. The device structure according to claim 1 or 2, wherein, The hydrogenated aromatic vinyl compound-conjugated diene block copolymer has a structure in which both non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds are hydrogenated.

5. The device structure according to claim 1 or 2, wherein, The organic sealing layer comprises one or more selected from hygroscopic particles and ultraviolet absorbers.

6. The device structure according to claim 1 or 2, wherein, The thickness of each constituent layer included in the sealing layer is less than 300 nm.

7. The device structure according to claim 1 or 2, wherein, The element section is an organic electroluminescent element section.

8. A method for manufacturing a device structure, comprising the following steps: Step (a) involves preparing a multilayer having a substrate and element portions disposed on the substrate; and Step (b) involves forming a sealing layer that seals the component portion. The step (b) of forming the sealing layer includes a step (b1) of forming an organic sealing layer and a step (b2) of forming an inorganic sealing layer after step (b1). The process (b1) includes a process (b1-1) of forming an organic intermediate layer containing a thermoplastic elastomer and a process (b1-2) of irradiating the organic intermediate layer with vacuum ultraviolet light to obtain the organic sealing layer in such a way that the residual film rate of the organic sealing layer in the dissolution test relative to dibutyl ether is more than 90%. The thermoplastic elastomer is a modified product based on silicon-containing polar groups of a hydrogenated aromatic vinyl compound-conjugated diene block copolymer. The process (b2) includes a process (b2-1) of forming an intermediate layer using a liquid composition comprising a polysilazane compound and a solvent, and a process (b2-2) of irradiating the intermediate layer with ultraviolet light to obtain an inorganic sealing layer comprising silicon nitride. The liquid composition in step (b2-1) contains dibutyl ether as the solvent.

9. The method for manufacturing the device structure according to claim 8, wherein, The process (b1-2) includes a process (b1-2-1) of irradiating the organic intermediate layer with vacuum ultraviolet light in an inert gas atmosphere and a process (b1-2-2) of irradiating the organic intermediate layer after process (b1-2-1) with vacuum ultraviolet light in a mixed atmosphere of inert gas and oxygen.

10. The method for manufacturing the device structure according to claim 8 or 9, wherein, Step (b) includes a step (b3) of forming a first sealing layer, a step (b4) of forming a second sealing layer disposed on the first sealing layer as the inorganic sealing layer, and a step (b5) of forming a third sealing layer disposed on the second sealing layer as the organic sealing layer. Step (b) includes alternatingly performing steps (b4) and (b5) at least twice. The process (b4) is the same as the process (b2). The process (b5) is the same as the process (b1).

11. The method for manufacturing the device structure according to claim 10, wherein, The process (b3) is the same as the process (b1), and the process (b3) is the process of forming the first sealing layer as the organic sealing layer.

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