Sealing material for photoelectric conversion element, dam material, and method for manufacturing device using dam material

Abstract

To provide a technology that enhances the reliability of devices using sealing materials.SOLUTION: A sealing material for photoelectric conversion elements used in the dam-and-fill method of the present invention contains (A) cationic polymerization compounds, (B) photo-cationic polymerization initiators, and (C) sensitizers, and the contact angle θa measured 15 seconds after liquid application is 35° or more and 90°or less in the contact angle measured over time according to the prescribed procedure i.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a sealing material for photoelectric conversion elements, a dam material, and a method for manufacturing a device using the dam material. More specifically, the present invention relates to a sealing material for photoelectric conversion elements, a dam material, a device including a photoelectric conversion element, and a method for manufacturing a device using the dam material. [Background technology]

[0002] BACKGROUND ART Conventionally, photoelectric conversion elements used in displays such as liquid crystal displays, organic electroluminescence displays, and electronic paper, as well as silicon-based solar cells, dye-sensitized solar cells, and organic thin-film solar cells, have been sealed with a sealing material having water vapor barrier properties and the like. Among these, organic electroluminescence (OLED) elements are attracting attention as elements capable of emitting light with high brightness. OLED elements are known to be easily affected by moisture, and their light-emitting properties are easily degraded by moisture or impurities that penetrate into the OLED element.

[0003] On the other hand, the dam-and-fill method is known as one sealing method. In the dam-and-fill method, a first curing adhesive is first applied to a substrate using a dispenser to form a ring-shaped dam (bank) for surrounding a photoelectric conversion element, and then a second curing adhesive is filled into the dam. After that, the photoelectric conversion element is embedded in the second curing adhesive inside the dam, and a transparent panel is placed on the dam so as to cover the dam. The second curing adhesive is then cured to bond the transparent panel to the substrate.

[0004] As an example of a sealant used in such a dam-and-fill method, Patent Document 1 (JP 2023-024361 A) discloses a thermosetting liquid composition for use as a sealant for organic light-emitting elements, which comprises a binder material containing an aliphatic tetrafunctional epoxy compound and a cationic initiator. Furthermore, for example, Patent Document 2 (WO 2017 / 099055) discloses a sealing composition containing at least one compound selected from N-glycidyl compounds, N-vinyl compounds, and N-allyl compounds (excluding N-glycidyl isocyanurate) as a dam material, in order to seal organic EL elements without directly exposing them to UV light.

[0005] Furthermore, for example, Patent Document 3 (WO 2017 / 094809) discloses a sealing composition containing a glycoluril compound that is weakly basic with respect to the cations generated from a photocationic polymerization initiator as a filler material, in order to seal an organic EL element without directly exposing it to UV light. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2023-024361 [Patent Document 2] International Publication No. 2017 / 099055 [Patent Document 3] International Publication No. 2017 / 094809 Summary of the Invention [Problem to be solved by the invention]

[0007] However, when a photoelectric conversion element is sealed by a dam-and-fill method using a conventional sealing material, there is room for improvement in the reliability of the sealing material in order to maintain the function of the photoelectric conversion element. More specifically, there have been cases where the adhesion between the dam material and the substrate was insufficient, or the amount of dam material dispensed was unstable when it was applied using a dispenser, making it difficult to form a dam of the desired shape. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to improve the reliability of sealing materials and have found that a sealing product having a desired shape can be obtained by controlling the contact angle of the sealing material over time. As a result of further research, they have devised a new index for the contact angle and found that a sealing material that satisfies this index can improve reliability, thereby completing the present invention.

[0009] According to the present invention, the following sealing material and related techniques are provided.

[0010] [1] An encapsulant for a photoelectric conversion element used in a dam-and-fill method, (A) a cationically polymerizable compound, (B) a photocationic polymerization initiator, and (C) a sensitizer; A sealing material for a photoelectric conversion element, wherein the contact angle θa measured over time by the following procedure i is 35° or more and 90° or less 15 seconds after contact with the liquid. (Step i) Prepare alkali-free glass that has been degreased with acetone and then cleaned with ozone for 15 minutes. Set a syringe filled with the photoelectric conversion element sealant in a contact angle meter, create a droplet under the following condition ii, and place the droplet on the prepared alkali-free glass to measure the contact angle over time. (condition ii) Measurement method: Change over time Control method: Standard ·Analysis methods and methods: Droplet method, θ / 2 method Field of View: Wide 2 ·Droplet volume: 5μl [2] The encapsulating material for a photoelectric conversion element according to [1], A sealing material for a photoelectric conversion element, wherein the contact angle over time measured by the procedure i above is a contact angle θb of 12° or more and 32° or less 120 seconds after contact with the liquid. [3] The encapsulating material for a photoelectric conversion element according to [2], The sealing material for a photoelectric conversion element, wherein the contact angle θa relative to the contact angle θb (θa / θb) is 1.5 or more and 5.0 or less. [4] The encapsulating material for a photoelectric conversion element according to any one of [1] to [3], A photoelectric conversion element encapsulant having a viscosity of 2,000 mPa·s or more and 50,000 mPa·s or less, measured using 0.5 ml of the encapsulant and a cone-type plate CPA-52Z at 25°C and a rotation speed of 25 rpm. [5] The encapsulating material for a photoelectric conversion element according to any one of [1] to [4], (D) A sealing material for a photoelectric conversion element, further comprising a phosphate compound. [6] The encapsulating material for a photoelectric conversion element according to any one of [1] to [5], The cationically polymerizable compound (A) contains one or more selected from the group consisting of (A-1) an alicyclic compound having an epoxy group, (A-2) an aromatic compound having an epoxy group, and (A-3) a glycidyl ether compound and derivatives thereof. [6] The encapsulating material for a photoelectric conversion element according to any one of [1] to [6], The encapsulant for a photoelectric conversion element further comprises a stabilizer. [8] A dam material comprising the encapsulant for a photoelectric conversion element according to any one of [1] to [7] and (E) an inorganic filler. [9] The dam material according to [8], (E) A dam material having an inorganic filler content of 20 to 300 parts by mass per 100 parts by mass of (A) a cationically polymerizable compound.

[10] The dam material according to [8] or [9], The dam material has a viscosity of 100,000 mPa·s or more and 1,200,000 mPa·s or less, measured using a cone-type plate CPA-52Z at 25°C and a rotation speed of 0.7 rpm, for 0.5 ml of the dam material.

[11] A hardened product of the dam material described in any one of [8] to

[10] .

[12] A device comprising a photoelectric conversion element sealed using the dam material according to [8].

[13] The device according to

[12] , The device, wherein the photoelectric conversion element is an organic electroluminescence element.

[14] A step of attaching a fill material and a dam material surrounding the fill material on a first member; Embedding a photoelectric conversion element in the fill material; placing a second member over the fill material and the dam material; a step of bonding the first member and the second member together and curing the fill material; and A method for manufacturing a device, wherein the dam material is the dam material described in [8].

[15] (A) a cationically polymerizable compound; and (B) a photocationic polymerization initiator, A composition, wherein the contact angle θa 15 seconds after contact with a liquid is 35° or more and 90° or less, as measured over time by the following procedure i. (Procedure i) Prepare alkali-free glass that has been degreased with acetone and then cleaned with ozone for 15 minutes. Set a syringe filled with the composition in a contact angle meter, create a droplet under the following condition ii, and place the droplet on the prepared alkali-free glass to measure the contact angle over time. (condition ii) Measurement method: Change over time Control method: Standard ·Analysis methods and methods: Droplet method, θ / 2 method Field of View: Wide 2 ·Droplet volume: 5μl [Effects of the Invention]

[0011] According to the present invention, a technique can be provided that can improve the reliability of a device that uses a sealing material. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an apparatus according to an embodiment of the present invention. [Figure 2] 1 is a diagram showing the positional relationship between a fill material and a dam material in a plan view of the device of this embodiment. FIG. [Figure 3] 5A to 5C are schematic diagrams illustrating an example of a method for manufacturing the device of the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0013] In this specification, the expression "a to b" in the description of a numerical range means from a to b, unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% to 5 mass%." Furthermore, the lower limit and upper limit of a numerical range can be arbitrarily combined with the lower limit and upper limit of another numerical range. Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more.

[0014] Hereinafter, embodiments of the present invention will be described with reference to the drawings. When multiple identical components are present in the same drawing, only one of them may be labeled with a reference symbol, and not all of them may be labeled with a reference symbol. All drawings are for illustrative purposes only. The shapes and dimensional ratios of each component in the drawings do not necessarily correspond to the actual product.

[0015] <Sealant for photoelectric conversion elements> The composition of this embodiment is as follows: (A) a cationic polymerizable compound; and (B) a photocationic polymerization initiator, A composition, wherein the contact angle θa 15 seconds after contact with a liquid is 35° or more and 90° or less, as measured over time by the following procedure i. (Procedure i) Prepare alkali-free glass that has been degreased with acetone and then cleaned with ozone for 15 minutes. Set a syringe filled with the composition in a contact angle meter, create a droplet under the following condition ii, and allow the droplet to land on the prepared alkali-free glass to measure the contact angle over time. (condition ii) Measurement method: Change over time Control method: Standard ·Analysis methods and methods: Droplet method, θ / 2 method Field of View: Wide 2 ·Droplet volume: 5μl The preferred aspects of this embodiment are as follows. The sealing material for photoelectric conversion elements of this embodiment is used in a dam-and-fill method, contains (A) a cationically polymerizable compound, (B) a photocationic polymerization initiator, and (C) a sensitizer, and has a contact angle over time measured by the following procedure i, where the contact angle θa 15 seconds after contact with the liquid is 35° or more and 90° or less.

[0016] (Step i) Prepare alkali-free glass that has been degreased with acetone and then cleaned with ozone for 15 minutes. Set a syringe filled with the photoelectric conversion element sealant in a contact angle meter, create a droplet under the following condition ii, and place the droplet on the prepared alkali-free glass to measure the contact angle over time. (condition ii) Measurement method: Change over time Control method: Standard ·Analysis methods and methods: Droplet method, θ / 2 method Field of View: Wide 2 ·Droplet volume: 5μl

[0017] By setting the contact angle θa 15 seconds after contact within the above range, the shape accuracy and position accuracy of the photoelectric conversion element sealing material can be improved, and a sealing body of a desired shape can be obtained. As a result, the reliability of a device using the photoelectric conversion element sealing material of this embodiment can be improved. The details of the reason for this are not clear, but it is speculated as follows. First, when the photoelectric conversion element encapsulant is applied with a dispenser, it is discharged from the tip of a nozzle and arranged in a desired shape while adhering to a substrate (first member). At this time, the photoelectric conversion element encapsulant that comes into contact with the substrate does not completely wet and spread, but gradually stabilizes its shape and adheres. Therefore, it is believed that controlling the contact angle when the photoelectric conversion element encapsulant comes into contact with the substrate and stabilizes its shape can enable more precise control of the arrangement and shape of the photoelectric conversion element encapsulant. Furthermore, when a dam is formed using the photoelectric conversion element encapsulant, it can be created as designed, and uniformity can be achieved by blocking the outflow of the fill material inside as a dam material, which is presumed to improve the reliability of devices using photoelectric conversion elements.

[0018] [Contact angle] The contact angle θa 15 seconds after contact with the ink is 35° or more, preferably 38° or more, and more preferably 40° or more, which reduces unevenness in ejection and suppresses waviness and bubble generation, while also improving reliability. On the other hand, the contact angle θa 15 seconds after contact with the ink is 90° or less, preferably 85° or less, and more preferably 70° or less. This reduces unevenness in ejection, suppresses waviness and bubble formation, and improves reliability. Furthermore, from the viewpoint of achieving even higher reliability, it is even more preferable that the contact angle θa be 55° or less.

[0019] Furthermore, in the contact angle over time measured by step i, the contact angle θb 120 seconds after contact with the liquid is preferably 12° or more and 32° or less. 120 seconds after contact with the liquid, it is considered that the discharged photoelectric conversion element sealing material has spread to some extent and its shape is almost stable. Therefore, by controlling the contact angle θb 120 seconds after contact with the liquid, a dam with a more stable width can be obtained.

[0020] Furthermore, the ratio of the contact angle θa (°) to the contact angle θb (°) (θa / θb) is preferably 1.3 or more, and more preferably 1.4 or more. On the other hand, the ratio of the contact angle θa (°) to the contact angle θb (°) (θa / θb) is preferably 3.0 or less, more preferably 2.6 or less, and even more preferably 2.2 or less.

[0021] A photoelectric conversion element encapsulant satisfying the above-mentioned contact angle can be realized by selecting the types of components constituting the photoelectric conversion element encapsulant and adjusting the amounts of the components. Specific examples include using (A-1) an alicyclic compound having an epoxy group, or using (D) a phosphoric acid compound and a stabilizer, in order to obtain wettability. Furthermore, in order to ensure the desired physical properties of the photoelectric conversion element encapsulant, a method of combining (A-2) an aromatic compound having an epoxy group and (A-3) a glycidyl ether compound, etc. with (A-1) an alicyclic compound having an epoxy group can also be used.

[0022] [viscosity] The viscosity of 0.5 ml of the photoelectric conversion element sealing material, measured using a cone-type plate CPA-52Z at 25°C and a rotation speed of 25 rpm, is preferably 2,000 mPa·s or more, more preferably 3,000 mPa·s or more, and even more preferably 3,500 mPa·s or more. On the other hand, the viscosity of the photoelectric conversion element sealing material is preferably 50,000 mPa·s or less, more preferably 40,000 mPa·s or less, and even more preferably 30,000 mPa·s or less. By setting the viscosity of the photoelectric conversion element sealing material within the above range, unevenness in discharge can be reduced, and the occurrence of waviness and bubbles can be suppressed. The term "wavy" refers to a phenomenon that occurs when the photoelectric conversion element encapsulant cannot be applied in a uniform line, when the photoelectric conversion element encapsulant does not spread evenly and the fluidity is reduced, or when the photoelectric conversion element encapsulant has too high a viscosity and cannot be uniformly discharged. The term "air bubbles" refers to a phenomenon that occurs when air bubbles contained in the photoelectric conversion element encapsulant do not escape even after application, or when bubbles are generated due to poor wetting of the substrate surface after application.

[0023] The components constituting the sealing material for photoelectric conversion elements will be described below.

[0024] (A) Cationic polymerizable compound The photoelectric conversion element sealing material of this embodiment contains (A) a cationically polymerizable compound as an essential component. (A) The cationically polymerizable compound is preferably photopolymerizable.

[0025] The cationically polymerizable compound (A) contains one or more selected from the group consisting of (A-1) an alicyclic compound having an epoxy group, (A-2) an aromatic compound having an epoxy group, and (A-3) a glycidyl ether compound and derivatives thereof, thereby providing good coating properties, adhesion, and low moisture permeability. The cationically polymerizable compound (A) may contain one or more halogen elements, such as a fluorine element or a bromine element.

[0026] (A-1) Alicyclic compound having an epoxy group Alicyclic compounds having an epoxy group (hereinafter sometimes referred to as alicyclic epoxy compounds) include compounds or derivatives thereof obtained by epoxidizing a compound having at least one cycloalkane ring (e.g., a cyclohexene ring, a cyclopentene ring, a pinene ring, etc.) with an appropriate oxidizing agent such as hydrogen peroxide or a peracid, and hydrogenated epoxy compounds obtained by hydrogenating an aromatic epoxy compound (e.g., a bisphenol A epoxy resin, a bisphenol F epoxy resin, etc.). One or more of these compounds may be selected and used.

[0027] Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylalkyl(meth)acrylate (for example, 3,4-epoxycyclohexylmethyl(meth)acrylate), (3,3',4,4'-diepoxy)bicyclohexyl, hydrogenated bisphenol A epoxy resin, and hydrogenated bisphenol F epoxy resin.

[0028] Among the alicyclic epoxy compounds, those having a 1,2-epoxycyclohexane structure are preferred. Among the alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure, the compound represented by the following formula (A1-1) is preferred.

[0029] [ka] (In formula (A1-1), X represents a single bond or a linking group (a divalent group having one or more atoms), and the linking group is a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked together.)

[0030] X is preferably a linking group. Among linking groups, a functional group having an ester bond is preferred. Among these, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferred.

[0031] The molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, even more preferably less than 300, and even more preferably 100 to 280, from the viewpoint of moisture permeability and storage stability.

[0032] When the alicyclic epoxy compound has a molecular weight distribution, the number average molecular weight of the alicyclic epoxy compound is preferably within the above range. In this specification, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and expressed in terms of polystyrene.

[0033] (A-2) Aromatic compound having an epoxy group As the aromatic compound having an epoxy group (hereinafter sometimes referred to as an aromatic epoxy compound), any of a monomer, an oligomer, and a polymer can be used, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, novolac phenol type epoxy resin, cresol novolac type epoxy resin, and modified products thereof.

[0034] Alternatively, the epoxy resin may be a polyfunctional epoxy resin having two or more epoxy groups. Examples of epoxy resins having two or more (particularly two) epoxy groups include bisphenol A-type polyfunctional epoxy resins, bisphenol F-type polyfunctional epoxy resins, bisphenol AF-type polyfunctional epoxy resins, hydrogenated bisphenol A-type polyfunctional epoxy resins, and biphenyl-type polyfunctional epoxy resins. Examples of epoxy resins having three or more epoxy groups include naphthalene-type multifunctional epoxy resins, phenol novolac-type multifunctional epoxy resins, cresol novolac-type multifunctional epoxy resins, dicyclopentadiene-type multifunctional epoxy resins, glycidylamine-type multifunctional epoxy resins, glycidyl ester-type multifunctional epoxy resins, rubber-modified multifunctional epoxy resins, chelate-modified multifunctional epoxy resins, multifunctional alicyclic epoxy resins, and multifunctional epoxidized polybutadienes.

[0035] One or more of these epoxy resins may be selected and used. Among these, aromatic epoxy compounds having a bisphenol structure are preferred. Among the aromatic epoxy compounds having a bisphenol structure, the compound represented by the following formula (A2-1) is preferred.

[0036] [ka] (In formula (A2-1), n ​​represents a real number from 0 to 30, and R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

[0037] R 21 , R 22 , R 23 and R 24 is preferably a hydrogen atom or a methyl group. 21 , R 22 , R 23 and R 24 and are preferably the same. n is preferably a real number of 0.1 to 30.

[0038] Among the aromatic epoxy compounds having a bisphenol structure, one or more selected from the group consisting of bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferred.

[0039] (A-2-1) Bisphenol A epoxy resin The bisphenol A type epoxy resin is, for example, a bisphenol A type epoxy resin represented by the formula (A2-1) 21 , R 22 , R 23 and R 24 may be an epoxy resin in which R is a methyl group. Bisphenol A epoxy resins refer to, for example, those obtained by condensing bisphenol A and epichlorohydrin in the presence of an alkali catalyst. Furthermore, modified epoxy resins may be used in which the epoxy groups or hydroxyl groups of the above bisphenol A epoxy resins are reacted with vegetable oil fatty acids or modifiers. Note that hydrogenated epoxy compounds obtained by hydrogenating bisphenol A epoxy resins (for example, hydrogenated bisphenol A epoxy resins corresponding to the above-mentioned alicyclic epoxy compounds) are not included in the bisphenol A epoxy resins.

[0040] (A-2-2) Bisphenol F epoxy resin The bisphenol F type epoxy resin is, for example, a bisphenol F type epoxy resin represented by the formula (A2-1) 21 , R 22 , R 23 and R 24 may be an epoxy resin in which R is a hydrogen atom. Bisphenol F epoxy resin refers to, for example, a resin obtained by condensing bisphenol F and epichlorohydrin in the presence of an alkali catalyst. Furthermore, modified epoxy resins may be used in which the epoxy groups or hydroxyl groups of the above-mentioned bisphenol F epoxy resins are reacted with vegetable oil fatty acids or modifiers. Note that hydrogenated epoxy compounds obtained by hydrogenating bisphenol F epoxy resins (for example, hydrogenated bisphenol F epoxy resins corresponding to the above-mentioned alicyclic epoxy compounds) are not included in the bisphenol F epoxy resins.

[0041] The molecular weight of the aromatic epoxy compound, particularly the molecular weight of the bisphenol A epoxy resin (A-2-1) and the bisphenol F epoxy resin (A-2-2), is preferably 100 to 5,000, more preferably 150 to 1,000, and most preferably 200 to 450, from the viewpoint of moisture permeability and the like.

[0042] When the aromatic epoxy compound has a molecular weight distribution, the number average molecular weight of the aromatic epoxy compound is preferably within the above range. In this specification, the number average molecular weight refers to a value measured by gel permeation chromatography (GPC) under the above-mentioned measurement conditions, expressed in terms of polystyrene.

[0043] (A-3) Glycidyl ether compound Examples of the glycidyl ether compound include monoglycidyl ether compounds and polyglycidyl ether compounds.

[0044] The monoglycidyl ether compound is not particularly limited, but examples thereof include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, mixed alkyl glycidyl ethers having 12 to 13 carbon atoms, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl ether, dibromocresyl glycidyl ether, decyl glycidyl ether, methoxypolyethylene glycol monoglycidyl ether, ethoxypolyethylene glycol monoglycidyl ether, butoxypolyethylene glycol monoglycidyl ether, phenoxypolyethylene glycol monoglycidyl ether, and dibromophenyl glycidyl ether.

[0045] The polyglycidyl ether compound is not particularly limited, but examples thereof include diglycidyl ethers of alkylene glycols (e.g., diglycidyl ethers of ethylene glycol, diglycidyl ethers of propylene glycol, diglycidyl ethers of 1,6-hexanediol, etc.), polyglycidyl ethers of polyhydric alcohols (e.g., di- or triglycidyl ethers of glycerin or its alkylene oxide adducts, etc.), and diglycidyl ethers of polyalkylene glycols (e.g., diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, diglycidyl ethers of polypropylene glycol or its alkylene oxide adducts, etc.). Here, examples of alkylene oxides include aliphatic ones such as ethylene oxide and propylene oxide.

[0046] Among these, the glycidyl ether compound preferably contains one or more halogen elements, and more preferably contains a bromine element. Specific examples include halophenyl glycidyl ethers such as bromophenyl glycidyl ether and dibromophenyl glycidyl ether, brominated cresyl glycidyl ether, and brominated bisphenol A epoxy resins (for example, diglycidyl ether of tetrabromobisphenol A).

[0047] The cationically polymerizable compound (A) of this embodiment may contain other cationically polymerizable compounds in addition to the above-mentioned (A-1), (A-2), and (A-3), and may contain, for example, one or more of oxetane compounds and vinyl ether compounds.

[0048] The oxetane compound is not particularly limited, but examples thereof include 3-ethyl-3-hydroxymethyloxetane (product name: Aron Oxetane OXT-101, manufactured by Toagosei Co., Ltd.), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (product name: OXT-121, manufactured by Toagosei Co., Ltd.), 3-ethyl-3-(phenoxymethyl)oxetane (product name: OXT-211, manufactured by Toagosei Co., Ltd.), di(1-ethyl-(3-oxetanyl))methyl ether (product name: OXT-221, manufactured by Toagosei Co., Ltd.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (product name: OXT-212, manufactured by Toagosei Co., Ltd.), etc. The oxetane compound refers to a compound having one or more oxetane rings in the molecule.

[0049] The vinyl ether compound is not particularly limited, but examples thereof include di- or trivinyl ether compounds such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylolpropane trivinyl ether; and monovinyl ether compounds such as ethylene glycol monovinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

[0050] The content of the (A-1) alicyclic compound having an epoxy group is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of the (A) cationically polymerizable compound, which tends to further improve the durability of the cured product. On the other hand, the content of the (A-1) alicyclic compound having an epoxy group is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less, per 100 parts by mass of the (A) cationically polymerizable compound.

[0051] When (A-2) an aromatic compound having an epoxy group is contained, the content of (A-2) an aromatic compound having an epoxy group is preferably 40 parts by mass or more, more preferably 45 parts by mass or more, and even more preferably 50 parts by mass or more, per 100 parts by mass of (A) the cationically polymerizable compound, which tends to further improve the durability of the cured product. On the other hand, the upper limit of the content of (A-2) aromatic compound having an epoxy group is not particularly limited, and may be, for example, 70 parts by mass or less per 100 parts by mass of (A) cationically polymerizable compound, or may not contain (A-2) aromatic compound having an epoxy group.

[0052] When the (A-3) glycidyl ether compound is contained, the content of the (A-3) glycidyl ether compound is preferably 60 parts by mass or more, more preferably 65 parts by mass or more, and even more preferably 70 parts by mass or more, per 100 parts by mass of the (A) cationically polymerizable compound, which tends to further improve the durability of the cured product. On the other hand, the upper limit of the content of the (A-3) glycidyl ether compound is not particularly limited, and may be, for example, 85 parts by mass or less per 100 parts by mass of the (A) cationically polymerizable compound, or may not contain any (A-3) glycidyl ether compound.

[0053] In 100 parts by mass of the cationically polymerizable compound (A), the total content of the alicyclic compound (A-1) having an epoxy group, the aromatic compound (A-2) having an epoxy group, and the glycidyl ether compound (A-3) is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, most preferably 90 parts by mass or more, and even more preferably 100 parts by mass.

[0054] (B) Photocationic polymerization initiator The photoelectric conversion element sealing material of this embodiment contains (B) a photocationic polymerization initiator as an essential component. When the photocationic polymerization initiator is used, the photoelectric conversion element sealing material of this embodiment can be cured by irradiation with energy rays such as ultraviolet rays.

[0055] (B) The photocationic polymerization initiator is not particularly limited, but examples thereof include arylsulfonium salt derivatives (e.g., Cyracure UVI-6990 and Cyracure UVI-6974 manufactured by The Dow Chemical Company; Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, and Adekaoptomer SP-172 manufactured by Asahi Denka Kogyo Co., Ltd.; CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-310FG, and LW-S1 manufactured by San-Apro Co., Ltd.; and Cibacur 1190 manufactured by Double Bond Corporation), aryl iodonium salt derivatives (e.g., Irgacure 250 manufactured by Ciba Specialty Chemicals and RP-2074 manufactured by Rhodia Japan), allene-ion complex derivatives, diazonium salt derivatives, triazine initiators, and acid generators such as other halides. The cationic species of the photocationic polymerization initiator is preferably an onium salt represented by formula (B-1).

[0056] The (B) photocationic polymerization initiator is not particularly limited, but includes an onium salt represented by formula (B-1).

[0057] [ka] (A represents an element of Group VIA to Group VIIA with a valence of m. m represents 1 to 2. p represents 0 to 3. m and p are preferably integers. R represents an organic group bonded to A. D represents the following formula (B-1-1): [ka] In formula (B-1-1), E represents a divalent group, and G represents -O-, -S-, -SO-, -SO2-, -NH-, -NR'-, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group (R' represents an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms). a represents 0 to 5. a+1 E's and a G's may be the same or different. a is preferably an integer. X - are the counterions of the onium, and there are p+1 of them per molecule.)

[0058] The onium ion of formula (B-1) is not particularly limited, and examples thereof include 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolyls ... Examples of such sulfonates include dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, and octadecylmethylphenacylsulfonium.

[0059] R is an organic group bonded to A. R represents, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, which may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, and nitro groups, and halogen. The number of R is m+p(m-1)+1, and they may be the same or different from each other. Two or more R's may be bonded to each other directly or via -O-, -S-, -SO-, -SO2-, -NH-, -NR'-, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group to form a ring structure containing the element A, where R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0060] Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl group, and condensed polycyclic aryl groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone.

[0061] The above-mentioned aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, or alkynyl group having 2 to 30 carbon atoms may have at least one substituent, and examples of the substituent include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; linear alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; cycloalkyl groups having 3 to 18 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxy groups; linear or branched alkoxy groups having 1 to 18 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, and octanoyl. linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms, such as octadecanoyl; arylcarbonyl groups having 7 to 11 carbon atoms, such as benzoyl and naphthoyl; linear or branched alkoxycarbonyl groups having 2 to 19 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl; phenoxycarbonyl, naphthoxy aryloxycarbonyl groups having 7 to 11 carbon atoms, such as carbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; linear or branched acyloxy groups having 2 to 19 carbon atoms, such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, and octadecylcarbonyloxy;Phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4-[4-(phenylthio)benzoyl] ]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthiobenzoyl)phenylthio, 4-(p-methylbenzoyl)phenylthio, 4-(p an arylthio group having 6 to 20 carbon atoms, such as 4-(p-tert-butylbenzoyl)phenylthio, 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio; a straight-chain or branched alkylthio group having 1 to 18 carbon atoms, such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, and dodecylthio; phenyl, tolyl, dimethylphenyl, aryl groups having 6 to 10 carbon atoms, such as naphthyl; heterocyclic groups having 4 to 20 carbon atoms, such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl;Aryloxy groups having 6 to 10 carbon atoms, such as phenoxy and naphthyloxy; linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl and octylsulfinyl; and linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms, such as phenylsulfinyl, tolylsulfinyl and naphthylsulfinyl. arylsulfinyl groups having 6 to 10 carbon atoms; linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, and octylsulfonyl; arylsulfonyl groups having 6 to 10 carbon atoms, such as phenylsulfonyl, tolylsulfonyl (tosyl), and naphthylsulfonyl; formula (B-1-2);

[0062] [ka] (Q represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 5); an unsubstituted amino group; an amino group mono- or di-substituted with alkyl having 1 to 5 carbon atoms and / or aryl having 6 to 10 carbon atoms; a cyano group; a nitro group; and halogens such as fluorine, chlorine, bromine, and iodine.

[0063] p in formula (B-1) is [DA + R m-1 ] represents the number of repeating units of the bond, and is preferably an integer of 0 to 3.

[0064] The onium ion [A + Preferred examples of the cation include sulfonium, iodonium, and selenium, and typical examples include the following:

[0065] Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, and bis[4-(diphenylsulfonio)phenyl nyl] sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl] sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl} sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl} sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl} sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-Dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium triarylsulfoniums such as 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, 5-tolylthiaanthrenenium, 5-(4-ethoxyphenyl)thiaanthrenenium, and 5-(2,4,6-trimethylphenyl)thiaanthrenenium; diarylsulfoniums such as diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, and diphenylmethylsulfonium; monoarylsulfoniums such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, and 9-anthracenylmethylphenacylsulfonium; and trialkylsulfoniums such as dimethylphenacylsulfonium, phenacyltrhydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium.

[0066] Among these onium ions, one or more of sulfonium ions and iodonium ions are preferred, with sulfonium ions being more preferred. Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, and 7-isopropyl-9-oxo-10-thia-9 Preferred are one or more of the following: 10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium and octadecylmethylphenacylsulfonium.

[0067] In formula (B-1), X - is a counter ion. The number of counter ions is p+1 per molecule. The counter ion is not particularly limited, but examples include boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, halides such as alkylsulfonic acid compounds, and methide compounds. X - For example, F - , Cl - , Br - , I -Halogen ions such as OH - ;ClO4 - ;FSO3 - , ClSO3 - , CH3SO3 - , C6H5SO3 - , CF3SO3 - Sulfonic acid ions such as HSO4 - , SO4 2- Sulfate ions such as HCO3 - , CO3 2- Carbonate ions such as H2PO4 - , HPO4 2- , PO4 3- Phosphate ions such as PF6 - , PF5OH - Fluorophosphate ions such as fluorinated alkyl fluorophosphate ions; BF4 - , B(C6F5)4 - , B(C6H4CF3)4 - Boric acid ions such as AlCl4 - ;BiF6 - Other examples include SbF6 - , SbF5OH - Fluoroantimonate ions such as AsF6 - , AsF5OH - and the like fluoroarsenate ions.

[0068] Examples of the fluorinated alkylfluorophosphate ion include a fluorinated alkylfluorophosphate ion represented by formula (B-1-3) and the like.

[0069] [(Rf) b PF 6-b ]- (B-1-3)

[0070] In formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom. The number b of Rf is 1 to 5 and is preferably an integer. The b Rfs may be the same or different. The number b of Rfs is more preferably 2 to 4, and most preferably 2 to 3. In the fluorinated alkylfluorophosphate ion represented by formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Specific examples include CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C.

[0071] A specific example of a preferred fluorinated alkyl fluorophosphate anion is [(CF3CF2)2PF4] - , [(CF3CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [(CF3CF2CF2)2PF4] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - , [(CF3CF2CF2CF2)2PF4] - and [(CF3CF2CF2CF2)3PF3] - etc.

[0072] The cationic photopolymerization initiator may be dissolved in advance in a solvent to facilitate dissolution in the epoxy compound or epoxy resin. Examples of the solvent include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate.

[0073] One or more of these photocationic polymerization initiators may be selected and used.

[0074] Examples of anion species of the (B) photocationic polymerization initiator include halides such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, and alkylsulfonic acid compounds. One or more of these anion species may be selected and used. Among these, fluorides are preferred because they have excellent photocurability and improved adhesiveness and adhesion durability. Of the fluorides, hexafluoroantimonate is preferred.

[0075] Among the (B) photocationic polymerization initiators, one or more of triarylsulfonium salt hexafluoroantimonate represented by formula (B-2) and diphenyl 4-thiophenoxyphenylsulfonium tris(pentafluoroethyl)trifluorophosphate represented by formula (B-3) are preferred, and triarylsulfonium salt hexafluoroantimonate is more preferred.

[0076] [ka]

[0077] [ka]

[0078] The content of the (B) cationic photopolymerization initiator is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.5 to 2 parts by mass, relative to 100 parts by mass of the (A) cationic polymerizable compound. When the content of the cationic photopolymerization initiator is 0.05 part by mass or more, the photocurability is further improved, and when it is 5 parts by mass or less, the adhesion durability tends to be further improved.

[0079] (C) Photosensitizer The encapsulating material for a photoelectric conversion element of this embodiment contains (C) a photosensitizer. (C) Photosensitizer refers to a compound that absorbs energy rays and efficiently generates cations from the photocationic polymerization initiator.

[0080] The (C) photosensitizer is not particularly limited, but examples thereof include benzophenone derivatives, phenothiazine derivatives, phenyl ketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, chrysene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazole derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, xanthone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, triallylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, and organic ruthenium complexes. Among these, phenyl ketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and anthracene derivatives are preferred, with anthracene derivatives being more preferred.

[0081] Examples of anthracene derivatives include anthracene, 1,2-benzanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diglycidyloxyanthracene, 9,10-bis(phenylethyl)anthracene, etc. Among these, 9,10-diethoxyanthracene is preferred.

[0082] The content of the (C) photosensitizer is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the (A) cationically polymerizable compound, in terms of not impairing photocurability or decreasing storage stability.

[0083] (D) Phosphate Compounds The photoelectric conversion element sealing material of this embodiment may contain (D) a phosphoric acid compound. This tends to reduce viscosity and improve storage stability, which in turn tends to improve reliability. The (D) phosphoric acid compound is at least one selected from the group consisting of (D1) phosphoric acid esters and (D2) phosphorous acid esters. As the phosphoric acid compound, organic phosphoric acid compounds are preferred, and (D1) phosphoric acid esters are more preferred.

[0084] Examples of (D1) phosphoric acid esters include diethylbenzyl phosphate, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, tris(butoxyethyl)phosphate, tris(2-ethylhexyl)phosphate (trioctyl phosphate), (RO)3P=O [R=lauryl group, cetyl group, stearyl group, or oleyl group], tris(2-chloroethyl)phosphate, tris(2-dichloropropyl)phosphate, triphenyl phosphate, butyl pyrophosphate, tricresyl phosphate, trixylenyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, xylenyl diphosphate, monobutyl phosphate, dibutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, ammonium ethyl acid phosphate, and 2-ethylhexyl acid phosphate salts.

[0085] The (D1) phosphate ester preferably contains at least one selected from the group consisting of a compound represented by formula (D1-1), a compound represented by formula (D1-2), and a compound represented by formula (D1-3), and more preferably contains a compound represented by formula (D1-2).

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] In formula (D1-1), formula (D1-2) and formula (D1-3), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represents a hydrocarbon group which may have a substituent.

[0090] R in formula (D1-2) 2 , R 3 and R 4 , and R in formula (D1-3) 5 and R 6 is preferably the same group in each formula.

[0091] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Examples of the substituent that the hydrocarbon group in R may have include an oxyalkyl group. 1 , R 2 , R 3 , R 4 , R 5 and R 6 The hydrocarbon group in is preferably an unsubstituted hydrocarbon group.

[0092] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 The hydrocarbon group in is preferably an alkyl group or an aryl group, more preferably an alkyl group or a phenyl group, and even more preferably an alkyl group. The alkyl group may have, for example, 1 to 18 carbon atoms, and preferably 4 to 13 carbon atoms.

[0093] The compound represented by formula (D1-1) includes, for example, monoalkyl phosphate (i.e., R 1 is an alkyl group), and specific examples include monoethyl phosphate, mono-n-butyl phosphate, mono(butoxyethyl) phosphate, mono(2-ethylhexyl) phosphate, and the like.

[0094] The compound represented by formula (D1-2) includes trialkyl phosphate (i.e., R 2 , R 3 and R 4 In this case, R is an alkyl group. 2 , R 3 and R 4 The alkyl group preferably has 1 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 8 carbon atoms.

[0095] Specific examples of trialkyl phosphates include triethyl phosphate, tri-n-butyl phosphate, tris(butoxyethyl) phosphate, tris(2-ethylhexyl) phosphate (trioctyl phosphate), (RO)3P=O (R is a lauryl group, a cetyl group, a stearyl group, or an oleyl group), and the like.

[0096] The compound represented by formula (D1-3) includes, for example, dialkyl phosphate (i.e., R 5 and R 6 is an alkyl group), etc. Specific examples of dialkyl phosphates include dibutyl phosphate and bis(2-ethylhexyl) phosphate.

[0097] In formula (D1-1), formula (D1-2) and formula (D1-3), R 1 , R 2 , R 3 , R 4 , R 5 and R 6may each independently be one or more of a hydrocarbon group containing an alkyl group, a hydrocarbon group containing an aromatic ring, and a hydrocarbon group containing an aliphatic ring. The hydrocarbon group may have a partially unsaturated group, and may have any atom or substituent. In this case, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 R is preferably a hydrocarbon group containing an alkyl group. The hydrocarbon group is preferably an unsubstituted saturated group. 1 , R 2 , R 3 , R 4 , R 5 and R 6 are preferably the same.

[0098] (D2) Examples of phosphites include trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tris(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl isooctyl phosphite, diphenyl monodecyl phosphite, diphenyl monoisodecyl phosphite, diphenyl mono(tridecyl) phosphite, bis(nonylphenyl)dinonylphenyl phosphite, tetraphenyl dipropylene glycol diphosphite, poly Examples of suitable phosphate phosphates include (dipropylene glycol)phenyl phosphite, diisodecyl pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl)-4,4'-isopropylidene diphenyl phosphite, trilauryl trithiophosphite, dimethyl hydrogen phosphite, dibutyl hydrogen phosphite, di(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, and diphenyl mono(tridecyl) phosphite.

[0099] The content of the (D) phosphoric acid compound is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the (A) cationically polymerizable compound. If the content of the (D) phosphoric acid compound is 0.01 parts by mass or more, the increase in viscosity after light irradiation can be suppressed and reliability can be improved, and if it is 5 parts by mass or less, good photocurability can be maintained.

[0100] [others] The photoelectric conversion element sealing material may further contain, in addition to the above components (A) to (D), known additives such as a silane coupling agent, an initiator, and a stabilizer such as crown ether. Furthermore, the encapsulating material for a photoelectric conversion element of this embodiment preferably does not contain (E) an inorganic filler.

[0101] (stabilizer) By including a stabilizer, storage stability can be improved. The stabilizer is not particularly limited, but includes amino acid derivative compounds such as carbonyldiimidazole, antioxidants, ether compounds, and mixtures thereof. Among these, ether compounds are preferred, such as polyalkylene oxides such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol, and cyclic crown ethers. Of these, carbonyldiimidazole and crown ethers are preferred. The crown ether is not particularly limited, and examples thereof include 12-crown-4, 15-crown-5, 18-crown-6, and dicyclohexano-18-crown-6.

[0102] When a stabilizer is contained, the content of the stabilizer is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the cationically polymerizable compound (A), thereby improving storage stability. On the other hand, the upper limit of the content of the stabilizer is not particularly limited, and may be, for example, 5 parts by mass or less per 100 parts by mass of the (A) cationically polymerizable compound.

[0103] (Silane coupling agent) The silane coupling agent is not particularly limited, but includes γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, γ-(meth)acryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-ureidopropyltriethoxysilane. One or more of these silane coupling agents may be selected and used. Among these, one or more selected from the group consisting of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane are preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred.

[0104] When a silane coupling agent is contained, the content of the silane coupling agent is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the (A) cationically polymerizable compound, which provides good adhesiveness and adhesion durability. On the other hand, the upper limit of the content of the silane coupling agent is not particularly limited, and may be, for example, 5 parts by mass or less per 100 parts by mass of the (A) cationically polymerizable compound, or the silane coupling agent may not be contained.

[0105] [Application] The encapsulant for photoelectric conversion elements of this embodiment is preferably used for displays such as liquid crystal displays, organic EL displays, and electronic paper, and for encapsulating photoelectric conversion elements such as silicon solar cells, dye-sensitized solar cells, and organic thin-film solar cells.

[0106] [Manufacturing method] The method for producing the encapsulant for photoelectric conversion elements according to this embodiment is not particularly limited as long as the above components can be mixed sufficiently. The method for mixing the components is not particularly limited, but examples include a stirring method that utilizes the stirring force associated with the rotation of a propeller, and a method that uses a conventional disperser such as a planetary stirrer that rotates and revolves. These mixing methods are preferred because they are low-cost and allow stable mixing.

[0107] <Dam material> The dam material of this embodiment contains the above-mentioned photoelectric conversion element encapsulant and (E) an inorganic filler. In the dam material, the photoelectric conversion element encapsulant and (E) an inorganic filler may be mixed or may be separate. The mixing method is not particularly limited, and the same method as for the photoelectric conversion element encapsulant can be used.

[0108] The dam material of this embodiment is suitable for use as a dam material in the dam-and-fill method. That is, by including the inorganic filler (E), the viscosity and mechanical strength can be improved. The dam material of this embodiment is hardened by the method described below to obtain a dam.

[0109] (E) Inorganic filler The dam material of this embodiment contains (E) inorganic filler as an essential component. (E) Inorganic filler is a solid component made of an inorganic substance.

[0110] (E) Examples of inorganic fillers include one or more selected from crystalline silica such as quartz, fused silica, and amorphous silica such as colloidal silica, zircon, zirconia, magnesia, olivine, spinel, chamotte, mullite, andalusite, sillimanite, kyanite, talc, kaolin, mica, chromite, mica, pottery stone, obsidian, perlite, glass, frit, diatomaceous earth, rosestone, vermiculite, expanded shale, aluminium shale, graphite, carbon, Gilsonite, zinc oxide, calcium oxide, titanium oxide, zinc carbonate, magnesium carbonate, calcium carbonate, silicon carbide, silicon nitride, and boron nitride.

[0111] The inorganic filler may have a hydrophobic surface, for example, by a known method using epoxysilane, aminosilane, (meth)acrylicsilane, vinylsilane, methylchlorosilane, dimethylpolysiloxane, or the like.

[0112] The content of the (E) inorganic filler is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, relative to 100 parts by mass of the (A) cationically polymerizable compound. From the viewpoint of further improving durability and reliability, the content is even more preferably 80 parts by mass or more, and particularly preferably 100 parts by mass or more. On the other hand, the content of the (E) inorganic filler is preferably 300 parts by mass or less, and more preferably 200 parts by mass or more, relative to 100 parts by mass of the (A) cationically polymerizable compound, which can improve the ejection properties.

[0113] [viscosity] The viscosity of 0.5 ml of the dam material of this embodiment, measured using a cone-type plate CPA-52Z at 25°C and a rotation speed of 0.7 rpm, is preferably 100,000 mPa·s or more, more preferably 200,000 mPa·s or more, and even more preferably 250,000 mPa·s or more. On the other hand, the viscosity of the dam material is preferably 1,200,000 mPa·s or less, more preferably 800,000 mPa·s or less, and even more preferably 500,000 mPa·s or less. By setting the viscosity of the dam material within the above range, unevenness in discharge can be reduced and the occurrence of waviness and bubbles can be suppressed.

[0114] <Device> The device of this embodiment includes a photoelectric conversion element sealed with the above-described sealing material for a photoelectric conversion element. An example of the device of this embodiment will be described below with reference to the drawings.

[0115] 1, the device 100 of this embodiment includes a photoelectric conversion element 31, a filler material 21 that covers the photoelectric conversion element 31, a dam material 22 that is arranged to surround the filler material 21, and a pair of members (members 11 and 12) that sandwich these. The photoelectric conversion element 31 is arranged on the member 12. In this embodiment, the dam material 22 is formed using the above-mentioned photoelectric conversion element sealing material and (E) inorganic filler. The photoelectric conversion element 31 is sealed by the fill material 21 and the dam material 22 .

[0116] 2 is a diagram showing the positional relationship between the fill material 21 and the dam material 22 in a plan view of the device 100. As shown in FIG. 2, the fill material 21 is surrounded by the dam material 22. In other words, the side wall of the fill material 21 is in contact with the dam material 22.

[0117] Specific examples of the device 100 include displays such as liquid crystal displays, organic EL displays, and electronic paper, as well as silicon-based solar cells, dye-sensitized solar cells, and organic thin-film solar cells.

[0118] Next, an example of a method for manufacturing the device 100 of this embodiment will be described. As shown in FIG. 3, the method for manufacturing the device 100 of this embodiment includes the following steps: A step of attaching a fill material 21 and a dam material 22 surrounding the fill material 21 onto a member 11 (first member); a step of embedding the photoelectric conversion element 31 in the fill material 21; a step of placing a member 12 (second member) so as to cover the fill material 21 and the dam material 22; and curing the filler material 21 so as to bond the member 11 and the member 12 together, wherein the dam material 22 contains the above-mentioned photoelectric conversion element sealing material and (E) an inorganic filler.

[0119] Details are explained below.

[0120] (Attachment process) First, as shown in FIG. 3(a), a filler material 21 and a dam material 22 surrounding the filler material 21 are applied to the member 11. The order in which the filler material 21 and the dam material 22 surrounding the filler material 21 are applied is not particularly limited. The dam material 22 is preferably applied by discharging the dam material 22 using a dispenser while placing it at the desired position. This makes it easier to form a dam with the desired shape. The application of the filler material 21 is not particularly limited, but for example, it can be applied in a planar manner within the frame of the dam material 22 using an inkjet method (see FIG. 2).

[0121] The thickness of the dam material 22 and the fill material 21 is not particularly limited as long as they can adequately seal the photoelectric conversion element 31 and can achieve flatness and thinness, but can be, for example, 5 to 10 μm. The member 11 can be a transparent panel that serves as the display surface of a display. Examples of the transparent panel include glass and transparent resin.

[0122] The filler material 21 applied to the member 11 may be further photocured (see FIG. 3(b)). That is, after activating the filler material 21 by irradiating it with light, the photoelectric conversion element 31 is embedded in the filler material 21, and the member 11 and the member 12 are bonded together, so that the photoelectric conversion element 31 does not need to be irradiated with light for activating the filler material 21.

[0123] The light is preferably ultraviolet light. For example, ultraviolet light (UV) is emitted from a high-pressure mercury lamp at 100 mW / cm 2 It is more preferable that the viscosity 10 minutes after irradiation with UV light for 30 seconds is less than 5 times the viscosity before UV irradiation.

[0124] (Embedding process) Next, the photoelectric conversion element 31 is embedded in the fill material 21. The embedding method is not particularly limited, but for example, as shown in FIG. 3(c), the photoelectric conversion element 31 may be embedded in the fill material 21 by preparing the photoelectric conversion element 31 placed on the member 12 in advance and arranging the surface of the member 12 on which the photoelectric conversion element 31 is placed facing the fill material 21 and dam material 22. It is also preferable to embed the photoelectric conversion element 31 before the fill material 21 that has been irradiated with light is completely cured. Furthermore, if the fill material 21 and the dam material 22 are thermosetting, they may be thermoset by heating instead of by light irradiation.

[0125] (Step of placing member 12 (second member)) 3(d), the member 12 is disposed so as to cover the fill material 21 and the dam material 22. As a result, the member 11 and the member 12 are stacked together with the photoelectric conversion element 31 embedded in the fill material 21, the fill material 21, and the dam material 22 interposed therebetween. The member 12 may be made of the same material as the member 11. The members 12 and 11 may be made of the same material or may be made of different materials. The member 12 may be embedded at the same time as the embedding step, as described above.

[0126] (Process for hardening the fill material) Next, the members 11 and 12 are bonded together, and the filler material 21 is cured. For example, the filler material 21 may be cured by heating to 60 to 200°C. This can accelerate the curing rate after light irradiation. When used to seal an organic electroluminescence element, the heating temperature is preferably 150°C or less, and more preferably 80°C or less, so as not to damage the organic electroluminescence element. The post-heating temperature is preferably 60°C or more.

[0127] The device 100 can be obtained through the above procedure.

[0128] Furthermore, the light source used in the manufacturing method of the device 100 is not particularly limited, but examples thereof include a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium, etc.), a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, a light-emitting diode (hereinafter referred to as an LED), etc. These light sources are preferred in that they can efficiently irradiate energy rays corresponding to the reaction wavelength of each (B) photocationic polymerization initiator.

[0129] The above light sources each have different radiation wavelengths and energy distributions. Therefore, the light source is appropriately selected depending on the reaction wavelength of the photocationic polymerization initiator. Natural light (sunlight) can also be used as a reaction initiation light source.

[0130] The irradiation from the light source may be direct irradiation or focused irradiation using a reflecting mirror, fiber, etc. A low wavelength cut filter, a heat ray cut filter, a cold mirror, etc. may also be used.

[0131] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. In the above embodiment, a sealing material for a photoelectric conversion element used in a dam-and-fill method has been described. However, the sealing material may also be a resin composition containing (A) a cationically polymerizable compound, (B) a photocationic polymerization initiator, and (C) a sensitizer, and having a contact angle θa measured over time by a predetermined procedure i, 15 seconds after contact with the liquid, of 35° or more and 90° or less. In this case, since the resin composition has good wettability, it can be used as a dam material and a fill material in a display device, an encapsulant for a light-emitting diode element (including an organic electroluminescence display element or a micro LED) or a solar cell (including a perovskite solar cell), and the like.

[0132] Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various other configurations can also be adopted. [Example]

[0133] Next, the present invention will be described in detail with reference to examples, but the content of the present invention is not limited to the examples.

[0134] 1. Raw materials for sealing materials and dam materials for photoelectric conversion elements (A-1) Alicyclic compound having an epoxy group Alicyclic compound with epoxy group 1: (3,3',4,4'-diepoxy)bicyclohexyl "Celloxide 8010" manufactured by Daicel Chemical Industries, Ltd. Alicyclic compound with epoxy group 2: 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate "Celloxide 2021P" manufactured by Daicel Chemical Industries, Ltd. (A-2) Aromatic compound having an epoxy group Aromatic compound with epoxy group 1: Bisphenol A type epoxy resin, epoxy equivalent weight 160-170g / eq, "JER-806" manufactured by Mitsubishi Chemical Corporation Aromatic compound with epoxy group 2: Bisphenol A type epoxy resin, epoxy equivalent weight 184-194g / eq, "JER-828" manufactured by Mitsubishi Chemical Corporation Aromatic compound 3 with epoxy groups: Phenol novolac type multifunctional epoxy, epoxy equivalent weight 184-194g / eq, "N-775" manufactured by DIC Corporation (A-3) Glycidyl ether compound Glycidyl ether compound 1: Dibromophenyl glycidyl ether "BR-250H" manufactured by Nippon Kayaku Co., Ltd. Glycidyl ether compound 2: Tetrabromobisphenol A glycidyl ether "Epicron 153" DIC Glycidyl ether compound 3: Phenyl glycidyl ether (PEG) Sakamoto Pharmaceutical Co., Ltd. "JP-200" Glycidyl ether compound 4: Epoxidized polybutadiene "JP-200" by Nippon Soda Co., Ltd.

[0135] (B) Photocationic polymerization initiator Photocationic polymerization initiator 1: Triarylsulfonium tetrakis(pentafluorophenyl)gallate "CPI-310FG" manufactured by San-Apro Co., Ltd. Photocationic polymerization initiator 2: Triarylsulfonium cation-hexafluoroantimony "SP-170" manufactured by ADEKA Corporation

[0136] (C) Sensitizer Sensitizer: 1: 9,10-diethoxyanthracene (DEA) manufactured by Kawasaki Kasei Chemical Industries, Ltd. Sensitizer 2: 2-hydroxy-2-methylpropiophenone "DAROCUR1173" manufactured by BASF Japan (formerly Ciba)

[0137] (D) Phosphate Compounds Phosphate compound 1: Trioctyl phosphate "TOP" manufactured by Daihachi Chemical Co., Ltd.

[0138] (others) Stabilizer: Crown ether (18-crown-6) "O-18" manufactured by Nippon Kayaku Co., Ltd. Silane coupling agent: Epoxy group-containing silane coupling agent, γ-glycidoxypropyltrimethoxysilane "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.

[0139] (E) Inorganic filler Inorganic filler 1: Fused spherical silica, commercially available Inorganic filler 2: Flake talc 1 "#5000PA" manufactured by Matsumura Sangyo Co., Ltd. Inorganic filler 3: Flake talc 2 "#5000PJ" manufactured by Matsumura Sangyo Co., Ltd.

[0140] 2. Encapsulant for photoelectric conversion elements The components (A-1) to (A-3), (B), (C), (D) and other ingredients were mixed in a glass container using a metal blade (Teflon coated) as a stirring blade in the proportions (parts by mass) shown in Table 1 to prepare a photoelectric conversion element encapsulant. The following measurements were carried out using the photoelectric conversion element encapsulant. [Contact angle] Using the photoelectric conversion element encapsulant, the contact angle was measured over time according to the following procedure i, and the contact angle θa 15 seconds after contact with the liquid and the contact angle θb 120 seconds after contact with the liquid were determined. A controller was used to create the droplets and remove bubbles. The results are shown in Table 1. (Procedure i) Prepared alkali-free glass that had been degreased with acetone and then cleaned with ozone for 15 minutes. A syringe filled with the photoelectric conversion element sealant was set in a contact angle meter, and a droplet was prepared under the following condition ii. The droplet was then placed on the prepared alkali-free glass, and the contact angle over time was measured. (condition ii) Measurement method: Change over time Control method: Standard ·Analysis methods and methods: Droplet method, θ / 2 method Field of View: Wide 2 ·Droplet volume: 5μl

[0141] The contact angle was measured using the following instruments and devices. Alkali-free glass: Threaded Corning Eagle XG (test piece) 0.7 x 100 x 100 mm Ozone cleaning device: Asumi Giken "ASM2001N" Contact angle measurement device: Dynamic contact angle meter DMo-602, controller DMC-3 (Kyowa Interface Science Co., Ltd.)

[0142] [Viscosity-1] The viscosity of 0.5 ml of the photoelectric conversion element encapsulant was measured using a cone-type plate CPA-52Z at 25°C and 25 rpm. The measurement was carried out in an air atmosphere. The results are shown in Table 1.

[0143] 3. Dam material The dam material was prepared by mixing (A-1) to (A-3), (B), (C), (D), (E) and other components in the proportions (parts by mass) shown in Table 1 in a glass container using a metal blade (Teflon coated) as a stirring blade. The obtained dam material was subjected to the following measurements and evaluations.

[0144] [Viscosity-2] The viscosity was measured using a cone-type plate CPA-52Z at 25°C and a rotation speed of 0.7 rpm using 0.5 ml of dam material. The measurement was carried out in an air atmosphere. The results are shown in Table 1.

[0145] The viscosity was measured using the following device. Measurement equipment: Brookfield

[0146] [evaluation] A dam material was applied to one side of a 25 mm square alkali-free glass substrate using a dispenser, extending from the outer edge of the substrate to 5 mm inward, and the dam material was arranged in a rectangular frame. Next, a 25 mm square alkali-free glass substrate was separately prepared and bonded to the dam material under an air pressure of 0.9 MPa. The dam material was then irradiated with 6000 mJ / cm of a high-pressure mercury lamp. 2 Subsequently, a 1 kg weight was placed on the center of the outermost layer of the substrate, and the dam material was heated and cured at 85°C for 60 minutes to form a dam and bond the substrates together, thereby obtaining a substrate with a dam.

[0147] (1) Variation in dam width The width of the dam material was measured when it was placed in a rectangular frame, and the variation U was calculated using the following formula from the maximum and minimum dam width values ​​(mm). Variation U = (maximum value - minimum value) / (maximum value + minimum value)

[0148] (2) Appearance of the dam width Furthermore, the appearance of the dam material when placed in a rectangular frame was evaluated according to the following criteria. (standard) ○: No rippling or foaming is observed ×: Waves and bubbles were observed

[0149] (3) Dam width storage: reliability The obtained substrate with the dam was stored under conditions of 85° C. and 85% RH, and the dam was observed before and after storage and evaluated according to the following criteria. (standard) ◎: Even after 6 weeks of storage, no peeling was observed at the interface between the dam and the substrate, demonstrating high reliability 〇: Even after one week of storage, no peeling was observed at the interface between the dam and the substrate, demonstrating high reliability. ×: After one week of storage, peeling was observed at the interface between the dam and the substrate, indicating low reliability.

[0150] [Table 1] In the table, "*1" indicates that the viscosity was too high and droplets could not be formed properly. [Explanation of symbols]

[0151] 11 Components 12 Components 21 Fill material 22 Dam material 31 Photoelectric conversion element 100 devices

Claims

1. An encapsulant for a photoelectric conversion element used in a dam-and-fill method, (A) a cationically polymerizable compound, (B) a photocationic polymerization initiator, and (C) a sensitizer, (A) the cationically polymerizable compound contains one or more compounds selected from (A-1) an alicyclic compound having an epoxy group, (A-2) an aromatic compound having an epoxy group, and (A-3) a glycidyl ether compound and derivatives thereof; the content of the alicyclic compound having an epoxy group (A-1) is 25 parts by mass or less in 100 parts by mass of the cationically polymerizable compound (A); A sealing material for a photoelectric conversion element, wherein the contact angle θa 15 seconds after contact with the liquid is measured over time by the following procedure i, is 35° or more and 90° or less. (Step i) Prepare alkali-free glass that has been degreased with acetone and then cleaned with ozone for 15 minutes. Set a syringe filled with the photoelectric conversion element sealing material in a contact angle meter, prepare a droplet under the following condition ii, and allow the droplet to land on the prepared alkali-free glass to measure the contact angle over time. (Condition ii) Measurement method: Change over time - Control method: Standard ・Analysis methods and methods: Droplet method, θ / 2 method ・Field of view: Wide 2 ・Droplet volume: 5μl

2. The encapsulant for a photoelectric conversion element according to claim 1, The sealing material for a photoelectric conversion element, wherein the contact angle over time measured by the procedure i is a contact angle θb of 12° or more and 32° or less 120 seconds after contact with the liquid.

3. The encapsulant for a photoelectric conversion element according to claim 2, The sealing material for a photoelectric conversion element, wherein the contact angle θa relative to the contact angle θb (θa / θb) is 1.5 or more and 5.0 or less.

4. The encapsulant for a photoelectric conversion element according to claim 1 or 2, The encapsulant for photoelectric conversion elements has a viscosity of 2,000 mPa·s or more and 50,000 mPa·s or less, measured using 0.5 ml of the encapsulant for photoelectric conversion elements and a cone-type plate CPA-52Z at 25°C and a rotation speed of 25 rpm.

5. The encapsulant for a photoelectric conversion element according to claim 1 or 2, (D) A sealing material for a photoelectric conversion element, further comprising a phosphoric acid compound.

6. The encapsulant for a photoelectric conversion element according to claim 1 or 2, The encapsulant for a photoelectric conversion element further comprises a stabilizer.

7. A dam material comprising the encapsulant for a photoelectric conversion element according to claim 1 or 2 and (E) an inorganic filler.

8. The dam material according to claim 7, (E) A dam material having an inorganic filler content of 20 to 300 parts by mass per 100 parts by mass of the (A) cationically polymerizable compound.

9. The dam material according to claim 7, The dam material has a viscosity of 100,000 mPa·s or more and 1,200,000 mPa·s or less, measured using a cone-type plate CPA-52Z at 25°C and a rotation speed of 0.7 rpm, for 0.5 ml of the dam material.

10. A cured product of the dam material according to claim 7.

11. A device comprising a photoelectric conversion element sealed with the dam material according to claim 7.

12. 12. The apparatus of claim 11, The device, wherein the photoelectric conversion element is an organic electroluminescence element.

13. depositing a fill material and a dam material surrounding the fill material on the first member; Embedding a photoelectric conversion element in the fill material; placing a second member over the fill material and the dam material; a step of bonding the first member and the second member together and curing the fill material; and The method for manufacturing a device, wherein the dam material is the dam material according to claim 7.

14. (A) a cationically polymerizable compound; and (B) a photocationic polymerization initiator, (A) the cationically polymerizable compound contains one or more compounds selected from (A-1) an alicyclic compound having an epoxy group, (A-2) an aromatic compound having an epoxy group, and (A-3) a glycidyl ether compound and derivatives thereof; the content of the alicyclic compound having an epoxy group (A-1) is 25 parts by mass or less in 100 parts by mass of the cationically polymerizable compound (A); A composition, wherein the contact angle θa 15 seconds after contact with a liquid is 35° or more and 90° or less, as measured over time by the following procedure i. (Step i) Prepare alkali-free glass that has been degreased with acetone and then cleaned with ozone for 15 minutes. The syringe into which the composition has been poured is set in a contact angle meter, a droplet is prepared under the following condition ii, and the droplet is allowed to land on the prepared alkali-free glass, and the contact angle over time is measured. (Condition ii) Measurement method: Change over time - Control method: Standard ・Analysis methods and methods: Droplet method, θ / 2 method ・Field of view: Wide 2 ・Droplet volume: 5μl

Images