Composition, cured product, sealing material for organic electroluminescent display element, and organic electroluminescent display device

Abstract

This application relates to compositions, cured products, sealing materials for organic electroluminescent display elements, and organic electroluminescent display devices. The composition comprises: a monomeric component containing a fluorinated monomer having fluorine atoms and carbon-carbon unsaturated double bonds; and a photopolymerization initiator, wherein at least a portion of the monomeric component is a high-viscosity monomer with a viscosity of 50 mPa·s or more as measured by an E-type viscometer at 25°C, and the composition has a viscosity of 3 mPa·s or more and 50 mPa·s or less as measured by an E-type viscometer at 25°C.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 202080071945.6 (PCT application number PCT / JP2020 / 042831), filed on November 17, 2020, entitled “Composition, Cured Product, Sealing Material for Organic Electroluminescent Display Element and Organic Electroluminescent Display Device”. Technical Field

[0002] This invention relates to compositions and cured products thereof. Additionally, this invention relates to sealing materials for organic electroluminescent (EL) display elements and organic EL display devices comprising the same. Background Technology

[0003] Organic electroluminescent display elements (also known as organic EL display elements, organic EL devices, or OLED devices) have attracted attention as devices capable of achieving high brightness emission. However, organic EL display elements face the challenge of degradation due to moisture, resulting in reduced light emission characteristics.

[0004] To address this issue, a technique has been developed to seal organic EL display elements with a sealing material made of stacked organic and inorganic films, thereby preventing deterioration caused by moisture (e.g., Patent Documents 1-2).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2001-307873

[0008] Patent Document 2: Japanese Patent Application Publication No. 2009-37812 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] In recent years, the higher performance requirements for organic EL display elements have necessitated sealing materials that can achieve greater reliability and durability.

[0011] As a method for forming a sealing material, an organic film is formed by coating and curing a resin composition, and an inorganic film is laminated on the organic film. However, this method suffers from a problem where the adhesion between the organic film and the inorganic film decreases when unevenness is created on the surface of the organic film. Furthermore, when coating the resin composition using an inkjet printer, the coating liquid ejected from the inkjet nozzle may serpentine or exceed a specified range, making it difficult to accurately form the organic film.

[0012] Therefore, an object of the present invention is to provide a composition capable of precisely forming an organic film with minimal surface unevenness within a specified range. Furthermore, an object of the present invention is to provide a cured product of the above composition, which is useful as a sealing material for organic EL display elements. Moreover, an object of the present invention is to provide a sealing material for organic EL display elements comprising the above-mentioned cured product, and an organic EL display device comprising the sealing material.

[0013] Methods for solving problems

[0014] One aspect of the present invention relates to a composition comprising: a monomeric component containing a fluorinated monomer having fluorine atoms and carbon-carbon unsaturated double bonds; and a photopolymerization initiator. At least a portion of the monomeric component is a high-viscosity monomer with a viscosity of 50 mPa·s or more as measured by an E-type viscometer at 25°C. Furthermore, the composition has a viscosity of 3 mPa·s or more and 50 mPa·s or less as measured by an E-type viscometer at 25°C.

[0015] Due to its excellent surface flatness and straightness, the above composition can precisely form an organic film with minimal surface irregularities within a specified range.

[0016] For a composition involving a particular method, 5 to 65% by mass of the aforementioned monomer components may be the aforementioned high-viscosity monomer.

[0017] In one approach, at least a portion of the aforementioned monomeric components may be a polyfunctional monomer having two or more carbon-carbon unsaturated double bonds.

[0018] For a composition involving a particular manner, 70 to 98% by mass of the aforementioned monomeric components may be the aforementioned multifunctional monomers.

[0019] In one approach, at least a portion of the aforementioned high-viscosity monomers may be monofunctional monomers having one carbon-carbon unsaturated double bond.

[0020] For a composition involving a particular manner, 10 to 60% by mass of the aforementioned high-viscosity monomer may be the aforementioned monofunctional monomer.

[0021] The above composition can be suitably used as a sealant for organic electroluminescent display elements.

[0022] Another aspect of the invention relates to a cured product obtained by curing the above-described composition.

[0023] One aspect of the present invention relates to a sealing material for organic electroluminescent display elements comprising the above-described cured material.

[0024] Another aspect of the present invention relates to a laminate comprising an inorganic film and an organic film, wherein the organic film comprises a cured material described in technical solution 8, and is used as a sealing material for an organic electroluminescent display element.

[0025] Another aspect of the present invention relates to an organic electroluminescent display device comprising an organic electroluminescent display element and a sealing material for the aforementioned organic electroluminescent display element.

[0026] Invention Effects

[0027] According to the present invention, a composition capable of precisely forming an organic film with minimal surface unevenness within a specified range can be provided. Furthermore, according to the present invention, a cured product of the above composition can be provided, which is useful as a sealing material for organic EL display elements. Moreover, according to the present invention, a sealing material for organic EL display elements comprising the above cured product, and an organic EL display device comprising the sealing material can be provided. Detailed Implementation

[0028] Hereinafter, preferred embodiments of the present invention will be described in detail.

[0029] <Composition>

[0030] The composition of this embodiment comprises a monomer component containing a fluorinated monomer and a photopolymerization initiator. In this embodiment, at least a portion of the monomer component is a high-viscosity monomer with a viscosity of 50 mPa·s or more as measured by an E-type viscometer at 25°C. Furthermore, the composition of this embodiment has a viscosity of 3 mPa·s or more and 50 mPa·s or less as measured by an E-type viscometer at 25°C.

[0031] The viscosity of the composition of this embodiment is within the above-mentioned range, and therefore it is suitable for use in inkjet printing. Due to its excellent surface flatness and straightness, it can accurately form an organic film with few surface irregularities within a specified range.

[0032] The reasons for achieving the above-mentioned effects are as follows (but not limited to these). First, since the composition of this embodiment contains a fluorinated monomer, the surface free energy is lower, making it easier to planarize the coating surface after coating, thus forming an organic film with fewer surface irregularities. In addition, for the composition of this embodiment, by containing a high-viscosity monomer, it is less prone to serpentine movement when exiting from the inkjet nozzle (i.e., straight-line performance is improved), enabling the precise formation of an organic film within a specified range.

[0033] At least a portion of the monomer component in this embodiment is a high-viscosity monomer with a viscosity of 50 mPa·s or more as measured by an E-type viscometer at 25°C. The viscosity of the high-viscosity monomer is preferably 100 mPa·s or more, more preferably 150 mPa·s or more. Furthermore, the viscosity of the high-viscosity monomer is preferably 1000 mPa·s or less, more preferably 500 mPa·s or less, and even more preferably 300 mPa·s or less. That is, the viscosity of the high-viscosity monomer, measured by an E-type viscometer at 25°C, is, for example, 50–1000 mPa·s, 50–500 mPa·s, 50–300 mPa·s, 100–1000 mPa·s, 100–500 mPa·s, 100–300 mPa·s, 150–1000 mPa·s, 150–500 mPa·s, or 150–300 mPa·s.

[0034] The viscosity of the composition of this embodiment (viscosity measured by an E-type viscometer at 25°C) is 3 mPa·s or more, preferably 5 mPa·s or more, and more preferably 10 mPa·s or more. Furthermore, the viscosity of the composition of this embodiment (viscosity measured by an E-type viscometer at 25°C) is 50 mPa·s or less, preferably 45 mPa·s or less, and more preferably 40 mPa·s or less. By using the above viscosity range, there is a tendency to further improve surface flatness. That is, for the viscosity of the composition of this embodiment, the viscometer used for measuring with an E-type viscometer at 25°C can be, for example, 3–50 mPa·s, 3–45 mPa·s, 3–40 mPa·s, 5–50 mPa·s, 5–45 mPa·s, 5–40 mPa·s, 10–50 mPa·s, 10–45 mPa·s, or 10–40 mPa·s.

[0035] The composition of this embodiment may be a composition containing a high-viscosity monomer and a low-viscosity monomer (a monomer with a viscosity less than 50 mPa·s as measured by an E-type viscometer at 25°C) as monomer components. The ratio of the high-viscosity monomer to the low-viscosity monomer may be appropriately varied within the above-mentioned viscosity range.

[0036] The proportion of high-viscosity monomers in the monomer composition can be, for example, 5% by mass or more, preferably 7% by mass or more, and more preferably 9% by mass or more. Increasing the proportion of high-viscosity monomers tends to further improve the flowability. Furthermore, the proportion of high-viscosity monomers in the monomer composition can be, for example, 65% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less. Reducing the proportion of high-viscosity monomers can lower the viscosity of the composition, tending to further improve its flowability. That is, the proportion of high-viscosity monomers in the monomer composition can be, for example, 5–65% by mass, 5–60% by mass, 5–55% by mass, 5–50% by mass, 5–45% by mass, 5–40% by mass, 5–35% by mass, 7–65% by mass, 7–60% by mass, 7–55% by mass, 7–50% by mass, 7–45% by mass, 7–40% by mass, 7–35% by mass, 9–65% by mass, 9–60% by mass, 9–55% by mass, 9–50% by mass, 9–45% by mass, 9–40% by mass, or 9–35% by mass.

[0037] The composition of this embodiment may be a composition containing a monofunctional monomer having one carbon-carbon unsaturated double bond and a polyfunctional monomer having two or more carbon-carbon unsaturated double bonds as monomer components.

[0038] The proportion of multifunctional monomers in the monomer composition can be, for example, 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more. Increasing the proportion of multifunctional monomers tends to improve the moisture permeability and straightness of the cured product. Furthermore, the proportion of multifunctional monomers in the monomer composition can be, for example, 98% by mass or less, preferably 97% by mass or less, and more preferably 96% by mass or less. Decreasing the proportion of multifunctional monomers tends to improve surface flatness. That is, the proportion of multifunctional monomers in the monomer composition can be, for example, 70–98% by mass, 70–97% by mass, 70–96% by mass, 75–98% by mass, 75–97% by mass, 75–96% by mass, 80–98% by mass, 80–97% by mass, or 80–96% by mass.

[0039] As a multifunctional monomer, a monomer having 2 to 6 carbon-carbon unsaturated double bonds is preferred, a monomer having 2 or 3 carbon-carbon unsaturated double bonds is more preferred, and a difunctional monomer having 2 carbon-carbon unsaturated double bonds is even more preferred.

[0040] The composition of this embodiment preferably contains a multifunctional monomer as a high-viscosity monomer, or it may contain a multifunctional monomer as a low-viscosity monomer, or it may contain both a multifunctional monomer that is a high-viscosity monomer and a multifunctional monomer that is a low-viscosity monomer.

[0041] The composition of this embodiment may contain a monofunctional monomer as a high-viscosity monomer, or a monofunctional monomer as a low-viscosity monomer, or both a monofunctional monomer belonging to the high-viscosity monomer category and a monofunctional monomer belonging to the low-viscosity monomer category.

[0042] In this embodiment, at least a portion of the high-viscosity monomer is preferably a monofunctional monomer.

[0043] The proportion of monofunctional monomers in high-viscosity monomers can be, for example, 9% by mass or more, preferably 10% by mass or more, more preferably 11% by mass or more, and even more preferably 12% by mass or more. Furthermore, the proportion of monofunctional monomers in high-viscosity monomers can be, for example, 60% by mass or less, preferably 55% by mass or less, and more preferably 50% by mass or less. By using more monofunctional monomers as high-viscosity monomers, there is a tendency to further improve the moisture permeability, softness, and flexibility of the cured product. That is, the proportion of monofunctional monomers in high-viscosity monomers can be, for example, 9–60% by mass, 9–55% by mass, 9–50% by mass, 10–60% by mass, 10–55% by mass, 10–50% by mass, 11–60% by mass, 11–55% by mass, 11–50% by mass, 12–60% by mass, 12–55% by mass, or 12–50% by mass.

[0044] <Fluorine-containing monomers>

[0045] Fluorinated monomers are monomers containing fluorine atoms and carbon-carbon unsaturated double bonds. Fluorinated monomers can be used alone or in combination of two or more.

[0046] Fluorinated monomers can also be included in the monomer composition as low-viscosity monomers. The viscosity of the fluorinated monomer (viscosity measured by an E-type viscometer at 25°C) can be, for example, less than 50 mPa·s, preferably less than 45 mPa·s, more preferably less than 40 mPa·s, and even more preferably less than 35 mPa·s. Furthermore, the viscosity of the fluorinated monomer (viscosity measured by an E-type viscometer at 25°C) can be, for example, 1 mPa·s or more, 2 mPa·s or more, or 3 mPa·s or more. That is, the viscosity of the fluorinated monomer can be measured by a type E viscometer at 25°C. For example, the viscometer can be 1 mPa·s or more and less than 50 mPa·s, 1 to 45 mPa·s, 1 to 40 mPa·s, 1 to 35 mPa·s, 2 mPa·s or more and less than 50 mPa·s, 2 to 45 mPa·s, 2 to 40 mPa·s, 2 to 35 mPa·s, 3 mPa·s or more and less than 50 mPa·s, 3 to 45 mPa·s, 3 to 40 mPa·s, or 3 to 35 mPa·s.

[0047] The fluorinated monomer may have one or more fluorine atoms, for example, two or more, preferably three or more. Furthermore, there is no particular upper limit to the number of fluorine atoms in the fluorinated monomer. The number of fluorine atoms in the fluorinated monomer may be, for example, 40 or less, preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less. That is, the number of fluorine atoms in the fluorinated monomer may be, for example, 1 to 40, 1 to 35, 1 to 30, 1 to 25, 2 to 40, 2 to 35, 2 to 30, 2 to 25, 3 to 40, 3 to 35, 3 to 30, or 3 to 25.

[0048] The fluorine atom content relative to the total amount of fluorinated monomers can be, for example, 1% by mass or more, preferably 2% by mass or more, and more preferably 5% by mass or more. Furthermore, based on the total amount of fluorinated monomers, the fluorine atom content can be, for example, 90% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. That is, based on the total amount of fluorinated monomers, the fluorine atom content can be 1–90% by mass, 1–75% by mass, 1–70% by mass, 1–65% by mass, 2–90% by mass, 2–75% by mass, 2–70% by mass, 2–65% by mass, 5–90% by mass, 5–75% by mass, 5–70% by mass, or 5–65% by mass.

[0049] The fluorinated monomer may have one or more carbon-carbon unsaturated double bonds. However, the number of carbon-carbon unsaturated double bonds in the fluorinated monomer may be, for example, four or fewer. From the viewpoint of easily obtaining a cured product with excellent flexibility, three or fewer is preferred, and two or fewer is more preferable. That is, the number of carbon-carbon unsaturated double bonds in the fluorinated monomer may be, for example, 1 to 4, 1 to 3, or 1 to 2.

[0050] Fluorinated monomers preferably have a (meth)acryloyl group as a group having a carbon-carbon double bond. That is, fluorinated monomers are preferably monomers having a fluorine atom and a (meth)acryloyl group. It should be noted that (meth)acryloyl group represents acryloyl group or methacryloyl group.

[0051] As a specific example of a fluorinated monomer, a compound represented by the following formula (A-1) can be cited.

[0052] [Chemical Formula 1]

[0053]

[0054] In equation (A-1), R 1 This indicates a hydrogen atom or a methyl group. Additionally, R... 2 A group that contains an oxygen atom inserted into a fluoroalkyl group, or a portion thereof, of a carbon-carbon bond or carbon-hydrogen bond in a fluoroalkyl group.

[0055] A fluoroalkyl group can be defined as a group in which some or all of the hydrogen atoms of an alkyl group are replaced by fluorine atoms. The number of carbon atoms in a fluoroalkyl group is not particularly limited; for example, it can have one or more, preferably two or more, and more preferably three or more. Furthermore, the number of carbon atoms in a fluoroalkyl group can be, for example, 25 or less, or 20 or less. That is, the number of carbon atoms in a fluoroalkyl group can be, for example, 1 to 25, 1 to 20, 2 to 25, 2 to 20, 3 to 25, or 3 to 20.

[0056] As a fluoroalkyl group, a group containing a difluoromethylene group (-CF2-) may be suitably used.

[0057] Specific examples of fluoroalkyl groups include difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 1,1,1-trifluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1,1,1,2,2-pentafluoropropyl, 1,1,2,2,3,3-hexafluoropropyl, perfluoropropyl, perfluoroethylmethyl, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl, 2,2,3,3-tetrafluoropropyl, perfluoropropyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,1,2,2,3,3-heptafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, and perfluoroethyl. Butyl, 1,1-bis(trifluoro)methyl-2,2,2-trifluoroethyl, 2-(perfluoropropyl)ethyl, 1,1,2,2,3,3,4,4-octafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, perfluoropentyl, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl, 1,1-bis(trifluoromethyl)- 2,2,3,3,3-Pentafluoropropyl, 2-(perfluorobutyl)ethyl, 1,1,1,2,2,3,3,4,4-Nonafluoropentyl, 1,1,2,2,3,3,4,4,5,5-Decafluorohexyl, 1,1,2,2,3,3,4,4,5,5,6,6-Dodecylfluorohexyl, perfluorohexyl, perfluoropentylmethyl and perfluorohexyl, etc.

[0058] For groups in fluoroalkyl groups in which oxygen atoms are inserted into a portion of the carbon-carbon and carbon-hydrogen bonds (hereinafter also referred to as R... 2 As for the oxygen-containing group, it can be a group that inserts an oxygen atom at one site or a group that inserts an oxygen atom at two or more sites.

[0059] It should be noted that if an oxygen atom is inserted into a carbon-carbon bond, an ether bond is formed. Conversely, if an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, R... 2 The oxygen-containing group can also be said to include at least one group selected from the group consisting of ether bonds and hydroxyl groups.

[0060] As R 2 Specific examples of oxygen-containing groups can be given, for example, groups represented by the following formula.

[0061] [Chemical Formula 2]

[0062]

[0063] The fluorine atom content in the compound represented by formula (A-1) can be, for example, 2% by mass or more, preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 30% by mass or more. Furthermore, the fluorine atom content in the compound represented by formula (A-1) can be, for example, 75% by mass or less, preferably 70% by mass or less, and more preferably 65% ​​by mass or less. That is, the fluorine atom content in the compound represented by formula (A-1) can be, for example, 2–75% by mass, 2–70% by mass, 2–65% by mass, 5–75% by mass, 5–70% by mass, 5–65% by mass, 15–75% by mass, 15–70% by mass, 15–65% by mass, 30–75% by mass, 30–70% by mass, or 30–65% by mass.

[0064] As one specific example of a compound represented by formula (A-1), a compound represented by formula (A-1-1) can be cited.

[0065] [Chemical Formula 3]

[0066]

[0067] In equation (A-1-1), R 1 R represents a hydrogen atom or a methyl group. 21 Represents a hydrogen or fluorine atom, where n is an integer greater than or equal to 1. Multiple existing R... 21 They can be the same or different. However, R 21 At least one of them is a fluorine atom.

[0068] n can be 1 or more, preferably 2 or more. Furthermore, there is no specific upper limit to n. n can be, for example, less than 25 or less than 20. That is, n can be, for example, 1–25, 1–20, 2–25, or 2–20.

[0069] R 21 Multiple atoms exist in formula (A-1-1), but at least one of them is a fluorine atom. Additionally, R... 21 Preferably, two or more of the atoms are fluorine atoms, and more preferably, three or more of the atoms are fluorine atoms. R 21 It can also consist entirely of fluorine atoms.

[0070] Relative to R 21 The proportion of fluorine atoms relative to the total number can be, for example, 4% or more, preferably 8% or more, more preferably 12% or more. This proportion can be, for example, 100% or less, preferably 80% or less, more preferably 75% or less. That is, relative to R... 21The percentage of fluorine atoms in the total number can be, for example, 4–100%, 4–80%, 4–75%, 8–100%, 8–80%, 8–75%, 12–100%, 12–80%, or 12–75%.

[0071] For compounds represented by formula (A-1-1), it is preferable to have a divalent group (-C(R)) enclosed in parentheses with n. 21 At least one of )2-) is a difluoromethylene (-CF2-).

[0072] Other examples of fluorinated monomers include compounds represented by formula (A-2).

[0073] [Chemical Formula 4]

[0074]

[0075] In equation (A-2), R 3 This indicates a hydrogen atom or a methyl group. Additionally, R... 4 A group indicating that an oxygen atom is inserted into part of the carbon-carbon and carbon-hydrogen bonds in a fluoroalkyl diester or fluoroalkyl diester. Multiple existing R groups... 3 They can be the same or different.

[0076] A fluoroalkyl dieryl can also be described as a group in which some or all of the hydrogen atoms of an alkyl dieryl are replaced with fluorine atoms. The number of carbon atoms in the fluoroalkyl dieryl is not particularly limited; for example, it can be 1 or more, preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. Furthermore, the number of carbon atoms in the fluoroalkyl dieryl can be, for example, 20 or less, preferably 17 or less, more preferably 15 or less, even more preferably 12 or less, and even more preferably 10 or less. That is, the number of carbon atoms in the fluoroalkyl dieryl can be, for example, 1–20, 1–17, 1–15, 1–12, 1–10, 2–20, 2–17, 2–15, 2–12, 2–10, 3–20, 3–17, 3–15, 3–12, 3–10, 4–20, 4–17, 4–15, 4–12, or 4–10.

[0077] As a fluoroalkyl diester, a group containing a difluoromethylene group (-CF2-) may be suitably used.

[0078] Specific examples of fluoroalkyl diesters include straight-chain or branched fluoroalkyl diesters with 1 to 17 carbon atoms (e.g., 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluoro-1,10-decane diesters), and fluorocycloalkyl diesters with 1 to 17 carbon atoms.

[0079] For a group (hereinafter also referred to as R) in which an oxygen atom is inserted into one part of the carbon-carbon bond and carbon-hydrogen bond in a fluoroalkane dimethyl group.4 As for the oxygen-containing group, it can be a group that inserts an oxygen atom at one site or a group that inserts an oxygen atom at two or more sites.

[0080] It should be noted that if an oxygen atom is inserted into a carbon-carbon bond, an ether bond is formed. Conversely, if an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, R... 4 The oxygen-containing group can also be said to include at least one group selected from the group consisting of ether bonds and hydroxyl groups.

[0081] As R 4 Specific examples of oxygen-containing groups can be given, for example, groups represented by the following formula.

[0082] [Chemical Formula 5]

[0083]

[0084] The fluorine atom content in the compound represented by formula (A-2) can be, for example, 4% by mass or more, preferably 8% by mass or more, and more preferably 12% by mass or more. Furthermore, the fluorine atom content in the compound represented by formula (A-2) can be, for example, 90% by mass or less, preferably 75% by mass or less, and more preferably 65% ​​by mass or less. That is, the fluorine atom content in the compound represented by formula (A-2) can be, for example, 4–90% by mass, 4–75% by mass, 4–65% by mass, 8–90% by mass, 8–75% by mass, 8–65% by mass, 12–90% by mass, 12–75% by mass, or 12–65% by mass.

[0085] As one specific example of a compound represented by formula (A-2), a compound represented by formula (A-2-1) can be cited.

[0086] [Chemical Formula 6]

[0087]

[0088] In equation (A-2-1), R 3 R represents a hydrogen atom or a methyl group. 41 Represents a hydrogen or fluorine atom, where m represents an integer greater than or equal to 1. Multiple existing R... 3 They can be the same or different. Multiple existing R... 41 They can be the same or different. However, R 41 At least one of them is a fluorine atom.

[0089] m can be 1 or more, preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. Furthermore, there is no particular upper limit to m. For example, m can be 20 or less, preferably 17 or less, more preferably 15 or less, even more preferably 12 or less, and even more preferably 10 or less. That is, m can be, for example, 1–20, 1–17, 1–15, 1–12, 1–10, 2–20, 2–17, 2–15, 2–12, 2–10, 3–20, 3–17, 3–15, 3–12, 3–10, 4–20, 4–17, 4–15, 4–12, or 4–10.

[0090] R 41 Multiple atoms exist in formula (A-2-1), but at least one of them is a fluorine atom. Additionally, R... 41 Preferably, two or more of the atoms are fluorine atoms, and more preferably, four or more of the atoms are fluorine atoms. R 41 It can also be entirely composed of fluorine atoms.

[0091] Relative to R 41 The proportion of fluorine atoms relative to the total number can be, for example, 1% or more, preferably 5% or more, more preferably 10% or more. This proportion can be, for example, 100% or less, preferably 95% or less, more preferably 90% or less. That is, relative to R... 41 The percentage of fluorine atoms in the total number can be, for example, 1–100%, 1–95%, 1–90%, 5–100%, 5–95%, 5–90%, 10–100%, 10–95%, or 10–90%.

[0092] For compounds represented by formula (A-2-1), it is preferable to have a divalent group (-C(R)) enclosed in parentheses with m. 41 At least one of )2-) is a difluoromethylene (-CF2-).

[0093] Other examples of fluorinated monomers include compounds represented by formula (A-3).

[0094] [Chemical Formula 7]

[0095]

[0096] In equation (A-3), R 5 This indicates a hydrogen atom or a methyl group. Additionally, R... 6 This indicates a group in which an oxygen atom is inserted into a part of a single bond, alkyl dienyllium, fluoroalkyl dienyllium, or a carbon-carbon bond or carbon-hydrogen bond in an alkyl dienyllium or fluoroalkyl dienyllium. Additionally, Ar... 1 It indicates a fluoroaryl group.

[0097] It should be noted that the so-called "R" 6 "Indicates a single bond", meaning Ar1 It bonds directly to oxygen atoms.

[0098] As Ar 1 The fluoroaryl group is preferred, especially the fluorophenyl group. A fluorophenyl group can also be defined as a group in which one to five hydrogen atoms in a phenyl group are replaced by fluorine atoms. A fluorophenyl group can have one or more fluorine atoms, or it can have five fluorine atoms.

[0099] R 6 The number of carbon atoms in the alkyl diene is not particularly limited; for example, it can be more than one. Additionally, R... 6 The number of carbon atoms in the alkyl diene is, for example, 17 or less, preferably 15 or less, and more preferably 12 or less. That is, R 6 The number of carbon atoms in the alkyl diene can be, for example, 1–17, 1–15, or 1–12.

[0100] Specific examples of alkyldiyl groups include straight-chain or branched alkyldiyl groups with 1 to 17 carbon atoms (e.g., methylene, ethylene, etc.) and cycloalkyldiyl groups with 1 to 17 carbon atoms.

[0101] R 6 The fluoroalkyl dimethyl group can also be described as a group in which some or all of the hydrogen atoms of the aforementioned alkyl dimethyl group are replaced with fluorine atoms. R 6 The number of carbon atoms in the fluoroalkyl dieryl group is not particularly limited; for example, it can be more than 1. Additionally, R... 6 The number of carbon atoms in the fluoroalkyl diol can be, for example, 17 or less, preferably 15 or less, and more preferably 12 or less. That is, R 6 The number of carbon atoms in the fluoroalkyl diester can be, for example, 1–17, 1–15, or 1–12.

[0102] As R 6 The fluoroalkyl dimethyl group may suitably use a group containing a difluoromethylene group (-CF2-).

[0103] A group (hereinafter also referred to as R) in which an oxygen atom is inserted into one part of the carbon-carbon bond and carbon-hydrogen bond in an alkyl or fluoroalkyl group. 6 For an oxygen-containing group, it can be a group that inserts an oxygen atom at one site or a group that inserts an oxygen atom at two or more sites.

[0104] It should be noted that if an oxygen atom is inserted into a carbon-carbon bond, an ether bond is formed. Conversely, if an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, R... 6 The oxygen-containing group can also be said to include at least one group selected from the group consisting of ether bonds and hydroxyl groups.

[0105] As R 6Specific examples of oxygen-containing groups include, for example, groups containing -CH2CH2O-.

[0106] The fluorine atom content in the compound represented by formula (A-3) can be, for example, 3% by mass or more, preferably 7% by mass or more, and more preferably 15% by mass or more. Furthermore, the fluorine atom content in the compound represented by formula (A-3) can be, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less. That is, the fluorine atom content in the compound represented by formula (A-3) can be, for example, 3–90% by mass, 3–80% by mass, 3–70% by mass, 7–90% by mass, 7–80% by mass, 7–70% by mass, 15–90% by mass, 15–80% by mass, or 15–70% by mass.

[0107] As one specific example of a compound represented by formula (A-3), a compound represented by formula (A-3-1) can be cited.

[0108] [Chemical Formula 8]

[0109]

[0110] In equation (A-3-1), R 5 R represents a hydrogen atom or a methyl group. 61 R represents a hydrogen atom or a fluorine atom. 62 Represents a hydrogen or fluorine atom, where p represents an integer greater than or equal to 0. When p is 1 or greater, multiple existing R atoms... 61 They can be the same or different. Furthermore, multiple existing R... 62 They can be the same or different. However, R 62 At least one of them is a fluorine atom.

[0111] p represents an integer greater than or equal to 0. Here, p being 0 means that the benzene ring is directly bonded to an oxygen atom. p can be an integer greater than or equal to 1. In addition, there is no particular upper limit to p. For example, p is 17 or less, preferably 15 or less, and more preferably 12 or less. That is, p can be, for example, 1 to 17, 1 to 15, or 1 to 12.

[0112] When R exists in equation (A-3-1) 61 When (i.e., when p is an integer greater than or equal to 1), R 61 It can be entirely composed of hydrogen atoms, entirely composed of fluorine atoms, or partially composed of hydrogen atoms while the rest (hereinafter sometimes referred to as the "other parts") is composed of fluorine atoms.

[0113] R 62 There are multiple atoms in formula (A-3-1), at least one of which is a fluorine atom. Additionally, R... 62It can contain two or more fluorine atoms, or three or more fluorine atoms. Additionally, it can be R. 62 All (5) of them are fluorine atoms.

[0114] Relative to R 61 and R 62 The proportion of fluorine atoms relative to the total number can be, for example, 5% or more, preferably 10% or more, more preferably 20% or more. This proportion can be, for example, 100% or less, preferably 95% or less, more preferably 80% or less. That is, relative to R... 61 and R 62 The percentage of fluorine atoms in the total number can be, for example, 5–100%, 5–95%, 5–80%, 10–100%, 10–95%, 10–80%, 20–100%, 20–95%, or 20–80%.

[0115] In a preferred embodiment, the fluorinated monomer preferably comprises at least one compound selected from the group consisting of compounds represented by formula (A-1), formula (A-2), and formula (A-3).

[0116] In another preferred embodiment, the fluorinated monomer preferably comprises at least one selected from the group consisting of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctyl(meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluoro-1,10-decanediol di(meth)acrylate, 1H,1H,5H-octafluoropentyl(meth)acrylate, and 1H,1H,2H,2H-tridecylfluorooctyl(meth)acrylate.

[0117] Fluorine-containing monomers are not limited to the compounds mentioned above.

[0118] In this embodiment, the monomer component may further include monomers other than fluorinated monomers (i.e., monomers without fluorine atoms) (hereinafter also referred to as monomer (B)). Monomer (B) can also be described as a monomer having a carbon-carbon unsaturated double bond but without fluorine atoms. Monomer (B) is preferably a monomer having a vinyl group as a carbon-carbon unsaturated double bond, and more preferably a monomer having a (meth)acryloyl group as a carbon-carbon unsaturated double bond.

[0119] The proportion of the fluorinated monomer in the monomer composition is not particularly limited, but can be, for example, 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.008% by mass or more. Furthermore, the proportion of the fluorinated monomer in the monomer composition can be, for example, 97% by mass or less, preferably 95% by mass or less, and more preferably 93% by mass or less. That is, the proportion of the fluorinated monomer in the monomer composition can be, for example, 0.001–97% by mass, 0.001–95% by mass, 0.001–93% by mass, 0.005–97% by mass, 0.005–95% by mass, 0.005–93% by mass, 0.008–97% by mass, 0.008–95% by mass, or 0.008–93% by mass.

[0120] Regarding the proportion of fluorinated monomers in the monomer composition, from the viewpoint of improving surface flatness and straightness, it is preferably 0.01% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.3 to 7% by mass, and even more preferably 0.5 to 5% by mass. That is, the proportion of fluorinated monomers in the monomer composition can be, for example, 0.01 to 10% by mass, 0.01 to 7% by mass, 0.01 to 5% by mass, 0.1 to 10% by mass, 0.1 to 7% by mass, 0.1 to 5% by mass, 0.3 to 10% by mass, 0.3 to 7% by mass, 0.3 to 5% by mass, 0.5 to 10% by mass, 0.5 to 7% by mass, or 0.5 to 5% by mass.

[0121] The fluorine atom content relative to the total amount of monomer components can be, for example, 0.005% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and even more preferably 5% by mass or more. Furthermore, based on the total amount of monomer components, the fluorine atom content can be, for example, 75% by mass or less, preferably 70% by mass or less, and more preferably 65% ​​by mass or less. That is, the fluorine atom content relative to the total amount of monomer components can be, for example, 0.005–75% by mass, 0.005–70% by mass, 0.005–65% by mass, 0.5–75% by mass, 0.5–70% by mass, 0.5–65% by mass, 1–75% by mass, 1–70% by mass, 1–65% by mass, 2–75% by mass, 2–70% by mass, 2–65% by mass, 5–75% by mass, 5–70% by mass, or 5–65% by mass.

[0122] Monomer (B) can be either a high-viscosity monomer or a low-viscosity monomer, but preferably at least a portion of monomer (B) is a high-viscosity monomer. The monomer composition may contain two or more monomers (B). In this case, both or more monomers (B) may be high-viscosity monomers, or a portion of the two or more monomers (B) may be high-viscosity monomers and the other portions may be low-viscosity monomers.

[0123] Among monomers (B), examples of high-viscosity monomers include 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, methyl phenoxy (meth)acrylate, ethyl phenoxy (meth)acrylate, propyl 2-hydroxy-3-phenoxy (meth)acrylate (2-HPA), 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalic acid, EO-modified phenol (meth)acrylate, EO-modified cresol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, PO-modified nonylphenol (meth)acrylate, ethoxylated o-phenylphenol (meth)acrylate, m-phenoxy (meth)acrylate benzyl ester, ethoxylated bisphenol A di(meth)acrylate, and propoxylated bisphenol. A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, ethoxylated o-phenylphenol (meth)acrylate, m-phenoxy (meth)acrylate benzyl ester, dicyclopentyl (meth)acrylate, dicyclopentyloxy (meth)acrylate ethyl ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate ethyl ester, tricyclodecanediethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0124] Among monomers (B), examples of low-viscosity monomers include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, isodecanyl methacrylate, lauryl methacrylate, stearyl methacrylate, etc.

[0125] The monomer (B) can be a monofunctional monomer or a polyfunctional monomer, but preferably at least a portion of the monomer (B) is a monofunctional monomer, more preferably a portion is a monofunctional monomer and the other portion is a polyfunctional monomer. That is, the monomer component can contain two or more monomers (B), preferably a portion of the two or more monomers (B) is a monofunctional monomer and the other portion is a polyfunctional monomer.

[0126] Among monomers (B), examples of monofunctional monomers include 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxy (meth)acrylate methyl ester, phenoxy (meth)acrylate ethyl ester, 2-hydroxy-3-phenoxy (meth)acrylate propyl ester (2-HPA), 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalic acid, EO-modified phenol (meth)acrylate, EO-modified cresol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, and PO-modified nonylphenol (meth)acrylate. Benzyl phenol (meth)acrylate, ethoxylated o-phenylphenol (meth)acrylate, m-phenoxy (meth)acrylate benzyl ester, dicyclopentyl (meth)acrylate, dicyclopentyloxy (meth)acrylate ethyl ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate ethyl ester, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isodecanyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc.

[0127] Among monomers (B), examples of multifunctional monomers include ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylolpropane tri(meth)acrylate. Esters, pentaerythritol tri(meth)acrylate, dimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, etc.

[0128] Photopolymerization initiators are simply compounds that can be activated by active light such as visible light or ultraviolet light, and can initiate or promote the polymerization of monomer components. A single photopolymerization initiator can be used, or two or more can be used in combination. Photoradical polymerization initiators are preferred as photopolymerization initiators.

[0129] Examples of photoradical polymerization initiators include:

[0130] Benzophenone and its derivatives;

[0131] Benzoyl and its derivatives;

[0132] Anthraquinones and their derivatives;

[0133] Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and other benzoin-type photopolymerization initiators;

[0134] Acetylphenyl-type photopolymerization initiators such as diethoxyacetylphenyl and 4-tert-butyltrichloroacetylphenyl;

[0135] 2-Dimethylaminoethylbenzoate;

[0136] p-Dimethylaminoethylbenzoate;

[0137] Diphenyl disulfide;

[0138] Thioxanone and its derivatives;

[0139] Camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-formyl chloride and other camphorquinone-type photopolymerization initiators;

[0140] α-aminoalkyl phenyl ketone photopolymerization initiators such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1;

[0141] Benzoyl diphenylphosphine oxide, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, benzoyl diethoxyphosphine oxide, 2,4,6-trimethylbenzoyl dimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyl diethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and other acylphosphine oxide type photopolymerization initiators;

[0142] phenyl-glyoxylic acid-methyl ester;

[0143] 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl oxy-phenyl-acetic acid;

[0144] 2-[2-hydroxy-ethoxy]-ethyl oxyphenyl-acetic acid; etc.

[0145] From the viewpoint that curing can be achieved using only visible light at 390 nm or higher, acylphosphine oxide-type photopolymerization initiators are preferred as photopolymerization initiators. It should be noted that acylphosphine oxide-type photopolymerization initiators can also be described as photopolymerization initiators containing acylphosphine oxide groups (-(C=O)-(P=O)<). Furthermore, from the viewpoint that curing with light at 395 nm or higher is possible and that cured products with higher visible light transmittance are easily obtained, diphenyl-2,4,6-trimethylbenzoylphosphine oxide is particularly preferred. Examples of diphenyl-2,4,6-trimethylbenzoylphosphine oxide include, for example, "Irgacure TPO" manufactured by BASF JAPAN.

[0146] The content of the photopolymerization initiator is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 2 parts by mass or more, and even more preferably 2.5 parts by mass or more, relative to 100 parts by mass of the total monomer components. Increasing the content of the photopolymerization initiator tends to improve the curing properties of the composition. The content of the photopolymerization initiator is preferably 12 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less, relative to 100 parts by mass of the total monomer components. Reducing the content of the photopolymerization initiator makes it easier to obtain a cured product with higher visible light transmittance. That is, relative to the total amount of 100 parts by mass of monomer components, the content of photopolymerization initiator can be, for example, 0.05–12 parts by mass, 0.05–8 parts by mass, 0.05–6 parts by mass, 0.5–12 parts by mass, 0.5–8 parts by mass, 0.5–6 parts by mass, 2–12 parts by mass, 2–8 parts by mass, 2–6 parts by mass, 2.5–12 parts by mass, 2.5–8 parts by mass, or 2.5–6 parts by mass.

[0147] The composition of this embodiment may also contain other components besides monomers and photopolymerization initiators. For example, the composition of this embodiment may also contain known additives used in the field of sealants for organic EL display elements. Examples of additives include antioxidants, metal passivators, fillers, stabilizers, neutralizers, lubricants, and antibacterial agents.

[0148] The composition of this embodiment can be cured by irradiation with at least one of visible light or ultraviolet light. It should be noted that, in this specification, the term "curing" of the composition is not limited to rigid curing; it can be achieved as long as the monomer components polymerize to form a polymer. For example, the cured product of the composition can be a rigid solid (e.g., glassy) or a rubbery substance.

[0149] Examples of energy sources used to irradiate visible light or ultraviolet light include deuterium lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, xenon-mercury lamps, halogen lamps, excimer lamps, indium lamps, thallium lamps, LED lamps, and electrodeless discharge lamps.

[0150] From the viewpoint of minimizing damage to the organic EL display element, the composition of this embodiment is preferably cured by light with a wavelength of 380 nm or higher, more preferably by light with a wavelength of 395 nm or higher, and most preferably by light with a wavelength of 395 nm. As for the wavelength of the irradiation light, since it avoids temperature rise in the irradiated part due to infrared light and minimizes the possibility of damage to the organic EL display element, wavelengths of 500 nm or lower are preferred. As the energy source, an LED lamp with a single wavelength of emission is preferred.

[0151] The preferred irradiation dose for curing the composition is 100–8000 mJ / cm. 2 More preferably, it is 300–2000 mJ / cm². 2 By setting the irradiation dose to 100 mJ / cm 2 The composition is fully cured, making it easy to obtain high adhesive strength. Furthermore, by setting the irradiation dose to 8000 mJ / cm... 2 The following method enables the composition to be cured without damaging the organic EL display element. Specifically, the irradiation dose during curing can be, for example, 100–8000 mJ / cm². 2 300~8000mJ / cm 2 100~2000mJ / cm 2 300~2000mJ / cm 2 .

[0152] The cured product of the composition in this embodiment preferably has excellent transparency. Specifically, when the thickness is 10 μm, the spectral transmittance of the cured product in the ultraviolet-visible light region of 360 nm to 800 nm is preferably 95% or more, more preferably 97% or more, and even more preferably 99% or more. If the spectral transmittance is 95% or more, it is easy to obtain an organic EL display device with excellent brightness and contrast.

[0153] For the cured product of the composition of this embodiment, the moisture permeability value at a thickness of 100 μm, measured according to JIS Z 0208:1976 after exposure for 24 hours at 85°C and 85% RH, is preferably 500 g / m². 2 The following is more preferably 400g / m 2 The following is even more preferred: 350g / m 2 The following applies. When the moisture permeability is low, it can more significantly suppress the formation of black spots caused by moisture reaching the organic light-emitting material layer.

[0154] The method of using the composition of this embodiment is not particularly limited. The composition of this embodiment can be suitably used as a sealant for organic EL display elements. Specifically, for example, the composition is applied to an object (e.g., an organic EL display element), and the composition is cured on the object, thereby forming a sealant material formed of the cured composition.

[0155] Alternatively, a sealing material with a predetermined shape can be formed by curing the composition into a fixed shape (e.g., film, sheet, etc.). In this case, for example, the organic EL display element can be sealed by applying the sealing material onto the organic EL display element.

[0156] The composition of this embodiment has excellent surface flatness and straightness, so even when applied to inkjet printing, it can accurately form an organic film with minimal surface unevenness within a specified range.

[0157] Therefore, the composition of this embodiment can be suitably used as a coating liquid for forming an organic film (preferably an organic film used as a sealing material for an organic EL display element) formed by inkjet printing.

[0158] Hereinafter, an example of an organic EL display device formed by using the composition of this embodiment as a sealant will be described. It should be noted that the organic EL display device using the composition of this embodiment is not limited to the top-emitting type, and may also be a bottom-emitting type organic EL display device in which light generated by irradiating the organic EL layer from the substrate side is emitted.

[0159] The top-emitting type organic EL display device includes: an organic EL display element, a sealing layer for sealing the organic EL display element, and a sealing substrate disposed on the sealing layer.

[0160] Organic EL display elements, for example, have a structure in which an anode, an organic EL layer containing a light-emitting layer, and a cathode are sequentially stacked on a substrate.

[0161] Examples of substrates used as organic EL display elements include glass substrates, silicon substrates, and plastic substrates. Among these, glass substrates and plastic substrates are preferred, and glass substrates are more preferred.

[0162] Examples of plastics used as plastic substrates include polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polybenzimidazole, polybenzobisthiazole, polybenzoxazole, polythiazole, poly(p-phenylenevinylene), polymethyl methacrylate, polystyrene, polycarbonate, polycyclic olefins, and polyacrylic acid. Among them, considering the excellent properties of low moisture permeability, low oxygen permeability, and heat resistance, one or more of the following are preferred: polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polybenzimidazole, polybenzobisthiazole, polybenzoxazole, polythiazole, and poly(p-phenylenevinylene). Considering the high transmittance of energy rays such as ultraviolet or visible light, one or more of the following are preferred: polyimide, polyetherimide, polyethylene terephthalate, and polyethylene naphthalate.

[0163] As the anode, conductive metal oxide films or semi-transparent metal films with a high work function (preferably greater than 4.0 eV) are typically used. Examples of anode materials include indium tin oxide (ITO), tin oxide, and other metal oxides; metals such as gold (Au), platinum (Pt), silver (Ag), and copper (Cu), or alloys containing at least one of these; organic transparent conductive films such as polyaniline or its derivatives; and polythiophene or its derivatives. Depending on the requirements, the anode can be formed from two or more layers. The anode film thickness can be appropriately selected considering conductivity (and, in the case of bottom-emitting types, light transmittance). The anode film thickness is preferably 10 nm to 10 μm, more preferably 20 nm to 1 μm, and most preferably 50 nm to 500 nm. That is, the thickness of the anode film can be, for example, 10nm–10μm, 10nm–1μm, 10nm–500nm, 20nm–10μm, 20nm–1μm, 20nm–500nm, 50nm–10μm, 50nm–1μm, or 50nm–500nm. Examples of methods for fabricating the anode include vacuum evaporation, sputtering, ion plating, and coating. In the case of a top-emitting type, a reflective film for reflecting light irradiated to the substrate side can also be disposed below the anode.

[0164] An organic EL layer includes at least a light-emitting layer formed of organic matter. This light-emitting layer contains a luminescent material. Examples of luminescent materials include fluorescent or phosphorescent organic materials (low-molecular-weight or high-molecular-weight compounds). The light-emitting layer may further contain a dopant material. Examples of organic materials include pigment-based materials, metal complex-based materials, and polymeric materials. The dopant material is a material incorporated into the organic matter for purposes such as improving the luminescence efficiency of the organic matter or changing the emission wavelength. The thickness of the light-emitting layer, containing the aforementioned organic matter and the dopant material as needed, is typically 2–200 nm.

[0165] Examples of pigment-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazolium quinoline derivatives, stilbene benzoylbenzene derivatives, stilbene arylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridine ring compounds, cyclic ketone derivatives, perylene derivatives, oligothiophene derivatives, trifumanyl amine derivatives, oxadiazole dimers, and pyrazolium dimers.

[0166] Examples of metal complex materials include iridium complexes, platinum complexes, and other metal complexes exhibiting luminescence from triple excited states; quinolinol aluminum complexes; benzoquinol beryllium complexes; benzoxazole zinc complexes; benzothiazol zinc complexes; azomethyl zinc complexes; porphyrin zinc complexes; europium complexes, and so on. Examples of metal complexes include those with a central metal of rare earth metals such as terbium (Tb), europium (Eu), or dysprosium (Dy), or those with a central metal of rare earth metals such as aluminum (Al), zinc (Zn), or beryllium (Be), and ligands with structures such as oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, or quinoline. Among these, metal complexes with a central metal of aluminum (Al) and ligands with quinoline structures are preferred. Among metal complexes with a central metal of aluminum (Al) and ligands with quinoline structures, tris(8-hydroxyquinoline)aluminum is preferred.

[0167] Examples of polymer materials include poly(p-phenylenevinylene) derivatives, polythiophene derivatives, poly(p-phenylene) derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and substances obtained by polymerizing the above-mentioned pigment bodies and metal complex luminescent materials, etc.

[0168] Among the aforementioned luminescent materials, those emitting blue light include stilbene aryl derivatives, oxadiazole derivatives, polyvinylcarbazole derivatives, poly(p-phenylene) derivatives, polyfluorene derivatives, and their polymers. Polymer materials are preferred. Among the polymer materials, one or more from the group consisting of polyvinylcarbazole derivatives, poly(p-phenylene) derivatives, and polyfluorene derivatives are preferred.

[0169] Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, poly(p-phenylenevinyl)ethylene derivatives, polyfluorene derivatives, and their polymers. Among these, polymeric materials are preferred. Of the polymeric materials, one or more from the group consisting of poly(p-phenylenevinyl)ethylene derivatives and polyfluorene derivatives are preferred.

[0170] Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, poly(p-phenylenevinyl chloride) derivatives, polythiophene derivatives, polyfluorene derivatives, and their polymers. Among these, polymeric materials are preferred. Of the polymeric materials, one or more from the group consisting of poly(p-phenylenevinyl chloride) derivatives, polythiophene derivatives, and polyfluorene derivatives are preferred.

[0171] Examples of dopant materials include perylene derivatives, coumarin derivatives, rubrogene derivatives, quinacridone derivatives, squaric acid cyanide derivatives, porphyrin derivatives, styrene-based pigments, tetraphenyl derivatives, pyrazolone derivatives, decacycloene, and phenoxazinone.

[0172] For organic EL layers, in addition to the light-emitting layer, layers disposed between the light-emitting layer and the anode, and layers disposed between the light-emitting layer and the cathode, can be appropriately provided. Firstly, as layers disposed between the light-emitting layer and the anode, examples include a hole injection layer that improves the hole injection efficiency from the anode, and a hole transport layer that transports holes injected from the anode or the hole injection layer to the light-emitting layer. As layers disposed between the light-emitting layer and the cathode, examples include an electron injection layer that improves the electron injection efficiency from the cathode, and an electron transport layer that transports electrons injected from the cathode or the electron injection layer to the light-emitting layer.

[0173] Materials that can be used to form the hole injection layer include phenylamines such as 4',4”-tri{2-naphthyl(phenyl)amino}triphenylamine, starburst-type amines, phthalocyanines, oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, amorphous carbon, polyaniline, and polythiophene derivatives.

[0174] Examples of materials constituting the hole transport layer include polyvinylcarbazole or its derivatives, polysilane or its derivatives, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, aromatic amine derivatives, stilbene derivatives, triphenyldiamine derivatives, benzidine derivatives, polyaniline or its derivatives, polythiophene or its derivatives, polyaromatic amine or its derivatives, polypyrrole or its derivatives, poly(p-phenylenevinyl) or its derivatives, poly(2,5-thiophenevinyl) or its derivatives, etc.

[0175] When the aforementioned hole injection layer or hole transport layer has the function of blocking electron transport, it is sometimes also called an electron blocking layer.

[0176] Examples of materials constituting the electron transport layer include dioxadiazole derivatives, anthraquinone dimethyl ether or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, tetracyananthraquinone dimethyl ether or derivatives thereof, fluorene derivatives, diphenyl dicyandiethylene or derivatives thereof, dibenzoquinone derivatives, 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, etc. Metal complexes are also examples of derivatives. Among these, 8-hydroxyquinoline or derivatives thereof are preferred. Of 8-hydroxyquinoline or derivatives thereof, tris(8-hydroxyquinoline)aluminum is preferred from the perspective of its potential use as an organic compound containing a light-emitting layer that emits fluorescence or phosphorescence.

[0177] As an electron injection layer, depending on the type of luminescent layer, examples include a single-layer structure formed by a calcium (Ca) layer; a single-layer structure formed by one or more metals from Group IA and Group IIA of the periodic table with a work function of 1.5 to 3.0 eV, and their oxides, halogens, and carbon oxides; or a layered structure formed by a Ca layer and one or more metals from Group IA and Group IIA of the periodic table with a work function of 1.5 to 3.0 eV, and their oxides, halogens, and carbon oxides. Examples of metals from Group IA of the periodic table with a work function of 1.5 to 3.0 eV, or their oxides, halogens, or carbon oxides, include lithium (Li), lithium fluoride, sodium oxide, lithium oxide, and lithium carbonate. Examples of metals or their oxides, halogens, and carbon oxides belonging to Group IIA of the periodic table with a work function of 1.5–3.0 eV include strontium (Sr), magnesium oxide, magnesium fluoride, strontium fluoride, barium fluoride, strontium oxide, and magnesium carbonate.

[0178] When the aforementioned electron transport layer or electron injection layer has the function of preventing the transport of holes, the aforementioned electron transport layer or electron injection layer can also be referred to as a hole blocking layer.

[0179] As a cathode, a transparent or translucent material with a low work function (preferably a material with a work function of less than 4.0 eV) that facilitates electron injection into the light-emitting layer is preferred. Materials that can be used as cathodes include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), aluminum (Al), scandium (Sc), vanadium (V), zinc (Zn), yttrium (Y), indium (In), cerium (Ce), samarium (Sm), europium (Eu), terbium (Tb), ytterbium (Yb), or alloys formed from two or more of the above metals, or alloys formed from one or more of them with one or more of gold (Au), silver (Ag), platinum (Pt), copper (Cu), chromium (Cr), manganese (Mn), titanium (Ti), cobalt (Co), nickel (Ni), tungsten (W), tin (Sn), or graphite or graphite interlayer compounds, or metal oxides such as ITO and tin oxide.

[0180] The cathode can have a stacked structure of two or more layers. Examples of stacked structures of two or more layers include the aforementioned metals, metal oxides, fluorides, their alloys, and stacked structures with metals such as Al, Ag, and Cr. The film thickness of the cathode can be appropriately selected considering conductivity and durability. The preferred film thickness of the cathode is 10 nm to 10 μm, more preferably 15 nm to 1 μm, and most preferably 20 nm to 500 nm. That is, the film thickness of the cathode can be, for example, 10 nm to 10 μm, 10 nm to 1 μm, 10 nm to 500 nm, 15 nm to 10 μm, 15 nm to 1 μm, 15 nm to 500 nm, 20 nm to 10 μm, 20 nm to 1 μm, or 20 nm to 500 nm. Examples of methods for manufacturing the cathode include vacuum evaporation, sputtering, and lamination by hot pressing of metal thin films.

[0181] The layers disposed between the light-emitting layer and the anode, and between the light-emitting layer and the cathode, can be appropriately selected according to the performance requirements of the organic EL display device to be manufactured. For example, the structure of the organic EL display element used in this embodiment may have any of the layer configurations described below (i) to (xv).

[0182] (i) Anode / hole transport layer / light-emitting layer / cathode

[0183] (ii) Anode / Light-emitting layer / Electron transport layer / Cathode

[0184] (iii) Anode / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Cathode

[0185] (iv) Anode / hole injection layer / light-emitting layer / cathode

[0186] (v) Anode / Light-emitting layer / Electron injection layer / Cathode

[0187] (vi) Anode / Hole Injection Layer / Light Emitting Layer / Electron Injection Layer / Cathode

[0188] (vii) Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Cathode

[0189] (viii) Anode / Hole Transport Layer / Light Emitting Layer / Electron Injection Layer / Cathode

[0190] (ix) Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Injection Layer / Cathode

[0191] (x) Anode / Hole Injection Layer / Light Emitting Layer / Electron Transport Layer / Cathode

[0192] (xi) Anode / Light-emitting layer / Electron transport layer / Electron injection layer / Cathode

[0193] (xii) Anode / Hole Injection Layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode

[0194] (xiii) Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Cathode

[0195] (xiv) Anode / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode

[0196] (xv) Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode

[0197] (Here, " / " indicates that the layers are adjacent and stacked. The same applies below.)

[0198] The sealing layer is designed to prevent water vapor, oxygen, and other gases from contacting the organic EL display element, sealing the organic EL display element with a layer that has high barrier properties relative to these gases. In this sealing layer, inorganic and organic films are formed alternately from bottom to top. The inorganic / organic laminate can also be formed more than twice.

[0199] The inorganic film in an inorganic / organic laminate is designed to prevent organic EL display elements from being exposed to gases such as water vapor and oxygen present in the environment where the organic EL display device is placed. The inorganic film in an inorganic / organic laminate is preferably a continuous, dense film with few defects such as pinholes. Examples of inorganic films include individual films such as SiN films, SiO films, SiON films, Al2O3 films, and AlN films, or laminates thereof.

[0200] The organic film in the inorganic / organic laminate is provided to cover defects such as pinholes formed on the inorganic film and to impart surface flatness. The organic film is formed in a region narrower than the region where the inorganic film is formed. This is because if the organic film is formed in a region that is the same as or wider than the region where the inorganic film is formed, the organic film will deteriorate in the exposed region. However, the uppermost organic film formed in the uppermost layer of the sealing layer is formed in a region that is approximately the same as the region where the inorganic film is formed. In addition, the upper surface of the sealing layer is formed in a planarized manner. The organic film may also be a film formed using the composition of this embodiment described above (i.e., a film containing a cured product of the composition).

[0201] As described above, the composition of this embodiment is suitable for inkjet coating due to its excellent inkjet ejection and the flatness of the coated surface. When using an inkjet-based coating method, an organic film can be formed quickly and uniformly.

[0202] If the inorganic / organic laminates are counted as one group, the sealing layers are preferably in groups of 1 to 5. This is because when there are 6 or more groups of inorganic / organic laminates, the sealing effect relative to the organic EL display element is approximately the same as when there are 5 groups. The thickness of the inorganic film in the inorganic / organic laminate is preferably 50 nm to 1 μm. The thickness of the organic film in the inorganic / organic laminate is preferably 1 to 15 μm, more preferably 3 to 10 μm. If the thickness of the organic film is 1 μm or more, the particles generated during element formation can be completely covered, and it can be coated on the inorganic film with good flatness. If the thickness of the organic film is 15 μm or less, moisture will not penetrate from the side of the organic film, and the reliability of the organic EL display element is improved. The thickness of the organic film in the inorganic / organic laminate can be, for example, 1 to 15 μm, 1 to 10 μm, 3 to 15 μm, or 3 to 10 μm.

[0203] The sealing substrate is formed in a way that the entire upper surface of the uppermost organic film covering the sealing layer is tightly bonded. Examples of such sealing substrates include the aforementioned substrates. Among these, a substrate that is relatively transparent to visible light is preferred. Among substrates that are relatively transparent to visible light (transparent sealing substrates), one or more of the group consisting of glass substrates and plastic substrates are preferred, with glass substrates being more preferred.

[0204] The thickness of the transparent sealing substrate is preferably 1 μm to 1 mm, more preferably 10 μm to 800 μm, and most preferably 50 μm to 300 μm. By placing the transparent sealing substrate on top of the sealing layer, the degradation that occurs when the surface of the uppermost organic film comes into contact with gas can be suppressed, thereby improving the barrier properties of the organic EL display device. The thickness of the transparent sealing substrate can be, for example, 1 μm to 1 mm, 1 μm to 800 μm, 1 μm to 300 μm, 10 μm to 1 mm, 10 μm to 800 μm, 10 μm to 300 μm, 50 μm to 1 mm, 50 μm to 800 μm, or 50 μm to 300 μm.

[0205] Next, a method for manufacturing an organic EL display device having this configuration will be described. First, an anode, an organic EL layer containing a light-emitting layer, and a cathode patterned into a predetermined shape are sequentially formed on a first substrate using conventional methods to form an organic EL display element. For example, when the organic EL display device is used as a dot matrix display device, dikes are formed to divide the light-emitting area into a matrix, and an organic EL layer containing a light-emitting layer is formed in the area enclosed by these dikes.

[0206] Next, on a substrate on which the organic EL display element is formed, a first inorganic film of a predetermined thickness is formed using film formation methods such as PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition) methods, including sputtering. Then, the composition (sealant) of this embodiment is attached to the first inorganic film using film formation methods such as solution coating, spray coating, flash deposition, or inkjet printing. Among these methods, inkjet printing is preferred from a productivity perspective. Then, the sealant is cured by irradiation with energy lines such as ultraviolet light or visible light to form a first organic film. Through the above steps, an inorganic / organic laminate is formed. The curing rate of the sealant is not particularly limited as long as the effect of this embodiment is achieved; for example, the value obtained by the measurement method described later can be set to 90% or more, preferably 95% or more.

[0207] The formation process of the inorganic / organic laminate shown above is repeated a specified number of times. However, for the final group, i.e. the uppermost inorganic / organic laminate, the sealant can also be applied to the upper surface of the inorganic film by means of coating, flash deposition, inkjet printing, etc., in a way that makes the upper surface flat.

[0208] Next, a transparent sealing substrate is bonded to the surface of the substrate to which the sealant is applied. During bonding, the positions are aligned. Then, by irradiating energy lines from the transparent sealing substrate side, the sealant of this embodiment, existing between the uppermost inorganic film and the transparent sealing substrate, is cured. As a result, the sealant cures, forming the uppermost organic film, and the uppermost organic film is bonded to the transparent sealing substrate. Based on the above, the manufacturing method of the organic EL display device is completed.

[0209] After the sealant is applied to the inorganic film, it can be polymerized by localized irradiation with energy lines. This prevents the collapse of the shape of the uppermost organic film when a transparent sealing substrate is mounted. The thickness of the inorganic and organic films can be the same or different for each inorganic / organic laminate.

[0210] In this embodiment, the organic EL display device can be used as a planar light source, a segmented display device, or a dot matrix display device.

[0211] The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.

[0212] Example

[0213] The present invention will be described in more detail below with reference to embodiments, but the present invention is not limited to the embodiments.

[0214] Details of the components used in the examples and comparative examples are described below. It should be noted that the viscosity of the monomer components is expressed as a value measured using an E-type viscometer at 25°C.

[0215] <Fluorine-containing monomers>

[0216] • "13F"

[0217] Manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat 13F"

[0218] Compound name: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctyl acrylate

[0219] Viscosity: 4 mPa·s

[0220] • "LINC-162A"

[0221] Manufactured by Kyoei Chemical Co., Ltd., trade name "LINC-162A"

[0222] Compound name: 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluoro-1,10-decanediacrylate

[0223] Viscosity: 32 mPa·s

[0224] <Monomer (B)>

[0225] • “A-LEN-10”

[0226] Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "NK ESTER A--LEN-10"

[0227] Compound name: Ethoxylated o-phenylphenol acrylate

[0228] Viscosity: 150 mPa·s

[0229] • "DCPA"

[0230] Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "NK ESTER A-DCP"

[0231] Compound name: Tricyclodecanediethanol diacrylate

[0232] Viscosity: 120 mPa·s

[0233] • "BPE200"

[0234] Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "NK ESTER BPE-200"

[0235] Compound name: Ethoxylated bisphenol A dimethacrylate

[0236] Viscosity: 600 mPa·s

[0237] • "SR262"

[0238] Manufactured by ARKEMA, product name "SR262"

[0239] Compound name: 1,12-dodecanediol dimethacrylate

[0240] Viscosity: 12 mPa·s

[0241] <Photopolymerization Initiator>

[0242] • "TPO"

[0243] Manufactured by iGM Resins, product name "Omnirad TPO"

[0244] Compound name: Diphenyl-2,4,6-trimethylbenzoylphosphine oxide

[0245] (Example 1)

[0246] A composition was prepared by mixing 1 part by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 5 parts by mass of "DCPA", 89 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Specifically, the proportion of the fluorinated monomer in the monomer composition was set to 1% by mass, the proportion of the high-viscosity monomer was set to 10% by mass, and the proportion of the difunctional monomer was set to 95% by mass. The viscosity of the resulting composition (measured using an E-type viscometer at 25°C) was 13 mPa·s.

[0247] (Example 2)

[0248] A composition was prepared by mixing 1 part by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 76 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Specifically, the monomer composition contained 1% by mass of fluorinated monomers, 23% by mass of high-viscosity monomers, and 95% by mass of difunctional monomers. The viscosity of the resulting composition (measured using an E-type viscometer at 25°C) was 16 mPa·s.

[0249] (Example 3)

[0250] A composition was prepared by mixing 1 part by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 50 parts by mass of "DCPA", 44 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Specifically, the proportion of the fluorinated monomer in the monomer composition was set to 1% by mass, the proportion of the high-viscosity monomer was set to 55% by mass, and the proportion of the difunctional monomer was set to 95% by mass. The viscosity of the resulting composition (measured using an E-type viscometer at 25°C) was 36 mPa·s.

[0251] (Example 4)

[0252] A composition was prepared by mixing 0.01 parts by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 76.99 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Specifically, the proportion of the fluorinated monomer in the monomer composition was set to 0.01% by mass, the proportion of the high-viscosity monomer was set to 23% by mass, and the proportion of the difunctional monomer was set to 95% by mass. The viscosity of the resulting composition (measured using an E-type viscometer at 25°C) was 16 mPa·s.

[0253] (Example 5)

[0254] A composition was prepared by mixing 90 parts by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 5 parts by mass of "DCPA", and 3.5 parts by mass of "TPO". Specifically, the monomer composition consisted of 90% by mass of fluorinated monomers, 10% by mass of high-viscosity monomers, and 95% by mass of difunctional monomers. The viscosity of the resulting composition (measured at 25°C using an E-type viscometer) was 35 mPa·s.

[0255] (Example 6)

[0256] A composition was prepared by mixing 1 part by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 15 parts by mass of "DCPA", 3 parts by mass of "BPE200", 76 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Specifically, the proportion of the fluorinated monomer in the monomer composition was set to 1% by mass, the proportion of the high-viscosity monomer was set to 23% by mass, and the proportion of the difunctional monomer was set to 95% by mass. The viscosity of the resulting composition (measured using an E-type viscometer at 25°C) was 17 mPa·s.

[0257] (Example 7)

[0258] A composition was prepared by mixing 1 part by mass of "13F", 5 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 76 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Specifically, the monomer composition consisted of 1% by mass of fluorinated monomers, 23% by mass of high-viscosity monomers, and 94% by mass of difunctional monomers. The viscosity of the resulting composition (measured at 25°C using an E-type viscometer) was 16 mPa·s.

[0259] (Comparative Example 1)

[0260] A composition was prepared by mixing 1 part by mass of "LINC-162A", 99 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Specifically, the proportion of the fluorinated monomer in the monomer composition was set to 1% by mass, the proportion of the high-viscosity monomer was set to 0% by mass, and the proportion of the difunctional monomer was set to 100% by mass. The viscosity of the resulting composition (measured using an E-type viscometer at 25°C) was 12 mPa·s.

[0261] (Comparative Example 2)

[0262] A composition was prepared by mixing 1 part by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 94 parts by mass of "DCPA", and 3.5 parts by mass of "TPO". Specifically, the proportion of the fluorinated monomer in the monomer composition was set to 1% by mass, the proportion of the high-viscosity monomer was set to 99% by mass, and the proportion of the difunctional monomer was set to 95% by mass. The viscosity of the resulting composition (measured using an E-type viscometer at 25°C) was 120 mPa·s.

[0263] (Comparative Example 3)

[0264] A composition was prepared by mixing 5 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 77 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Specifically, the proportion of fluorinated monomers in the monomer composition was set to 0% by mass, the proportion of high-viscosity monomers was set to 23% by mass, and the proportion of difunctional monomers was set to 95% by mass. The viscosity of the resulting composition (measured using an E-type viscometer at 25°C) was 16 mPa·s.

[0265] The compositions obtained in Examples 1-7 and Comparative Examples 1-3 were evaluated according to the following method. The results are shown in Tables 1 and 2.

[0266] <E-type viscosity>

[0267] The viscosity of the composition was measured using an E-type viscometer (cone plate type: cone angle 1°34′, cone rotor radius 24 mm) at a temperature of 25°C and a rotation speed of 100 rpm.

[0268] <Surface tension>

[0269] The surface tension of the composition was measured using a contact angle meter (DM500, Kyowa Interface Science Co., Ltd.) in an atmosphere at 23°C using the pendant drop method.

[0270] <Evaluation of Surface Flatness>

[0271] On a 70mm × 70mm × 0.7mm substrate (alkali-free glass (Eagle XG, Corning)), recesses of 25μm × 25μm × 3μm were etched at 10μm intervals on all sides. Next, a 200nm SiN film was formed on the substrate with the recesses using plasma CVD. Then, the composition was patterned using an inkjet printer (Musashi Engineering MID500B, solvent-based printhead "MID printhead") to a size of 15mm × 15mm × 8μm. It should be noted that the substrate was cleaned with acetone and isopropanol before patterning, and then cleaned for 5 minutes using a Technovision UV-208 UV ozone cleaning system. After pattern coating, the sample was placed in a nitrogen atmosphere at 23°C and 50% relative humidity for 4 minutes. Using an LED lamp (HOYA UV-LED LIGHT SOURCE H-4MLH200-V1) emitting light at a wavelength of 395nm under nitrogen atmosphere, the cumulative light intensity at 395nm wavelength was 1,500 mJ / cm². 2 The composition is photocured under certain conditions.

[0272] Next, using a stylus-type shape measuring device (BRUKER DektakXT), the thickness of the cured film was measured in a direction perpendicular to the direction of nozzle movement. The difference between the maximum and minimum thickness within the plane, excluding 0.2 mm from the end of the cured film, was used as the evaluation result for surface flatness.

[0273] <Evaluation of Directness>

[0274] A 200 nm SiN film was formed on a 70 mm × 70 mm × 0.7 mm substrate (alkali-free glass (Corning Eagle XG)) using plasma CVD. Next, a pattern of the composition was applied to a specified area using an inkjet printer (Musashi Engineering MID500B, solvent-based printhead "MID HEAD") at a size of 15 mm × 15 mm × 8 μm. After patterning, the substrate was placed in a nitrogen atmosphere at 23°C and 50% relative humidity for 4 minutes. Under nitrogen atmosphere, the cumulative light intensity at a wavelength of 395 nm using an LED lamp (HOYA UV-LED LIGHT SOURCE H-4MLH200-V1) emitting light at 395 nm was 1,500 mJ / cm². 2 The composition is photocured under certain conditions.

[0275] Next, the length of the solidified material extending from the specified area was measured using an optical microscope at 15 locations on one side, for a total of 60 locations, and the maximum value was taken as the straightness value.

[0276] <Evaluation of moisture permeability>

[0277] A sheet-like cured material with a thickness of 0.1 mm was prepared under the above-mentioned light curing conditions. According to JIS Z0208:1976 "Test method for moisture permeability of moisture-proof packaging materials (cup method)", calcium chloride (anhydrous) was used as the desiccant, and the material was exposed for 24 hours at a temperature of 85°C and a relative humidity of 85%. The moisture permeability of a 100 μm thick cured material was then measured.

[0278] [Table 1]

[0279]

[0280] [Table 2]

[0281]

[0282] As shown in Table 1, the compositions of the examples simultaneously achieve excellent surface flatness and straightness. Furthermore, it has been confirmed that the cured products formed from the compositions of the examples have sufficiently low moisture permeability, making them useful as sealing materials for organic EL display elements.

[0283] Furthermore, as shown in Table 2, in Comparative Example 1, the coating liquid tended to snake and its straightness deteriorated during inkjet coating. In Comparative Example 3, the surface flatness deteriorated. Additionally, in Comparative Example 2, the high viscosity of the composition made it difficult to exit the inkjet nozzle, thus preventing the evaluation of surface flatness and straightness.

Claims

1. A composition comprising: Monomer components, containing fluorine-containing monomers with fluorine atoms and carbon-carbon unsaturated double bonds; and Photopolymerization initiator, The monomer component, comprising 5-23% by mass, is a high-viscosity monomer with a viscosity of 50 mPa·s or higher, measured using an E-type viscometer at 25°C. The high-viscosity monomer is composed of ethoxylated o-phenylphenol acrylate, tricyclodecanediethanol diacrylate, and ethoxylated bisphenol A dimethacrylate. The monomer component comprises 0.1 to 10% by mass of the fluorinated monomer. The viscosity of the composition, measured by an E-type viscometer at 25°C, is 3 mPa·s or more and 50 mPa·s or less.

2. The composition of claim 1, wherein, 70-98% by mass of the monomer component is a polyfunctional monomer having two or more carbon-carbon unsaturated double bonds.

3. The composition of claim 1, wherein, 10-60% by mass of the high-viscosity monomer is a monofunctional monomer having one carbon-carbon unsaturated double bond.

4. The composition according to any one of claims 1 to 3, wherein it is a sealant for organic electroluminescent display elements.

5. A cured product, which is formed by curing the composition according to any one of claims 1 to 4.

6. A sealing material for organic electroluminescent display elements, comprising the cured product as described in claim 5.

7. A sealing material for organic electroluminescent display elements, comprising a laminate composed of inorganic and organic films. The organic film comprises the cured product as described in claim 5.

8. An organic electroluminescent display device, comprising: Organic electroluminescent display elements; and The sealing material for organic electroluminescent display elements as described in claim 6 or 7.

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