Device and method for manufacturing device

Abstract

The purpose of the present invention is to provide a device or the like capable of suppressing generation of stains and interlayer peeling when a laminated structure including a substrate, a protective layer, and an adhesive layer between the substrate and the protective layer is cut by an ultraviolet beam. The present invention relates to a device (10) having a substrate (14), a protective layer (11), and an adhesive layer (15) provided between the substrate (14) and the protective layer (11) and on the protective layer (11). The ultraviolet ray (wavelength of 355 nm) transmittance of the adhesive layer (15) is 30% or less.

Description

Technical Field

[0001] The present invention relates to a device and a method for manufacturing the device. Background Art

[0002] When manufacturing a device, it is known to cut a predetermined layer or a predetermined stacked body by irradiating light (Patent Documents 1 to 4). Patent Document 1 describes laser processing of a laminated body including an element substrate, a lower electrode, and a protective layer, and laser scribing of the lower electrode. Patent Document 2 describes bonding a dicing adhesive sheet having a substrate and an adhesive layer provided on the substrate to a semiconductor wafer having a low-dielectric material layer formed thereon, and dicing the low-dielectric material layer by laser irradiation. Patent Document 3 teaches laminating the surface of a base material to the adhesive layer of an adhesive tape and subjecting the substrate to laser processing. Patent Document 4 describes irradiating a laminated film comprising a heat-resistant polymer film and protective films formed on both surfaces thereof with ultraviolet laser light to cut the protective film and the heat-resistant polymer film, and laminating the cut product to an inorganic substrate. Prior art literature Patent Literature

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-49518 Patent Document 2: Japanese Patent Application Laid-Open No. 2013-21105 Patent Document 3: Japanese Patent Application Laid-Open No. 2015-21065 Patent Document 4: Japanese Patent Application Laid-Open No. 2020-100026 Summary of the Invention Problems to be solved by the invention

[0004] Thus, the technology of patent documents 1 to 4 can be said to be patterning or cutting by light irradiation during the device manufacturing stage, but it is also expected to efficiently produce the target device by light irradiation cutting of devices with protective layers such as gas barrier films attached to substrates and stacked bodies manufactured on the substrates (the substrates and stacked bodies are also collectively referred to as structures).

[0005] For example, when light irradiation is used to cut a multilayer structure made of different materials, the different cutting behaviors of each material can cause internal layers to be preferentially cut, resulting in smear (e.g., black matter produced by light irradiation) and / or accumulation of gas generated in the internal layers (further, bubbles are generated by gas accumulation). Furthermore, when layers containing gas barrier materials are present, especially when the laminate is sandwiched between a glass substrate and a gas barrier film in the laminate structure, the generated gas cannot escape, resulting in delamination of other layers.

[0006] At this time, the object of the present invention is to provide a device and a method for manufacturing the device that can suppress the generation of stains and interlayer delamination when a stacked structure including a substrate, a protective layer, and an adhesive layer between the substrate and the protective layer is cut by an ultraviolet beam. Technical means to solve the problem

[0007] While using an ultraviolet laser allows for precise cutting, as mentioned above, it preferentially cuts from the inner layers of a laminated structure, leading to problems such as smearing and interlayer delamination. As a solution to this problem, the present inventors have discovered a method for adjusting the ultraviolet transmittance of an adhesive layer provided on a protective layer. The present invention, which achieves the above-mentioned objectives, has the following key features. The device of the present invention comprises a substrate, a protective layer, and an adhesive layer disposed between the substrate and the protective layer and on the protective layer, wherein the adhesive layer has an ultraviolet light (wavelength 355 nm) transmittance of 30% or less.

[0008] It is preferred that the protective layer have an ultraviolet light (wavelength: 355 nm) transmittance of 70% or less.

[0009] The difference between the ultraviolet transmittance of the adhesive layer and the ultraviolet transmittance of the protective layer is preferably 13% or less.

[0010] The adhesive layer is preferably composed of at least one selected from epoxy-based adhesives and urethane-based adhesives.

[0011] The adhesive layer is preferably a room temperature curable or heat curable adhesive layer, and the adhesive layer preferably further contains an ultraviolet absorber.

[0012] The device of the present invention is preferably a device for cutting using an ultraviolet beam.

[0013] Another embodiment of the present invention includes a method for manufacturing a device, which comprises: a process of forming a structure comprising a substrate, a first stack on a first region of the substrate, and a second stack on a second region of the substrate different from the first region; a process of bonding a protective layer having an adhesive layer having an ultraviolet (wavelength 355 nm) transmittance of less than 30% to the structure from the first stack to the second stack via the adhesive layer; and a process of melting the substrate, the adhesive layer, and the portion of the protective layer located in the third region by irradiating a third region between the first stack and the second stack in the structure with an ultraviolet beam.

[0014] In the manufacturing method of the device of the present invention, the first stack preferably includes a first electron transport layer, a first hole transport layer, and a first active layer between the first electron transport layer and the first hole transport layer; and the second stack preferably includes a second electron transport layer, a second hole transport layer, and a second active layer between the second electron transport layer and the second hole transport layer.

[0015] In the third region, the substrate may be in contact with the adhesive layer. Depending on the situation, an electrical wiring may be provided between the substrate and the adhesive layer. Effects of the Invention

[0016] According to the present invention, a device and a method for manufacturing the device can be provided that can suppress the generation of stains and interlayer delamination when a structure including a substrate, a protective layer, and an adhesive layer between the substrate and the protective layer is cut by an ultraviolet beam.

[0017] Furthermore, the present invention enables efficient device segmentation, resulting in devices with good cut sections and excellent power generation characteristics after storage. For example, by simultaneously producing a stack of multiple devices on a single substrate and then performing segmentation as described above, advantages can be achieved in both production efficiency and manufacturing costs when producing devices other than solar cells, such as display devices, sensors, and input devices. Because the protective layer (protective film) is present during the segmentation, the risk of device damage during segmentation is also reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] [ Figure 1 ] Figure 1 (a) is a top view of a device according to one embodiment of the present invention. Figure 1 (b) Figure 1 The dotted line AA' in (a) corresponds to the cross-sectional view of the device. [ Figure 2 ] Figure 2 (a) shows a top view of the device after the protective layer is bonded from the first stack on the first region to the second stack on the second region via the adhesive layer in the device manufacturing method according to one embodiment of the present invention; Figure 2 (b) is a top view of a device after a protective layer is bonded to each of the stacked bodies on the first region, the second region, the fourth region, and the fifth region via an adhesive layer in a device manufacturing method according to another embodiment of the present invention. Explanation of symbols 10, 100: Device 11: Protective layer 12: Transparent conductive layer 13: Conductive layer 14: Substrate 15: Adhesive layer 16: Electron transport layer 17: Active layer 18: Hole transport layer 20: Third region A: First region B: Second region C: Fourth region D: Fifth region DETAILED DESCRIPTION

[0019] The present invention will be described in more detail below based on the following embodiments. However, the present invention is not limited to the following embodiments and can be implemented with appropriate modifications within the scope of the aforementioned and subsequent descriptions. Such modifications are within the technical scope of the present invention. In addition, in the drawings, hatching, component symbols, etc. may be omitted for convenience. In such cases, reference should be made to the specification or other drawings. Furthermore, since the dimensions of various components in the drawings are primarily provided for understanding the characteristics of the present invention, they may differ from actual dimensions.

[0020] 1. Device refer to Figure 1 (a) and (b) illustrate the basic structure of the device. Figure 1 (a) is a top view showing a device according to one embodiment of the present invention, Figure 1 (b) indicates Figure 1 The dotted line AA' in (a) corresponds to the cross-sectional view of the device.

[0021] like Figure 1 As shown in (a), the device 10 of the present invention is a device in which a substrate or the like is covered with a protective layer 11. An opening is provided in a portion of the protective layer 11, and preferably, the transparent conductive layer 12 and the conductive layer 13 are exposed in the opening. The opening enables current to be extracted.

[0022] like Figure 1 As shown in Figure (b), the device 10 of the present invention comprises a substrate 14, a protective layer 11, and an adhesive layer 15 disposed between the substrate 14 and the protective layer 11 and on the protective layer 11. The adhesive layer 15 has an ultraviolet (wavelength 355 nm) transmittance of 30% or less. The adhesive layer 15 is preferably in contact with the protective layer 11, but another layer may be interposed between the adhesive layer 15 and the protective layer 11 to the extent that the effects of the present invention are not affected. In the present invention, the device 10 not only has a substrate 14, a protective layer 11, and an adhesive layer 15, but may also have structures other than these (for example, a stacked structure that can perform photoelectric conversion). For example, by melting (cutting) the portion consisting of the substrate 14, the protective layer 11, and the adhesive layer 15 by ultraviolet irradiation, the device 10 can be efficiently divided.

[0023] The transmittance of the adhesive layer 15 to ultraviolet light (wavelength 355 nm) is 30% or less, preferably 29% or less, more preferably 28% or less, further preferably 27% or less, still preferably 1% or more or 2% or more, more preferably 5% or more or 10% or more. When the transmittance is within the above range, the substrate 14, protective layer 11, and adhesive layer 15 have good characteristics for cutting by ultraviolet light, thereby achieving a device with a small area of deterioration due to ultraviolet light irradiation and good storage characteristics. When the transmittance exceeds 30%, there is a concern that the characteristics of the substrate 14, protective layer 11, and adhesive layer 15 for cutting by ultraviolet light will be insufficient, the area of deterioration due to ultraviolet light irradiation will become larger, and the storage characteristics will also be insufficient. The ultraviolet transmittance of the adhesive layer 15 can be determined, for example, by measuring the linear transmission component using an ultraviolet-visible spectrophotometer (for example, UV3600, manufactured by Shimadzu Corporation).

[0024] Examples of the adhesive constituting the adhesive layer 15 include acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, polyurethane adhesives, polyamide adhesives, epoxy adhesives, vinyl alkyl ether adhesives, and fluorine adhesives. These adhesives may be used alone or in combination of two or more. Among them, from the viewpoints of adhesion to the protective layer and the substrate and melting due to ultraviolet rays, the adhesive is preferably at least one selected from epoxy-based adhesives and urethane-based adhesives.

[0025] Furthermore, from the viewpoint of adhesiveness, the adhesive preferably contains a hydroxyl group, and the adhesive containing a hydroxyl group is preferably a hydroxyl-containing acrylic adhesive, a hydroxyl-containing polyester adhesive, a hydroxyl-containing polyurethane adhesive, or a hydroxyl-containing fluorine adhesive (hereinafter collectively referred to as adhesive component (A)).

[0026] The hydroxyl-containing acrylic adhesive may be any acrylic resin obtained by polymerizing a hydroxyl-containing acrylate or hydroxyl-containing methacrylate as an essential component. Hereinafter, acrylic acid and methacrylic acid are collectively referred to as (meth)acrylic acid.

[0027] Acrylic resins can be easily produced, for example, by copolymerizing carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, and maleic anhydride with (meth)acrylic acid esters as essential components. Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, and isobornyl (meth)acrylate.

[0028] By using a hydroxyl group-containing (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or hydroxybutyl (meth)acrylate as a copolymerization component with the (meth)acrylate, a hydroxyl group-containing (meth)acrylic resin having hydroxyl groups introduced into the side chains of the acrylic resin skeleton can be obtained. The hydroxyl group-containing acrylic adhesive is, for example, a methacrylate resin obtained by copolymerizing methyl methacrylate and 2-hydroxyethyl methacrylate, and commercially available products such as ACRYDIC A-808-T (DIC Corporation) may be used.

[0029] Hydroxyl-containing polyester adhesives can be polyester resins obtained by reacting diols, dibasic acids, or their derivatives as essential components. Using ester-forming derivatives such as dibasic acid anhydrides or dibasic acid lower alkyl esters in place of these dibasic acids allows the production of polyester resins through not only polycondensation reactions but also addition reactions and transesterification reactions.

[0030] Examples of the polyester resin include: aliphatic polyester resins obtained by reacting aliphatic diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol, and cyclohexanedimethanol with aliphatic dibasic acids such as succinic acid, adipic acid, sebacic acid, fumaric acid, suberic acid, azelaic acid, 1,10-decamethylenedicarboxylic acid, and cyclohexanedicarboxylic acid as essential raw material components; and aromatic polyester resins obtained by reacting aliphatic diols such as ethylene glycol, propylene glycol, and butanediol with aromatic dibasic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid as essential raw material components.

[0031] The hydroxyl-containing polyurethane adhesive may be any polyurethane resin obtained by reacting a polyisocyanate compound with a compound containing at least two hydroxyl groups in one molecule in a ratio in which the hydroxyl groups are in excess of the isocyanate groups. Examples of polyisocyanate compounds include hexamethylene diisocyanate, toluene diisocyanate, m-xylylenediisocyanate, and isophorone diisocyanate. Examples of compounds containing at least two hydroxyl groups in one molecule include polyols (e.g., glycerol), polyester diols, polyethylene glycol, polypropylene glycol, and polycarbonate diols.

[0032] The hydroxyl-containing fluorocarbon adhesive may be any hydroxyl-containing fluorocarbon resin obtained by polymerizing a vinyl fluoride monomer as an essential component. Examples of the vinyl fluoride monomer include fluoroolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, 1,1,3,3,3-pentafluoropropylene, 2,2,3,3-tetrafluoropropylene, 1,1,2-trifluoropropylene, and 3,3,3-trifluoropropylene. Further examples include fluoroolefins having a halogen atom other than a fluorine atom, such as chlorotrifluoroethylene, bromotrifluoroethylene, 1-chloro-1,2-difluoroethylene, and 1,1-dichloro-2,2-difluoroethylene.

[0033] Furthermore, as a component copolymerized with the fluororesin, for example, by using in combination a hydroxyl-containing (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or hydroxybutyl (meth)acrylate, or a hydroxyl-containing vinyl ether such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, or 4-hydroxybutyl vinyl ether, a hydroxyl-containing fluororesin in which a hydroxyl group is introduced into the side chain of the fluororesin skeleton can be obtained.

[0034] The adhesive component (A) preferably has a glass transition temperature of 20 to 110°C, more preferably 40 to 100°C, and even more preferably 60 to 80°C in order to form a coating film having excellent adhesion on a substrate. The glass transition temperature can be determined according to, for example, JIS K7121.

[0035] The adhesive component (A) preferably has a hydroxyl value of 1 mgKOH / g or more and less than 80 mgKOH / g, more preferably 2 mgKOH / g or more and 70 mgKOH / g or less, and even more preferably 5 mgKOH / g or more and 60 mgKOH / g or less. The hydroxyl value can be determined, for example, according to JIS K1557-1.

[0036] The adhesive component (A) preferably has an average molecular weight of 5,000 to 100,000, more preferably 10,000 to 80,000, and even more preferably 20,000 to 60,000. The average molecular weight is preferably a number average molecular weight.

[0037] In addition to the adhesive component (A), the adhesive may contain an adhesive component (B) having a molecular weight lower than the average molecular weight of the adhesive component (A) or a higher hydroxyl value than the adhesive component (A). Examples of the adhesive component (B) include one or more resins selected from the group consisting of acrylic polyols, polyether polyols, polyester polyols, polyolefin polyols, polycarbonate polyols, urethane polyols, and fluorine-based polyols. The adhesive component (B) is preferably a polycarbonate polyol, more preferably a polycarbonate diol.

[0038] The hydroxyl value of the adhesive component (B) is preferably greater than 80 mgKOH / g and 500 mgKOH / g or less, more preferably 90 mgKOH / g or more and 400 mgKOH / g or less, and even more preferably 100 mgKOH / g or more and 300 mgKOH / g or less.

[0039] The average molecular weight of the adhesive component (B) is preferably 200 or more and less than 5000, more preferably 250 or more and 4000 or less, and even more preferably 400 or more and 3000 or less. The average molecular weight is preferably a number average molecular weight.

[0040] The mixing ratio of the adhesive component (A) to the adhesive component (B) is preferably 1 to 50 parts by weight of the adhesive component (B) per 100 parts by weight of the adhesive component (A) because the adhesive strength can be improved.

[0041] In addition to the adhesive component (A) and the adhesive component (B), a polyisocyanate compound (C) may be used. Examples of the polyisocyanate compound (C) include organic compounds having at least two isocyanate groups in the molecule. Examples of the organic polyisocyanate compound include polyisocyanates such as tolylene diisocyanate, xylylenediisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, 1,5-naphthalene diisocyanate, and triphenylmethane triisocyanate; and derivatives (modified products) of these polyisocyanates, such as adducts of these polyisocyanates, biuret forms of these polyisocyanates, and isocyanurate forms of these polyisocyanates.

[0042] The polyisocyanate compound (C) may be appropriately selected depending on the intended use. When superior weather resistance is required, non-yellowing polyisocyanates such as aliphatic or alicyclic polyisocyanates are preferably used. Non-yellowing polyisocyanates such as hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are preferably used.

[0043] The weight ratio of the hydroxyl-containing adhesive component (A) and / or (B) to the polyisocyanate compound as a curing agent varies depending on the types of the main agent and curing agent used, the content of various functional groups, etc. When the total weight of the two is 100%, the proportion of the curing agent used is generally 0.1 to 30%, preferably 1 to 20%. Furthermore, the polyisocyanate compound is preferably mixed so that the isocyanate group content of the polyisocyanate compound becomes 0.5 to 10.0 equivalents, and more preferably 0.8 to 5.0 equivalents, relative to the hydroxyl group of the hydroxyl-containing resin.

[0044] An epoxy resin (D) may be added to the adhesive. Examples of the epoxy resin include bisphenol-A epoxy resin, bisphenol-F epoxy resin, bisphenol-S epoxy resin, bisphenol-AD epoxy resin, and other bisphenol-type epoxy resins, o-cresol novolac epoxy resins, phenol novolac epoxy resins, naphthol novolac epoxy resins, bisphenol-A novolac epoxy resins, brominated phenol novolac epoxy resins, and alkylphenol novolac epoxy resins. The epoxy compounds may be used alone or as a mixture of two or more thereof. Moreover, the mixture of one or more types selected from the adhesive component (A), the adhesive component (B), the polyisocyanate compound (C), and the epoxy resin (D) can be regarded as an epoxy-based adhesive.

[0045] The epoxy resin may have a predetermined epoxy equivalent, which is preferably 100 to 400 g / equivalent, more preferably 150 to 350 g / equivalent, and even more preferably 200 to 300 g / equivalent. The epoxy equivalent can be determined, for example, according to JIS K7236.

[0046] The adhesive is preferably a combination of a hydroxyl-containing acrylic adhesive (preferably a copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate) as the adhesive component (A) and a polyisocyanate compound (C) (preferably hexamethylene diisocyanate). Also preferred is a combination of a hydroxyl-containing acrylic adhesive as the adhesive component (A), a polycarbonate diol as the adhesive component (B), a polyisocyanate compound (C) (hexamethylene diisocyanate), and an epoxy resin (D) (preferably a bisphenol A-type epoxy resin).

[0047] To the above components, an organic solvent may be added from the viewpoint of viscosity adjustment. Specific examples include hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as dioxane and ethylene glycol diethyl ether, and aliphatic hydrocarbons such as pentane, hexane, and heptane.

[0048] From the viewpoint of satisfying the above-mentioned ultraviolet transmittance, the adhesive layer 15 preferably contains an ultraviolet absorber. As the ultraviolet absorber, a known ultraviolet absorber can be used. Examples of the ultraviolet absorber include organic ultraviolet absorbers and inorganic ultraviolet absorbers, but organic ultraviolet absorbers are preferred from the viewpoint of transparency.

[0049] Examples of the organic ultraviolet absorber include benzotriazole-based, benzophenone-based, cyclic imine ester-based, and combinations thereof.

[0050] Examples of the benzotriazole-based ultraviolet absorber include 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, and 2-[2'-hydroxy-5'-tert-butyl-3'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole. H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)-2H-benzotriazole, and the like.

[0051] Examples of the benzophenone-based ultraviolet absorber include 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone (2 sodium salt).

[0052] Examples of the cyclic iminoester ultraviolet absorber include 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1- or 2-naphthyl)-3,1-benzoxazin-4-one, 2-(4-biphenyl)-3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4-one, 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one)2,2'-bis(3, 1-benzoxazin-4-one), 2,2'-ethylenebis(3,1-benzoxazin-4-one), 2,2'-tetramethylenebis(3,1-benzoxazin-4-one), 2,2'-decamethylenebis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6 -or 1,5-naphthalene)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazine-4-one), 1,3,5-tris(3,1-benzoxazine-4-one-2-yl)benzene, etc.

[0053] In addition, as the above-mentioned cyclic imine ester-based ultraviolet absorbers, 1,3,5-tris(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,4,6-tris(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d')bis-(1,3)-oxazine-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d;5,4-d')bis-(1,3)-oxazine-4,9-dione, 2,8-diphenyl-4H,8H-benzo(1,2-d;5,4-d')bis-(1,3)-oxazine-4,6-dione, 2,7-diphenyl-4H,9H-benzo(1,2-d;5,4-d')bis-(1,3)-oxazine-4,6-dione, 6,6'-bis(2-methyl-4H,3,1-benzoxazine-4-one), 6,6'-bis(2-ethyl-4H,3,1-benzoxazine-4-one), 6,6'-bis(2-phenyl-4H,3,1-benzoxazine-4-one), 6,6'-methylenebis(2-methyl-4H,3,1-benzoxazine-4-one), 6,6'-methylenebis(2-phenyl-4H,3,1-benzoxazine-4-one), 6,6'-ethylenebis(2-methyl-4H,3,1-benzoxazine-4-one), 6,6'-ethylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-butylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-butylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-oxybis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-oxybis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-sulfonylbis(2-phenyl-4H,3 ,1-benzoxazin-4-one), 6,6'-carbonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-carbonylbis(2-phenyl-4H,3,1-benzoxazin-4-one), 7,7'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 7,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-ethylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-oxybis (2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-carbonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-bis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,7'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), etc. ;

[0054] Among them, the ultraviolet absorber is preferably a benzotriazole-based ultraviolet absorber.

[0055] The content of the ultraviolet absorber is preferably 0.1 to 15 mass %, more preferably 0.3 to 10 mass %, and even more preferably 0.5 to 7 mass %, based on 100 mass % of the solid content constituting the adhesive layer 15 .

[0056] As other ingredients besides adhesives and ultraviolet absorbers, the adhesive layer 15 may also contain processing aids, pigments, flame retardants, fillers, softeners, hydrolysis inhibitors, light stabilizers, curing agents, cross-linking agents (such as polyisocyanate compounds), solvents, etc. When using a cross-linking agent (such as a polyisocyanate compound), the main agent and the auxiliary agent containing the cross-linking agent (such as a polyisocyanate compound) may be separated in advance and then mixed when used. The adhesive layer is preferably a room temperature curable or heat curable adhesive layer.

[0057] The amount of adhesive applied on the substrate is, for example, 0.5 to 80 g / m 2 , which can be from 1 to 10g / m 2 For the coating, for example, a gravure coater, a micro gravure coater, a reverse coater, a rod coater, a roll coater, a die coater, a doctor blade method, a knife coating method, etc. can be used.

[0058] The laminated body having the adhesive layer formed thereon is preferably subjected to an aging treatment after production. The aging conditions are, for example, room temperature to 100° C. for 1 to 240 hours, during which the curing reaction proceeds.

[0059] The thickness of the adhesive layer 15 is, for example, 1 to 200 μm, preferably 3 to 150 μm, more preferably 5 to 100 μm, and further preferably 10 to 50 μm.

[0060] The protective layer 11 is preferably a gas barrier layer. A combination of a resin film and a gas barrier layer, or a resin layer exhibiting gas barrier properties, is preferably used as the protective layer 11. Gas barrier layers made of resins are also available, but a gas barrier inorganic thin film is more preferred. A multilayer of a gas barrier inorganic thin film and a resin layer may also be used as the protective layer 11. Examples of the resin constituting the protective layer 11 include polyester resins and the like.

[0061] The polyester resin may be any condensation product containing monomer components of a polycarboxylic acid and a polyol. Specific examples of the polyester resin include polyethylene terephthalate resins, polyethylene naphthalate resins, polyethylene terephthalate resins, polybutylene naphthalate resins, and polytrimethylene terephthalate resins. These resins may be used alone or in combination of two or more. Among them, polyethylene terephthalate-based resins and polyethylene naphthalate-based resins are preferred.

[0062] The polyethylene terephthalate resin contains terephthalic acid and ethylene glycol as monomer components, but may contain other monomers such as isophthalic acid in addition to these.

[0063] The content of other monomers is, for example, 20 mol% or less, preferably 10 mol% or less, and more preferably 5 mol% or less in the monomer components.

[0064] The protective layer 11 may contain a third component other than the polyester resin. The content of the third component is not limited as long as it does not impair the effects of the present invention. However, the content is, for example, 10% by mass or less, preferably 5% by mass or less, and more preferably 1% by mass or less, relative to the solid content of the protective layer 11.

[0065] To impart desired functions to the polyester film constituting the protective layer 11, a third component may be included. Examples of the third component include inorganic particles and organic particles. Examples of the inorganic particles include silica particles, metal oxide particles such as zirconium oxide, titanium oxide, and zinc oxide, and carbonate particles such as calcium carbonate. Examples of the organic particles include cross-linked acrylic resin particles. Inorganic particles and organic particles may be used alone or in combination of two or more.

[0066] The polyester film may have a single-layer structure or a composite layer structure in which a plurality of polyester layers are stacked.

[0067] Examples of the composite layer structure include a two-layer structure consisting of a first polyester layer and a second polyester layer, a three-layer structure consisting of a first polyester layer (surface layer), a second polyester layer (middle layer) and a third polyester layer (surface layer), and a three-layer structure consisting of a first polyester layer (surface layer), a second polyester layer (middle layer) and a first polyester layer (surface layer).

[0068] From the viewpoint of ultraviolet absorption and ultraviolet melting, the ultraviolet (wavelength 355nm) transmittance of the protective layer 11 is preferably less than 70%, more preferably less than 65%, further preferably less than 60%, further preferably less than 30%, further more preferably less than 25%, particularly preferably less than 20%, most preferably less than 15%, further preferably more than 1% or more than 2%, or may be more than 5% or more than 10%. The ultraviolet transmittance of the protective layer 11 can be measured in the same manner as described above.

[0069] The thickness of the protective layer 11 is, for example, 0.05 μm or more and 200 μm or less, preferably 5 μm or more and 100 μm or less, and more preferably 20 μm or more and 50 μm or less.

[0070] The difference between the ultraviolet transmittance of the adhesive layer and the ultraviolet transmittance of the protective layer is preferably 13% or less, more preferably 10% or less, further preferably 8% or less, and even more preferably 7% or less.

[0071] The protective layer 11 and the adhesive layer 15 are preferably laminated as follows. The adhesive layer 15 can be obtained by applying an adhesive composition solution on the protective layer 11 to form a coating film, and then drying the coating film under predetermined conditions. The coating method is not particularly limited, and examples thereof include roller coating, screen coating, and gravure coating. In addition, the drying conditions can be, for example, a drying temperature of 80 to 150° C. and a drying time of 0.5 to 5 minutes. In addition, the adhesive composition can be applied to a separator to form a coating film, and then the coating film can be dried under the above-mentioned drying conditions to form the adhesive layer 15, and then the adhesive layer 15 can be attached to the protective layer 11 together with the separator.

[0072] As the constituent material of the substrate 14, for example, there can be cited: inorganic materials such as quartz, glass, sapphire, and titanium oxide; organic materials such as polyethylene (for example, polyethylene terephthalate, polyethylene naphthalate), polyethersulfone, polyimide, polyamide (for example, nylon), polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluororesin, vinyl chloride, polyolefin (for example, polyethylene, polypropylene), cellulose, polyvinylidene chloride, aramid fiber, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, and epoxy resin; paper materials; composite materials obtained by coating resin on metals such as stainless steel, titanium, and aluminum, etc. The substrate 14 is preferably made of an inorganic material, more preferably glass.

[0073] Examples of the shape of the substrate 14 include a plate, a film, and a sheet. The thickness of the substrate 14 is preferably 5 μm or greater, more preferably 20 μm or greater, and even more preferably 50 μm or greater, and is preferably 20 mm or less, more preferably 1 mm or less, and even more preferably 0.7 mm or less.

[0074] In addition to the substrate 14, the protective layer 11, and the adhesive layer 15, the device 10 of the present invention may also have a transparent conductive layer 12, a conductive layer 13, an electron transport layer 16, an active layer 17, and a hole transport layer 18, preferably having an area composed of the substrate 14, the protective layer 11 and the adhesive layer 15 and an area composed of the substrate 14, the transparent conductive layer 12, the electron transport layer 16, the active layer 17, the hole transport layer 18, the conductive layer 13, the adhesive layer 15, and the protective layer 11.

[0075] The transparent conductive layer 12 and the conductive layer 13 are composed of a conductive material that serves as a cathode or an anode.

[0076] The cathode is preferably composed of a conductive material having a smaller work function than the anode. The cathode has the function of extracting electrons generated in the active layer. Examples of the constituent materials of the cathode include: conductive metal oxides such as nickel oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium-zirconium oxide (IZO), titanium oxide, indium oxide, zinc oxide; and metals such as gold, platinum, silver, chromium, cobalt, and their alloys. In the case where the cathode is a transparent electrode, it is preferred to use a light-transmitting conductive metal oxide such as ITO, zinc oxide, or tin oxide, and ITO is particularly preferred.

[0077] The anode is preferably composed of a conductive material having a larger work function than the cathode. The anode has the function of extracting holes generated in the active layer. Examples of materials constituting the anode include: metals such as platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium, magnesium, and their alloys; inorganic salts such as lithium fluoride and cesium fluoride; metal oxides such as nickel oxide, aluminum oxide, lithium oxide, and cesium oxide. In addition, as a constituent material of the hole transport layer, when using an n-type semiconductor compound such as zinc oxide and a conductive material, a material with a small work function such as ITO can also be used as the anode material.

[0078] The thickness of each of the transparent conductive layer 12 and the conductive layer 13 is preferably 10 nm or more, more preferably 15 nm or more, and further preferably 20 nm or more, and is preferably 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 40 nm or less.

[0079] The electron transport layer 16 extracts electrons from the active layer 17 to the cathode. The constituent material of the electron transport layer 16 is preferably an electron transport material that improves electron extraction efficiency. It can be an organic compound or an inorganic compound, but is preferably an inorganic compound.

[0080] As the inorganic compound constituting the electron transport layer 16, a metal compound is preferably used, and examples thereof include salts of alkali metals such as lithium, sodium, potassium, and cesium, and metal oxides. Among them, the alkali metal salt is preferably a fluoride salt such as lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride, and the metal oxide is preferably titanium oxide (TiO x ), a metal oxide having n-type semiconductor characteristics such as zinc oxide (ZnO). Examples of the organic compound constituting the electron transport layer 16 include conductive organic compounds, such as polyethyleneimine ethoxylate.

[0081] The thickness of the electron transport layer 16 is preferably 0.5 nm or more, more preferably 5.0 nm or more, and even more preferably 10.0 nm or more, and is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 60 nm or less.

[0082] Active layer 17 is a layer that performs photoelectric conversion and preferably contains a p-type semiconductor compound and an n-type semiconductor compound. When the photoelectric conversion element is illuminated by light, the light is absorbed by active layer 17, generating electricity at the interface between the p-type and n-type semiconductor compounds. This electricity is then extracted from the cathode and anode. The cathode and anode correspond to the transparent conductive layer and the conductive layer.

[0083] Known p-type and n-type semiconductor compounds can be used. Examples of p-type semiconductor compounds include conjugated copolymer semiconductor compounds such as polythiophene, polyfluorene, polyphenylene vinylene, polythiophene vinylene, polyacetylene, and polyaniline; and copolymer semiconductor compounds such as oligothiophene substituted with other substituents such as alkyl groups. Furthermore, copolymer semiconductor compounds formed by copolymerizing two or more monomer units can also be used.

[0084] Examples of n-type semiconductor compounds include fullerene and its derivatives (e.g., PCBM), octaazaporphyrin, and perfluoro compounds in which hydrogen atoms of p-type semiconductor compounds are replaced with fluorine atoms (e.g., perfluoropentacene and perfluorophthalocyanine). Furthermore, polymer compounds containing aromatic carboxylic anhydrides such as naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic diimide, perylenetetracarboxylic anhydride, and perylenetetracarboxylic diimide as their backbones, and their imides, can also be used.

[0085] As the layer structure of the active layer 17, there can be cited: a thin film stacked structure in which a p-type semiconductor compound and an n-type semiconductor compound are stacked, a bulk heterojunction structure having a layer mixed with a p-type semiconductor compound and an n-type semiconductor compound, and the like. The bulk heterojunction structure has a layer (i layer) mixed with a p-type semiconductor compound and an n-type semiconductor compound. The i layer has a structure in which the p-type semiconductor compound and the n-type semiconductor compound are phase-separated, carrier separation occurs at the phase interface, and the generated carriers (holes and electrons) are transported to the electrode. From the viewpoint of improving the photoelectric conversion efficiency by obtaining a good phase separation structure, the mass ratio of the p-type semiconductor compound to the n-type semiconductor compound in the i layer (p-type semiconductor compound / n-type semiconductor compound) is preferably greater than 0.5 and less than 2, and more preferably greater than 0.8 and less than 1.25.

[0086] In addition to p-type and n-type semiconductor compounds, active layer 17 may also contain additives. The phase-separated structure of the p-type and n-type semiconductor compounds in the bulk heterojunction active layer affects light absorption, exciton generation and diffusion, exciton dissociation (carrier separation), and carrier transport. Therefore, optimizing the phase-separated structure is expected to achieve good photoelectric conversion efficiency. By including a p-type or n-type semiconductor compound with a highly compatible additive in active layer 17, an active layer with a preferred phase-separated structure can be obtained, thereby improving photoelectric conversion efficiency.

[0087] Examples of additives include aliphatic hydrocarbon compounds having 8 to 20 carbon atoms and aromatic compounds having 8 to 20 carbon atoms. These aliphatic hydrocarbon compounds and aromatic compounds may have substituents. Examples of substituents that may be present in aliphatic hydrocarbon compounds include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, amino groups, carbamoyl groups, carbonyloxy groups, carboxyl groups, carbonyl groups, and aromatic groups. Examples of substituents that may be present in aromatic compounds include halogen atoms, hydroxyl groups, cyano groups, amino groups, amide groups, carbonyloxy groups, carboxyl groups, carbonyl groups, oxycarbonyl groups, silyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, and aromatic groups. Preferred examples of additives include benzene that may have substituents, naphthalene that may have substituents, and octane that may have substituents. Halogen atoms are particularly preferred as substituents.

[0088] In the present invention, from the perspective of obtaining a photoelectric conversion element such as an organic thin-film solar cell exhibiting high conversion efficiency, the above-mentioned active layer 17 is preferably an organic semiconductor, and more preferably contains the polymer compound p-type semiconductor compound described later and / or the polymer compound n-type semiconductor compound described later or the above-mentioned n-type semiconductor compound.

[0089] As polymer compound p-type semiconductor compounds, for example, there can be mentioned: PDPPBDT, PDPPDTT, PFs, KP115, PCDTBT, DPPT-TT, PDPP2FT, F82T, F8TBT, F8BT, P3HT-Br10, PPP-P3HT, P3HT, PhxSDT-DTZ, PBDTDPP-1, P3DDT, PPDTBT, PPDT2FBT, PBDTDPP-2, PCPDTBT-1, PCPDTBT-2, PBDBT2F(PM6), etc.

[0090] Examples of high molecular compound n-type semiconductor compounds include MEH-CN-PPV, F8TBT, PZ1, DCNBT-IDT, P-BNBP-fBT, PF2-DTSi, PDI-V, PYTM, PJ1-H, N2200, and Y6.

[0091] In the present invention, the active layer 17 may contain a polymer compound having a benzobisthiazole structural unit. Specifically, it preferably contains a polymer compound having a benzobisthiazole structural unit represented by the following formula (1) (hereinafter referred to as "polymer compound P").

[0092] [Chemistry 1]

[0093] In the above formula (1), T 1、T 2 Each independently represents a thiophene ring which may be substituted with an alkoxy group, an alkylthio group, a hydrocarbon group or an organosilicon group, a thiazole ring which may be substituted with a hydrocarbon group or an organosilicon group, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, an alkylthio group, an organosilicon group, a halogen atom or a trifluoromethyl group. 1 、B 2 represents a thiophene ring which may be substituted with a hydrocarbon group, a thiazole ring which may be substituted with a hydrocarbon group, or an ethynyl group. Furthermore, an organosilicon group refers to a monovalent group in which one or more hydrocarbon groups are substituted with Si atoms. The number of hydrocarbon groups substituted with Si atoms is preferably 2 or more and 3 or less, and more preferably 3.

[0094] The polymer compound P is a p-type semiconductor compound. By having a benzobisthiazole structural unit represented by formula (1), the HOMO energy level can be deepened while the band gap is narrowed, thereby improving the photoelectric conversion efficiency.

[0095] In the benzobisthiazole structural unit represented by formula (1), T 1 、T 2 They may be the same or different from each other, but are preferably the same from the viewpoint of ease of manufacture. 1 、B 2 They may be the same as or different from each other, but are preferably the same from the viewpoint of ease of production.

[0096] In the benzobisthiazole structural unit represented by formula (1), T 1 、T 2 Each is preferably a group represented by the following formula (t1) to (t5). Specifically, as T 1 、T 2 The alkoxy group is preferably a group represented by the following formula (t1); the alkylthio group is preferably a group represented by the following formula (t2); the thiophene ring which may be substituted by a hydrocarbon group or an organosilicon group is preferably a group represented by the following formula (t3); the thiazole ring which may be substituted by a hydrocarbon group or an organosilicon group is preferably a group represented by the following formula (t4); the phenyl group which may be substituted by a hydrocarbon group, an alkoxy group, an alkylthio group, an organosilicon group, a halogen atom or a trifluoromethyl group is preferably a group represented by the following formula (t5). 1 、T 2 When the groups are represented by the following formulas (t1) to (t5), they can absorb short-wavelength light and, due to their high planarity, can efficiently form π-π stacking, thereby improving photoelectric conversion efficiency. Furthermore, the groups represented by formulas (t1) to (t3) exhibit electron-donating properties, while the groups represented by formulas (t4) to (t5) exhibit electron-withdrawing properties.

[0097] [Chemistry 2]

[0098] In the above formulas (t1) to (t5), R 13 ~R 14 Each independently represents a hydrocarbon group having 6 to 30 carbon atoms. 15 ~R 16 Each independently represents a hydrocarbon group having 6 to 30 carbon atoms or *-Si(R 18 )3 represented by the group. 15’ represents a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, *-Si(R 18 )3 represented by the group. 17 represents a halogen atom, a hydrocarbon group having 6 to 30 carbon atoms, *-OR 19 、*-SR 20 、*-Si(R 18 )3 or *-CF3. R 18 Each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R 18 Can be the same or different. 19 ~R 20 represents a hydrocarbon group having 6 to 30 carbon atoms. The symbol * in each formula represents a bond to the thiazole ring of benzobisthiazole.

[0099] In the above formulas (t1) to (t5), as R 13 ~R 17 、R 19 ~R 20 、R 15’ The hydrocarbon group having 6 to 30 carbon atoms is preferably a branched hydrocarbon group, and more preferably a branched saturated hydrocarbon group. 13 ~R 17 、R 19 ~R 20 、R 15’ The hydrocarbon group of R can improve its solubility in organic solvents by having a branched chain. 13 ~R 17 、R 19 ~R 20 、R 15’ The number of carbon atoms in the hydrocarbon group is preferably 8-25, more preferably 8-20, and even more preferably 8-16.

[0100] In the above formulas (t1) to (t5), in R 15 ~R 17 、R 15’ *-Si(R 18 )3, R 18 The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 18, more preferably 1 to 8. 18The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 8, more preferably 6 to 7, and further preferably 6. 18 The aromatic hydrocarbon group of R is, for example, a phenyl group. 18 , preferably an aliphatic hydrocarbon group, more preferably an aliphatic hydrocarbon group having a branched chain, and further preferably an isopropyl group. 18 They may be the same or different, but are preferably the same. 15 ~R 17 、R 15’ *-Si(R 18 )3, the solubility of the polymer compound P in the organic solvent is improved. 18 ) 3 is preferably an alkylsilyl group, more preferably a trimethylsilyl group or a triisopropylsilyl group.

[0101] In the above formula (t5), R 17 When it is a halogen atom, fluorine, chlorine, bromine, and iodine can be used. 17 , preferably a halogen atom or *-CF3.

[0102] R 15’ A hydrogen atom or R 15 The hydrocarbon group having 6 to 30 carbon atoms or the ... 18 )3 is the same group as the group represented by, preferably a hydrogen atom.

[0103] As T 1 、T 2 From the viewpoint of excellent planarity of the structural unit represented by formula (1) as a whole, groups represented by formulas (t1), (t3), and (t5) are more preferred, and groups represented by formula (t3) are even more preferred.

[0104] In the benzobisthiazole structural unit represented by formula (1), B 1 、B 2 Each is preferably a group represented by any one of the following formulae (b1) to (b3). 1 、B 2 When the groups are represented by the following formulae (b1) to (b3), the planarity of the polymer compound P is improved, and the photoelectric conversion efficiency can be improved.

[0105] [Chemistry 3]

[0106] In the above formulas (b1) to (b3), R 21 、R 22 、R 21’represents a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms. The symbol * in each formula represents a bond, and in particular, the symbol * on the left side represents a bond to the benzene ring of the benzobisthiazole compound.

[0107] As R 21 、R 22 、R 21’ A hydrocarbon group having 6 to 30 carbon atoms can be preferably used as R 13 ~R 17 、R 19 ~R 20 、R 15’ The group is a hydrocarbon group having 6 to 30 carbon atoms. 21 、R 22 、R 21’ When it is a hydrocarbon group having 6 to 30 carbon atoms, the photoelectric conversion efficiency may be further improved, which is preferred. 21 、R 22 、R 21’ When it is a hydrogen atom, a donor-acceptor type semiconductor polymer is easily formed.

[0108] As B 1 、B 2 , more preferably a group represented by formula (b1) or (b2). 1 、B 2 When the group is represented by formula (b1) or (b2), the interaction between the S atom and the N atom occurs in the benzobisthiazole structural unit, further improving the planarity. As a result, the planarity of the obtained polymer compound P can be improved.

[0109] The polymer compound P is preferably a donor-acceptor type semiconductor polymer, and therefore the polymer compound P preferably has a specific structural unit that provides a donor unit or an acceptor unit while having a benzobisthiazole structural unit represented by formula (1). The donor unit refers to an electron-donating structural unit, and the acceptor unit refers to an electron-accepting structural unit. The donor-acceptor type semiconductor polymer preferably has donor units and acceptor units alternately arranged, and therefore the donor-acceptor type semiconductor polymer is preferably a polymer compound in which the benzobisthiazole structural unit represented by formula (1) and the specific structural unit are alternately arranged. By forming such a structure, the polymer compound P can be suitably used as a p-type semiconductor compound.

[0110] As the specific structural unit, a conventionally known structural unit that provides a donor unit or an acceptor unit can be used. Specifically, the specific structural unit includes the structural units of the following formulae, among which preferred are structural units represented by formulae (c1), (c3) to (c5), (c7), (c9), (c12), (c21), (c27), (c37), and (c42), and more preferred are structural units represented by formulae (c1), (c5), (c9), (c21), (c37), and (c42).

[0111] [Chemistry 4]

[0112] [Chemistry 5]

[0113] In the above formulas (c1) to (c43), R 30 ~R 76 Each independently represents a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms. 30 、A 31 Each independently represents T 1 、T 2 The same group, j represents an integer of 1 to 4. · represents B of the structural unit represented by formula (1) 1 or B 2 Bonded keys.

[0114] The groups represented by the above formulae (c1) to (c30) are groups that function as acceptor units, and the groups represented by the formulae (c32) to (c43) are groups that function as donor units. 30 、A 31 There are different types of ligands, some of which function as acceptor units and some as donor units.

[0115] The repetition ratio of the benzobisthiazole structural unit represented by formula (1) in the polymer compound P is usually 1 mol% or more, preferably 5 mol% or more, more preferably 15 mol% or more, and further preferably 30 mol% or more, and is also usually 99 mol% or less, preferably 95 mol% or less, more preferably 85 mol% or less, and further preferably 70 mol% or less.

[0116] The repetition ratio of the specific structural unit in the polymer compound P is usually 1 mol% or more, preferably 5 mol% or more, more preferably 15 mol% or more, and further preferably 30 mol% or more, and is also usually 99 mol% or less, preferably 95 mol% or less, more preferably 85 mol% or less, and further preferably 70 mol% or less.

[0117] The arrangement of the benzobisthiazole structural units represented by formula (1) and the specific structural units in the polymer compound P may be any of alternating, block, and random. That is, the polymer compound P may be any of alternating copolymers, block copolymers, and random copolymers. Preferably, the benzobisthiazole structural units represented by formula (1) and the specific structural units are arranged alternately.

[0118] The weight average molecular weight and number average molecular weight of the polymer compound P are preferably 2,000 or more and 500,000 or less, and more preferably 3,000 or more and 200,000 or less. The weight average molecular weight and number average molecular weight of the polymer compound P can be calculated using a gel permeation chromatograph based on a calibration curve prepared using polystyrene as a standard sample.

[0119] The thickness of the active layer 17 is preferably 70 nm or more, more preferably 90 nm or more, and even more preferably 100 nm or more, and is preferably 1000 nm or less, more preferably 500 nm or less, and even more preferably 300 nm or less.

[0120] The hole transport layer 18 is a layer that extracts holes from the active layer 17 to the anode. The material constituting the hole transport layer 18 is not particularly limited as long as it is a hole transport material that can improve hole extraction efficiency, and examples thereof include conductive organic compounds and metal compounds.

[0121] As the conductive organic compound constituting the hole transport layer 18, for example, there can be mentioned: conductive polymers in which sulfonic acid and / or iodine are doped in polythiophene, polypyrrole, polyacetylene, triphenylenediamine, polyaniline, etc., polythiophene derivatives having sulfonyl groups as substituents, aromatic amines, etc. As the metal compound constituting the hole transport layer, there can be mentioned: metal oxides having p-type semiconductor characteristics such as molybdenum trioxide, vanadium pentoxide, nickel oxide, and metals such as gold, indium, silver, and palladium. In addition, the hole transport layer can also be formed by a p-type semiconductor compound. Among these, as the constituent material of the hole transport layer 18, a conductive polymer doped with sulfonic acid is preferred, and poly(3,4-ethylenedioxythiophene) poly(styrenesulfonic acid) (PEDOT:PSS) in which polystyrenesulfonic acid is doped in a polythiophene derivative is more preferred. In addition, metal oxides such as molybdenum oxide and vanadium oxide are also preferred.

[0122] The thickness of the hole transport layer 18 is preferably 0.2 nm or more, more preferably 5.0 nm or more, further preferably 30.0 nm or more, and is preferably 400 nm or less, more preferably 200 nm or less, further preferably 100 nm or less, and further more preferably 70 nm or less.

[0123] 2. Device Manufacturing Method The manufacturing method of the device of the present invention includes a process of forming a structure comprising a substrate, a first stack on a first region of the substrate, and a second stack on a second region of the substrate different from the first region (hereinafter also referred to as a structure forming process); a process of bonding a protective layer provided with an adhesive layer having an ultraviolet (wavelength 355 nm) transmittance of less than 30% from the first stack to the second stack via the adhesive layer and bonding the protective layer to the structure (hereinafter also referred to as a bonding process of the protective layer and the structure); and a process of melting the substrate, the adhesive layer, and the portion of the protective layer located in the third region by irradiating the third region between the first stack and the second stack in the structure with an ultraviolet beam (hereinafter also referred to as a melting process). The device manufacturing method according to the present invention can cut a structure including a substrate, a protective layer, and an adhesive layer between the substrate and the protective layer by ultraviolet irradiation, thereby efficiently dividing the device, making the cut portion good and the power generation characteristics after storage also good.

[0124] Structure formation process A step of providing a stacked body (e.g., a first stacked body and a second stacked body) in predetermined regions (e.g., a first region and a second region) of a substrate to form a structure including the substrate and the stacked body.

[0125] The substrate may have one or two or more regions, and the regions are preferably different regions or independent regions. The laminates provided in the regions are preferably capable of operating independently.

[0126] As an example, when a substrate has a first region and a second region, and a first stack and a second stack are provided in the first region and the second region, respectively, it is preferred that the first stack include a first electron transport layer, a first hole transport layer, and a first active layer between the first electron transport layer and the first hole transport layer, and the second stack include a second electron transport layer, a second hole transport layer, and a second active layer between the second electron transport layer and the second hole transport layer.

[0127] The first stack may further include a first transparent conductive layer and a first conductive layer, and the second stack may further include a second transparent conductive layer and a second conductive layer. The first transparent conductive layer is preferably arranged between the substrate and the first electron transport layer, and the first conductive layer is preferably arranged opposite to the first hole transport layer. The second transparent conductive layer is preferably arranged between the substrate and the second electron transport layer, and the second conductive layer is preferably arranged opposite to the second hole transport layer.

[0128] That is, the first transparent conductive layer, the first electron transport layer, the first active layer, the first hole transport layer, and the first conductive layer are preferably formed in sequence on the first area of the substrate, and the second transparent conductive layer, the second electron transport layer, the second active layer, the second hole transport layer, and the second conductive layer are preferably formed in sequence on the second area of the substrate.

[0129] The materials of the substrate, transparent conductive layer, electron transport layer, active layer, hole transport layer and conductive layer are the same as those mentioned above.

[0130] In the structure, a third region is preferably present between the portion provided with the first stack and the portion provided with the second stack, serving as the ultraviolet irradiation region. The third region is preferably a portion of the substrate where the transparent conductive layer, hole transport layer, active layer, electron transport layer, and conductive layer are not formed, and is preferably a portion of the substrate exposed before the protective layer is attached. The third region may be a region that divides each region (for example, the first region and the second region) into equal parts.

[0131] In the device manufacturing method of the present invention, the substrate is not limited to the first region and the second region, and may also have a fourth region, a fifth region, etc., and independently operable stacks may be provided in each region to form a structure. When the substrate has three or more regions, the third region may be located between each region. For example, when the substrate has four regions (first region, second region, fourth region, and fifth region), the third region may be located at a position that divides these regions equally.

[0132] Bonding process between protective layer and structure A step of bonding the protective layer provided with an adhesive layer to the structural body by bonding the protective layer from the first laminate to the second laminate via the adhesive layer. This step is not particularly limited as long as air is not mixed between the protective layer and the laminate. Existing methods such as lamination in air, vacuum lamination, pressing, and pressing in vacuum can be used, and heating in an oven, a pressure oven, an autoclave, etc. can also be added after these steps.

[0133] The transmittance of the adhesive layer to ultraviolet light (wavelength 355nm) is 30% or less, preferably 29% or less, more preferably 28% or less, further preferably 27% or less, further preferably 1% or more or 2% or more, more preferably 5% or more, or 10% or more. When the transmittance is within the above range, the substrate, protective layer, and adhesive layer have good characteristics for cutting by ultraviolet light. In addition, the area of deterioration caused by ultraviolet light irradiation is small, and the storage characteristics are also improved. When the transmittance exceeds 30%, the characteristics of the substrate, protective layer, and adhesive layer for cutting by ultraviolet light are insufficient, and there is a concern that the area of deterioration caused by ultraviolet light irradiation becomes large, and the storage characteristics may not be sufficient.

[0134] The materials of the protective layer and the adhesive layer may be the same as those described above. Openings for drawing current from the transparent conductive layer and the conductive layer may be formed in advance on the protective layer and the adhesive layer.

[0135] In this step, the substrate is preferably in contact with the adhesive layer in the third region. That is, the portion of the structure located in the third region is preferably composed of the substrate, the adhesive layer, and the protective layer.

[0136] Below, reference Figure 2 (a) and (b) illustrate the relationship between the various regions of the substrate. Figure 2 (a) shows a top view of a device after a protective layer is bonded from a first stack on a first region to a second stack on a second region via an adhesive layer in a device manufacturing method according to one embodiment of the present invention. Figure 2 (b) is a top view of a device after a protective layer is bonded to each of the stacked bodies on the first region, the second region, the fourth region, and the fifth region via an adhesive layer in a device manufacturing method according to another embodiment of the present invention.

[0137] exist Figure 2 In (a), the device 100 adheres the protective layer 11 to a structure containing a substrate and a stack via an adhesive layer. The substrate has a first region A and a second region B. The protective layer 11 is adhered to a structure comprising a substrate, a first stack on the first region A, and a second stack on the second region B via an adhesive layer. The structure has a region (third region 20) located between the first region A and the second region B. In the structure, the portion located in the third region 20 can be composed of, for example, a substrate, an adhesive layer, and a protective layer, and serve as an ultraviolet irradiation region. A plurality of openings are provided on the protective layer 11 and the adhesive layer in each region, one of the openings being used as an exposed portion of the transparent conductive layer 12, and the other openings being used as exposed portions of the conductive layer 13. By providing these openings, current can be drawn from the device 100.

[0138] exist Figure 2In (b), the device 100 is formed by bonding a protective layer 11 to a structure comprising a substrate and a laminate via an adhesive layer. The substrate has a first region A, a second region B, a fourth region C, and a fifth region D. The protective layer 11 is bonded to the structure comprising the substrate, the laminate comprising the first region A, the laminate comprising the second region B, the laminate comprising the fourth region C, and the laminate comprising the fifth region D via an adhesive layer. The third region 20 of the structure may be located between the first region A and the second region B, between the first region A and the fourth region C, between the second region B and the fifth region D, and between the fourth region C and the fifth region D, respectively. In the structure, the portion located in the third region 20, for example, composed of the substrate, the adhesive layer, and the protective layer, may serve as an ultraviolet irradiation region. A plurality of openings are provided on the protective layer 11 and the adhesive layer in each region, wherein one opening serves as an exposed portion of the transparent conductive layer 12 and the other openings serve as exposed portions of the conductive layer 13 . These openings allow current to be drawn from the device 100 .

[0139] Melting process In the structure, the step of irradiating a third region between the first stack and the second stack with an ultraviolet beam to melt portions of the substrate, the adhesive layer, and the protective layer located in the third region.

[0140] The ultraviolet light beam is irradiated to the third area as the ultraviolet irradiation area. As a result, the substrate, adhesive layer, and protective layer present in the third area are melted and cut into a structure including the first area of the substrate and the first laminate and a structure including the second area of the substrate and the second laminate.

[0141] The device and the method for manufacturing the device of the present invention can be preferably used in organic electroluminescent devices EL, organic thin film transistors, organic thin film solar cells, and the like.

[0142] This application claims the benefit of priority based on Japanese Patent Application No. 2023-004043, filed on January 13, 2023. The entire contents of the specification of Japanese Patent Application No. 2023-004043, filed on January 13, 2023, are incorporated herein by reference. Example

[0143] The present invention will be described in more detail below with reference to the following examples. However, the present invention is not limited to the following examples and can be implemented with appropriate modifications within the scope of the present invention. These modifications are within the technical scope of the present invention. In addition, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0144] (Fabrication of Photoelectric Conversion Elements) A glass substrate (700 μm thick) manufactured by GEOMATEC, patterned with a transparent conductive film of indium tin oxide (ITO) as the electrode (cathode), was ultrasonically cleaned with acetone, then ultrasonically cleaned with ethanol, and then dried using a nitrogen purge. The dried glass substrate was then treated with UV-ozone to form the electron transport layer.

[0145] The electron transport layer was formed by applying a 0.5 M zinc acetate / 0.5 M aminoethanol / 2-methoxyethanol solution on a glass substrate using a spin coater (1500 rpm, 50 seconds), followed by annealing at 135° C. for 10 minutes.

[0146] A glass substrate with an electron transport layer was placed in a glove box. A mixed solution of p-type and n-type semiconductor compounds (1) was spin-coated (1000 rpm, 45 seconds) under an inert gas atmosphere. Annealing was performed on a hot plate at 100°C for 5 minutes to form an active layer. Commercially available reagents of P3HT and PCBM were used as the p-type and n-type semiconductor compounds. After each layer was formed, the area around the element was wiped to form four independent element layers on a single glass substrate.

[0147] Next, molybdenum oxide as a hole transport layer was deposited on the active layer using a vapor deposition machine. Before the start of the vapor deposition, it was confirmed that the vacuum degree reached 7×10 -4 After the Pa, vacuum evaporation was performed using a resistance-heated crucible. Silver, the electrode (anode), was then deposited on the hole transport layer to create a flip-chip device consisting of four independent elements. The evaporation rate was initially 0.05 Å / s, and was gradually increased until it remained below 0.5 Å / s.

[0148] On the flip-chip structure element including four elements obtained, a film with an adhesive having gas barrier properties was laminated and bonded (reference Figure 2 (b)) as a protective layer with an adhesive layer. In this case, the above-mentioned film with holes opened in the electrode portion is used.

[0149] As the base film, a 100 μm thick PET film E4100 manufactured by Toyobo Co., Ltd. or a 50 μm thick PEN film Q65HA manufactured by Toyobo Co., Ltd. was used. An epoxy adhesive or a urethane adhesive was applied to the PET film or PEN film using a bar coater.

[0150] In Example 1, as the epoxy adhesive, a mixture of 52 parts of ACRYDIC A-808-T (DIC Corporation, hydroxyl-containing acrylic resin, Tg 70°C, hydroxyl value 20-40 mgKOH / g), 6 parts of EPICLON 860 (DIC Corporation, bisphenol A epoxy resin, epoxy equivalent 240 g / equivalent), 2 parts of DURANOL T-5651 (Asahi Kasei Chemicals Corporation, polycarbonate diol, number average molecular weight 1000, hydroxyl value 100-120 mgKOH / g), 1 part of ELASTOSTAB (Elastogran AG, isocyanate), 5 parts of Tinuvin 123 (BASF Japan Co., Ltd., light stabilizer), 37 parts of ethyl acetate, and 4 parts of SUMIDUR was used. An adhesive containing N3300 (Sumika Bayer Urethanes Co., Ltd., HDI-based isocyanate polyisocyanate, NCO 22%) and about 1 part of benzotriazole (also called UV absorber A).

[0151] In Example 2, as a urethane-based adhesive, a hydroxyl-introduced methacrylate resin having a number average molecular weight of 50,000 obtained by copolymerizing 65% of methyl methacrylate and 35% of 2-hydroxyethyl methacrylate was mixed with 5% of 2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol (TINUVIN 328; manufactured by Ciba Specialty Chemicals Co., Ltd.) (also referred to as UV absorber B) as a benzotriazole-based UV absorber and 5% of bis[2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl]sebacate (TINUVIN 123; manufactured by Ciba Specialty Chemicals Co., Ltd.) as a hindered amine-based light stabilizer. The mixture was diluted with methyl ethyl ketone for viscosity adjustment to obtain a main component (a) adjusted to a solid content of 20%. Separately, as a crosslinking agent (curing agent), a curing agent (b) was prepared by adjusting an adduct-type hexamethylene diisocyanate with methyl ethyl ketone to a solid content of 75%. A coating solution was prepared by adding 15% of the curing agent (b) to the main agent (a).

[0152] The ultraviolet light (wavelength: 355 nm) transmittance of the adhesive layer and the protective layer was determined by measuring the linear transmission component using an ultraviolet-visible spectrometer (UV3600 manufactured by Shimadzu Corporation).

[0153] In Example 3, an adhesive was used in which only the content of UV absorber A in the epoxy adhesive of Example 1 was changed, so that the ultraviolet light transmittance (wavelength 355 nm) of the adhesive layer reached the values shown in Table 1. In Example 4 and Comparative Example 1, an adhesive was used in which only the content of UV absorber B in the urethane adhesive of Example 2 was changed, so that the ultraviolet light transmittance (wavelength 355 nm) of the adhesive layer reached the values shown in Table 1.

[0154] Adhesive coating: Use a bar coater to apply adhesive to the corona-treated surface of the PET or PEN film. Adjust the adhesive layer to approximately 50 μm.

[0155] Cutting test: Cutting tests were conducted using a YAG third-harmonic pulse laser with a wavelength of 355nm. The laser device was manufactured by Takei Electric Co., Ltd., and the oscillator was a nanolaser manufactured by Spectra-Physics Co., Ltd. Cutting was performed from the protective layer side at a pulse frequency of 100kHz and a power of 3W. Laser irradiation site Figure 2 As shown in (b), it is the third region 20 that separates each element. The third region is composed of the substrate, the adhesive layer and the protective layer.

[0156] Cutting properties and appearance: As for the appearance of the cut portion, the presence of blackening due to stains of 1 mm or more was marked as ×, and the absence of stains was marked as ○. The results are shown in Table 1.

[0157] Deterioration Width: The cut ends were observed under a microscope, and the average width of the blackened portion due to peeling or staining inside the laminate was taken as the deterioration width. The results are shown in Table 1.

[0158] Storage Characteristics: The devices were stored indoors in an atmosphere of approximately 15°C to 25°C for one month. The power generation characteristics of the devices were evaluated before and after storage. A decrease of 10% or more was marked as "X," and a decrease of 5% or less was marked as "○." The results are shown in Table 1.

[0159] [Table 1]

[0160] Even when a 50 μm thick UV-absorbing PET film (HB3 manufactured by Toyobo Co., Ltd., with an ultraviolet transmittance of 1%) was used as the base film, the same results as those in the example were shown, with the cutting appearance being ○, the deterioration width being at the same level as that in the example, and the storage characteristics being ○.

[0161] Even when the film forming conditions of the protective layer were changed so that the ultraviolet transmittance of the protective layer was 60%, and the other conditions were the same as in Examples 1 to 4, the same results as in Examples 1 to 4 were shown, with the cut appearance being ○, the deterioration width being at the same level as in the examples, and the storage characteristics being ○.

Claims

1. A device comprising a substrate, a protective layer, and an adhesive layer provided between the substrate and the protective layer and on the protective layer, wherein the adhesive layer has a transmittance of 30% or less with respect to ultraviolet rays having a wavelength of 355 nm. 2 . The device according to claim 1 , wherein the transmittance of the protective layer to ultraviolet rays having a wavelength of 355 nm is 70% or less. 3 . The device according to claim 1 , wherein a difference between the ultraviolet transmittance of the adhesive layer and the ultraviolet transmittance of the protective layer is 13% or less. 4 . The device according to claim 1 , wherein the adhesive layer is composed of at least one selected from the group consisting of an epoxy-based adhesive and a urethane-based adhesive. The device according to claim 4 , wherein the adhesive layer is a room temperature curable or heat curable adhesive layer. 6 . The device according to claim 1 , wherein the adhesive layer further contains an ultraviolet absorber.

7. The device according to claims 1 to 5, which is used for cutting using an ultraviolet beam.

8. A method for manufacturing a device, comprising the following steps: forming a structure including a substrate, a first stacked body on a first region of the substrate, and a second stacked body on a second region of the substrate different from the first region; A step of bonding a protective layer having an adhesive layer with a transmittance of 30% or less for ultraviolet rays with a wavelength of 355 nm to the structural body via the adhesive layer from the first laminate to the second laminate; A step of irradiating a third region between the first stack and the second stack in the structure with an ultraviolet beam to melt portions of the substrate, the adhesive layer, and the protective layer located in the third region.

9. The method for manufacturing a device according to claim 8, wherein the first stack comprises a first electron transport layer, a first hole transport layer, and a first active layer between the first electron transport layer and the first hole transport layer. The second stack includes a second electron transport layer, a second hole transport layer, and a second active layer between the second electron transport layer and the second hole transport layer. 10 . The device manufacturing method according to claim 8 , wherein the substrate and the adhesive layer are in contact with each other in the third region.

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