WO2024024841A1 - Composition for electronic device sealing, electronic device sealing film, and method for forming electronic device sealing film - Google Patents

Composition for electronic device sealing, electronic device sealing film, and method for forming electronic device sealing film Download PDF

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Publication number
WO2024024841A1
WO2024024841A1 PCT/JP2023/027397 JP2023027397W WO2024024841A1 WO 2024024841 A1 WO2024024841 A1 WO 2024024841A1 JP 2023027397 W JP2023027397 W JP 2023027397W WO 2024024841 A1 WO2024024841 A1 WO 2024024841A1
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Prior art keywords
electronic device
meth
composition
acrylate
sealing
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PCT/JP2023/027397
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French (fr)
Japanese (ja)
Inventor
昇太 広沢
慎一郎 森川
理英子 れん
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コニカミノルタ株式会社
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Publication of WO2024024841A1 publication Critical patent/WO2024024841A1/en

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values

Definitions

  • the present invention relates to an electronic device encapsulation composition, an electronic device encapsulation film, and a method for forming an electronic device encapsulation film, and in particular, to a composition that has good appearance after a reliability test in a folded state and has good bending reliability.
  • the present invention relates to a composition for sealing an electronic device, etc., which provides a sealing film with excellent luminous efficiency after testing and a low dielectric constant.
  • organic electroluminescent devices (hereinafter also referred to as “organic EL devices” or “organic EL elements”), are designed to prevent the organic materials and electrodes used from deteriorating due to moisture. It has been proposed to cover the surface of the device with a sealing layer.
  • the technique described in Patent Document 1 includes a photopolymerizable (photocurable) monomer and an initiator, and the photopolymerizable monomer does not contain a silicon-based photopolymerizable monomer.
  • the organic light emitting device is folded after a reliability test in a folded state, resulting in a problem with the appearance. Furthermore, there is a problem in that the luminous efficiency decreases after the organic light emitting device is bent. Furthermore, it is preferable that the material is difficult to polarize when an electric field is applied to the electronic device, and it is also desired that the dielectric constant is low.
  • the present invention was made in view of the above-mentioned problems and circumstances, and the object to be solved is to provide a good appearance after a reliability test in a folded state, excellent luminous efficiency after a folding reliability test,
  • An object of the present invention is to provide a composition for encapsulating an electronic device that provides a encapsulating film with a low relative dielectric constant.
  • Another object of the present invention is to provide an electronic device sealing film using the electronic device sealing composition and a method for forming the same.
  • the present inventors discovered a sealing film containing (meth)acrylate as a photopolymerizable monomer and cured by irradiation under specific environmental conditions. It was discovered that by setting the refractive index and extinction coefficient of the material within a specific range, a sealing film with excellent appearance and luminous efficiency after a reliability test in a folded state and with a low dielectric constant can be obtained, which led to the present invention. Ta. That is, the above-mentioned problems related to the present invention are solved by the following means.
  • An electronic device encapsulation composition containing a photopolymerizable monomer and a photopolymerization initiator Contains (meth)acrylate as a photopolymerizable monomer, When cured by irradiating 1.5 Jcm -2 of ultraviolet light with a wavelength of 395 nm in a nitrogen environment, The refractive index of the formed electronic device sealing film at a wavelength of 380 nm is within the range of 1.45 to 1.56, and the extinction coefficient of the electronic device sealing film at a wavelength of 380 nm is 50 ⁇
  • composition for encapsulating an electronic device according to item 1 wherein the refractive index is within the range of 1.50 to 1.53.
  • composition for encapsulating an electronic device according to item 1 wherein the extinction coefficient is within the range of 125 ⁇ 10 ⁇ 5 to 200 ⁇ 10 ⁇ 5 .
  • composition for encapsulating an electronic device according to item 1 wherein the refractive index n and the extinction coefficient k satisfy the following relationship. k/n ⁇ 100 ⁇ 10-5
  • composition for encapsulating an electronic device according to item 1, wherein the photopolymerizable monomer contained in the composition for encapsulating an electronic device has an average number of double bonds of 5 or less.
  • An electronic device sealing film that seals an electronic device by curing an electronic device sealing composition containing a photopolymerizable monomer and a photopolymerization initiator,
  • the photopolymerizable monomer contains (meth)acrylate
  • the refractive index of the electronic device sealing film at a wavelength of 380 nm is within the range of 1.45 to 1.56, and
  • the electronic device sealing film has an extinction coefficient within the range of 50 ⁇ 10 ⁇ 5 to 200 ⁇ 10 ⁇ 5 at a wavelength of 380 nm.
  • An electronic device sealing film that seals an electronic device, a first sealing layer containing silicon nitride, silicon oxide or silicon oxynitride;
  • An electronic device sealing film comprising: a second sealing layer using the electronic device sealing composition according to any one of Items 1 to 6;
  • the electronic device sealing film forming method according to item 10 comprising the step of forming a third sealing layer on the second sealing layer by a vapor phase method.
  • an electronic device sealing film that has a good appearance after a reliability test in a folded state, has excellent luminous efficiency after a bending reliability test, and has a low dielectric constant can be obtained.
  • a composition for use can be provided.
  • Another object of the present invention is to provide an electronic device sealing film using the electronic device sealing composition and a method for forming the same.
  • the amount of change in the optical path length before and after the reliability test in the folded state becomes smaller, and the amount of reflected light from the outside decreases due to light absorption. It is possible to improve the appearance by suppressing folding after a reliability test.
  • Luminous efficiency after bending reliability test Repeated bending reliability tests may cause deformation or cracks in the cured film. If the cured film is deformed or minute cracks occur, the way light is emitted from the light emitting element may change. In other words, when deformed, light may be emitted in the lateral direction due to changes in the optical path length and refraction of light, and when cracks occur, light may not come out due to the difference in refractive index with the air in the gap between the cracks.
  • the present invention by setting the refractive index of the sealing film within the above-mentioned specific range, it is possible to suppress the refraction of light, suppress the difference in refractive index with the air layer in micro cracks, and to It is presumed that high luminous efficiency can also be maintained.
  • the dielectric constant becomes low.
  • the mechanism of action is not clear, it is thought that within a certain range the energy gap becomes larger and electronic transitions become less likely to occur.
  • the dielectric constant depends on electronic polarization. Electronic polarization occurs when an electron distribution occurs due to perturbation of an electric field, but it is thought that a large electron distribution is unlikely to occur because electronic transitions are difficult to occur.
  • the composition for encapsulating an electronic device of the present invention is a composition for encapsulating an electronic device containing a photopolymerizable monomer and a photopolymerization initiator, which contains (meth)acrylate as the photopolymerizable monomer, and contains nitrogen.
  • the refractive index at a wavelength of 380 nm of the electronic device sealing film formed is within the range of 1.45 to 1.56, Moreover, the extinction coefficient of the electronic device sealing film at a wavelength of 380 nm is within the range of 50 ⁇ 10 ⁇ 5 to 200 ⁇ 10 ⁇ 5 . This feature is a technical feature common to or corresponding to each of the embodiments described below.
  • the refractive index is within the range of 1.50 to 1.53, and the extinction coefficient is within the range of 125 ⁇ 10 ⁇ 5 to 200 ⁇ 10 ⁇ 5 . It is more preferable in terms of appearance after a reliability test in a folded state and luminous efficiency.
  • the refractive index n and the extinction coefficient k satisfy the relationship k/n ⁇ 100 ⁇ 10 ⁇ 5 in terms of the appearance after the reliability test in the folded state and the luminous efficiency after the bending reliability test. It is preferable.
  • the average number of double bonds of the photopolymerizable monomer contained in the electronic device encapsulating composition is 5 or less, which improves the appearance after the reliability test in the folded state and the reliability test after the bending reliability test. This is preferable in terms of luminous efficiency.
  • the energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the photopolymerizable monomer contained in the electronic device encapsulating composition are 5.9eV ⁇ LUMO-HOMO ⁇ 6.5eV It is preferable to satisfy the following relationship in terms of appearance after a reliability test in a folded state, luminous efficiency after a bending reliability test, and relative permittivity.
  • An electronic device sealing film is an electronic device sealing film that seals an electronic device by curing an electronic device sealing composition containing a photopolymerizable monomer and a photopolymerization initiator.
  • the electronic device sealing film contains (meth)acrylate as the photopolymerizable monomer, and the electronic device sealing film has a refractive index of 1.45 to 1.56 at a wavelength of 380 nm.
  • the extinction coefficient of the stopping film at a wavelength of 380 nm is within the range of 50 ⁇ 10 ⁇ 5 to 200 ⁇ 10 ⁇ 5 .
  • An electronic device sealing film is an electronic device sealing film that seals an electronic device, and includes a first sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride, and a first sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride; and a second sealing layer using a device sealing composition.
  • a third sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride on the second sealing layer from the viewpoint of excellent sealing performance.
  • the electronic device sealing film forming method of the present invention is a method of forming a sealing film using the electronic device sealing composition, wherein a first sealing layer is formed on the electronic device by a vapor phase method. and forming a second sealing layer by applying the electronic device sealing composition on the first sealing layer.
  • a step of forming a third sealing layer on the second sealing layer by a vapor phase method in terms of excellent sealing performance. Further, it is preferable that the step of forming the second sealing layer uses an inkjet method because the layer can be formed with high precision.
  • ⁇ is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
  • the electronic device encapsulation composition of the present invention (hereinafter also simply referred to as “encapsulation composition”) is an electronic device encapsulation composition containing a photopolymerizable monomer and a photopolymerization initiator, It contains (meth)acrylate as a photopolymerizable monomer, and is formed when it is cured by irradiating 1.5 Jcm -2 of ultraviolet light with a wavelength of 395 nm in a nitrogen environment (hereinafter simply referred to as "sealing").
  • the extinction coefficient of the electronic device sealing film at a wavelength of 380 nm is 50 ⁇ 10 - It is within the range of 5 to 200 ⁇ 10 ⁇ 5 .
  • the refractive index of the sealing film formed at a wavelength of 380 nm is 1.45 to 1. It is within the range of 1.56. More preferably, it is within the range of 1.50 to 1.53.
  • the refractive index was determined by spectroscopic ellipsometry (UVSEL/FUV-FGMS, manufactured by Horiba JYOBIN-YVON). Specifically, the refractive index at 250 nm to 800 nm was measured, and the refractive index n at 380 nm was determined.
  • the monomer structure has a structure with a small number of hetero atoms, an alicyclic hydrocarbon structure, a chain hydrocarbon structure.
  • the structures of alicyclic hydrocarbons include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and cyclohexyl.
  • Alicyclic (meth)acrylate such as (meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate , 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 1-adamantyl (meth)acrylate, tricyclodecane dimethanol (meth)acrylate, etc.
  • examples include, but are not limited to, acrylates.
  • the structures of chain hydrocarbons include 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, and 1,9-nonane.
  • Another example is adding particles having a desired refractive index within a range that does not impair inkjet ejection properties.
  • the refractive index of the photopolymerizable monomer constituting the sealing composition can be determined using an Abbe refractometer, and the refractive index (nd25) of the D line at 25°C is 1.43 to 1.50. is preferred.
  • the sealing composition of the present invention is cured by irradiating 1.5 Jcm -2 of ultraviolet light with a wavelength of 395 nm in a nitrogen environment
  • the extinction coefficient of the sealing film formed at a wavelength of 380 nm is 50 ⁇ 10 -5 to 200 ⁇ 10 -5 . More preferably, it is within the range of 125 ⁇ 10 ⁇ 5 to 200 ⁇ 10 ⁇ 5 .
  • the extinction coefficient was determined by spectroscopic ellipsometry (UVSEL/FUV-FGMS, manufactured by Horiba JYOBIN-YVON) in the same manner as the refractive index. Specifically, the extinction coefficient at 250 nm to 800 nm was measured, and the extinction coefficient k at 380 nm was determined.
  • Examples of means for making the extinction coefficient within the range of 50 ⁇ 10 ⁇ 5 to 200 ⁇ 10 ⁇ 5 include a monomer structure with a small number of heteroatoms, a structure with a small number of aromatic hydrocarbons, and multiple bonds.
  • One example is to use a structure with a small amount of
  • Another example is adding a dye within a range that does not impair the light emitting characteristics of the organic EL.
  • the refractive index n and the extinction coefficient k satisfy the following relationship in terms of appearance after a reliability test in a folded state and luminous efficiency after a bending reliability test. k/n ⁇ 100 ⁇ 10-5
  • composition of electronic device encapsulation composition contains a photopolymerizable monomer and a photopolymerization initiator.
  • the photopolymerizable monomer contains (meth)acrylate.
  • (meth)acrylate means at least one of acrylate and methacrylate.
  • the term “electronic device” in the present invention refers to an element that generates, amplifies, converts, or controls electrical signals by utilizing the kinetic energy, potential energy, etc. of electrons. Examples include active devices such as light emitting diode devices, organic electroluminescent devices, photoelectric conversion devices, and transistors.
  • electronic devices include passive elements such as resistors and capacitors that perform passive work such as “resistance” and "storage” in response to actions from others. Therefore, the sealing composition of the present invention is used to form a sealing film for sealing the electronic device described above.
  • Photopolymerizable monomer refers to a photopolymerizable monomer (“photocurable monomer”) that can perform a polymerization (curing) reaction by itself or a photopolymerization initiator absorbing light and producing active ions or radicals. Also referred to as ).
  • photopolymerizable monomer a non-silicon monomer that does not contain silicon (Si) may be used, for example, a monomer consisting only of elements selected from C, H, O, N, or S. Good, but not limited to this.
  • the photopolymerizable monomer may be synthesized and used by a conventional synthesis method, or a commercially available product may be purchased and used.
  • photopolymerizable monomer examples include the following photopolymerizable monomers (A) that do not have an aromatic hydrocarbon group, and photopolymerizable monomers (B) that have an aromatic hydrocarbon group, as described above.
  • the photopolymerizable monomer is appropriately selected from these photopolymerizable monomers so that, when used as a sealing film, the refractive index and extinction coefficient satisfy the above ranges.
  • the average number of double bonds of the photopolymerizable monomer contained in the composition for encapsulating an electronic device of the present invention is 5 or less. This is preferable in terms of later luminous efficiency.
  • HOMO and LUMO energy levels The average value of the energy level of the highest occupied molecular orbital (HOMO) and the average value of the energy level of the lowest unoccupied molecular orbital (LUMO) of the photopolymerizable monomer contained in the encapsulating composition of the present invention.
  • HOMO the average value of the energy level of the highest occupied molecular orbital
  • LUMO the average value of the energy level of the lowest unoccupied molecular orbital
  • HOMO HOMO1 ⁇ w1+HOMO2 ⁇ w2+...
  • LUMO LUMO1 ⁇ w1+LUMO2 ⁇ w2+...
  • HOMO and LUMO can be calculated by using chemical structure information computer software.
  • the calculation software include the quantum chemical calculation program "Gaussian series" manufactured by HULINKS. From the HOMO and LUMO values of each monomer obtained using the software, calculate the average HOMO value and the average LUMO value, and calculate the gap between the average HOMO value and the average LUMO value. did. In the calculation, B3LYP was used as a functional.
  • Gap (unit: eV) Average value of LUMO - Average value of HOMO As a means for making the above Gap 5.9eV ⁇ LUMO-HOMO ⁇ 6.5eV, monomer structures with a small number of heteroatoms, fats, etc. Examples include using a cyclic hydrocarbon structure and a chain hydrocarbon structure.
  • photopolymerizable monomer (A) having no aromatic hydrocarbon group The photopolymerizable monomer (A) that does not have an aromatic hydrocarbon group (hereinafter also simply referred to as "photopolymerizable monomer (A)") does not contain an aromatic hydrocarbon group and has no photocurable functionality.
  • the group (photopolymerizable functional group) may include a monomer having 1 to 20, specifically 1 to 6, one or more of vinyl groups, acrylic groups, and methacrylic groups, for example, 1 to 3 It may contain 1 to 2, 1, or 2.
  • the weight average molecular weight of the photopolymerizable monomer (A) may be within the range of 100 to 500 g/mol, may be within the range of 130 to 400 g/mol, or may be within the range of 200 to 300 g/mol. It may be within the range of mol. By keeping the weight average molecular weight of the monomer within the range, more advantageous effects can be exhibited in terms of the process.
  • the photopolymerizable monomer (A) may include a monofunctional monomer having a photocurable functional group, a polyfunctional monomer, or a mixture thereof.
  • the photopolymerizable monomer (A) may be a (meth)acrylate monomer, and may include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a hydroxy group, and a hydroxyl group having 1 to 20 carbon atoms.
  • Unsaturated carboxylic acid esters having ⁇ 20 alkyl groups Unsaturated carboxylic acid esters having aminoalkyl groups having 1 to 20 carbon atoms; Vinyl esters of saturated or unsaturated carboxylic acids having 1 to 20 carbon atoms; Vinyl cyanide compounds ; unsaturated amide compound; monofunctional or polyfunctional (meth)acrylate of monoalcohol or polyhydric alcohol.
  • polyhydric alcohol means an alcohol having two or more hydroxy groups, preferably 2 to 20, preferably 2 to 10, more preferably 2 to 6 hydroxy groups. obtain.
  • the (meth)acrylate monomer that does not have an aromatic hydrocarbon group is a substituted or unsubstituted C1 to C20 (1 to 20 carbon atoms) alkyl group, a substituted or Mono(meth)acrylates having an unsubstituted C1 to C20 alkylsilyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkylene group, an amine group, an ethylene oxide group, etc.
  • Di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate, etc. may be used.
  • (meth)acrylate monomers having no aromatic hydrocarbon group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy Butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decanyl (meth)acrylate, undecanyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.
  • Unsaturated carboxylic acid esters including meth)acrylic acid esters; unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; saturated or unsaturated carboxylic acid esters such as vinyl acetate Acid vinyl ester; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth) Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, Undecanediol
  • the photopolymerizable monomer (A) is a non-aromatic type that does not contain an aromatic group, and is a mono(meth)acrylate having an alkyl group having 1 to 20 carbon atoms, or an amine group.
  • mono(meth)acrylates having a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include decyl(meth)acrylate, undecyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, It may be tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, arachidyl (meth)acrylate or a mixture thereof. However, it is not limited to this.
  • the mono(meth)acrylate having an amine group may be, but is not limited to, 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, or a mixture thereof.
  • the di(meth)acrylate having a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms may be, for example, a di(meth)acrylate having an alkylene group having 1 to 20 carbon atoms; It may also be a non-silicon di(meth)acrylate containing a long-chain alkylene group.
  • Di(meth)acrylates having a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms include, for example, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, undecanediol It may be, but is not limited to, di(meth)acrylate, dodecanediol di(meth)acrylate, or a mixture thereof.
  • the sealing composition of the present invention can further improve the photocuring rate and lower the viscosity.
  • the di(meth)acrylate or tri(meth)acrylate having an ethylene oxide group is ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, or a mixture thereof. may be used, but is not limited to this.
  • mono(meth)acrylates and di(meth)acrylates having a cyclic carbonized alkyl group include isobonyl(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and dicyclopentanyl(meth)acrylate. , dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentenyl (meth)acrylate, but are not limited thereto.
  • the photopolymerizable monomer (A) monomer is contained within the range of 55 to 95% by mass based on the total mass of the photopolymerizable monomers (photopolymerizable monomer (A) and photopolymerizable monomer (B)).
  • the content is preferably in the range of 60 to 90% by mass.
  • Photopolymerizable monomer (B) having an aromatic hydrocarbon group Two or more photopolymerizable monomers (B) having an aromatic hydrocarbon group (hereinafter also simply referred to as "photopolymerizable monomers (B)") have a structure represented by the following general formula (1). phenyl group and hetero atom, and the photopolymerizable monomer (B) contains at least mono(meth)acrylate or di(meth)acrylate.
  • P represents a hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or a heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups.
  • Z 1 and Z 2 each independently have a structure represented by the following general formula (2). a and b are each an integer of 0 to 2, and a+b is an integer of 1 to 4. ]
  • * is a linking portion of P to carbon.
  • X represents a single bond, O or S.
  • Y represents a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • c is an integer of 0 or 1.
  • P represents a hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or a heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups.
  • the hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or the heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups is a substituted or unsubstituted hydrocarbon group containing two or more phenyl groups.
  • the hydrocarbon group containing two or more phenyl groups or the heteroatom-containing hydrocarbon group containing two or more phenyl groups may include a substituted or unsubstituted biphenyl group, a substituted or unsubstituted triphenylmethyl group, or a substituted or unsubstituted triphenylmethyl group.
  • substituted or unsubstituted terphenyl group substituted or unsubstituted biphenylene group, substituted or unsubstituted terphenylene group, substituted or unsubstituted quaterphenylene group, substituted or unsubstituted 2-phenyl-2-(phenylthio)ethyl group , substituted or unsubstituted 2,2-diphenylpropane group, substituted or unsubstituted diphenylmethane group, substituted or unsubstituted cumylphenyl group, substituted or unsubstituted bisphenol F group, substituted or unsubstituted bisphenol A group, substituted or It may include an unsubstituted biphenyloxy group, a substituted or unsubstituted terphenyloxy group, a substituted or unsubstituted quarterphenyloxy group, a substituted or unsubstituted quinchyphenyloxy group, and structural
  • the substituted or unsubstituted monomer having two or more phenyl groups may be mono(meth)acrylate, di(meth)acrylate, or a mixture thereof; examples thereof include 4-(meth)acryloxy -2-hydroxybenzophenone, ethyl-3,3-diphenyl (meth)acrylate, benzoyloxyphenyl (meth)acrylate, bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate Acrylate, ethoxylated bisphenol F di(meth)acrylate, 4-cumylphenoxyethyl acrylate, ethoxylated bisphenylfluorenediacrylate, 2-phenylphenoxyethyl (meth)acrylate, 2,2'-phenylphenoxyethyl di(meth) Acrylate, 2-phenylphenoxypropyl (meth)acrylate, 2,2'-phenylphenoxyprop
  • the (meth)acrylate mentioned in the present invention is only an example, and is not limited thereto.
  • the present invention includes all acrylates that are in structural isomer relationship.
  • 2,2'-phenylphenoxyethyl di(meth)acrylate is mentioned as an example of the present invention
  • the present invention also covers 3,2'-phenylphenoxyethyl di(meth)acrylate, which corresponds to this structural isomer. Includes di(meth)acrylate, 3,3'-phenylphenoxyethyl di(meth)acrylate, etc.
  • the monomer having two or more phenyl groups may be a mono(meth)acrylate represented by the following general formula (4).
  • R 2 is hydrogen or a methyl group
  • R 3 is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted linear alkylene group having 1 to 20 carbon atoms.
  • R 4 is a hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or a heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups.
  • the hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or the heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups includes two or more substituted or unsubstituted phenyl groups.
  • a phenyl group is not fused, a single bond, an oxygen atom, a sulfur atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, an alkylene group having 3 to 6 carbon atoms substituted or unsubstituted with a hetero atom, It means a group connected by an ethenylene group, an ethynylene group, or a carbonyl group.
  • the hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or the heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups is a substituted or unsubstituted biphenyl group, Substituted or unsubstituted triphenylmethyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted biphenylene group, substituted or unsubstituted terphenylene group, substituted or unsubstituted quarterphenylene group, substituted or unsubstituted 2-phenyl-2-(phenylthio)ethyl group, substituted or unsubstituted 2,2-diphenylpropane group, substituted or unsubstituted diphenylmethane group, substituted or unsubstituted cumylphenyl group, substituted or unsubstituted bisphenol F group, Substituted bi
  • the monomer having two or more phenyl groups may be a di(meth)acrylate represented by the following general formula (5).
  • R 5 and R 9 are each independently hydrogen or a methyl group
  • R 6 and R 8 are each independently a substituted or unsubstituted linear chain having 1 to 10 carbon atoms.
  • R 7 is a hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or a substituted or unsubstituted two or more phenyl group. It is a heteroatom-containing hydrocarbon group including a phenyl group.
  • the hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or the heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups includes two or more substituted or unsubstituted phenyl groups.
  • a phenyl group is not fused, a single bond, an oxygen atom, a sulfur atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, an alkylene group having 3 to 6 carbon atoms substituted or unsubstituted with a hetero atom, It means a group connected by an ethenylene group, an ethynylene group, or a carbonyl group.
  • the hydrocarbon group is a substituted or unsubstituted biphenylene group, a substituted or unsubstituted triphenylmethylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quarterphenylene group, a 2-phenyl-2- It may include, but is not limited to, a (phenylthio)ethylene group, a 2,2-diphenylpropylene group, a diphenylmethylene group, and the like.
  • a and b are each an integer of 0 to 2
  • a+b is an integer of 1 to 4
  • a+b is an integer of 1 or 2.
  • the weight average molecular weight of the monomer having two or more substituted or unsubstituted phenyl groups is preferably within the range of 100 to 1000 g/mol, more preferably within the range of 130 to 700 g/mol, and 150 to 600 g It is particularly preferable that the amount is within the range of /mol. By setting it within the above range, a sealing film with more excellent transmittance can be provided.
  • the photopolymerizable monomer (B) having an aromatic hydrocarbon group is 5 to 45% by mass based on the total mass of the photopolymerizable monomers (photopolymerizable monomer (A) and photopolymerizable monomer (B)).
  • the content is preferably within the range of 10 to 40% by mass, and more preferably 10 to 40% by mass. By setting it within the above range, the viscosity becomes suitable for forming a sealing film.
  • photopolymerizable monomers (A) and (B) include monomers listed in Examples described later. Further, preferred combinations of photopolymerizable monomers in the present invention are as described in the Examples below.
  • the photopolymerization initiator is not particularly limited as long as it is a normal photopolymerization initiator that can perform a photocuring reaction.
  • the photopolymerization initiator may include, for example, a triazine type, an acetophenone type, a benzophenone type, a thioxanthone type, a benzoin type, a phosphorus type, an oxime type, or a mixture thereof.
  • Triazine-based initiators include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4 , 6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, Bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-
  • Acetophenone initiators include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone , 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)-butan-1-one, and mixtures thereof.
  • Benzophenone initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 3 , 3'-dimethyl-2-methoxybenzophenone or a mixture thereof.
  • the thioxanthone initiator may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, or a mixture thereof.
  • the benzoin-based initiator may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, or a mixture thereof.
  • the phosphorus initiator may be bisbenzoylphenylphosphine oxide, benzoyldiphenylphosphine oxide, or a mixture thereof.
  • Oxime systems include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(o-acetyloxime)-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, or a mixture thereof.
  • the photopolymerization initiator is contained in the sealing composition of the present invention in an amount of about 0.1 to 20 parts by mass based on 100 parts by mass of the photopolymerizable monomer and photoinitiator. Preferably. By setting it within the above range, photopolymerization can sufficiently occur during exposure, and it is possible to prevent transmittance from decreasing due to unreacted initiator remaining after photopolymerization.
  • the photopolymerization initiator is preferably contained in an amount of 0.5 to 10 parts by weight, more specifically 1 to 5 parts by weight.
  • the photopolymerization initiator is preferably contained in the sealing composition of the present invention in an amount of 0.1 to 10% by mass based on solid content, more preferably 0.1% by mass. It is within the range of ⁇ 5% by mass. By setting it within the above range, photopolymerization can sufficiently occur, and it is possible to prevent the transmittance from decreasing due to the remaining unreacted initiator.
  • a photoacid generator or photopolymerization initiator such as a carbazole type, diketone type, sulfonium type, iodonium type, diazo type, or biimidazole type may be used.
  • the encapsulating composition of the present invention may contain other components including an antioxidant, a heat stabilizer, a photosensitizer, a dispersant, a thermal crosslinking agent, and a surfactant within the range where the effects of the present invention can be obtained. It may further contain. Only one kind of these components may be contained in the sealing composition of the present invention, or two or more kinds thereof may be contained in the sealing composition of the present invention.
  • the antioxidant can improve the thermal stability of the sealing layer.
  • the antioxidant may include one or more selected from the group consisting of phenol, quinone, amine, and phosphite, but is not limited thereto.
  • examples of antioxidants include tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, tris(2,4-di-tert-butylphenyl)phosphite, etc. be able to.
  • the antioxidant may be contained in the sealing composition in an amount of 0.01 to 3 parts by mass based on a total of 100 parts by mass of the photopolymerizable monomer and the photopolymerization initiator. It is preferably contained in a range of 0.01 to 1 part by mass. By setting it within the above range, excellent thermal stability can be exhibited.
  • the heat stabilizer is contained in the sealing composition and suppresses the change in viscosity of the sealing composition at room temperature, and any ordinary heat stabilizer can be used without any restriction.
  • a heat stabilizer a sterically hindered phenolic heat stabilizer may be used, specifically poly(di-cyclopentadiene-co-p-cresol), octadecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methano-bi(4-methyl-6-tert) -butyl-phenol), 6,6'-di-tert-butyl-2,2'-thiodi-p-cresol, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, Triethylene glycol-bis(3-tert-butyl-4-hydroxy-5-methylphenyl), 4,
  • the heat stabilizer is present in the sealing composition in an amount of 2000 ppm or less, preferably in the range of 0.01 to 2000 ppm, based on the solid content of the total of the photopolymerizable monomer and the photopolymerization initiator. More preferably, the content is in the range of 100 to 1000 ppm. By setting it within the above range, the heat stabilizer can further improve the storage stability and processability of the sealing composition in a liquid state.
  • the photosensitizer has the function of transferring the absorbed light energy to the photopolymerization initiator, so even if the photopolymerization initiator used does not have absorption corresponding to the light from the light source, it will not have the original photopolymerizability. It is a compound that can have an initiator function.
  • photosensitizers include anthracene derivatives such as 9,10-dibutoxyanthracene; benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4 , 6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride, etc.
  • anthracene derivatives such as 9,10-d
  • Benzophenone derivative 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4- Examples include compounds such as thioxanthone derivatives such as dimethyl-9Hthioxanthon-9-one mesochloride; Among these, it is preferable to use anthracene derivatives, benzoin derivatives, benzophenone derivatives, anthraquinone derivatives, and thioxanthone derivatives.
  • the ultraviolet rays irradiated to cure the sealing composition of the present invention can be any known means, and are not particularly limited as long as they are cured by irradiating ultraviolet rays within the range of 200 to 400 nm.
  • a 395 nm LED is preferably used from the viewpoint of preventing deterioration of the electronic device.
  • the environment for irradiating ultraviolet rays is not particularly limited as long as the sealing composition is cured by any known means, and is not particularly limited as long as it is cured by irradiating ultraviolet rays.
  • the irradiation is performed in an inert gas environment from the viewpoint of preventing deterioration of the electronic device and preventing the influence of oxygen from inhibiting curing.
  • the viscosity of the sealing composition of the present invention is preferably within the range of 3 to 30 mPa ⁇ s from the viewpoint of further improving ejection properties from an inkjet head.
  • the surface tension is preferably 15 mN/m or more and less than 45 mN/m from the viewpoint of further improving the ejection performance from the inkjet head.
  • the viscosity of the sealing composition of the present invention can be determined by measuring the temperature change in the dynamic viscoelasticity of the sealing composition using, for example, various rheometers. In the present invention, these viscosities are values obtained by the following method.
  • the sealing composition of the present invention is set in a stress-controlled rheometer Physica MCR300 (cone plate diameter: 75 mm, cone angle: 1.0°) manufactured by Anton Paar. Next, the sealing composition was heated to 100° C., and the sealing composition was cooled to 20° C. under the following conditions: a temperature decrease rate of 0.1° C./s, a strain of 5%, and an angular frequency of 10 radian/s. to obtain a temperature change curve of dynamic viscoelasticity.
  • the sealing composition of the present invention may contain pigment particles. From the viewpoint of further improving ejection properties from an inkjet head, when the sealing composition of the present invention contains a pigment, the average particle diameter of the pigment particles is within the range of 0.08 to 0.5 ⁇ m. The maximum particle size is preferably within the range of 0.3 to 10 ⁇ m.
  • the average particle diameter of pigment particles in the present invention means a value determined by a dynamic light scattering method using Datasizer Nano ZSP, manufactured by Malvern. Note that the sealing composition containing a coloring material has a high concentration and does not allow light to pass through this measuring device, so the sealing composition is diluted 200 times before measurement.
  • the measurement temperature is room temperature (25°C).
  • the sealing composition of the present invention is an Ohnesolge expressed by the following formula 1, which is expressed by the density ⁇ , the surface tension ⁇ of the sealing composition, the viscosity ⁇ of the sealing composition, and the nozzle diameter D0 . It is preferable that the number (Oh) is within the range of 0.1 to 1 from the viewpoint of inkjet ejection performance and stabilization of droplets during ink flight.
  • the encapsulating composition of the present invention is prepared to provide a cured polymer having a Tg (glass transition temperature) of 80° C. or higher in the polymerized film.
  • Tg glass transition temperature
  • the Tg of the film after polymerization is preferably 80° C. or higher from the viewpoint of ensuring stability in the electronic device formation process, driving temperature, and reliability test.
  • the electronic device sealing film forming method of the present invention is a method of forming a sealing film using the above-described composition for electronic device sealing of the present invention, wherein a first sealing film is formed on the electronic device by a vapor phase method.
  • the method includes a step of forming a sealing layer, and a step of forming a second sealing layer by applying the electronic device sealing composition on the first sealing layer. Further, it is preferable to include a step of forming a third sealing layer on the second sealing layer by a vapor phase method, since the sealing performance of the electronic device can be further improved.
  • the first sealing layer is formed on the electronic device by a vapor phase method.
  • Gas phase methods include sputtering methods (for example, reactive sputtering methods such as magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, bipolar AC rotating magnetron sputtering, etc.), vapor deposition methods (for example, resistance heating evaporation, electron beam evaporation, ion beam evaporation, plasma-assisted deposition, etc.), thermal CVD, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD (CCP-CVD), optical CVD, plasma CVD (PECVD), epitaxial growth method, and chemical vapor deposition method such as atomic layer deposition (ALD).
  • sputtering methods for example, reactive sputtering methods such as magnetron cathode sputtering, flat plate magnetron sputtering, bipolar
  • the first sealing layer contains silicon nitride (SiNx), silicon oxynitride (SiNOx), or silicon oxide (SiOx).
  • SiNx silicon nitride
  • SiNOx silicon oxynitride
  • SiOx silicon oxide
  • the pressure inside the chamber is reduced, and raw material gases such as silane (SiH 4 ), ammonia (NH 3 ), and hydrogen (H 2 ) are heated and supplied into the chamber.
  • a method of forming The thickness of the first sealing layer is, for example, preferably within the range of 10 to 1000 nm, more preferably within the range of 100 to 500 nm.
  • a second sealing layer is formed by applying the above-described sealing composition of the present invention on the first sealing layer. Specifically, the sealing composition is applied onto the first sealing layer (coating step), and the resulting coating film is modified by irradiating vacuum ultraviolet rays in a nitrogen atmosphere. May have.
  • any suitable method can be used to apply the sealing composition, such as spin coating, roll coating, flow coating, inkjet coating, spray coating, printing, and dip coating. , a casting film forming method, a bar coating method, a gravure printing method, and the like.
  • it is preferable to use the inkjet method because it allows on-demand fine patterning, which is required when sealing electronic devices such as organic EL elements.
  • Drop-on-demand methods include electro-mechanical conversion methods (e.g., single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (e.g., thermal Ink jet type, bubble jet (registered trademark) type, etc.), electrostatic suction type (eg, electric field control type, slit jet type, etc.), and discharge type (eg, spark jet type, etc.).
  • electro-mechanical conversion methods e.g., single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.
  • electro-thermal conversion methods e.g., thermal Ink jet type, bubble jet (registered trademark) type, etc.
  • electrostatic suction type eg, electric field control type, slit jet type, etc.
  • discharge type eg, spark jet type, etc.
  • an electro-mechanical conversion type or an electro-thermal conversion type head From the viewpoint of cost and productivity of the inkjet head, it is preferable to use an electro-mechanical conversion type or an electro-thermal conversion type head.
  • a method of dropping liquid droplets (for example, a coating liquid) using an inkjet method is sometimes referred to as an "inkjet method.”
  • the sealing composition When applying the sealing composition, it is preferable to apply it under a nitrogen atmosphere.
  • the modification treatment step may include, after the coating step, a step of irradiating the obtained coating film with vacuum ultraviolet rays in a nitrogen atmosphere to perform modification treatment.
  • the modification treatment refers to a conversion reaction of polysilazane to silicon oxide or silicon oxynitride.
  • the reforming treatment is similarly performed in a nitrogen atmosphere such as in a glove box or under reduced pressure.
  • a known method based on a conversion reaction of polysilazane can be selected.
  • a conversion reaction using plasma, ozone, or ultraviolet light which allows the conversion reaction to occur at a low temperature, is preferred. Conventionally known methods can be used for plasma and ozone.
  • it is preferable to form the second sealing layer according to the present invention by providing the coating film and performing a modification treatment by irradiating vacuum ultraviolet light (also referred to as VUV) with a wavelength of 200 nm or less. .
  • VUV vacuum ultraviolet light
  • the thickness of the second sealing layer is preferably within the range of 0.5 to 20 ⁇ m, more preferably within the range of 3 to 10 ⁇ m.
  • the entire layer may be a modified layer, but the thickness of the modified layer treated with modification is preferably within the range of 1 to 50 nm, and preferably 1 to 30 nm. More preferably within this range.
  • the illuminance of the vacuum ultraviolet rays on the coating film surface that the coating film receives is preferably within the range of 30 to 200 mW/cm 2 , and 50 to 160 mW/cm 2 It is more preferable that it be within the range of .
  • the modification efficiency can be sufficiently improved, and if it is 200 mW/cm 2 or less, the incidence of damage to the coating film can be extremely suppressed, and it can also cause damage to the base material. This is preferable because it can also reduce damage to.
  • the amount of energy irradiated with vacuum ultraviolet rays on the coated film surface is preferably within the range of 1 to 10 J/cm 2 , and from the viewpoint of barrier properties and moist heat resistance to maintain desiccant function, More preferably, it is within the range of 7 J/cm 2 .
  • a rare gas excimer lamp is preferably used as the vacuum ultraviolet light source. Since vacuum ultraviolet light is absorbed by oxygen, the efficiency in the vacuum ultraviolet irradiation step tends to decrease, so it is preferable to perform vacuum ultraviolet light irradiation in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration during vacuum ultraviolet light irradiation is preferably within the range of 10 to 10,000 ppm, more preferably within the range of 50 to 5,000 ppm, still more preferably within the range of 80 to 4,500 ppm, and most preferably 100 to 1,000 ppm. is within the range of
  • Modification treatment can also be performed in combination with heat treatment.
  • the heating conditions are preferably in the range of 50 to 300°C, more preferably in the range of 60 to 150°C, preferably for 1 second to 60 minutes, more preferably for 10 seconds to 10 minutes, in combination with heat treatment. By doing so, the dehydration condensation reaction during modification can be promoted and a modified product can be formed more efficiently.
  • Examples of heat treatment include: heating the coating film by heat conduction by bringing the substrate into contact with a heating element such as a heat block; heating the atmosphere with an external heater such as a resistance wire; and heating in an infrared region such as an IR heater. Examples include, but are not particularly limited to, methods using light. Further, any method that can maintain the smoothness of the coating film containing the silicon compound may be selected as appropriate.
  • a third sealing layer is formed on the second sealing layer by a vapor phase method.
  • gas phase method similar to the gas phase method used in the first sealing layer forming step, sputtering methods (for example, magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, bipolar AC rotating magnetron sputtering, etc.) are used.
  • the third sealing layer contains silicon nitride (SiNx), silicon oxynitride (SiNOx), or silicon oxide (SiOx).
  • the third sealing layer As a specific example of forming the third sealing layer, the pressure inside the chamber is reduced, and raw material gases such as silane (SiH 4 ), ammonia (NH 3 ), and hydrogen (H 2 ) are heated and supplied into the chamber.
  • raw material gases such as silane (SiH 4 ), ammonia (NH 3 ), and hydrogen (H 2 ) are heated and supplied into the chamber.
  • a method of forming The thickness of the third sealing layer is, for example, preferably within the range of 10 to 1000 nm, more preferably within the range of 100 to 500 nm.
  • a conductive film for a touch sensor may be further formed.
  • the conductive film may be, for example, a metal compound film such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide), as well as a graphene film or a metal nanowire film (such as silver nanowire or copper nanowire film) that has excellent flexibility.
  • a film containing wires a metal nanoparticle film (for example, a film containing silver nanoparticles or copper nanoparticles).
  • it can be constructed of a laminated film of multiple metals such as Al film/Ti film/Al film, for example.
  • An electronic device sealing film is an electronic device sealing film that seals an electronic device by curing an electronic device sealing composition containing a photopolymerizable monomer and a photopolymerization initiator.
  • the electronic device sealing film contains (meth)acrylate as the photopolymerizable monomer, and the electronic device sealing film has a refractive index of 1.45 to 1.56 at a wavelength of 380 nm.
  • the extinction coefficient of the stopping film at a wavelength of 380 nm is within the range of 50 ⁇ 10 ⁇ 5 to 200 ⁇ 10 ⁇ 5 .
  • an electronic device sealing film is an electronic device sealing film that seals an electronic device, and includes a first sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride; and a second sealing layer using the electronic device sealing composition of the present invention described above.
  • Such an electronic device sealing film of the present invention is formed by the electronic device sealing film forming method described above. That is, the second sealing layer is formed using the electronic device sealing composition of the present invention described above.
  • the second sealing layer has a refractive index at a wavelength of 380 nm in a range of 1.45 to 1.56, and an extinction coefficient at a wavelength of 380 nm in a range of 50 ⁇ 10 ⁇ 5 to 200 ⁇ 10 ⁇ 5 . It is within.
  • the electronic device sealing film of the present invention further includes a third sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride on the second sealing layer.
  • the first sealing layer is a layer formed on the electronic device by the above-mentioned vapor phase method. Specifically, it contains silicon nitride, silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride.
  • the second sealing layer is provided adjacent to the first sealing layer, and is formed by applying the sealing composition on the first sealing layer. Therefore, the second sealing layer contains a polymer made of the specific photopolymerizable monomer contained in the sealing composition.
  • Methods for detecting that the second sealing layer contains the polymer include various conventionally known analytical methods, such as chromatography, infrared spectroscopy, ultraviolet/visible spectroscopy, nuclear magnetic resonance analysis, Line diffraction, mass spectrometry, X-ray photoelectron spectroscopy, etc. can be used.
  • the content of the polymer in the second sealing layer is preferably in the range of 85 to 100% by mass, more preferably in the range of 90 to 95% by mass.
  • the third sealing layer is a layer that is provided adjacent to the second sealing layer and is formed by the above-mentioned vapor phase method. Specifically, like the first sealing layer, it contains silicon nitride, silicon oxide (silicon monoxide, silicon dioxide, etc.), or silicon oxynitride.
  • Examples of electronic devices to be sealed include organic EL elements, LED elements, liquid crystal display elements (LCD), thin film transistors, touch panels, and electronic paper. , solar cells (PV), and the like. From the viewpoint that the effects of the present invention can be obtained more efficiently, organic EL elements, solar cells, or LED elements are preferable, and organic EL elements are particularly preferable.
  • the organic EL element employed as the electronic device according to the present invention may be of a bottom emission type, that is, one that extracts light from the transparent substrate side.
  • the bottom emission type is constructed by laminating, in this order, a transparent electrode serving as a cathode, a light emitting functional layer, and a counter electrode serving as an anode on a transparent base material.
  • the organic EL element according to the present invention may be of a top emission type, that is, the organic EL element may be of a top emission type, in which light is extracted from the side of the transparent electrode serving as the cathode, which is opposite to the base material.
  • the top emission type has a configuration in which a counter electrode that serves as an anode is provided on the base material side, and a light emitting functional layer and a transparent electrode that serves as a cathode are laminated in this order on the surface of this counter electrode.
  • the intermediate layer may be a charge generation layer or may have a multi-photon unit configuration.
  • organic EL elements applicable to the present invention, see, for example, JP-A No. 2013-157634, JP-A No. 2013-168552, JP-A No. 2013-177361, JP-A No. 2013-187211, and JP-A No. 2013-187211.
  • Examples include configurations described in publications such as Japanese Patent Application Publication No. 2014-017494.
  • a base material (hereinafter also referred to as a support substrate, substrate, substrate, support, etc.) that can be used in the organic EL element, glass or a resin film is preferably used, and flexibility is required.
  • the film is a resin film, it is preferable to use a resin film.
  • it may be transparent or opaque.
  • the base material is preferably transparent.
  • Preferred resins include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, and cellulose acylate resin.
  • base materials containing thermoplastic resins such as polyester resins and acryloyl compounds. These resins can be used alone or in combination of two or more.
  • the base material is preferably made of a heat-resistant material. Specifically, a base material having a linear expansion coefficient of 15 ppm/K or more and 100 ppm/K or less and a glass transition temperature (Tg) of 100° C. or more and 300° C. or less is used.
  • Tg glass transition temperature
  • the base material satisfies the requirements for use in electronic components and as a laminated film for displays. That is, when using the sealing film of the present invention for these uses, the base material may be exposed to a process at 150° C. or higher.
  • the linear expansion coefficient of the base material exceeds 100 ppm/K, the dimensions of the base material will not be stable when it is passed through the process at the above-mentioned temperature, and the barrier performance will deteriorate due to thermal expansion and contraction. , or the problem of not being able to withstand a thermal process is likely to occur. If it is less than 15 ppm/K, the film may break like glass and its flexibility may deteriorate.
  • thermoplastic resins that can be used as the base material include polyethylene terephthalate (PET: 70°C), polyethylene naphthalate (PEN: 120°C), polycarbonate (PC: 140°C), alicyclic resins, etc.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • alicyclic resins etc.
  • Polyolefin for example, Zeonor (registered trademark) 1600 manufactured by Nippon Zeon Co., Ltd.: 160°C
  • PAr polyarylate
  • PES polyethersulfone
  • PSF polysulfone
  • 190°C cycloolefin copolymer
  • COC Compound described in JP-A No.
  • the base material is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105:1981, that is, using an integrating sphere type light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
  • the above-mentioned base material may be an unstretched film or a stretched film.
  • the base material can be manufactured by a conventionally known general method. Regarding the manufacturing method of these base materials, the matters described in paragraphs "0051" to "0055" of International Publication No. 2013/002026 can be adopted as appropriate.
  • the surface of the base material may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments may be combined as necessary. You can leave it there. Further, the base material may be subjected to adhesion-facilitating treatment.
  • the base material may be a single layer or may have a laminated structure of two or more layers.
  • each base material may be of the same type or of different types.
  • the thickness of the base material according to the present invention is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m.
  • a film base material it is preferably a film base material with a gas barrier layer.
  • the gas barrier layer for the film base material may have an inorganic film, an organic film, or a hybrid film of both formed on the surface of the film base material, and is measured by a method based on JIS K 7129-1992.
  • it is preferably a barrier film with a water vapor permeability (25 ⁇ 0.5°C, relative humidity (90 ⁇ 2)% RH) of 0.01 g/m 2 ⁇ 24 h or less, and furthermore, JIS K 7126- High gas barrier with an oxygen permeability of 1 ⁇ 10 -3 mL/m 2.24 h ⁇ atm or less and a water vapor permeability of 1 ⁇ 10 ⁇ 3 g/m 2.24 h or less, measured using a method based on the 1987 Act. It is preferable that the film is a transparent film.
  • the material forming the gas barrier layer may be any material that has the function of suppressing the infiltration of substances that cause deterioration of elements, such as moisture and oxygen, such as silicon monoxide, silicon dioxide, silicon nitride, silicon oxynitride, Silicon carbide, silicon oxycarbide, etc. can be used.
  • the gas barrier layer is not particularly limited, but for example, in the case of an inorganic gas barrier layer such as silicon monoxide, silicon dioxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, etc., the inorganic material is sputtered (e.g.
  • magnetron cathode sputtering magnetron cathode sputtering, planar magnetron sputtering, bipolar AC planar magnetron sputtering, bipolar AC rotating magnetron sputtering, etc.
  • vapor deposition methods e.g., resistance heating evaporation, electron beam evaporation, ion beam evaporation, plasma assisted deposition, etc.
  • thermal CVD method e.g., resistance heating evaporation, electron beam evaporation, ion beam evaporation, plasma assisted deposition, etc.
  • thermal CVD method e.g., thermal CVD method, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD (CCP-CVD), optical CVD, plasma CVD (PE-CVD), epitaxial growth, atomic layer deposition (ALD), reaction
  • Cat-CVD catalytic chemical vapor deposition
  • CCP-CVD capacitively coupled plasma CVD
  • a coating solution containing an inorganic precursor such as polysilazane or tetraethyl orthosilicate (TEOS) is applied onto a support, and then a modification treatment is performed by irradiation with vacuum ultraviolet light to form an inorganic gas barrier layer.
  • the inorganic gas barrier layer can also be formed by film metallization techniques such as metal plating on a resin base material, bonding of a metal foil and a resin base material, and the like.
  • the inorganic gas barrier layer may include an organic layer containing an organic polymer. That is, the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.
  • the organic layer can be formed by, for example, applying an organic monomer or an organic oligomer to a resin substrate to form a layer, followed by polymerization using, for example, an electron beam device, a UV light source, an electrical discharge device, or other suitable device. It can also be formed by crosslinking, if necessary. It can also be formed, for example, by flash evaporation and vapor deposition of radiation crosslinkable organic monomers or organic oligomers followed by formation of polymers from organic monomers or organic oligomers. Coating efficiency can be improved by cooling the resin substrate.
  • Examples of methods for applying the organic monomer or organic oligomer include roll coating (eg, gravure roll coating), spray coating (eg, electrostatic spray coating), and the like.
  • Examples of the laminate of an inorganic layer and an organic layer include the laminates described in International Publication No. 2012/003198 and International Publication No. 2011/013341.
  • the thickness of each layer may be the same or different.
  • the thickness of the inorganic layer is preferably within the range of 3 to 1000 nm, more preferably within the range of 10 to 300 nm.
  • the thickness of the organic layer is preferably within the range of 100 nm to 100 ⁇ m, more preferably within the range of 1 to 50 ⁇ m.
  • the monomers used to prepare the encapsulating composition are as follows. Further, the HOMO and LUMO values of each monomer were calculated by the method described later and are shown in Table I below. Further, the D-line refractive index (nd25) at 25° C. was calculated for each monomer using an Abbe refractometer and is shown in Table I below.
  • sealing compositions 1 to 28 Each monomer was weighed in a nitrogen environment so that the types and parts by weight were shown in Table II below. Furthermore, 5 parts by mass of a phosphorus initiator (manufactured by IGM, Omnirad 819) as a photopolymerization initiator and 0.5 parts by mass of 2-isopropylthioxanthone (manufactured by Merck) as a sensitizer were placed in a brown bottle, and the mixture was heated at 65°C. The mixture was stirred on a hot plate for 3 hours to obtain each of the sealing compositions 1 to 28.
  • a phosphorus initiator manufactured by IGM, Omnirad 819
  • 2-isopropylthioxanthone manufactured by Merck
  • a coating film of the sealing composition was formed to a thickness of 100 nm on a glass substrate having dimensions of 50 mm x 50 mm in a nitrogen environment.
  • This coating film was irradiated with ultraviolet rays with a wavelength of 395 nm (MZ 240 mm 395 nm UVLED manufactured by IST) under a nitrogen environment at 300 mW/cm 2 conditions so that the cumulative light amount was 1.5 J/cm 2 . was cured and used as a measurement sample.
  • the refractive index and extinction coefficient of the measurement sample at 250 nm to 800 nm were measured by spectroscopic ellipsometry using UVSEL/FUV-FGMS manufactured by Horiba JYOBIN-YVON, and the refractive index n at 380 nm and the refractive index n at 380 nm of the cured film of the sealing composition were measured.
  • the extinction coefficient k was determined and shown in Table III below.
  • the ratio k/n of the extinction coefficient k at 380 nm to the refractive index n at 380 nm was determined and shown in Table III below.
  • Average value of LUMO LUMO1 ⁇ w1+LUMO2 ⁇ w2+...
  • w represents the mass ratio of each monomer described above.
  • the subscripts w, HOMO, and LUMO represent the monomer numbers.
  • Gap (unit: eV) LUMO average value - HOMO average value
  • first electrode metal layer
  • the thickness of the first electrode formed was 150 nm. Note that the thickness of the first electrode is a value measured using a contact type surface profile measuring device (DECTAK).
  • the Al film was formed using a tungsten resistance heating crucible after reducing the pressure to a degree of vacuum of 1 ⁇ 10 ⁇ 4 Pa using a vacuum evaporation device.
  • each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the materials listed below constituting each layer of the organic functional layer in amounts optimal for device fabrication.
  • the crucible for vapor deposition was made of a resistance heating material made of molybdenum or tungsten.
  • capping layer After that, it is transferred to the original vacuum chamber, and ⁇ -NPD (4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl) is deposited on the second electrode. was deposited to a thickness of 40 nm at a deposition rate of 0.1 to 0.2 nm/sec to form a capping layer for the purpose of improving light extraction.
  • ⁇ -NPD 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • first sealing layer As a first sealing layer covering the light emitting part of the organic EL element produced above, silicon nitride (SiNx) with a thickness of 500 nm (Vickers hardness HV900) was formed by plasma CVD method. was formed.
  • the sealing composition 1 prepared above was filled into an inkjet head (KM1024i-MHE-D manufactured by Konica Minolta) in a nitrogen environment. Then, the organic EL element formed up to the first sealing layer was coated with the sealing composition 1 using an inkjet method in a nitrogen environment so that the coating thickness was 10 ⁇ m. Thereafter, a second sealing layer was formed by irradiating ultraviolet light with a wavelength of 395 nm (MZ 240 mm 395 nm UVLED manufactured by IST) under 300 mW/cm 2 conditions so that the cumulative light amount was 1.5 J/cm 2 .
  • MZ 240 mm 395 nm UVLED manufactured by IST 395 nm
  • silicon nitride (SiNx) with a thickness of 500 nm (Vickers hardness HV900) is formed as a third sealing layer on the second sealing layer by plasma CVD method.
  • An organic EL element 1 for evaluation in which the first to third sealing layers were formed was obtained.
  • organic EL elements 2 to 28 were prepared in the same manner except that the sealing composition 1 in forming the second sealing layer was changed as shown in the table below. Created.
  • Ranks 2 to 4 were considered passing. (Evaluation criteria) Rank 1: Less than 80% Rank 2: 80% or more and less than 90% Rank 3: 90% or more and less than 95% Rank 4: 95% or more
  • a coating film of the sealing composition having a thickness of 50 ⁇ m was produced on a releasable film substrate having dimensions of 100 mm ⁇ 100 mm in a nitrogen environment.
  • This coating film was irradiated with ultraviolet rays with a wavelength of 395 nm (MZ 240 mm 395 nm UVLED manufactured by IST) under a nitrogen environment at 300 mW/cm 2 conditions so that the cumulative light amount was 1.5 mJ/cm 2 . hardened.
  • the obtained cured film was peeled off from the release film, and then Ag films were formed on both sides by sputtering to prepare a measurement sample.
  • the impedance of the measurement sample was measured using an impedance measuring device (126096 manufactured by Solartron) at a frequency of 100 kHz and AC 0.1 (V), and the relative dielectric constant was measured. A dielectric constant of less than 2.9 was considered a pass, and a dielectric constant of 2.9 or more was judged a fail.
  • the encapsulating composition of the present invention has a better appearance after the reliability test in the folded state and has better bending reliability than the encapsulating composition of the comparative example. It can be seen that a sealing film with excellent luminous efficiency after the test and a low dielectric constant can be obtained.
  • the present invention provides a composition for encapsulating electronic devices that provides a sealing film that has a good appearance after a reliability test in a folded state, has excellent luminous efficiency after a reliability test after being folded, and has a low dielectric constant. , it can be used for an electronic device sealing film and a method for forming an electronic device sealing film.

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Abstract

A composition for electronic device sealing according to the present invention contains a photopolymerizable monomer and a photopolymerization initiator. With respect to this composition for electronic device sealing, a (meth)acrylate is contained as the photopolymerizable monomer; an electronic device sealing film which is formed by curing this composition for electronic device sealing by means of irradiation of ultraviolet light having a wavelength of 395 nm at 1.5 Jcm-2 in a nitrogen environment has a refractive index within the range of from 1.45 to 1.56 at a wavelength of 380 nm; and this electronic device sealing film has an extinction coefficient within the range of from 50 × 10-5 to 200 × 10-5 at a wavelength of 380 nm.

Description

電子デバイス封止用組成物、電子デバイス封止膜及び電子デバイス封止膜の形成方法Electronic device encapsulation composition, electronic device encapsulation film, and method for forming an electronic device encapsulation film
　本発明は、電子デバイス封止用組成物、電子デバイス封止膜及び電子デバイス封止膜の形成方法に関し、特に、折り曲げた状態での信頼性試験後の見栄えが良好で、かつ、折り曲げ信頼性試験後の発光効率に優れ、比誘電率の低い封止膜が得られる電子デバイス封止用組成物等に関する。 The present invention relates to an electronic device encapsulation composition, an electronic device encapsulation film, and a method for forming an electronic device encapsulation film, and in particular, to a composition that has good appearance after a reliability test in a folded state and has good bending reliability. The present invention relates to a composition for sealing an electronic device, etc., which provides a sealing film with excellent luminous efficiency after testing and a low dielectric constant.
　電子デバイス、特に有機エレクトロルミネッセンスデバイス（以下、「有機ＥＬデバイス」又は「有機ＥＬ素子」ともいう。）は、用いられている有機材料や電極が水分により劣化することを防止するため、有機ＥＬ素子の表面を封止層により覆うことが提案されている。 Electronic devices, especially organic electroluminescent devices (hereinafter also referred to as "organic EL devices" or "organic EL elements"), are designed to prevent the organic materials and electrodes used from deteriorating due to moisture. It has been proposed to cover the surface of the device with a sealing layer.
　有機ＥＬ素子を封止する技術として、例えば、特許文献１に記載の技術では、光重合性（光硬化性）モノマー及び開始剤を含み、光重合性モノマーはシリコン系光重合性モノマーを含まず、特定の芳香族基含有モノマー及び非芳香族基含有モノマーを含む、有機発光素子封止用組成物が開示されている。当該技術によって、高い屈折率と高い硬化率とを有し、拡散性に優れ、硬化後のプラズマエッチング率が低い有機発光素子封止用組成物を提供することができるとされている。 As a technique for sealing an organic EL element, for example, the technique described in Patent Document 1 includes a photopolymerizable (photocurable) monomer and an initiator, and the photopolymerizable monomer does not contain a silicon-based photopolymerizable monomer. discloses a composition for encapsulating an organic light-emitting device, which includes a specific aromatic group-containing monomer and a non-aromatic group-containing monomer. It is said that this technique can provide a composition for encapsulating an organic light emitting device that has a high refractive index and a high curing rate, has excellent diffusivity, and has a low plasma etching rate after curing.
　しかしながら、上記特許文献１に記載の技術では、有機発光素子を折り曲げた状態での信頼性試験後の折りぐせができてしまい、見栄えに問題があった。
　また、有機発光素子の折り曲げ状態後においては、発光効率が低下するという問題があった。
　さらに、電子デバイスに電界を印加したときに分極しにくいことが好ましく、比誘電率が低いことも望まれている。 However, in the technique described in Patent Document 1, the organic light emitting device is folded after a reliability test in a folded state, resulting in a problem with the appearance.
Furthermore, there is a problem in that the luminous efficiency decreases after the organic light emitting device is bent.
Furthermore, it is preferable that the material is difficult to polarize when an electric field is applied to the electronic device, and it is also desired that the dielectric constant is low.
特開２０２０－１９８３０４号公報Japanese Patent Application Publication No. 2020-198304
　本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、折り曲げた状態での信頼性試験後の見栄えが良好で、かつ、折り曲げ信頼性試験後の発光効率に優れ、比誘電率の低い封止膜が得られる電子デバイス封止用組成物を提供することである。また、当該電子デバイス封止用組成物を用いた電子デバイス封止膜及びその形成方法を提供することである。 The present invention was made in view of the above-mentioned problems and circumstances, and the object to be solved is to provide a good appearance after a reliability test in a folded state, excellent luminous efficiency after a folding reliability test, An object of the present invention is to provide a composition for encapsulating an electronic device that provides a encapsulating film with a low relative dielectric constant. Another object of the present invention is to provide an electronic device sealing film using the electronic device sealing composition and a method for forming the same.
　本発明者は、上記課題を解決すべく、上記問題の原因等について検討する過程において、光重合性モノマーとして（メタ）アクリレートを含有し、特定の環境条件下で照射して硬化した封止膜の屈折率及び消衰係数を特定範囲とすることにより、折り曲げた状態での信頼性試験後における見栄えと発光効率に優れ、比誘電率の低い封止膜が得られることを見いだし本発明に至った。
　すなわち、本発明に係る上記課題は、以下の手段により解決される。 In order to solve the above problems, in the process of investigating the causes of the above problems, the present inventors discovered a sealing film containing (meth)acrylate as a photopolymerizable monomer and cured by irradiation under specific environmental conditions. It was discovered that by setting the refractive index and extinction coefficient of the material within a specific range, a sealing film with excellent appearance and luminous efficiency after a reliability test in a folded state and with a low dielectric constant can be obtained, which led to the present invention. Ta.
That is, the above-mentioned problems related to the present invention are solved by the following means.
　１．光重合性モノマー及び光重合開始剤を含有する電子デバイス封止用組成物であって、
　光重合性モノマーとして、（メタ）アクリレートを含有し、
　窒素環境下で波長３９５ｎｍの紫外線を１．５Ｊｃｍ－２照射して硬化したとき、
　形成される電子デバイス封止膜の、波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内であり、かつ、当該電子デバイス封止膜の、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である電子デバイス封止用組成物。 1. An electronic device encapsulation composition containing a photopolymerizable monomer and a photopolymerization initiator,
Contains (meth)acrylate as a photopolymerizable monomer,
When cured by irradiating 1.5 Jcm -2 of ultraviolet light with a wavelength of 395 nm in a nitrogen environment,
The refractive index of the formed electronic device sealing film at a wavelength of 380 nm is within the range of 1.45 to 1.56, and the extinction coefficient of the electronic device sealing film at a wavelength of 380 nm is 50× A composition for encapsulating an electronic device having a molecular weight within the range of 10 −5 to 200×10 −5 .
　２．前記屈折率が、１．５０～１．５３の範囲内である第１項に記載の電子デバイス封止用組成物。 2. 2. The composition for encapsulating an electronic device according to item 1, wherein the refractive index is within the range of 1.50 to 1.53.
　３．前記消衰係数が、１２５×１０－５～２００×１０－５の範囲内である第１項に記載の電子デバイス封止用組成物。 3. 2. The composition for encapsulating an electronic device according to item 1, wherein the extinction coefficient is within the range of 125×10 −5 to 200×10 −5 .
　４．前記屈折率ｎと前記消衰係数ｋが、下記の関係を満たす第１項に記載の電子デバイス封止用組成物。
　ｋ／ｎ≧１００×１０－５ 4. The composition for encapsulating an electronic device according to item 1, wherein the refractive index n and the extinction coefficient k satisfy the following relationship.
k/n≧100× 10-5
　５．前記電子デバイス封止用組成物に含有される前記光重合性モノマーの平均二重結合数が、５以下である第１項に記載の電子デバイス封止用組成物。 5. 2. The composition for encapsulating an electronic device according to item 1, wherein the photopolymerizable monomer contained in the composition for encapsulating an electronic device has an average number of double bonds of 5 or less.
　６．前記電子デバイス封止用組成物に含有される前記光重合性モノマーの最高被占分子軌道（ＨＯＭＯ）及び最低空分子軌道（ＬＵＭＯ）のエネルギー準位が、下記の関係を満たす第１項に記載の電子デバイス封止用組成物。
　５．９ｅＶ≦ＬＵＭＯ－ＨＯＭＯ≦６．５ｅＶ 6. As described in item 1, wherein the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the photopolymerizable monomer contained in the electronic device encapsulating composition satisfy the following relationship. Composition for encapsulating electronic devices.
5.9eV≦LUMO-HOMO≦6.5eV
　７．光重合性モノマー及び光重合開始剤を含有する電子デバイス封止用組成物を硬化して電子デバイスを封止する電子デバイス封止膜であって、
　前記光重合性モノマーとして、（メタ）アクリレートを含有し、
　前記電子デバイス封止膜の波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内であり、かつ、
　前記電子デバイス封止膜の、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である電子デバイス封止膜。 7. An electronic device sealing film that seals an electronic device by curing an electronic device sealing composition containing a photopolymerizable monomer and a photopolymerization initiator,
The photopolymerizable monomer contains (meth)acrylate,
The refractive index of the electronic device sealing film at a wavelength of 380 nm is within the range of 1.45 to 1.56, and
The electronic device sealing film has an extinction coefficient within the range of 50×10 −5 to 200×10 −5 at a wavelength of 380 nm.
　８．電子デバイスを封止する電子デバイス封止膜であって、
　窒化ケイ素、酸化ケイ素又は酸窒化ケイ素を含有する第１封止層と、
　第１項から第６項までのいずれか一項に記載の電子デバイス封止用組成物を用いた第２封止層と、を有する電子デバイス封止膜。 8. An electronic device sealing film that seals an electronic device,
a first sealing layer containing silicon nitride, silicon oxide or silicon oxynitride;
An electronic device sealing film comprising: a second sealing layer using the electronic device sealing composition according to any one of Items 1 to 6;
　９．前記第２封止層上に、窒化ケイ素、酸化ケイ素又は酸窒化ケイ素を含有する第３封止層を有する第８項に記載の電子デバイス封止膜。 9. 9. The electronic device sealing film according to item 8, further comprising a third sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride on the second sealing layer.
　１０．第１項から第６項までのいずれか一項に記載の電子デバイス封止用組成物を用いて、電子デバイス封止膜を形成する方法であって、
　電子デバイス上に気相法により第１封止層を形成する工程と、
　前記第１封止層上に前記電子デバイス封止用組成物を塗布することにより第２封止層を形成する工程と、を備える電子デバイス封止膜形成方法。 10. A method of forming an electronic device sealing film using the electronic device sealing composition according to any one of Items 1 to 6, comprising:
forming a first sealing layer on the electronic device by a vapor phase method;
A method for forming an electronic device sealing film, comprising: forming a second sealing layer by applying the electronic device sealing composition on the first sealing layer.
　１１．前記第２封止層上に、気相法により第３封止層を形成する工程を備える第１０項に記載の電子デバイス封止膜形成方法。 11. 11. The electronic device sealing film forming method according to item 10, comprising the step of forming a third sealing layer on the second sealing layer by a vapor phase method.
　１２．インクジェット法により前記第２封止層を形成する第１０項に記載の電子デバイス封止膜形成方法。 12. 11. The electronic device sealing film forming method according to item 10, wherein the second sealing layer is formed by an inkjet method.
　本発明の上記手段により、折り曲げた状態での信頼性試験後の見栄えが良好で、かつ、折り曲げ信頼性試験後の発光効率に優れ、比誘電率の低い封止膜が得られる電子デバイス封止用組成物を提供することができる。また、当該電子デバイス封止用組成物を用いた電子デバイス封止膜及びその形成方法を提供することである。
　本発明の効果の発現機構又は作用機構については、明確にはなっていないが、以下のように推察している。 By the above means of the present invention, an electronic device sealing film that has a good appearance after a reliability test in a folded state, has excellent luminous efficiency after a bending reliability test, and has a low dielectric constant can be obtained. A composition for use can be provided. Another object of the present invention is to provide an electronic device sealing film using the electronic device sealing composition and a method for forming the same.
Although the mechanism of expression or action of the effects of the present invention is not clear, it is speculated as follows.
　（折り曲げた状態での信頼性試験後の見栄え）
　折り曲げた状態での信頼性試験を行うと、長期間加わり続ける曲げ応力によりクリープ現象がおきて、硬化膜の変形が生じる。この変形により、光路長が変化してしまい、信頼性試験後の見栄えの変化が生じてしまう。
　本発明では、封止膜の屈折率と、光を吸収する尺度となる消衰係数を前記した特定範囲にすることで、光の屈折と吸収のバランスにより、折り曲げた状態での変形に伴う光学的な見栄えの変化が生じにくい。つまり、低い屈折率によって光路長が短くなることで折り曲げた状態での信頼性試験前後での光路長変化量が小さくなり、さらに光の吸収により外部から反射光量が減少することになり、折り曲げた状態での信頼性試験後の折りぐせを抑制して見栄えを良好にすることができる。 (Appearance after reliability test in folded state)
When a reliability test is performed in a bent state, a creep phenomenon occurs due to the bending stress that continues to be applied over a long period of time, causing deformation of the cured film. This deformation changes the optical path length, resulting in a change in appearance after the reliability test.
In the present invention, by setting the refractive index of the sealing film and the extinction coefficient, which is a measure of light absorption, within the above-mentioned specific range, the optical Changes in appearance are less likely to occur. In other words, as the optical path length becomes shorter due to the lower refractive index, the amount of change in the optical path length before and after the reliability test in the folded state becomes smaller, and the amount of reflected light from the outside decreases due to light absorption. It is possible to improve the appearance by suppressing folding after a reliability test.
　（折り曲げ信頼性試験後の発光効率）
　繰り返しの折り曲げ信頼性試験を行うことで、硬化膜変形やクラックが生じるおそれがある。硬化膜が変形したり、微小なクラックが生じると発光素子からの光の出方が変化ししうる。つまり、変形すると光路長変化及び光の屈折により光が横方向へ発光したり、クラックが発生するとクラックの隙間の空気との屈折率差で光が出て来ないおそれがある。
　そこで、本発明では封止膜の屈折率を前記した特定範囲にすることで、光の屈折を抑制でき、微小クラックでの空気層との屈折率差を抑制することができ、折り曲げ状態後においても高い発光効率を維持することができると推察される。 (Luminous efficiency after bending reliability test)
Repeated bending reliability tests may cause deformation or cracks in the cured film. If the cured film is deformed or minute cracks occur, the way light is emitted from the light emitting element may change. In other words, when deformed, light may be emitted in the lateral direction due to changes in the optical path length and refraction of light, and when cracks occur, light may not come out due to the difference in refractive index with the air in the gap between the cracks.
Therefore, in the present invention, by setting the refractive index of the sealing film within the above-mentioned specific range, it is possible to suppress the refraction of light, suppress the difference in refractive index with the air layer in micro cracks, and to It is presumed that high luminous efficiency can also be maintained.
　（比誘電率）
　さらに驚くべきことに、封止膜の屈折率と、光を吸収する尺度となる消衰係数が前記した特定範囲にあるとき、比誘電率が低くなる。作用機構は明らかではないが、特定範囲にあることでエネルギーギャップが大きくなり、電子遷移が起こりにくくなると考えられる。誘電率は、電子分極による。電子分極は電界の摂動を受けて電子分布が生じることで発生するが、電子遷移が起きにくいことで大きな電子分布が生じにくいと考えられる。 (relative permittivity)
More surprisingly, when the refractive index of the sealing film and the extinction coefficient, which is a measure of light absorption, are within the above-mentioned specific ranges, the dielectric constant becomes low. Although the mechanism of action is not clear, it is thought that within a certain range the energy gap becomes larger and electronic transitions become less likely to occur. The dielectric constant depends on electronic polarization. Electronic polarization occurs when an electron distribution occurs due to perturbation of an electric field, but it is thought that a large electron distribution is unlikely to occur because electronic transitions are difficult to occur.
　本発明の電子デバイス封止用組成物は、光重合性モノマー及び光重合開始剤を含有する電子デバイス封止用組成物であって、光重合性モノマーとして、（メタ）アクリレートを含有し、窒素環境下で波長３９５ｎｍの紫外線を１．５Ｊｃｍ－２照射して硬化したとき、形成される電子デバイス封止膜の、波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内であり、かつ、当該電子デバイス封止膜の、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である。
　この特徴は、下記各実施形態に共通又は対応する技術的特徴である。 The composition for encapsulating an electronic device of the present invention is a composition for encapsulating an electronic device containing a photopolymerizable monomer and a photopolymerization initiator, which contains (meth)acrylate as the photopolymerizable monomer, and contains nitrogen. When cured by irradiating 1.5 Jcm −2 of ultraviolet light with a wavelength of 395 nm in an environment, the refractive index at a wavelength of 380 nm of the electronic device sealing film formed is within the range of 1.45 to 1.56, Moreover, the extinction coefficient of the electronic device sealing film at a wavelength of 380 nm is within the range of 50×10 −5 to 200×10 −5 .
This feature is a technical feature common to or corresponding to each of the embodiments described below.
　本発明の実施態様としては、前記屈折率が、１．５０～１．５３の範囲内であること、また、前記消衰係数が、１２５×１０－５～２００×１０－５の範囲内であることが、折り曲げた状態での信頼性試験後の見栄え及び発光効率の点でより好ましい。 In an embodiment of the present invention, the refractive index is within the range of 1.50 to 1.53, and the extinction coefficient is within the range of 125×10 −5 to 200×10 −5 . It is more preferable in terms of appearance after a reliability test in a folded state and luminous efficiency.
　前記屈折率ｎと前記消衰係数ｋが、ｋ／ｎ≧１００×１０－５の関係を満たすことが、折り曲げた状態での信頼性試験後の見栄え、折り曲げ信頼性試験後の発光効率の点で好ましい。 The refractive index n and the extinction coefficient k satisfy the relationship k/n≧100×10 −5 in terms of the appearance after the reliability test in the folded state and the luminous efficiency after the bending reliability test. It is preferable.
　前記電子デバイス封止用組成物に含有される前記光重合性モノマーの平均二重結合数が、５以下であることが、折り曲げた状態での信頼性試験後の見栄え、折り曲げ信頼性試験後の発光効率の点で好ましい。 The average number of double bonds of the photopolymerizable monomer contained in the electronic device encapsulating composition is 5 or less, which improves the appearance after the reliability test in the folded state and the reliability test after the bending reliability test. This is preferable in terms of luminous efficiency.
　また、前記電子デバイス封止用組成物に含有される前記光重合性モノマーの最高被占分子軌道（ＨＯＭＯ）及び最低空分子軌道（ＬＵＭＯ）のエネルギー準位が、
　５．９ｅＶ≦ＬＵＭＯ－ＨＯＭＯ≦６．５ｅＶ
の関係を満たすことが、折り曲げた状態での信頼性試験後の見栄え、折り曲げ信頼性試験後の発光効率、比誘電率の点で好ましい。 Furthermore, the energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the photopolymerizable monomer contained in the electronic device encapsulating composition are
5.9eV≦LUMO-HOMO≦6.5eV
It is preferable to satisfy the following relationship in terms of appearance after a reliability test in a folded state, luminous efficiency after a bending reliability test, and relative permittivity.
　本発明の一の態様の電子デバイス封止膜は、光重合性モノマー及び光重合開始剤を含有する電子デバイス封止用組成物を硬化して電子デバイスを封止する電子デバイス封止膜であって、前記光重合性モノマーとして、（メタ）アクリレートを含有し、前記電子デバイス封止膜の波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内であり、かつ、前記電子デバイス封止膜の、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である。
　これにより、折り曲げた状態での信頼性試験後の見栄えが良好で、かつ、折り曲げ信頼性試験後の発光効率に優れ、また、比誘電率の低い電子デバイス封止膜とすることができる。 An electronic device sealing film according to one aspect of the present invention is an electronic device sealing film that seals an electronic device by curing an electronic device sealing composition containing a photopolymerizable monomer and a photopolymerization initiator. The electronic device sealing film contains (meth)acrylate as the photopolymerizable monomer, and the electronic device sealing film has a refractive index of 1.45 to 1.56 at a wavelength of 380 nm. The extinction coefficient of the stopping film at a wavelength of 380 nm is within the range of 50×10 −5 to 200×10 −5 .
As a result, it is possible to obtain an electronic device sealing film that has a good appearance after a reliability test in a folded state, has excellent luminous efficiency after a bending reliability test, and has a low dielectric constant.
　本発明の他の態様の電子デバイス封止膜は、電子デバイスを封止する電子デバイス封止膜であって、窒化ケイ素、酸化ケイ素又は酸窒化ケイ素を含有する第１封止層と、前記電子デバイス封止用組成物を用いた第２封止層と、を有する。
　これにより、折り曲げた状態での信頼性試験後の見栄えが良好で、かつ、折り曲げ信頼性試験後の発光効率に優れ、また、比誘電率の低い電子デバイス封止膜とすることができる。 An electronic device sealing film according to another aspect of the present invention is an electronic device sealing film that seals an electronic device, and includes a first sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride, and a first sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride; and a second sealing layer using a device sealing composition.
As a result, it is possible to obtain an electronic device sealing film that has a good appearance after a reliability test in a folded state, has excellent luminous efficiency after a bending reliability test, and has a low dielectric constant.
　また、前記第２封止層上に、窒化ケイ素、酸化ケイ素又は酸窒化ケイ素を含有する第３封止層を有することが、封止性能に優れる点で好ましい。 Furthermore, it is preferable to have a third sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride on the second sealing layer from the viewpoint of excellent sealing performance.
　本発明の電子デバイス封止膜形成方法は、前記電子デバイス封止用組成物を用いて、封止膜を形成する方法であって、電子デバイス上に気相法により第１封止層を形成する工程と、前記第１封止層上に前記電子デバイス封止用組成物を塗布することにより第２封止層を形成する工程と、を備える。
　これにより、折り曲げた状態での信頼性試験後の見栄えが良好で、かつ、折り曲げ信頼性試験後の発光効率に優れた電子デバイス封止膜を形成することができる。 The electronic device sealing film forming method of the present invention is a method of forming a sealing film using the electronic device sealing composition, wherein a first sealing layer is formed on the electronic device by a vapor phase method. and forming a second sealing layer by applying the electronic device sealing composition on the first sealing layer.
Thereby, it is possible to form an electronic device sealing film that has a good appearance after a reliability test in a folded state and has excellent luminous efficiency after a bending reliability test.
　前記第２封止層上に、気相法により第３封止層を形成する工程を備えることが、封止性能に優れる点で好ましい。
　また、前記第２封止層を形成する工程が、インクジェット法を用いることが、高精度に層形成できる点で好ましい。 It is preferable to include a step of forming a third sealing layer on the second sealing layer by a vapor phase method in terms of excellent sealing performance.
Further, it is preferable that the step of forming the second sealing layer uses an inkjet method because the layer can be formed with high precision.
　以下、本発明とその構成要素及び本発明を実施するための形態・態様について説明をする。なお、本願において、「～」は、その前後に記載される数値を下限値及び上限値として含む意味で使用する。 Hereinafter, the present invention, its constituent elements, and forms and aspects for carrying out the present invention will be explained. In this application, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
［本発明の電子デバイス封止用組成物の概要］
　本発明の電子デバイス封止用組成物（以下、単に「封止用組成物」ともいう。）は、光重合性モノマー及び光重合開始剤を含有する電子デバイス封止用組成物であって、光重合性モノマーとして、（メタ）アクリレートを含有し、窒素環境下で波長３９５ｎｍの紫外線を１．５Ｊｃｍ－２照射して硬化したとき、形成される電子デバイス封止膜（以下、単に「封止膜」ともいう。）の、波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内であり、かつ、当該電子デバイス封止膜の、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である。 [Overview of the composition for encapsulating electronic devices of the present invention]
The electronic device encapsulation composition of the present invention (hereinafter also simply referred to as "encapsulation composition") is an electronic device encapsulation composition containing a photopolymerizable monomer and a photopolymerization initiator, It contains (meth)acrylate as a photopolymerizable monomer, and is formed when it is cured by irradiating 1.5 Jcm -2 of ultraviolet light with a wavelength of 395 nm in a nitrogen environment (hereinafter simply referred to as "sealing"). ) has a refractive index at a wavelength of 380 nm within the range of 1.45 to 1.56, and the extinction coefficient of the electronic device sealing film at a wavelength of 380 nm is 50×10 - It is within the range of 5 to 200×10 −5 .
＜屈折率＞
　本発明の封止用組成物は、窒素環境下で波長３９５ｎｍの紫外線を１．５Ｊｃｍ－２照射して硬化したとき、形成される封止膜の、波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内である。より好ましくは１．５０～１．５３の範囲内である。 <Refractive index>
When the sealing composition of the present invention is cured by irradiating 1.5 Jcm -2 of ultraviolet light with a wavelength of 395 nm in a nitrogen environment, the refractive index of the sealing film formed at a wavelength of 380 nm is 1.45 to 1. It is within the range of 1.56. More preferably, it is within the range of 1.50 to 1.53.
　前記屈折率は、分光エリプソメトリー（ＵＶＳＥＬ／ＦＵＶ－ＦＧＭＳ、堀場ＪＹＯＢＩＮ－ＹＶＯＮ社製）により求めた。具体的には、２５０ｎｍ～８００ｎｍにおける屈折率を測定し、３８０ｎｍにおける屈折率ｎを求めた。 The refractive index was determined by spectroscopic ellipsometry (UVSEL/FUV-FGMS, manufactured by Horiba JYOBIN-YVON). Specifically, the refractive index at 250 nm to 800 nm was measured, and the refractive index n at 380 nm was determined.
　前記屈折率を１．４５～１．５６の範囲内とするための手段としては、例えば、モノマーの構造にヘテロ原子数が少ない構造、脂環式炭化水素の構造、鎖状炭化水素の構造を用いることが挙げられるが、これに限定されない。
　脂環式炭化水素の構造としては、具体的には、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等の脂環式（メタ）アクリレート、１，３－アダマンタンジオールジ（メタ）アクリレート、１，３－アダマンタンジメタノールジ（メタ）アクリレート、２－メチル－２－アダマンチル（メタ）アクリレート、２－エチル－２－アダマンチル（メタ）アクリレート、３－ヒドロキシ－１－アダマンチル（メタ）アクリレート、１－アダマンチル（メタ）アクリレート、トリシクロデカンジメタノール（メタ）アクリレート等の脂環式（メタ）アクリレートが挙げられるが、これに限定されない。
　鎖状炭化水素の構造としては、１，６－ヘキサンジオールジ（メタ）アクリレート、１，７－ヘプタンジオールジ（メタ）アクリレート、１，８－オクタンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、１，１１－ウンデカンジオールジ（メタ）アリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、ヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレートが挙げられるが、これに限定されない。また、インクジェットの吐出性を損なわない範囲で、所望の屈折率を有する粒子を添加すること等が挙げられる。
　また、封止用組成物を構成する光重合性モノマーの屈折率はアッベ屈折計で求めることができ、２５℃におけるD線の屈折率（nd25）としては１．４３～１．５０であることが好ましい。 As a means for setting the refractive index within the range of 1.45 to 1.56, for example, the monomer structure has a structure with a small number of hetero atoms, an alicyclic hydrocarbon structure, a chain hydrocarbon structure. Examples include, but are not limited to, the use of
Specifically, the structures of alicyclic hydrocarbons include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and cyclohexyl. Alicyclic (meth)acrylate such as (meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate , 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 1-adamantyl (meth)acrylate, tricyclodecane dimethanol (meth)acrylate, etc. Examples include, but are not limited to, acrylates.
The structures of chain hydrocarbons include 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, and 1,9-nonane. Diol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecanediol di(meth)arylate, 1,12-dodecanediol di(meth)acrylate, 2-ethylhexyl(meth)acrylate , isostearyl (meth)acrylate, lauryl (meth)acrylate, hexyl (meth)acrylate, and isodecyl (meth)acrylate, but are not limited thereto. Another example is adding particles having a desired refractive index within a range that does not impair inkjet ejection properties.
Furthermore, the refractive index of the photopolymerizable monomer constituting the sealing composition can be determined using an Abbe refractometer, and the refractive index (nd25) of the D line at 25°C is 1.43 to 1.50. is preferred.
＜消衰係数＞
　本発明の封止用組成物は、窒素環境下で波長３９５ｎｍの紫外線を１．５Ｊｃｍ－２照射して硬化したとき、形成される封止膜の、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である。より好ましくは、１２５×１０－５～２００×１０－５の範囲内である。 <Extinction coefficient>
When the sealing composition of the present invention is cured by irradiating 1.5 Jcm -2 of ultraviolet light with a wavelength of 395 nm in a nitrogen environment, the extinction coefficient of the sealing film formed at a wavelength of 380 nm is 50 × 10 -5 to 200×10 -5 . More preferably, it is within the range of 125×10 −5 to 200×10 −5 .
　前記消衰係数は、前記屈折率と同様にして、分光エリプソメトリー（ＵＶＳＥＬ／ＦＵＶ－ＦＧＭＳ、堀場ＪＹＯＢＩＮ－ＹＶＯＮ社製）により求めた。具体的には、２５０ｎｍ～８００ｎｍにおける消衰係数を測定し、３８０ｎｍにおける消衰係数ｋを求めた。 The extinction coefficient was determined by spectroscopic ellipsometry (UVSEL/FUV-FGMS, manufactured by Horiba JYOBIN-YVON) in the same manner as the refractive index. Specifically, the extinction coefficient at 250 nm to 800 nm was measured, and the extinction coefficient k at 380 nm was determined.
　前記消衰係数を５０×１０－５～２００×１０－５の範囲内とするための手段としては、例えば、モノマーの構造にヘテロ原子数が少ない構造、芳香族炭化水素が少ない構造、多重結合が少ない構造を用いることが挙げられる。また、有機ＥＬの発光特性を損なわない範囲で、色素を添加すること等が挙げられる。 Examples of means for making the extinction coefficient within the range of 50×10 −5 to 200×10 −5 include a monomer structure with a small number of heteroatoms, a structure with a small number of aromatic hydrocarbons, and multiple bonds. One example is to use a structure with a small amount of Another example is adding a dye within a range that does not impair the light emitting characteristics of the organic EL.
　また、前記屈折率ｎと前記消衰係数ｋが、下記の関係を満たすことが、折り曲げた状態での信頼性試験後の見栄え、折り曲げ信頼性試験後の発光効率の点で好ましい。
　ｋ／ｎ≧１００×１０－５ Further, it is preferable that the refractive index n and the extinction coefficient k satisfy the following relationship in terms of appearance after a reliability test in a folded state and luminous efficiency after a bending reliability test.
k/n≧100× 10-5
［電子デバイス封止用組成物の組成］
　本発明の電子デバイス封止用組成物は、光重合性モノマー及び光重合開始剤を含有する。
　光重合性モノマーとしては、（メタ）アクリレートを含有する。 [Composition of electronic device encapsulation composition]
The composition for encapsulating an electronic device of the present invention contains a photopolymerizable monomer and a photopolymerization initiator.
The photopolymerizable monomer contains (meth)acrylate.
　本明細書において、「（メタ）アクリレート」とは、アクリレート及びメタクリレートの少なくとも一方を意味する。
　また、本発明における「電子デバイス」とは、電子のもつ運動エネルギー、位置エネルギーなどを利用して電気信号の発生、増幅、変換、又は制御などを行う素子をいう。例えば、発光ダイオード素子、有機エレクトロルミネッセンス素子、光電変換素子及びトランジスターなどの能動素子が挙げられる。また、本発明においては、他からの働きかけに対し、「抵抗する」「蓄える」などの受け身的な仕事をする受動素子、例えば、抵抗器・コンデンサーなども電子デバイスに含める。
　したがって、本発明の封止用組成物は、前記した電子デバイスを封止するための封止膜を形成するために用いられる。 As used herein, "(meth)acrylate" means at least one of acrylate and methacrylate.
Furthermore, the term "electronic device" in the present invention refers to an element that generates, amplifies, converts, or controls electrical signals by utilizing the kinetic energy, potential energy, etc. of electrons. Examples include active devices such as light emitting diode devices, organic electroluminescent devices, photoelectric conversion devices, and transistors. Furthermore, in the present invention, electronic devices include passive elements such as resistors and capacitors that perform passive work such as "resistance" and "storage" in response to actions from others.
Therefore, the sealing composition of the present invention is used to form a sealing film for sealing the electronic device described above.
＜光重合性モノマー＞
　「光重合性モノマー」とは、それ自体又は光重合開始剤が光を吸収し、活性なイオン又はラジカルを生成することによって重合（硬化）反応を行える光重合性モノマー（「光硬化性モノマー」ともいう。）を意味する。
　前記光重合性モノマーとしては、シリコン（Ｓｉ）を含まない非－シリコン系モノマーを使用してもよく、例えば、Ｃ、Ｈ、Ｏ、Ｎ又はＳから選ばれる元素のみからなるモノマーであってもよいが、これに限定されない。光重合性モノマーは、通常の合成方法で合成して使用してもよく、商業的に販売する製品を購入して使用してもよい。
　前記光重合性モノマーとしては、下記の芳香族炭化水素基を有さない光重合性モノマー（Ａ）や、芳香族炭化水素基を有する光重合性モノマー（Ｂ）等が挙げられ、前記したように封止膜としたときに、前記屈折率及び消衰係数が前記した範囲を満たすように、これらの光重合性モノマーから適宜選択する。 <Photopolymerizable monomer>
"Photopolymerizable monomer" refers to a photopolymerizable monomer ("photocurable monomer") that can perform a polymerization (curing) reaction by itself or a photopolymerization initiator absorbing light and producing active ions or radicals. Also referred to as ).
As the photopolymerizable monomer, a non-silicon monomer that does not contain silicon (Si) may be used, for example, a monomer consisting only of elements selected from C, H, O, N, or S. Good, but not limited to this. The photopolymerizable monomer may be synthesized and used by a conventional synthesis method, or a commercially available product may be purchased and used.
Examples of the photopolymerizable monomer include the following photopolymerizable monomers (A) that do not have an aromatic hydrocarbon group, and photopolymerizable monomers (B) that have an aromatic hydrocarbon group, as described above. The photopolymerizable monomer is appropriately selected from these photopolymerizable monomers so that, when used as a sealing film, the refractive index and extinction coefficient satisfy the above ranges.
　（平均二重結合数）
　本発明の電子デバイス封止用組成物に含有される前記光重合性モノマーの平均二重結合数は、５以下であることが、折り曲げた状態での信頼性試験後の見栄え、折り曲げ信頼性試験後の発光効率の点で好ましい。 (Average number of double bonds)
The average number of double bonds of the photopolymerizable monomer contained in the composition for encapsulating an electronic device of the present invention is 5 or less. This is preferable in terms of later luminous efficiency.
　前記平均二重結合数は、各モノマーに含まれる二重結合の数をｄ、全モノマーの合計質量を１にしたときの、各モノマーの質量比率ｗを用いて以下のように計算することができる。
　平均二重結合数＝ｄ１×ｗ１＋ｄ２×ｗ２＋・・・
　（ｄ及びｗの添え字はモノマーの番号を表す。） The average number of double bonds can be calculated as follows using the mass ratio w of each monomer when the number of double bonds contained in each monomer is d and the total mass of all monomers is 1. can.
Average number of double bonds = d1 x w1 + d2 x w2 +...
(The suffixes d and w represent the monomer numbers.)
　（ＨＯＭＯ及びＬＵＭＯのエネルギー準位）
　本発明の封止用組成物に含有される前記光重合性モノマーの最高被占分子軌道（ＨＯＭＯ）のエネルギー準位の平均値と、及び最低空分子軌道（ＬＵＭＯ）のエネルギー準位の平均値が、下記の関係を満たすことが、折り曲げた状態での信頼性試験後の見栄え、折り曲げ信頼性試験後の発光効率、比誘電率の点で好ましい。
　５．９ｅＶ≦ＬＵＭＯ－ＨＯＭＯ≦６．５ｅＶ
　ここで、前記最高被占分子軌道（ＨＯＭＯ）のエネルギー準位の平均値と、最低空分子軌道（ＬＵＭＯ）のエネルギー準位の平均値は、以下の式によって算出する。
　ＨＯＭＯの平均値＝ＨＯＭＯ１×ｗ１＋ＨＯＭＯ２×ｗ２＋・・・
　ＬＵＭＯの平均値＝ＬＵＭＯ１×ｗ１＋ＬＵＭＯ２×ｗ２＋・・・
　前記式において、ｗは前記した各モノマーの質量比率を表す。また、ｗ、ＨＯＭＯ及びＬＵＭＯの添え字はモノマーの番号を表す。 (HOMO and LUMO energy levels)
The average value of the energy level of the highest occupied molecular orbital (HOMO) and the average value of the energy level of the lowest unoccupied molecular orbital (LUMO) of the photopolymerizable monomer contained in the encapsulating composition of the present invention. However, it is preferable that the following relationship be satisfied in terms of the appearance after the reliability test in a folded state, the luminous efficiency after the bending reliability test, and the dielectric constant.
5.9eV≦LUMO-HOMO≦6.5eV
Here, the average value of the energy level of the highest occupied molecular orbital (HOMO) and the average value of the energy level of the lowest unoccupied molecular orbital (LUMO) are calculated by the following formula.
Average value of HOMO=HOMO1×w1+HOMO2×w2+...
Average value of LUMO = LUMO1×w1+LUMO2×w2+...
In the above formula, w represents the mass ratio of each monomer described above. Furthermore, the subscripts w, HOMO, and LUMO represent the monomer numbers.
　ＨＯＭＯとＬＵＭＯは、化学構造情報コンピューターソフトウエアを用いることによって計算できる。計算ソフトとしては、例えば、ＨＵＬＩＮＫＳ社製の量子化学計算プログラム「Ｇａｕｓｓｉａｎ　シリーズ」等が挙げられる。
　前記ソフトウェアを用いて得られた各モノマーのＨＯＭＯとＬＵＭＯの値から、前記ＨＯＭＯの平均値及び前記ＬＵＭＯの平均値を算出し、これらＨＯＭＯの平均値及びＬＵＭＯの平均値のギャップ（Ｇａｐ）を計算した。計算においては、汎関数としてＢ３ＬＹＰを用いた。
　Ｇａｐ（単位：ｅＶ）＝ＬＵＭＯの平均値－ＨＯＭＯの平均値
　前記Ｇａｐを５．９ｅＶ≦ＬＵＭＯ－ＨＯＭＯ≦６．５ｅＶとするための手段としては、モノマーの構造にヘテロ原子数が少ない構造、脂環式炭化水素の構造、鎖状炭化水素の構造を用いること等が挙げられる。 HOMO and LUMO can be calculated by using chemical structure information computer software. Examples of the calculation software include the quantum chemical calculation program "Gaussian series" manufactured by HULINKS.
From the HOMO and LUMO values of each monomer obtained using the software, calculate the average HOMO value and the average LUMO value, and calculate the gap between the average HOMO value and the average LUMO value. did. In the calculation, B3LYP was used as a functional.
Gap (unit: eV) = Average value of LUMO - Average value of HOMO As a means for making the above Gap 5.9eV≦LUMO-HOMO≦6.5eV, monomer structures with a small number of heteroatoms, fats, etc. Examples include using a cyclic hydrocarbon structure and a chain hydrocarbon structure.
＜芳香族炭化水素基を有さない光重合性モノマー（Ａ）＞
　前記芳香族炭化水素基を有さない光重合性モノマー（Ａ）（以下、単に「光重合性モノマー（Ａ）」ともいう。）は、芳香族炭化水素基を含んでおらず、光硬化官能基（光重合性官能基）として、ビニル基、アクリル基、及びメタクリル基のうちの一つ以上を１～２０個、具体的に１～６個有するモノマーを含んでもよく、例えば、１～３個、１～２個、１個、又は２個含んでもよい。 <Photopolymerizable monomer (A) having no aromatic hydrocarbon group>
The photopolymerizable monomer (A) that does not have an aromatic hydrocarbon group (hereinafter also simply referred to as "photopolymerizable monomer (A)") does not contain an aromatic hydrocarbon group and has no photocurable functionality. The group (photopolymerizable functional group) may include a monomer having 1 to 20, specifically 1 to 6, one or more of vinyl groups, acrylic groups, and methacrylic groups, for example, 1 to 3 It may contain 1 to 2, 1, or 2.
　本発明において、前記光重合性モノマー（Ａ）の重量平均分子量は、１００～５００ｇ／ｍｏｌの範囲内であってもよく、１３０～４００ｇ／ｍｏｌの範囲内であってもよく、２００～３００ｇ／ｍｏｌの範囲内であってもよい。前記モノマーの重量平均分子量の範囲内とすることにより、工程的により有利な効果を示すことができる。 In the present invention, the weight average molecular weight of the photopolymerizable monomer (A) may be within the range of 100 to 500 g/mol, may be within the range of 130 to 400 g/mol, or may be within the range of 200 to 300 g/mol. It may be within the range of mol. By keeping the weight average molecular weight of the monomer within the range, more advantageous effects can be exhibited in terms of the process.
　前記光重合性モノマー（Ａ）は、光硬化官能基を有する単官能モノマー、多官能モノマー、又はこれらの混合物を含んでもよい。 The photopolymerizable monomer (A) may include a monofunctional monomer having a photocurable functional group, a polyfunctional monomer, or a mixture thereof.
　具体的に、前記光重合性モノマー（Ａ）は、（メタ）アクリレートモノマーであってもよく、炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、ヒドロキシ基及び炭素数１～２０のアルキル基を有する不飽和カルボン酸エステル；炭素数１～２０のアミノアルキル基を有する不飽和カルボン酸エステル；炭素数１～２０の飽和又は不飽和カルボン酸のビニルエステル；シアン化ビニル化合物；不飽和アミド化合物；モノアルコール又は多価アルコールの単官能又は多官能（メタ）アクリレートなどになってもよい。
　前記「多価アルコール」は、ヒドロキシ基を２個以上有するアルコールであって、ヒドロキシ基を２個～２０個、好ましくは２個～１０個、より好ましくは２個～６個有するアルコールを意味し得る。 Specifically, the photopolymerizable monomer (A) may be a (meth)acrylate monomer, and may include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a hydroxy group, and a hydroxyl group having 1 to 20 carbon atoms. Unsaturated carboxylic acid esters having ~20 alkyl groups; Unsaturated carboxylic acid esters having aminoalkyl groups having 1 to 20 carbon atoms; Vinyl esters of saturated or unsaturated carboxylic acids having 1 to 20 carbon atoms; Vinyl cyanide compounds ; unsaturated amide compound; monofunctional or polyfunctional (meth)acrylate of monoalcohol or polyhydric alcohol.
The above-mentioned "polyhydric alcohol" means an alcohol having two or more hydroxy groups, preferably 2 to 20, preferably 2 to 10, more preferably 2 to 6 hydroxy groups. obtain.
　一例において、光重合性モノマー（Ａ）のうち、芳香族炭化水素基を有さない（メタ）アクリレートモノマーは、置換又は非置換のＣ１～Ｃ２０（炭素数１～２０）のアルキル基、置換又は非置換のＣ１～Ｃ２０のアルキルシリル基、置換又は非置換のＣ３～Ｃ２０のシクロアルキル基、置換又は非置換のＣ１～Ｃ２０のアルキレン基、アミン基、エチレンオキシド基などを有するモノ（メタ）アクリレート、ジ（メタ）アクリレート、トリ（メタ）アクリレート、テトラ（メタ）アクリレートなどであってもよい。 In one example, among the photopolymerizable monomers (A), the (meth)acrylate monomer that does not have an aromatic hydrocarbon group is a substituted or unsubstituted C1 to C20 (1 to 20 carbon atoms) alkyl group, a substituted or Mono(meth)acrylates having an unsubstituted C1 to C20 alkylsilyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkylene group, an amine group, an ethylene oxide group, etc. Di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate, etc. may be used.
　具体的に、芳香族炭化水素基を有さない（メタ）アクリレートモノマーは、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デカニル（メタ）アクリレート、ウンデカニル（メタ）アクリレート、ドデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートなどの（メタ）アクリル酸エステルを含む不飽和カルボン酸エステル；２－アミノエチル（メタ）アクリレート、２－ジメチルアミノエチル（メタ）アクリレートなどの不飽和カルボン酸アミノアルキルエステル；ビニルアセテートなどの飽和又は不飽和カルボン酸ビニルエステル；（メタ）アクリロニトリルなどのシアン化ビニル化合物；（メタ）アクリルアミドなどの不飽和アミド化合物；エチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、オクタンジオールジ（メタ）アクリレート、ノナンジオールジ（メタ）アクリレート、デカンジオールジ（メタ）アクリレート、ウンデカンジオールジ（メタ）アクリレート、ドデカンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート又はこれらの混合物を含んでもよいが、これに限定されない。 Specifically, (meth)acrylate monomers having no aromatic hydrocarbon group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy Butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decanyl (meth)acrylate, undecanyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. Unsaturated carboxylic acid esters including meth)acrylic acid esters; unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; saturated or unsaturated carboxylic acid esters such as vinyl acetate Acid vinyl ester; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth) Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, Undecanediol di(meth)acrylate, dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di Pentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate or mixtures thereof. Good, but not limited to this.
　本発明の一例において、前記光重合性モノマー（Ａ）は、芳香族基を含まない非－芳香族系であって、炭素数１～２０のアルキル基を有するモノ（メタ）アクリレート、アミン基を有するモノ（メタ）アクリレート、置換又は非置換の炭素数１～２０のアルキレン基を有するジ（メタ）アクリレート、エチレンオキシド基を有するジ（メタ）アクリレート、エチレンオキシド基を有するトリ（メタ）アクリレート、環状炭化アルキル基を有するモノ（メタ）アクリレート及びジ（メタ）アクリレートのうち少なくともいずれかを含んでもよい。 In one example of the present invention, the photopolymerizable monomer (A) is a non-aromatic type that does not contain an aromatic group, and is a mono(meth)acrylate having an alkyl group having 1 to 20 carbon atoms, or an amine group. mono(meth)acrylate with, di(meth)acrylate with substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, di(meth)acrylate with ethylene oxide group, tri(meth)acrylate with ethylene oxide group, cyclic carbonization It may contain at least one of mono(meth)acrylate and di(meth)acrylate having an alkyl group.
　置換又は非置換の炭素数１～２０のアルキル基を有するモノ（メタ）アクリレートは、具体的に、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ノナデシル（メタ）アクリレート、アラキジル（メタ）アクリレート又はこれらの混合物であってもよいが、これに限定されない。 Specifically, mono(meth)acrylates having a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include decyl(meth)acrylate, undecyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, It may be tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, arachidyl (meth)acrylate or a mixture thereof. However, it is not limited to this.
　アミン基を有するモノ（メタ）アクリレートは、２－アミノエチル（メタ）アクリレート、２－ジメチルアミノエチル（メタ）アクリレート又はこれらの混合物であってもよいが、これに限定されない。 The mono(meth)acrylate having an amine group may be, but is not limited to, 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, or a mixture thereof.
　置換又は非置換の炭素数１～２０のアルキレン基を有するジ（メタ）アクリレートは、例えば、炭素数１～２０のアルキレン基を有するジ（メタ）アクリレートであってもよく、置換又は非置換の長鎖のアルキレン基を含む非－シリコン系ジ（メタ）アクリレートであってもよい。
　置換又は非置換の炭素数１～２０のアルキレン基を有するジ（メタ）アクリレートは、例えば、オクタンジオールジ（メタ）アクリレート、ノナンジオールジ（メタ）アクリレート、デカンジオールジ（メタ）アクリレート、ウンデカンジオールジ（メタ）アクリレート、ドデカンジオールジ（メタ）アクリレート又はこれらの混合物であってもよいが、これに限定されない。
　前記置換又は非置換の炭素数１～２０のアルキレン基を有する（メタ）アクリレートを含む場合、本発明の封止用組成物は、光硬化率がさらに向上し、粘度が低くなり得る。 The di(meth)acrylate having a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms may be, for example, a di(meth)acrylate having an alkylene group having 1 to 20 carbon atoms; It may also be a non-silicon di(meth)acrylate containing a long-chain alkylene group.
Di(meth)acrylates having a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms include, for example, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, undecanediol It may be, but is not limited to, di(meth)acrylate, dodecanediol di(meth)acrylate, or a mixture thereof.
When containing the substituted or unsubstituted (meth)acrylate having an alkylene group having 1 to 20 carbon atoms, the sealing composition of the present invention can further improve the photocuring rate and lower the viscosity.
　エチレンオキシド基を有するジ（メタ）アクリレート又はトリ（メタ）アクリレートは、具体的に、エチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート又はこれらの混合物であってもよいが、これに限定されない。 Specifically, the di(meth)acrylate or tri(meth)acrylate having an ethylene oxide group is ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, or a mixture thereof. may be used, but is not limited to this.
　環状炭化アルキル基を有するモノ（メタ）アクリレート及びジ（メタ）アクリレートは、具体的に、イソボニル（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレ－ト、ジシクロペンテニルオキシエチル（メタ）アクリレ－ト、ジシクロペンテニル（メタ）アクリレ－トであってもよいが、これに限定されない。 Specifically, mono(meth)acrylates and di(meth)acrylates having a cyclic carbonized alkyl group include isobonyl(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and dicyclopentanyl(meth)acrylate. , dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentenyl (meth)acrylate, but are not limited thereto.
　前記光重合性モノマー（Ａ）モノマーは、光重合性モノマー（光重合性モノマー（Ａ）及び光重合性モノマー（Ｂ））の総質量に対して５５～９５質量％の範囲内で含有されていることが好ましく、６０～９０質量％の範囲内で含有されていることがより好ましい。前記範囲内とすることにより、本発明の封止用組成物の粘度が電子デバイスの封止膜形成に適切となる。 The photopolymerizable monomer (A) monomer is contained within the range of 55 to 95% by mass based on the total mass of the photopolymerizable monomers (photopolymerizable monomer (A) and photopolymerizable monomer (B)). The content is preferably in the range of 60 to 90% by mass. By setting the viscosity within the above range, the viscosity of the sealing composition of the present invention becomes suitable for forming a sealing film of an electronic device.
＜芳香族炭化水素基を有する光重合性モノマー（Ｂ）＞
　前記芳香族炭化水素基を有する光重合性モノマー（Ｂ）（以下、単に「光重合性モノマー（Ｂ）」ともいう。）が、下記一般式（１）で表される構造を有する２個以上のフェニル基及びヘテロ原子を含み、かつ、前記光重合性モノマー（Ｂ）が、少なくともモノ（メタ）アクリレート又はジ（メタ）アクリレートを含む。
Figure JPOXMLDOC01-appb-C000001
 <Photopolymerizable monomer (B) having an aromatic hydrocarbon group>
Two or more photopolymerizable monomers (B) having an aromatic hydrocarbon group (hereinafter also simply referred to as "photopolymerizable monomers (B)") have a structure represented by the following general formula (1). phenyl group and hetero atom, and the photopolymerizable monomer (B) contains at least mono(meth)acrylate or di(meth)acrylate.
Figure JPOXMLDOC01-appb-C000001
［前記一般式（１）において、Ｐは、置換又は非置換の２個以上のフェニル基を含む炭化水素基、又は置換又は非置換の２個以上のフェニル基を含むヘテロ原子含有炭化水素基を表す。Ｚ１及びＺ２は、それぞれ独立的に下記一般式（２）で表される構造を有する。ａ及びｂは、それぞれ０～２の整数であり、ａ＋ｂは、１～４の整数である。］ [In the general formula (1), P represents a hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or a heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups. represent. Z 1 and Z 2 each independently have a structure represented by the following general formula (2). a and b are each an integer of 0 to 2, and a+b is an integer of 1 to 4. ]
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
［前記一般式（２）において、＊は、Ｐの炭素に対する連結部である。Ｘは、単一結合、Ｏ又はＳを表す。Ｙは、置換又は非置換の炭素数１～１０の直鎖状アルキレン基、又は置換又は非置換の炭素数１～２０のアルコキシ基を表す。Ｒ１は、水素原子又は炭素数１～５のアルキル基を表す。ｃは、０又は１の整数である。］ [In the general formula (2) above, * is a linking portion of P to carbon. X represents a single bond, O or S. Y represents a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. c is an integer of 0 or 1. ]
　前記一般式（１）において、Ｐは、置換又は非置換の２個以上のフェニル基を含む炭化水素基、又は置換又は非置換の２個以上のフェニル基を含むヘテロ原子含有炭化水素基を表す。
　前記置換又は非置換の２個以上のフェニル基を含む炭化水素基、又は置換又は非置換の２個以上のフェニル基を含むヘテロ原子含有炭化水素基は、置換又は非置換の２個以上のフェニル基が縮合されず、単一結合、酸素原子、硫黄原子、置換又は非置換の炭素数１～５のアルキル基、ヘテロ原子に置換又は非置換された炭素数３～６のアルキレン基、エテニレン基、エチニレン基又はカルボニル基によって連結されたものを意味する。 In the general formula (1), P represents a hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or a heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups. .
The hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or the heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, is a substituted or unsubstituted hydrocarbon group containing two or more phenyl groups. Groups that are not fused, a single bond, an oxygen atom, a sulfur atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, an alkylene group having 3 to 6 carbon atoms substituted or unsubstituted with a hetero atom, an ethenylene group , means linked by an ethynylene group or a carbonyl group.
　例えば、前記２個以上のフェニル基を含む炭化水素基又は２個以上のフェニル基を含むヘテロ原子含有炭化水素基は、置換又は非置換のビフェニル基、置換又は非置換のトリフェニルメチル基、置換又は非置換のターフェニル基、置換又は非置換のビフェニレン基、置換又は非置換のターフェニレン基、置換又は非置換のクォーターフェニレン基、置換又は非置換の２－フェニル－２－（フェニルチオ）エチル基、置換又は非置換の２，２－ジフェニルプロパン基、置換又は非置換のジフェニルメタン基、置換又は非置換のクミルフェニル基、置換又は非置換のビスフェノールＦ基、置換又は非置換のビスフェノールＡ基、置換又は非置換のビフェニルオキシ基、置換又は非置換のターフェニルオキシ基、置換又は非置換のクォーターフェニルオキシ基、置換又は非置換のキンキフェニルオキシ基及びこれらの構造異性質体などを含んでもよいが、これに限定されない。 For example, the hydrocarbon group containing two or more phenyl groups or the heteroatom-containing hydrocarbon group containing two or more phenyl groups may include a substituted or unsubstituted biphenyl group, a substituted or unsubstituted triphenylmethyl group, or a substituted or unsubstituted triphenylmethyl group. or unsubstituted terphenyl group, substituted or unsubstituted biphenylene group, substituted or unsubstituted terphenylene group, substituted or unsubstituted quaterphenylene group, substituted or unsubstituted 2-phenyl-2-(phenylthio)ethyl group , substituted or unsubstituted 2,2-diphenylpropane group, substituted or unsubstituted diphenylmethane group, substituted or unsubstituted cumylphenyl group, substituted or unsubstituted bisphenol F group, substituted or unsubstituted bisphenol A group, substituted or It may include an unsubstituted biphenyloxy group, a substituted or unsubstituted terphenyloxy group, a substituted or unsubstituted quarterphenyloxy group, a substituted or unsubstituted quinchyphenyloxy group, and structural isomers thereof, It is not limited to this.
　前記置換又は非置換の２個以上のフェニル基を有するモノマーは、モノ（メタ）アクリレート、ジ（メタ）アクリレート又はこれらの混合物であってもよく、その例としては、４－（メタ）アクリルオキシ－２－ヒドロキシベンゾフェノン、エチル－３，３－ジフェニル（メタ）アクリレート、ベンゾイルオキシフェニル（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、エトキシ化ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＦジ（メタ）アクリレート、エトキシ化ビスフェノールＦジ（メタ）アクリレート、４－クミルフェノキシエチルアクリレート、エトキシ化ビスフェニルフルオレンジアクリレート、２－フェニルフェノキシエチル（メタ）アクリレート、２，２’－フェニルフェノキシエチルジ（メタ）アクリレート、２－フェニルフェノキシプロピル（メタ）アクリレート、２，２’－フェニルフェノキシプロピルジ（メタ）アクリレート、２－フェニルフェノキシブチル（メタ）アクリレート、２，２’－フェニルフェノキシブチルジ（メタ）アクリレート、２－（３－フェニルフェニル）エチル（メタ）アクリレート、２－（４－ベンジルフェニル）エチル（メタ）アクリレート、２－フェニル－２－（フェニルチオ）エチル（メタ）アクリレート、２－（トリフェニルメチルオキシ）エチル（メタ）アクリレート、４－（トリフェニルメチルオキシ）ブチル（メタ）アクリレート、３－（ビフェニル－２－イルオキシ）ブチル（メタ）アクリレート、２－（ビフェニル－２－イルオキシ）ブチル（メタ）アクリレート、４－（ビフェニル－２－イルオキシ）プロピル（メタ）アクリレート、３－（ビフェニル－２－イルオキシ）プロピル（メタ）アクリレート、２－（ビフェニル－２－イルオキシ）プロピル（メタ）アクリレート、４－（ビフェニル－２－イルオキシ）エチル（メタ）アクリレート、３－（ビフェニル－２－イルオキシ）エチル（メタ）アクリレート、２－（４－ベンジルフェニル）エチル（メタ）アクリレート、４，４’－ジ（アクリロイルオキシメチル）ビフェニル、２，２’－ジ（２－アクリロイルオキシエトキシ）ビフェニル、これらの構造異性質体又はこれらの混合物を含んでもよいが、これに制限されるものではない。
　また、本発明で言及した（メタ）アクリレートは一例に過ぎなく、これに限定されるものではない。
　さらに、本発明は、構造異性質体関係にあるアクリレートを全て含む。例えば、本発明の一例として、２，２’－フェニルフェノキシエチルジ（メタ）アクリレートのみが言及されているとしても、本発明は、この構造異性質体に該当する３，２’－フェニルフェノキシエチルジ（メタ）アクリレート、３，３’－フェニルフェノキシエチルジ（メタ）アクリレートなどを全て含む。 The substituted or unsubstituted monomer having two or more phenyl groups may be mono(meth)acrylate, di(meth)acrylate, or a mixture thereof; examples thereof include 4-(meth)acryloxy -2-hydroxybenzophenone, ethyl-3,3-diphenyl (meth)acrylate, benzoyloxyphenyl (meth)acrylate, bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate Acrylate, ethoxylated bisphenol F di(meth)acrylate, 4-cumylphenoxyethyl acrylate, ethoxylated bisphenylfluorenediacrylate, 2-phenylphenoxyethyl (meth)acrylate, 2,2'-phenylphenoxyethyl di(meth) Acrylate, 2-phenylphenoxypropyl (meth)acrylate, 2,2'-phenylphenoxypropyl di(meth)acrylate, 2-phenylphenoxybutyl (meth)acrylate, 2,2'-phenylphenoxybutyl di(meth)acrylate, 2-(3-phenylphenyl)ethyl (meth)acrylate, 2-(4-benzylphenyl)ethyl (meth)acrylate, 2-phenyl-2-(phenylthio)ethyl (meth)acrylate, 2-(triphenylmethyloxy) ) Ethyl (meth)acrylate, 4-(triphenylmethyloxy)butyl (meth)acrylate, 3-(biphenyl-2-yloxy)butyl (meth)acrylate, 2-(biphenyl-2-yloxy)butyl (meth)acrylate , 4-(biphenyl-2-yloxy)propyl (meth)acrylate, 3-(biphenyl-2-yloxy)propyl (meth)acrylate, 2-(biphenyl-2-yloxy)propyl (meth)acrylate, 4-(biphenyl) -2-yloxy)ethyl (meth)acrylate, 3-(biphenyl-2-yloxy)ethyl (meth)acrylate, 2-(4-benzylphenyl)ethyl (meth)acrylate, 4,4'-di(acryloyloxymethyl) ) biphenyl, 2,2'-di(2-acryloyloxyethoxy)biphenyl, structural isomers thereof, or mixtures thereof, but are not limited thereto.
Moreover, the (meth)acrylate mentioned in the present invention is only an example, and is not limited thereto.
Furthermore, the present invention includes all acrylates that are in structural isomer relationship. For example, even if only 2,2'-phenylphenoxyethyl di(meth)acrylate is mentioned as an example of the present invention, the present invention also covers 3,2'-phenylphenoxyethyl di(meth)acrylate, which corresponds to this structural isomer. Includes di(meth)acrylate, 3,3'-phenylphenoxyethyl di(meth)acrylate, etc.
　本発明の一例において、２個以上のフェニル基を有するモノマーは、下記一般式（４）で表されるモノ（メタ）アクリレートであってもよい。 In one example of the present invention, the monomer having two or more phenyl groups may be a mono(meth)acrylate represented by the following general formula (4).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　前記一般式（４）において、Ｒ２は、水素又はメチル基で、Ｒ３は、置換又は非置換の炭素数１～１０の直鎖状アルキレン基、又は置換又は非置換の炭素数１～２０のアルコキシ基で、Ｒ４は、置換又は非置換の２個以上のフェニル基を含む炭化水素基、又は置換又は非置換の２個以上のフェニル基を含むヘテロ原子含有炭化水素基である。 In the general formula (4), R 2 is hydrogen or a methyl group, and R 3 is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted linear alkylene group having 1 to 20 carbon atoms. In the alkoxy group, R 4 is a hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or a heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups.
　例えば、前記置換又は非置換の２個以上のフェニル基を含む炭化水素基、又は置換又は非置換の２個以上のフェニル基を含むヘテロ原子含有炭化水素基は、置換又は非置換の２個以上のフェニル基が縮合されず、単一結合、酸素原子、硫黄原子、置換又は非置換の炭素数１～３のアルキル基、ヘテロ原子に置換又は非置換された炭素数３～６のアルキレン基、エテニレン基、エチニレン基又はカルボニル基によって連結されたものを意味する。
　例えば、前記置換又は非置換の２個以上のフェニル基を含む炭化水素基、又は置換又は非置換の２個以上のフェニル基を含むヘテロ原子含有炭化水素基は、置換又は非置換のビフェニル基、置換又は非置換のトリフェニルメチル基、置換又は非置換のターフェニル基、置換又は非置換のビフェニレン基、置換又は非置換のターフェニレン基、置換又は非置換のクォーターフェニレン基、置換又は非置換の２－フェニル－２－（フェニルチオ）エチル基、置換又は非置換の２，２－ジフェニルプロパン基、置換又は非置換のジフェニルメタン基、置換又は非置換のクミルフェニル基、置換又は非置換のビスフェノールＦ基、置換又は非置換のビスフェノールＡ基、置換又は非置換のビフェニルオキシ基、置換又は非置換のターフェニルオキシ基、置換又は非置換のクォーターフェニルオキシ基、置換又は非置換のキンキフェニルオキシ基などを含んでもよいが、これに限定されない。 For example, the hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or the heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, includes two or more substituted or unsubstituted phenyl groups. A phenyl group is not fused, a single bond, an oxygen atom, a sulfur atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, an alkylene group having 3 to 6 carbon atoms substituted or unsubstituted with a hetero atom, It means a group connected by an ethenylene group, an ethynylene group, or a carbonyl group.
For example, the hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or the heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, is a substituted or unsubstituted biphenyl group, Substituted or unsubstituted triphenylmethyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted biphenylene group, substituted or unsubstituted terphenylene group, substituted or unsubstituted quarterphenylene group, substituted or unsubstituted 2-phenyl-2-(phenylthio)ethyl group, substituted or unsubstituted 2,2-diphenylpropane group, substituted or unsubstituted diphenylmethane group, substituted or unsubstituted cumylphenyl group, substituted or unsubstituted bisphenol F group, Substituted or unsubstituted bisphenol A group, substituted or unsubstituted biphenyloxy group, substituted or unsubstituted terphenyloxy group, substituted or unsubstituted quarterphenyloxy group, substituted or unsubstituted quinkyphenyloxy group, etc. However, it is not limited to this.
　本発明の一例において、２個以上のフェニル基を有するモノマーは、下記の一般式（５）で表されるジ（メタ）アクリレートであってもよい。 In one example of the present invention, the monomer having two or more phenyl groups may be a di(meth)acrylate represented by the following general formula (5).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　前記一般式（５）において、Ｒ５、Ｒ９は、それぞれ独立的に水素又はメチル基で、Ｒ６、Ｒ８は、それぞれ独立的に置換又は非置換の炭素数１～１０の直鎖状アルキレン基、又は置換又は非置換の炭素数１～２０のアルコキシ基で、Ｒ７は、置換又は非置換の２個以上のフェニル基を含む炭化水素基、又は置換又は非置換の２個以上のフェニル基を含むヘテロ原子含有炭化水素基である。 In the general formula (5), R 5 and R 9 are each independently hydrogen or a methyl group, and R 6 and R 8 are each independently a substituted or unsubstituted linear chain having 1 to 10 carbon atoms. An alkylene group or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and R 7 is a hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or a substituted or unsubstituted two or more phenyl group. It is a heteroatom-containing hydrocarbon group including a phenyl group.
　例えば、前記置換又は非置換の２個以上のフェニル基を含む炭化水素基、又は置換又は非置換の２個以上のフェニル基を含むヘテロ原子含有炭化水素基は、置換又は非置換の２個以上のフェニル基が縮合されず、単一結合、酸素原子、硫黄原子、置換又は非置換の炭素数１～４のアルキル基、ヘテロ原子に置換又は非置換された炭素数３～６のアルキレン基、エテニレン基、エチニレン基又はカルボニル基によって連結されたものを意味する。
　例えば、前記炭化水素基は、置換又は非置換のビフェニレン基、置換又は非置換のトリフェニルメチレン基、置換又は非置換のターフェニレン基、置換又は非置換のクォーターフェニレン基、２－フェニル－２－（フェニルチオ）エチレン基、２，２－ジフェニルプロピレン基、ジフェニルメチレン基などを含んでもよいが、これに限定されない。 For example, the hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, or the heteroatom-containing hydrocarbon group containing two or more substituted or unsubstituted phenyl groups, includes two or more substituted or unsubstituted phenyl groups. A phenyl group is not fused, a single bond, an oxygen atom, a sulfur atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, an alkylene group having 3 to 6 carbon atoms substituted or unsubstituted with a hetero atom, It means a group connected by an ethenylene group, an ethynylene group, or a carbonyl group.
For example, the hydrocarbon group is a substituted or unsubstituted biphenylene group, a substituted or unsubstituted triphenylmethylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quarterphenylene group, a 2-phenyl-2- It may include, but is not limited to, a (phenylthio)ethylene group, a 2,2-diphenylpropylene group, a diphenylmethylene group, and the like.
　前記一般式（１）において、ａ、ｂは、それぞれ０～２の整数で、ａ＋ｂは、１～４の整数であり、一例において、ａ＋ｂは、１又は２の整数である。 In the general formula (1), a and b are each an integer of 0 to 2, a+b is an integer of 1 to 4, and in one example, a+b is an integer of 1 or 2.
　前記置換又は非置換の２個以上のフェニル基を有するモノマーの重量平均分子量は、１００～１０００ｇ／ｍｏｌの範囲内が好ましく、１３０～７００ｇ／ｍｏｌの範囲内であることがより好ましく、１５０～６００ｇ／ｍｏｌの範囲内であることが特に好ましい。
　前記範囲内とすることにより、透過率により優れた封止膜を提供することができる。 The weight average molecular weight of the monomer having two or more substituted or unsubstituted phenyl groups is preferably within the range of 100 to 1000 g/mol, more preferably within the range of 130 to 700 g/mol, and 150 to 600 g It is particularly preferable that the amount is within the range of /mol.
By setting it within the above range, a sealing film with more excellent transmittance can be provided.
　前記芳香族炭化水素基を有する光重合性モノマー（Ｂ）は、前記光重合性モノマー（光重合性モノマー（Ａ）及び光重合性モノマー（Ｂ））の総質量に対して５～４５質量％の範囲内で含有されていることが好ましく、１０～４０質量％の範囲内で含有されていることがより好ましい。前記範囲内とすることにより、粘度が封止膜の形成に適切となる。 The photopolymerizable monomer (B) having an aromatic hydrocarbon group is 5 to 45% by mass based on the total mass of the photopolymerizable monomers (photopolymerizable monomer (A) and photopolymerizable monomer (B)). The content is preferably within the range of 10 to 40% by mass, and more preferably 10 to 40% by mass. By setting it within the above range, the viscosity becomes suitable for forming a sealing film.
　なお、光重合性モノマー（Ａ）及び（Ｂ）の具体例としては、前記したモノマー以外にも後述する実施例で挙げるモノマー等が挙げられる。また、本発明における光重合性モノマーとして好ましい組み合わせは後述する実施例に記載のとおりである。 In addition to the above-mentioned monomers, specific examples of the photopolymerizable monomers (A) and (B) include monomers listed in Examples described later. Further, preferred combinations of photopolymerizable monomers in the present invention are as described in the Examples below.
＜光重合開始剤＞
　前記光重合開始剤は、光硬化性反応を行える通常の光重合開始剤であれば特に限定されない。
　光重合開始剤としては、例えば、トリアジン系、アセトフェノン系、ベンゾフェノン系、チオキサントン系、ベンゾイン系、リン系、オキシム系又はこれらの混合物を含んでもよい。 <Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it is a normal photopolymerization initiator that can perform a photocuring reaction.
The photopolymerization initiator may include, for example, a triazine type, an acetophenone type, a benzophenone type, a thioxanthone type, a benzoin type, a phosphorus type, an oxime type, or a mixture thereof.
　トリアジン系開始剤は、２，４，６－トリクロロ－ｓ－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（３’，４’－ジメトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４’－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－トリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ビフェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、ビス（トリクロロメチル）－６－スチリル－ｓ－トリアジン、２－（ナフト－１－イル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフト－１－イル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－トリクロロメチル（ピペロニル）－６－トリアジン、２，４－（トリクロロメチル（４’－メトキシスチリル）－６－トリアジン又はこれらの混合物であってもよい。 Triazine-based initiators include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4 , 6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, Bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth-1-yl) -4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl(piperonyl)-6-triazine, 2,4-(trichloromethyl(4'-methoxystyryl)-6-triazine or these) It may be a mixture.
　アセトフェノン系開始剤は、２，２’－ジエトキシアセトフェノン、２，２’－ジブトキシアセトフェノン、２－ヒドロキシ－２－メチルプロピオフェノン、ｐ－ｔ－ブチルトリクロロアセトフェノン、ｐ－ｔ－ブチルジクロロアセトフェノン、４－クロロアセトフェノン、２，２’－ジクロロ－４－フェノキシアセトフェノン、２－メチル－１－（４－（メチルチオ）フェニル）－２－モルホリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、及びこれらの混合物であってもよい。 Acetophenone initiators include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone , 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)-butan-1-one, and mixtures thereof.
　ベンゾフェノン系開始剤は、ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、ヒドロキシベンゾフェノン、アクリル化ベンゾフェノン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ジクロロベンゾフェノン、３，３’－ジメチル－２－メトキシベンゾフェノン又はこれらの混合物であってもよい。 Benzophenone initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 3 , 3'-dimethyl-2-methoxybenzophenone or a mixture thereof.
　チオキサントン系開始剤は、チオキサントン、２－メチルチオキサントン、イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン、２－クロロチオキサントン又はこれらの混合物であってもよい。 The thioxanthone initiator may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, or a mixture thereof.
　ベンゾイン系開始剤は、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール又はこれらの混合物であってもよい。 The benzoin-based initiator may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, or a mixture thereof.
　リン系開始剤は、ビスベンゾイルフェニルホスフィンオキシド、ベンゾイルジフェニルホスフィンオキシド又はこれらの混合物であってもよい。 The phosphorus initiator may be bisbenzoylphenylphosphine oxide, benzoyldiphenylphosphine oxide, or a mixture thereof.
　オキシム系は、２－（ｏ－ベンゾイルオキシム）－１－［４－（フェニルチオ）フェニル］－１，２－オクタンジオン及び１－（ｏ－アセチルオキシム）－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン、又はこれらの混合物であってもよい。 Oxime systems include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(o-acetyloxime)-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, or a mixture thereof.
　前記光重合開始剤は、本発明の封止用組成物中に、前記光重合性モノマーと光重合開始剤の合計１００質量部に対して約０．１～２０質量部の範囲内含まれていることが好ましい。前記範囲内とすることにより、露光時に光重合が十分に起こり、光重合後、残った未反応開始剤によって透過率が低下することを防止することができる。
　具体的に、前記光重合開始剤は、０．５～１０質量部、より具体的に１～５質量部の範囲内で含有されることが好ましい。
　また、前記光重合開始剤は、本発明の封止用用組成物中に、固形分を基準にして０．１～１０質量％の範囲内で含有されること好ましく、より好ましくは０．１～５質量％の範囲内である。前記範囲内とすることにより、光重合が十分に起こり、残った未反応開始剤によって透過率が低下することを防止することができる。 The photopolymerization initiator is contained in the sealing composition of the present invention in an amount of about 0.1 to 20 parts by mass based on 100 parts by mass of the photopolymerizable monomer and photoinitiator. Preferably. By setting it within the above range, photopolymerization can sufficiently occur during exposure, and it is possible to prevent transmittance from decreasing due to unreacted initiator remaining after photopolymerization.
Specifically, the photopolymerization initiator is preferably contained in an amount of 0.5 to 10 parts by weight, more specifically 1 to 5 parts by weight.
Further, the photopolymerization initiator is preferably contained in the sealing composition of the present invention in an amount of 0.1 to 10% by mass based on solid content, more preferably 0.1% by mass. It is within the range of ~5% by mass. By setting it within the above range, photopolymerization can sufficiently occur, and it is possible to prevent the transmittance from decreasing due to the remaining unreacted initiator.
　また、前記光重合開始剤の代わりに、カルバゾール系、ジケトン類、スルホニウム系、ヨードニウム系、ジアゾ系、ビイミダゾール系などの光酸発生剤又は光重合開始剤を使用してもよい。 Furthermore, instead of the photopolymerization initiator, a photoacid generator or photopolymerization initiator such as a carbazole type, diketone type, sulfonium type, iodonium type, diazo type, or biimidazole type may be used.
＜その他の添加剤＞
　本発明の封止用組成物は、本発明の効果が得られる範囲において、酸化防止剤、熱安定化剤、光増感剤、分散剤、熱架橋剤及び界面活性剤を含むその他の成をさらに含んでいてもよい。これらの成分は、本発明の封止用組成物中に、一種のみが含まれていてもよく、二種類以上が含まれていてもよい。 <Other additives>
The encapsulating composition of the present invention may contain other components including an antioxidant, a heat stabilizer, a photosensitizer, a dispersant, a thermal crosslinking agent, and a surfactant within the range where the effects of the present invention can be obtained. It may further contain. Only one kind of these components may be contained in the sealing composition of the present invention, or two or more kinds thereof may be contained in the sealing composition of the present invention.
　前記酸化防止剤は、封止層の熱的安定性を向上させることができる。酸化防止剤は、フェノール系、キノン系、アミン系及びホスファイト系からなる群から選ばれる１種以上を含んでもよいが、これらに制限されるものではない。例えば、酸化防止剤としては、テトラキス［メチレン（３，５－ジ－ｔ－ブチル－４－ヒドロキシヒドロシンナメート）］メタン、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイトなどを挙げることができる。 The antioxidant can improve the thermal stability of the sealing layer. The antioxidant may include one or more selected from the group consisting of phenol, quinone, amine, and phosphite, but is not limited thereto. For example, examples of antioxidants include tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, tris(2,4-di-tert-butylphenyl)phosphite, etc. be able to.
　前記酸化防止剤は、前記封止用組成物中に、前記光重合性モノマーと前記光重合開始剤の合計１００質量部に対して０．０１～３質量部の範囲内含有されていることが好ましく、０．０１～１質量部の範囲内含有されていることがより好ましい。前記範囲内とすることにより、優れた熱安定性を示すことができる。 The antioxidant may be contained in the sealing composition in an amount of 0.01 to 3 parts by mass based on a total of 100 parts by mass of the photopolymerizable monomer and the photopolymerization initiator. It is preferably contained in a range of 0.01 to 1 part by mass. By setting it within the above range, excellent thermal stability can be exhibited.
　前記熱安定化剤は、封止用組成物に含まれ、当該封止用組成物の常温での粘度変化を抑制するものであって、通常の熱安定化剤を制限なく使用可能である。
　例えば、熱安定化剤としては、立体障害のある（ｓｔｅｒｉｃａｌｌｙ　ｈｉｎｄｅｒｅｄ）フェノール性熱安定剤を使用してもよく、具体的に、ポリ（ジ－シクロペンタジエン－ｃｏ－ｐ－クレゾール）、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，２’－メタノ－ビ（４－メチル－６－ｔｅｒｔ－ブチル－フェノール）、６，６’－ジ－ｔｅｒｔ－ブチル－２，２’－チオジ－ｐ－クレゾール、トリス（４－ｔｅｒｔ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）イソシアヌレート、トリエチレングリコール－ビス（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）、４，４’－チオビス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）、３，３’－ビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）－Ｎ，Ｎ’－ヘキサメチレン－ジプロピオンアミド、ペンタエリスリトールテトラキス（３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート）、ステアリル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオネート、ペンタエリスリトールテトラキス１，３，５－トリス（２，６－ジ－メチル－３－ヒドロキシ－４－ｔｅｒｔ－ブチル－ベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート、１，３，５－トリス（２－ヒドロキシエチル）イソシアヌレート－トリス（３，５－ジ－ｔｅｒｔ－ブチルヒドロキシフェニルプロピオネート）のうちの一つ以上を含んでもよいが、これに制限されない。 The heat stabilizer is contained in the sealing composition and suppresses the change in viscosity of the sealing composition at room temperature, and any ordinary heat stabilizer can be used without any restriction.
For example, as a heat stabilizer, a sterically hindered phenolic heat stabilizer may be used, specifically poly(di-cyclopentadiene-co-p-cresol), octadecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methano-bi(4-methyl-6-tert) -butyl-phenol), 6,6'-di-tert-butyl-2,2'-thiodi-p-cresol, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, Triethylene glycol-bis(3-tert-butyl-4-hydroxy-5-methylphenyl), 4,4'-thiobis(6-tert-butyl-m-cresol), 3,3'-bis(3,5 -di-tert-butyl-4-hydroxyphenyl)-N,N'-hexamethylene-dipropionamide, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), Stearyl-3,5-di-tert-butyl-4-hydroxyphenylpropionate, pentaerythritol tetrakis 1,3,5-tris(2,6-di-methyl-3-hydroxy-4-tert-butyl-benzyl) Isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(2-hydroxyethyl)isocyanurate-tris(3,5 -di-tert-butylhydroxyphenylpropionate), but is not limited thereto.
　前記熱安定化剤は、前記封止用組成物中に、固形分を基準にして前記光重合性モノマーと前記光重合開始剤の合計に対して２０００ｐｐｍ以下、好ましくは０．０１～２０００ｐｐｍの範囲内、より好ましくは１００～１０００ｐｐｍの範囲内含有されている。前記範囲内とすることにより、熱安定化剤は、封止用組成物の液状状態の貯蔵安定性と工程性をさらに良好にすることができる。 The heat stabilizer is present in the sealing composition in an amount of 2000 ppm or less, preferably in the range of 0.01 to 2000 ppm, based on the solid content of the total of the photopolymerizable monomer and the photopolymerization initiator. More preferably, the content is in the range of 100 to 1000 ppm. By setting it within the above range, the heat stabilizer can further improve the storage stability and processability of the sealing composition in a liquid state.
　前記光増感剤は、吸収した光エネルギーを光重合開始剤にエネルギー移動させる働きを
有するため、使用する光重合開始剤に、光源からの光に対応した吸収がなくとも、本来の光重合性開始剤機能を持たせることができる化合物である。
　光増感剤としては、例えば、９，１０－ジブトキシアントラセン等のアントラセン誘導体；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン誘導体；
　ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４－ベンゾイル－４′－メチル－ジフェニルサルファイド、３，３′，４，４′－テトラ（ｔ－ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４－ベンゾイル－Ｎ，Ｎ－ジメチル－Ｎ－［２－（１－オキソ－２－プロペニルオキシ）エチル］ベンゼンメタナミニウムブロミド、（４－ベンゾイルベンジル）トリメチルアンモニウムクロリド等のベンゾフェノン誘導体；
　２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン、１－クロロ－４－プロポキシチオキサントン、２－（３－ジメチルアミノ－２－ヒドロキシ）－３，４－ジメチル－９Ｈチオキサントン－９－オンメソクロリド等のチオキサントン誘導体；などの化合物が挙げられる。なかでも、アントラセン誘導体、ベンゾイン誘導体、ベンゾフェノン誘導体、アントラキノン誘導体、チオキサントン誘導体を用いることが好ましい。 The photosensitizer has the function of transferring the absorbed light energy to the photopolymerization initiator, so even if the photopolymerization initiator used does not have absorption corresponding to the light from the light source, it will not have the original photopolymerizability. It is a compound that can have an initiator function.
Examples of photosensitizers include anthracene derivatives such as 9,10-dibutoxyanthracene; benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;
Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4 , 6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride, etc. Benzophenone derivative;
2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4- Examples include compounds such as thioxanthone derivatives such as dimethyl-9Hthioxanthon-9-one mesochloride; Among these, it is preferable to use anthracene derivatives, benzoin derivatives, benzophenone derivatives, anthraquinone derivatives, and thioxanthone derivatives.
＜紫外線硬化＞
　本発明の封止用組成物を硬化するために照射する紫外線としては、公知の手段を使用することができ、２００～４００ｎｍの範囲内で、紫外線を照射することで硬化すれば特に限定されない。好ましくは、電子デバイスの劣化を防ぐ観点で３９５ｎｍのＬＥＤを用いることが好ましい。
　紫外線を照射する環境は、封止用組成物が硬化すれば公知の手段を使うことができ、紫外線を照射することで硬化すれば特に限定されない。好ましくは、電子デバイスの劣化を防ぐ観点、酸素による硬化阻害の影響を防ぐ観点で、不活性ガス環境で照射するのが好ましい。特に窒素やアルゴンガス雰囲気下で照射することが好ましい。 <Ultraviolet curing>
The ultraviolet rays irradiated to cure the sealing composition of the present invention can be any known means, and are not particularly limited as long as they are cured by irradiating ultraviolet rays within the range of 200 to 400 nm. Preferably, a 395 nm LED is preferably used from the viewpoint of preventing deterioration of the electronic device.
The environment for irradiating ultraviolet rays is not particularly limited as long as the sealing composition is cured by any known means, and is not particularly limited as long as it is cured by irradiating ultraviolet rays. Preferably, the irradiation is performed in an inert gas environment from the viewpoint of preventing deterioration of the electronic device and preventing the influence of oxygen from inhibiting curing. In particular, it is preferable to irradiate under a nitrogen or argon gas atmosphere.
＜物性＞
　本発明の封止用組成物の粘度は３～３０ｍＰａ・ｓの範囲内であることが、インクジェットヘッドからの吐出性をより高める観点から好ましい。表面張力は、１５ｍＮ／ｍ以上４５ｍＮ／ｍ未満であることがインクジェットヘッドからの吐出性をより高める観点から好ましい。 <Physical properties>
The viscosity of the sealing composition of the present invention is preferably within the range of 3 to 30 mPa·s from the viewpoint of further improving ejection properties from an inkjet head. The surface tension is preferably 15 mN/m or more and less than 45 mN/m from the viewpoint of further improving the ejection performance from the inkjet head.
　本発明の封止用組成物の粘度は、例えば各種レオメーターにより、封止用組成物の動的粘弾性の温度変化を測定することにより求めることができる。
　本発明において、これらの粘度は、以下の方法によって得られた値である。本発明の封止用組成物をストレス制御型レオメーターＰｈｙｓｉｃａ　ＭＣＲ３００（コーンプレートの直径：７５ｍｍ、コーン角：１．０°）、Ａｎｔｏｎ　Ｐａａｒ社製にセットする。次いで、前記封止用組成物を１００℃に加熱し、降温速度０．１℃／ｓ、歪み５％、角周波数１０ｒａｄｉａｎ／ｓで、の条件で２０℃まで前記封止用組成物を冷却して、動的粘弾性の温度変化曲線を得る。 The viscosity of the sealing composition of the present invention can be determined by measuring the temperature change in the dynamic viscoelasticity of the sealing composition using, for example, various rheometers.
In the present invention, these viscosities are values obtained by the following method. The sealing composition of the present invention is set in a stress-controlled rheometer Physica MCR300 (cone plate diameter: 75 mm, cone angle: 1.0°) manufactured by Anton Paar. Next, the sealing composition was heated to 100° C., and the sealing composition was cooled to 20° C. under the following conditions: a temperature decrease rate of 0.1° C./s, a strain of 5%, and an angular frequency of 10 radian/s. to obtain a temperature change curve of dynamic viscoelasticity.
　本発明の封止用組成物は顔料粒子を含んでいても良い。顔料粒子は、インクジェットヘッドからの吐出性をより高める観点からは、本発明の封止用組成物が顔料を含有するときの顔料粒子の平均粒径は０．０８～０．５μｍの範囲内であり、最大粒径は０．３～１０μｍの範囲内であることが好ましい。
　本発明における顔料粒子の平均粒径とは、データサイザーナノＺＳＰ、Ｍａｌｖｅｒｎ社製を使用して動的光散乱法によって求めた値を意味する。なお、着色材を含む封止用組成物は濃度が高く、この測定機器では光が透過しないので、封止用組成物を２００倍で希釈してから測定する。測定温度は常温（２５℃）とする。 The sealing composition of the present invention may contain pigment particles. From the viewpoint of further improving ejection properties from an inkjet head, when the sealing composition of the present invention contains a pigment, the average particle diameter of the pigment particles is within the range of 0.08 to 0.5 μm. The maximum particle size is preferably within the range of 0.3 to 10 μm.
The average particle diameter of pigment particles in the present invention means a value determined by a dynamic light scattering method using Datasizer Nano ZSP, manufactured by Malvern. Note that the sealing composition containing a coloring material has a high concentration and does not allow light to pass through this measuring device, so the sealing composition is diluted 200 times before measurement. The measurement temperature is room temperature (25°C).
　また、本発明の封止用組成物は、その密度ρ、前記封止用組成物の表面張力σ、前記封止用組成物の粘度μ、ノズル直径Ｄ０でされる下記式１に示すオーネゾルゲ数（Ｏｈ）が０．１～１の範囲内であることがインクジェットの吐出性、インクの飛翔時の液滴安定化の観点で好ましい。 Further, the sealing composition of the present invention is an Ohnesolge expressed by the following formula 1, which is expressed by the density ρ, the surface tension σ of the sealing composition, the viscosity μ of the sealing composition, and the nozzle diameter D0 . It is preferable that the number (Oh) is within the range of 0.1 to 1 from the viewpoint of inkjet ejection performance and stabilization of droplets during ink flight.
Figure JPOXMLDOC01-appb-M000005
Figure JPOXMLDOC01-appb-M000005
　本発明の封止用組成物を調製し、重合後の膜において、８０℃又はそれよりも高いＴｇ（ガラス転移点）を有する硬化ポリマーを提供することが好ましい。重合後の膜のＴｇは、電子デバイスの形成プロセス、駆動温度、信頼性試験における安定性確保の観点で、８０℃以上であることが好ましい。 Preferably, the encapsulating composition of the present invention is prepared to provide a cured polymer having a Tg (glass transition temperature) of 80° C. or higher in the polymerized film. The Tg of the film after polymerization is preferably 80° C. or higher from the viewpoint of ensuring stability in the electronic device formation process, driving temperature, and reliability test.
［電子デバイス封止膜形成方法］
　本発明の電子デバイス封止膜形成方法は、前記した本発明の電子デバイス封止用組成物を用いて、封止膜を形成する方法であって、電子デバイス上に気相法により第１封止層を形成する工程と、前記第１封止層上に前記電子デバイス封止用組成物を塗布することにより第２封止層を形成する工程と、を備える。
　また、前記第２封止層上に、気相法により第３封止層を形成する工程を備えることが、電子デバイスの封止性能をより高めることができる点で好ましい。 [Electronic device sealing film forming method]
The electronic device sealing film forming method of the present invention is a method of forming a sealing film using the above-described composition for electronic device sealing of the present invention, wherein a first sealing film is formed on the electronic device by a vapor phase method. The method includes a step of forming a sealing layer, and a step of forming a second sealing layer by applying the electronic device sealing composition on the first sealing layer.
Further, it is preferable to include a step of forming a third sealing layer on the second sealing layer by a vapor phase method, since the sealing performance of the electronic device can be further improved.
＜第１封止層形成工程＞
　第１封止層形成工程は、電子デバイス上に気相法により第１封止層を形成する。
　気相法としては、スパッタリング法（例えば、マグネトロンカソードスパッタリング、平板マグネトロンスパッタリング、二極ＡＣ平板マグネトロンスパッタリング、二極ＡＣ回転マグネトロンスパッタリングなど、反応性スパッタ法を含む。）、蒸着法（例えば、抵抗加熱蒸着、電子ビーム蒸着、イオンビーム蒸着、プラズマ支援蒸着など）、熱ＣＶＤ法、触媒化学気相成長法（Ｃａｔ－ＣＶＤ）、容量結合プラズマＣＶＤ法（ＣＣＰ－ＣＶＤ）、光ＣＶＤ法、プラズマＣＶＤ法（ＰＥＣＶＤ）、エピタキシャル成長法、原子層成長法（ＡＬＤ）等の化学蒸着法等が挙げられる。中でも、ＡＬＤ法、ＣＶＤ法により形成することが好ましい。
　第１封止層は、窒化ケイ素（ＳｉＮｘ）、酸窒化ケイ素（ＳｉＮＯｘ）又は酸化ケイ素（ＳｉＯｘ）を含有する。
　第１封止層を形成する具体例としては、チャンバー内を減圧しておき、原料ガスとして、シラン（ＳｉＨ４）、アンモニア（ＮＨ３）、水素（Ｈ２）を加熱してチャンバー内に供給し形成する方法が挙げられる。
　第１封止層の厚さは、例えば、１０～１０００ｎｍの範囲内であることが好ましく、１００～５００ｎｍの範囲内であることがより好ましい。 <First sealing layer forming step>
In the first sealing layer forming step, the first sealing layer is formed on the electronic device by a vapor phase method.
Gas phase methods include sputtering methods (for example, reactive sputtering methods such as magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, bipolar AC rotating magnetron sputtering, etc.), vapor deposition methods (for example, resistance heating evaporation, electron beam evaporation, ion beam evaporation, plasma-assisted deposition, etc.), thermal CVD, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD (CCP-CVD), optical CVD, plasma CVD (PECVD), epitaxial growth method, and chemical vapor deposition method such as atomic layer deposition (ALD). Among these, it is preferable to form by ALD method or CVD method.
The first sealing layer contains silicon nitride (SiNx), silicon oxynitride (SiNOx), or silicon oxide (SiOx).
As a specific example of forming the first sealing layer, the pressure inside the chamber is reduced, and raw material gases such as silane (SiH 4 ), ammonia (NH 3 ), and hydrogen (H 2 ) are heated and supplied into the chamber. For example, a method of forming
The thickness of the first sealing layer is, for example, preferably within the range of 10 to 1000 nm, more preferably within the range of 100 to 500 nm.
＜第２封止層形成工程＞
　第２封止層形成工程は、前記第１封止層上に前記した本発明の封止用組成物を塗布することにより第２封止層を形成する。
　具体的には、前記第１封止層上に、前記封止用組成物を塗布し（塗布工程）、得られた塗布膜に窒素雰囲気下にて真空紫外線照射して改質処理する工程を有してもよい。 <Second sealing layer forming step>
In the second sealing layer forming step, a second sealing layer is formed by applying the above-described sealing composition of the present invention on the first sealing layer.
Specifically, the sealing composition is applied onto the first sealing layer (coating step), and the resulting coating film is modified by irradiating vacuum ultraviolet rays in a nitrogen atmosphere. May have.
　（塗布工程）
　封止用組成物の塗布方法としては、任意の適切な方法を採用することができ、例えば、スピンコート法、ロールコート法、フローコート法、インクジェット法、スプレーコート法、プリント法、ディップコート法、流延成膜法、バーコート法、グラビア印刷法等が挙げられる。中でも、インクジェット法を用いることが有機ＥＬ素子などの電子デバイスを封止する際に求められる微細なパターニングをオンデマンドで行える点で好ましい。 (Coating process)
Any suitable method can be used to apply the sealing composition, such as spin coating, roll coating, flow coating, inkjet coating, spray coating, printing, and dip coating. , a casting film forming method, a bar coating method, a gravure printing method, and the like. Among these, it is preferable to use the inkjet method because it allows on-demand fine patterning, which is required when sealing electronic devices such as organic EL elements.
　インクジェット方式としては、公知の方法を用いることができる。
　インクジェット方式は、大別するとドロップオンデマンド方式とコンティニュアス方式二つに分けられ、どちらも使用することができる。ドロップオンデマンド方式としては、電気－機械変換方式（例えば、シングルキャビティー型、ダブルキャビティー型、ベンダー型、ピストン型、シェアーモード型、シェアードウォール型等）、電気－熱変換方式（例えば、サーマルインクジェット型、バブルジェット（登録商標）型等）、静電吸引方式（例えば、電界制御型、スリットジェット型等）及び放電方式（例えば、スパークジェット型等）等がある。インクジェットヘッドのコストや生産性の観点からは、電気－機械変換方式、又は電気－熱変換方式のヘッドを用いることが好ましい。なお、インクジェット方式により、液滴（例えば、塗布液）を滴下させる方法を「インクジェット法」と呼ぶ場合がある。 As the inkjet method, a known method can be used.
The inkjet method can be roughly divided into two types: a drop-on-demand method and a continuous method, both of which can be used. Drop-on-demand methods include electro-mechanical conversion methods (e.g., single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (e.g., thermal Ink jet type, bubble jet (registered trademark) type, etc.), electrostatic suction type (eg, electric field control type, slit jet type, etc.), and discharge type (eg, spark jet type, etc.). From the viewpoint of cost and productivity of the inkjet head, it is preferable to use an electro-mechanical conversion type or an electro-thermal conversion type head. Note that a method of dropping liquid droplets (for example, a coating liquid) using an inkjet method is sometimes referred to as an "inkjet method."
　前記封止用組成物を塗布する際には、窒素雰囲気下にて行うことが好ましい。 When applying the sealing composition, it is preferable to apply it under a nitrogen atmosphere.
　（改質処理工程）
　前記改質処理工程では、塗布工程後、得られた塗布膜に窒素雰囲気下にて真空紫外線照射して改質処理する工程を有してもよい。
　改質処理とは、ポリシラザンの酸化ケイ素又は酸窒化ケイ素への転化反応をいう。改質処理も、同様に、グローブボックス内といった窒素雰囲気下や減圧下で行う。
　本発明における改質処理は、ポリシラザンの転化反応に基づく公知の方法を選ぶことができる。本発明においては、低温で転化反応が可能なプラズマやオゾンや紫外線を使う転化反応が好ましい。プラズマやオゾンは従来公知の方法を用いることができる。本発明においては、上記塗布膜を設け、波長２００ｎｍ以下の真空紫外光（ＶＵＶともいう。）を照射して改質処理することにより、本発明に係る第２封止層を形成することが好ましい。 (Reforming treatment process)
The modification treatment step may include, after the coating step, a step of irradiating the obtained coating film with vacuum ultraviolet rays in a nitrogen atmosphere to perform modification treatment.
The modification treatment refers to a conversion reaction of polysilazane to silicon oxide or silicon oxynitride. The reforming treatment is similarly performed in a nitrogen atmosphere such as in a glove box or under reduced pressure.
For the modification treatment in the present invention, a known method based on a conversion reaction of polysilazane can be selected. In the present invention, a conversion reaction using plasma, ozone, or ultraviolet light, which allows the conversion reaction to occur at a low temperature, is preferred. Conventionally known methods can be used for plasma and ozone. In the present invention, it is preferable to form the second sealing layer according to the present invention by providing the coating film and performing a modification treatment by irradiating vacuum ultraviolet light (also referred to as VUV) with a wavelength of 200 nm or less. .
　第２封止層の厚さは、０．５～２０μｍの範囲内が好ましく、より好ましくは３～１０μｍの範囲内である。
　当該第２封止層のうち、層全体が改質された層であってもよいが、改質処理された改質層の厚さは、１～５０ｎｍの範囲内が好ましく、１～３０ｎｍの範囲内がさらに好ましい。 The thickness of the second sealing layer is preferably within the range of 0.5 to 20 μm, more preferably within the range of 3 to 10 μm.
Of the second sealing layer, the entire layer may be a modified layer, but the thickness of the modified layer treated with modification is preferably within the range of 1 to 50 nm, and preferably 1 to 30 nm. More preferably within this range.
　前記真空紫外線を照射して改質処理する工程において、塗布膜が受ける塗布膜面での該真空紫外線の照度は３０～２００ｍＷ／ｃｍ２の範囲内であることが好ましく、５０～１６０ｍＷ／ｃｍ２の範囲内であることがより好ましい。真空紫外線の照度を３０ｍＷ／ｃｍ２以上とすることで、改質効率を十分に向上することができ、２００ｍＷ／ｃｍ２以下では、塗布膜への損傷発生率を極めて抑え、また、基材への損傷も低減させることができるため、好ましい。 In the step of irradiating with vacuum ultraviolet rays to perform a modification treatment, the illuminance of the vacuum ultraviolet rays on the coating film surface that the coating film receives is preferably within the range of 30 to 200 mW/cm 2 , and 50 to 160 mW/cm 2 It is more preferable that it be within the range of . By setting the illuminance of vacuum ultraviolet rays to 30 mW/cm 2 or more, the modification efficiency can be sufficiently improved, and if it is 200 mW/cm 2 or less, the incidence of damage to the coating film can be extremely suppressed, and it can also cause damage to the base material. This is preferable because it can also reduce damage to.
　真空紫外線の照射は、塗布膜面における真空紫外線の照射エネルギー量は、１～１０Ｊ／ｃｍ２の範囲内であることが好ましく、デシカント機能を維持するためのバリア性及び湿熱耐性の観点から、３～７Ｊ／ｃｍ２の範囲内であることがより好ましい。 In the irradiation of vacuum ultraviolet rays, the amount of energy irradiated with vacuum ultraviolet rays on the coated film surface is preferably within the range of 1 to 10 J/cm 2 , and from the viewpoint of barrier properties and moist heat resistance to maintain desiccant function, More preferably, it is within the range of 7 J/cm 2 .
　なお、真空紫外線の光源としては、希ガスエキシマランプが好ましく用いられる。真空紫外光は、酸素による吸収があるため真空紫外線照射工程での効率が低下しやすいことか
ら、真空紫外光の照射は、可能な限り酸素濃度の低い状態で行うことが好ましい。すなわち、真空紫外光照射時の酸素濃度は、１０～１００００ｐｐｍの範囲内とすることが好ましく、より好ましくは５０～５０００ｐｐｍの範囲内、さらに好ましくは８０～４５００ｐｐｍの範囲内、最も好ましくは１００～１０００ｐｐｍの範囲内である。 Note that a rare gas excimer lamp is preferably used as the vacuum ultraviolet light source. Since vacuum ultraviolet light is absorbed by oxygen, the efficiency in the vacuum ultraviolet irradiation step tends to decrease, so it is preferable to perform vacuum ultraviolet light irradiation in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration during vacuum ultraviolet light irradiation is preferably within the range of 10 to 10,000 ppm, more preferably within the range of 50 to 5,000 ppm, still more preferably within the range of 80 to 4,500 ppm, and most preferably 100 to 1,000 ppm. is within the range of
　改質処理は、加熱処理と組み合わせて行うこともできる。加熱条件としては、好ましくは５０～３００℃の範囲内、より好ましくは６０～１５０℃の範囲内の温度で、好ましくは１秒～６０分間、より好ましくは１０秒～１０分間、加熱処理を併用することで、改質時の脱水縮合反応を促進し、より効率的に改質体を形成することができる。 Modification treatment can also be performed in combination with heat treatment. The heating conditions are preferably in the range of 50 to 300°C, more preferably in the range of 60 to 150°C, preferably for 1 second to 60 minutes, more preferably for 10 seconds to 10 minutes, in combination with heat treatment. By doing so, the dehydration condensation reaction during modification can be promoted and a modified product can be formed more efficiently.
　加熱処理としては、例えば、ヒートブロック等の発熱体に基材を接触させ熱伝導により塗膜を加熱する方法、抵抗線等による外部ヒーターにより雰囲気を加熱する方法、ＩＲヒーターのような赤外領域の光を用いた方法等が挙げられるが、特に限定されない。また、ケイ素化合物を含有する塗膜の平滑性を維持できる方法を適宜選択してよい。 Examples of heat treatment include: heating the coating film by heat conduction by bringing the substrate into contact with a heating element such as a heat block; heating the atmosphere with an external heater such as a resistance wire; and heating in an infrared region such as an IR heater. Examples include, but are not particularly limited to, methods using light. Further, any method that can maintain the smoothness of the coating film containing the silicon compound may be selected as appropriate.
＜第３封止層形成工程＞
　第３封止層形成工程は、前記第２封止層上に気相法により第３封止層を形成する。
　気相法としては、第１封止層形成工程で用いた気相法と同様に、スパッタリング法（例えば、マグネトロンカソードスパッタリング、平板マグネトロンスパッタリング、二極ＡＣ平板マグネトロンスパッタリング、二極ＡＣ回転マグネトロンスパッタリングなど、反応性スパッタ法を含む。）、蒸着法（例えば、抵抗加熱蒸着、電子ビーム蒸着、イオンビーム蒸着、プラズマ支援蒸着など）、熱ＣＶＤ法、触媒化学気相成長法（Ｃａｔ－ＣＶＤ）、容量結合プラズマＣＶＤ法（ＣＣＰ－ＣＶＤ）、光ＣＶＤ法、プラズマＣＶＤ法（ＰＥ－ＣＶＤ）、エピタキシャル成長法、原子層成長法（ＡＬＤ）等の化学蒸着法等が挙げられる。中でも、ＡＬＤ法、ＣＶＤ法により形成することが好ましい。
　第３封止層は、窒化ケイ素（ＳｉＮｘ）、酸窒化ケイ素（ＳｉＮＯｘ）又は酸化ケイ素（ＳｉＯｘ）を含有する。
　第３封止層を形成する具体例としては、チャンバー内を減圧しておき、原料ガスとして、シラン（ＳｉＨ４）、アンモニア（ＮＨ３）、水素（Ｈ２）を加熱してチャンバー内に供給し形成する方法が挙げられる。
　第３封止層の厚さは、例えば、１０～１０００ｎｍの範囲内であることが好ましく、１００～５００ｎｍの範囲内であることがより好ましい。 <Third sealing layer forming step>
In the third sealing layer forming step, a third sealing layer is formed on the second sealing layer by a vapor phase method.
As the gas phase method, similar to the gas phase method used in the first sealing layer forming step, sputtering methods (for example, magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, bipolar AC rotating magnetron sputtering, etc.) are used. , reactive sputtering methods), vapor deposition methods (e.g., resistance heating vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma-assisted vapor deposition, etc.), thermal CVD methods, catalytic chemical vapor deposition (Cat-CVD), capacitive Examples include chemical vapor deposition methods such as coupled plasma CVD method (CCP-CVD), optical CVD method, plasma CVD method (PE-CVD), epitaxial growth method, and atomic layer deposition method (ALD). Among these, it is preferable to form by ALD method or CVD method.
The third sealing layer contains silicon nitride (SiNx), silicon oxynitride (SiNOx), or silicon oxide (SiOx).
As a specific example of forming the third sealing layer, the pressure inside the chamber is reduced, and raw material gases such as silane (SiH 4 ), ammonia (NH 3 ), and hydrogen (H 2 ) are heated and supplied into the chamber. For example, a method of forming
The thickness of the third sealing layer is, for example, preferably within the range of 10 to 1000 nm, more preferably within the range of 100 to 500 nm.
　なお、前記したように封止膜形成後に、さらにタッチセンサー用の導電膜を形成してもよい。
　前記導電膜は、例えば、ＩＴＯ（Indium Tin Oxide）、ＩＺＯ（Indium Zinc Oxide）等の金属化合物膜のほか、フレキシブル性に優れた、グラフェン膜、金属ナノワイヤー膜（例えば、銀ナノワイヤー又は銅ナノワイヤーを含む膜）、金属ナノ粒子膜（例えば、銀ナノ粒子又は銅ナノ粒子を含む膜）で構成することができる。また、例えばＡｌ膜／Ｔｉ膜／Ａｌ膜のような複数金属の積層膜で構成することができる。 Note that, as described above, after forming the sealing film, a conductive film for a touch sensor may be further formed.
The conductive film may be, for example, a metal compound film such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide), as well as a graphene film or a metal nanowire film (such as silver nanowire or copper nanowire film) that has excellent flexibility. (a film containing wires), a metal nanoparticle film (for example, a film containing silver nanoparticles or copper nanoparticles). Further, it can be constructed of a laminated film of multiple metals such as Al film/Ti film/Al film, for example.
［電子デバイス封止膜］
　本発明の一の態様の電子デバイス封止膜は、光重合性モノマー及び光重合開始剤を含有する電子デバイス封止用組成物を硬化して電子デバイスを封止する電子デバイス封止膜であって、前記光重合性モノマーとして、（メタ）アクリレートを含有し、前記電子デバイス封止膜の波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内であり、かつ、前記電子デバイス封止膜の、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である。
　また、本発明の他の態様の電子デバイス封止膜は、電子デバイスを封止する電子デバイス封止膜であって、窒化ケイ素、酸化ケイ素又は酸窒化ケイ素を含有する第１封止層と、前記した本発明の電子デバイス封止用組成物を用いた第２封止層と、を有する。
　このような本発明の電子デバイス封止膜は、前記電子デバイス封止膜形成方法により形成される。すなわち、前記した本発明の電子デバイス封止用組成物を用いて第２封止層が形成される。
　前記第２封止層の波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内であり、かつ、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である。
　また、本発明の電子デバイス封止膜は、前記第２封止層上に、さらに窒化ケイ素、酸化ケイ素又は酸窒化ケイ素を含有する第３封止層を有することが好ましい。 [Electronic device sealing film]
An electronic device sealing film according to one aspect of the present invention is an electronic device sealing film that seals an electronic device by curing an electronic device sealing composition containing a photopolymerizable monomer and a photopolymerization initiator. The electronic device sealing film contains (meth)acrylate as the photopolymerizable monomer, and the electronic device sealing film has a refractive index of 1.45 to 1.56 at a wavelength of 380 nm. The extinction coefficient of the stopping film at a wavelength of 380 nm is within the range of 50×10 −5 to 200×10 −5 .
Further, an electronic device sealing film according to another aspect of the present invention is an electronic device sealing film that seals an electronic device, and includes a first sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride; and a second sealing layer using the electronic device sealing composition of the present invention described above.
Such an electronic device sealing film of the present invention is formed by the electronic device sealing film forming method described above. That is, the second sealing layer is formed using the electronic device sealing composition of the present invention described above.
The second sealing layer has a refractive index at a wavelength of 380 nm in a range of 1.45 to 1.56, and an extinction coefficient at a wavelength of 380 nm in a range of 50×10 −5 to 200×10 −5 . It is within.
Moreover, it is preferable that the electronic device sealing film of the present invention further includes a third sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride on the second sealing layer.
＜第１封止層＞
　第１封止層は、電子デバイス上に前記した気相法により形成される層である。具体的には、窒化ケイ素、酸化ケイ素（一酸化ケイ素、二酸化ケイ素等）又は酸窒化ケイ素を含有する。 <First sealing layer>
The first sealing layer is a layer formed on the electronic device by the above-mentioned vapor phase method. Specifically, it contains silicon nitride, silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride.
＜第２封止層＞
　第２封止層は、前記第１封止層に隣接して設けられ、前記第１封止層上に前記封止用組成物を塗布することにより形成される。
　したがって、第２封止層は、前記封止用組成物に含有される特定の光重合性モノマーからなる重合体を含有する。 <Second sealing layer>
The second sealing layer is provided adjacent to the first sealing layer, and is formed by applying the sealing composition on the first sealing layer.
Therefore, the second sealing layer contains a polymer made of the specific photopolymerizable monomer contained in the sealing composition.
　前記第２封止層が、前記重合体を含有することを検出する方法としては、従来公知の種々の分析法、例えばクロマトグラフィー、赤外線分光法、紫外・可視分光法、核磁気共鳴分析、Ｘ線回折法、及び質量分析、Ｘ線光電子分光法等を用いることができる。 Methods for detecting that the second sealing layer contains the polymer include various conventionally known analytical methods, such as chromatography, infrared spectroscopy, ultraviolet/visible spectroscopy, nuclear magnetic resonance analysis, Line diffraction, mass spectrometry, X-ray photoelectron spectroscopy, etc. can be used.
　前記第２封止層における前記重合体の含有量は、８５～１００質量％の範囲内であることが好ましく、９０～９５質量％の範囲内であることがより好ましい。 The content of the polymer in the second sealing layer is preferably in the range of 85 to 100% by mass, more preferably in the range of 90 to 95% by mass.
＜第３封止層＞
　第３封止層は、前記第２封止層に隣接して設けられ、前記した気相法により形成される層である。具体的には、第１封止層と同様に窒化ケイ素、酸化ケイ素（一酸化ケイ素、二酸化ケイ素等）又は酸窒化ケイ素を含有する。 <Third sealing layer>
The third sealing layer is a layer that is provided adjacent to the second sealing layer and is formed by the above-mentioned vapor phase method. Specifically, like the first sealing layer, it contains silicon nitride, silicon oxide (silicon monoxide, silicon dioxide, etc.), or silicon oxynitride.
［電子デバイス］
　本発明の電子デバイス封止膜形成方法及び電子デバイス封止膜において、封止される電子デバイスとしては、例えば、有機ＥＬ素子、ＬＥＤ素子、液晶表示素子（ＬＣＤ）、薄膜トランジスター、タッチパネル、電子ペーパー、太陽電池（ＰＶ）等を挙げることができる。本発明の効果がより効率的に得られるという観点から、有機ＥＬ素子、太陽電池又はＬＥＤ素子が好ましく、有機ＥＬ素子が特に好ましい。 [Electronic devices]
In the electronic device sealing film forming method and electronic device sealing film of the present invention, examples of electronic devices to be sealed include organic EL elements, LED elements, liquid crystal display elements (LCD), thin film transistors, touch panels, and electronic paper. , solar cells (PV), and the like. From the viewpoint that the effects of the present invention can be obtained more efficiently, organic EL elements, solar cells, or LED elements are preferable, and organic EL elements are particularly preferable.
＜有機ＥＬ素子＞
　本発明に係る電子デバイスとして採用される有機ＥＬ素子は、ボトムエミッション型、すなわち、透明基材側から光を取り出すようにしたものであってもよい。
　ボトムエミッション型は、具体的には、透明基材上に、カソードとなる透明電極、発光機能層、アノードとなる対向電極をこの順で積層することにより構成されている。
　また、本発明に係る有機ＥＬ素子は、トップエミッション型、すなわち、基材とは逆のカソードとなる透明電極側から光を取り出すようにしたものであってもよい。
　トップエミッション型は、具体的には、基材側にアノードとなる対向電極を設け、この表面に発光機能層、カソードとなる透明電極を順に積層した構成である。 <Organic EL element>
The organic EL element employed as the electronic device according to the present invention may be of a bottom emission type, that is, one that extracts light from the transparent substrate side.
Specifically, the bottom emission type is constructed by laminating, in this order, a transparent electrode serving as a cathode, a light emitting functional layer, and a counter electrode serving as an anode on a transparent base material.
Further, the organic EL element according to the present invention may be of a top emission type, that is, the organic EL element may be of a top emission type, in which light is extracted from the side of the transparent electrode serving as the cathode, which is opposite to the base material.
Specifically, the top emission type has a configuration in which a counter electrode that serves as an anode is provided on the base material side, and a light emitting functional layer and a transparent electrode that serves as a cathode are laminated in this order on the surface of this counter electrode.
　以下に、有機ＥＬ素子の構成の代表例を示す。
　（ｉ）陽極／正孔注入輸送層／発光層／電子注入輸送層／陰極
　（ii）陽極／正孔注入輸送層／発光層／正孔阻止層／電子注入輸送層／陰極
　（iii）陽極／正孔注入輸送層／電子阻止層／発光層／正孔阻止層／電子注入輸送層／
陰極
　（iv）陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／電子注入層／陰極
　（ｖ）陽極／正孔注入層／正孔輸送層／発光層／正孔阻止層／電子輸送層／電子注入層／陰極
　（vi）陽極／正孔注入層／正孔輸送層／電子阻止層／発光層／正孔阻止層／電子輸送層／電子注入層／陰極
　さらに、有機ＥＬ素子は、非発光性の中間層を有していても良い。中間層は電荷発生層であっても良く、マルチフォトンユニット構成であっても良い。
　本発明に適用可能な有機ＥＬ素子の概要については、例えば、特開２０１３－１５７６３４号公報、特開２０１３－１６８５５２号公報、特開２０１３－１７７３６１号公報、特開２０１３－１８７２１１号公報、特開２０１３－１９１６４４号公報、特開２０１３－１９１８０４号公報、特開２０１３－２２５６７８号公報、特開２０１３－２３５９９４号公報、特開２０１３－２４３２３４号公報、特開２０１３－２４３２３６号公報、特開２０１３－２４２３６６号公報、特開２０１３－２４３３７１号公報、特開２０１３－２４５１７９号公報、特開２０１４－００３２４９号公報、特開２０１４－００３２９９号公報、特開２０１４－０１３９１０号公報、特開２０１４－０１７４９３号公報、特開２０１４－０１７４９４号公報等に記載されている構成を挙げることができる。 Typical examples of the configuration of organic EL elements are shown below.
(i) Anode/Hole injection transport layer/Emissive layer/Electron injection transport layer/Cathode (ii) Anode/Hole injection transport layer/Emissive layer/Hole blocking layer/Electron injection transport layer/Cathode (iii) Anode/ Hole injection transport layer/Electron blocking layer/Light emitting layer/Hole blocking layer/Electron injection transport layer/
Cathode (iv) Anode/Hole injection layer/Hole transport layer/Emissive layer/Electron transport layer/Electron inject layer/Cathode (v) Anode/Hole injection layer/Hole transport layer/Emissive layer/Hole blocking layer /Electron transport layer/Electron injection layer/Cathode (vi) Anode/Hole injection layer/Hole transport layer/Electron blocking layer/Light emitting layer/Hole blocking layer/Electron transport layer/Electron injection layer/Cathode Furthermore, organic EL The device may have a non-emissive intermediate layer. The intermediate layer may be a charge generation layer or may have a multi-photon unit configuration.
For an overview of organic EL elements applicable to the present invention, see, for example, JP-A No. 2013-157634, JP-A No. 2013-168552, JP-A No. 2013-177361, JP-A No. 2013-187211, and JP-A No. 2013-187211. 2013-191644, 2013-191804, 2013-225678, 2013-235994, 2013-243234, 2013-243236, 2013- 242366, 2013-243371, 2013-245179, 2014-003249, 2014-003299, 2014-013910, 2014-017493 Examples include configurations described in publications such as Japanese Patent Application Publication No. 2014-017494.
＜基材＞
　前記有機ＥＬ素子に用いることのできる基材（以下、支持基板、基体、基板、支持体等ともいう。）としては、具体的には、ガラス又は樹脂フィルムの適用が好ましく、フレキシブル性を要求される場合は、樹脂フィルムであることが好ましい。
　また、透明であっても不透明であってもよい。基材側から光を取り出す、いわゆるボトムエミッション型の場合には、基材は透明であることが好ましい。 <Base material>
Specifically, as a base material (hereinafter also referred to as a support substrate, substrate, substrate, support, etc.) that can be used in the organic EL element, glass or a resin film is preferably used, and flexibility is required. In the case where the film is a resin film, it is preferable to use a resin film.
Moreover, it may be transparent or opaque. In the case of a so-called bottom emission type in which light is extracted from the base material side, the base material is preferably transparent.
　好ましい樹脂としては、ポリエステル樹脂、メタクリル樹脂、メタクリル酸－マレイン酸共重合体、ポリスチレン樹脂、透明フッ素樹脂、ポリイミド、フッ素化ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、セルロースアシレート樹脂、ポリウレタン樹脂、ポリエーテルエーテルケトン樹脂、ポリカーボネート樹脂、脂環式ポリオレフィン樹脂、ポリアリレート樹脂、ポリエーテルスルホン樹脂、ポリスルホン樹脂、シクロオレフィンコポリマー、フルオレン環変性ポリカーボネート樹脂、脂環変性ポリカーボネート樹脂、フルオレン環変性ポリエステル樹脂、アクリロイル化合物などの熱可塑性樹脂を含む基材が挙げられる。該樹脂は、単独でも又は２種以上組み合わせても用いることができる。 Preferred resins include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, and cellulose acylate resin. , polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic-modified polycarbonate resin, fluorene ring-modified resin Examples include base materials containing thermoplastic resins such as polyester resins and acryloyl compounds. These resins can be used alone or in combination of two or more.
　基材は、耐熱性を有する素材からなることが好ましい。具体的には、線膨張係数が１５ｐｐｍ／Ｋ以上１００ｐｐｍ／Ｋ以下で、かつガラス転移温度（Ｔｇ）が１００℃以上３００℃以下の基材が使用される。
　該基材は、電子部品用途、ディスプレイ用積層フィルムとしての必要条件を満たしている。すなわち、これらの用途に本発明の封止膜を用いる場合、基材は、１５０℃以上の工程に曝されることがある。この場合、基材の線膨張係数が１００ｐｐｍ／Ｋを超えると、前記のような温度の工程に流す際に基板寸法が安定せず、熱膨張及び収縮に伴い、遮断性性能が劣化する不都合や、又は熱工程に耐えられないという不具合が生じやすくなる。１５ｐｐｍ／Ｋ未満では、フィルムがガラスのように割れてしまいフレキシビリティが劣化する場合がある。 The base material is preferably made of a heat-resistant material. Specifically, a base material having a linear expansion coefficient of 15 ppm/K or more and 100 ppm/K or less and a glass transition temperature (Tg) of 100° C. or more and 300° C. or less is used.
The base material satisfies the requirements for use in electronic components and as a laminated film for displays. That is, when using the sealing film of the present invention for these uses, the base material may be exposed to a process at 150° C. or higher. In this case, if the linear expansion coefficient of the base material exceeds 100 ppm/K, the dimensions of the base material will not be stable when it is passed through the process at the above-mentioned temperature, and the barrier performance will deteriorate due to thermal expansion and contraction. , or the problem of not being able to withstand a thermal process is likely to occur. If it is less than 15 ppm/K, the film may break like glass and its flexibility may deteriorate.
　基材のＴｇや線膨張係数は、添加剤などによって調整することができる。
　基材として用いることができる熱可塑性樹脂のより好ましい具体例としては、例えば、ポリエチレンテレフタレート（ＰＥＴ：７０℃）、ポリエチレンナフタレート（ＰＥＮ：１２０℃）、ポリカーボネート（ＰＣ：１４０℃）、脂環式ポリオレフィン（例えば日本ゼオン株式会社製、ゼオノア（登録商標）１６００：１６０℃）、ポリアリレート（ＰＡｒ：２１０℃）、ポリエーテルスルホン（ＰＥＳ：２２０℃）、ポリスルホン（ＰＳＦ：１９０℃）、シクロオレフィンコポリマー（ＣＯＣ：特開２００１－１５０５８４号公報に記載の化合物：１６２℃）、ポリイミド（例えば三菱ガス化学株式会社製、ネオプリム（登録商標）：２６０℃）、フルオレン環変性ポリカーボネート（ＢＣＦ－ＰＣ：特開２０００－２２７６０３号公報に記載の化合物：２２５℃）、脂環変性ポリカーボネート（ＩＰ－ＰＣ：特開２０００－２２７６０３号公報に記載の化合物：２０５℃）、アクリロイル化合物（特開２００２－８０６１６号公報に記載の化合物：３００℃以上）等が挙げられる（括弧内温度はＴｇを示す）。 The Tg and linear expansion coefficient of the base material can be adjusted using additives and the like.
More preferable specific examples of thermoplastic resins that can be used as the base material include polyethylene terephthalate (PET: 70°C), polyethylene naphthalate (PEN: 120°C), polycarbonate (PC: 140°C), alicyclic resins, etc. Polyolefin (for example, Zeonor (registered trademark) 1600 manufactured by Nippon Zeon Co., Ltd.: 160°C), polyarylate (PAr: 210°C), polyethersulfone (PES: 220°C), polysulfone (PSF: 190°C), cycloolefin copolymer (COC: Compound described in JP-A No. 2001-150584: 162°C), polyimide (for example, Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd.: 260°C), fluorene ring-modified polycarbonate (BCF-PC: JP-A No. Compounds described in JP-A No. 2000-227603: 225°C), alicyclic-modified polycarbonates (IP-PC: compounds described in JP-A No. 2000-227603: 205°C), acryloyl compounds (as described in JP-A No. 2002-80616) (Temperature in parentheses indicates Tg).
　本発明に係る電子デバイスは、有機ＥＬ素子等の電子デバイスであることから、基材は透明であることが好ましい。すなわち、光線透過率が通常８０％以上、好ましくは８５％以上、さらに好ましくは９０％以上である。光線透過率は、ＪＩＳ　Ｋ７１０５：１９８１に記載された方法、すなわち積分球式光線透過率測定装置を用いて全光線透過率及び散乱光量を測定し、全光線透過率から拡散透過率を引いて算出することができる。 Since the electronic device according to the present invention is an electronic device such as an organic EL element, the base material is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105:1981, that is, using an integrating sphere type light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
　また、上記に挙げた基材は、未延伸フィルムでもよく、延伸フィルムでもよい。当該基材は、従来公知の一般的な方法により製造することが可能である。これらの基材の製造方法については、国際公開第２０１３／００２０２６号の段落「００５１」～「００５５」の記載された事項を適宜採用することができる。 Furthermore, the above-mentioned base material may be an unstretched film or a stretched film. The base material can be manufactured by a conventionally known general method. Regarding the manufacturing method of these base materials, the matters described in paragraphs "0051" to "0055" of International Publication No. 2013/002026 can be adopted as appropriate.
　基材の表面は、密着性向上のための公知の種々の処理、例えばコロナ放電処理、火炎処理、酸化処理、又はプラズマ処理等を行っていてもよく、必要に応じて上記処理を組み合わせて行っていてもよい。また、基材には易接着処理を行ってもよい。 The surface of the base material may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments may be combined as necessary. You can leave it there. Further, the base material may be subjected to adhesion-facilitating treatment.
　該基材は、単層でもよいし２層以上の積層構造であってもよい。該基材が２層以上の積層構造である場合、各基材は同じ種類であってもよいし異なる種類であってもよい。 The base material may be a single layer or may have a laminated structure of two or more layers. When the base material has a laminated structure of two or more layers, each base material may be of the same type or of different types.
　本発明に係る基材の厚さ（２層以上の積層構造である場合はその総厚）は、１０～２００μｍであることが好ましく、２０～１５０μｍであることがより好ましい。 The thickness of the base material according to the present invention (in the case of a laminated structure of two or more layers, the total thickness) is preferably 10 to 200 μm, more preferably 20 to 150 μm.
　また、フィルム基材の場合は、ガスバリアー層付きフィルム基材であることが好ましい。 In addition, in the case of a film base material, it is preferably a film base material with a gas barrier layer.
　前記フィルム基材用のガスバリアー層は、フィルム基材の表面には、無機物、有機物の被膜又はその両者のハイブリッド被膜が形成されていてもよく、ＪＩＳ　Ｋ　７１２９－１９９２に準拠した方法で測定された、水蒸気透過度（２５±０．５℃、相対湿度（９０±２）％ＲＨ）が０．０１ｇ／ｍ２・２４ｈ以下のバリアー性フィルムであることが好ましく、さらには、ＪＩＳ　Ｋ　７１２６－１９８７に準拠した方法で測定された酸素透過度が、１×１０－３ｍＬ／ｍ２・２４ｈ・ａｔｍ以下、水蒸気透過度が、１×１０－３ｇ／ｍ２・２４ｈ以下の高ガスバリアー性フィルムであることが好ましい。 The gas barrier layer for the film base material may have an inorganic film, an organic film, or a hybrid film of both formed on the surface of the film base material, and is measured by a method based on JIS K 7129-1992. In addition, it is preferably a barrier film with a water vapor permeability (25±0.5°C, relative humidity (90±2)% RH) of 0.01 g/m 2 ·24 h or less, and furthermore, JIS K 7126- High gas barrier with an oxygen permeability of 1×10 -3 mL/m 2.24 h・atm or less and a water vapor permeability of 1×10 −3 g/m 2.24 h or less, measured using a method based on the 1987 Act. It is preferable that the film is a transparent film.
　前記ガスバリアー層を形成する材料としては、水分や酸素等素子の劣化をもたらすものの浸入を抑制する機能を有する材料であればよく、例えば、一酸化ケイ素、二酸化ケイ素、窒化ケイ素、酸窒化ケイ素、炭化ケイ素、酸炭化ケイ素等を用いることができる。 The material forming the gas barrier layer may be any material that has the function of suppressing the infiltration of substances that cause deterioration of elements, such as moisture and oxygen, such as silicon monoxide, silicon dioxide, silicon nitride, silicon oxynitride, Silicon carbide, silicon oxycarbide, etc. can be used.
　当該ガスバリアー層は、特に限定されないが、例えば、一酸化ケイ素、二酸化ケイ素、窒化ケイ素、酸窒化ケイ素、炭化ケイ素、酸炭化ケイ素等の無機ガスバリアー層の場合は、無機材料をスパッタリング法（例えば、マグネトロンカソードスパッタリング、平板マグネトロンスパッタリング、二極ＡＣ平板マグネトロンスパッタリング、二極ＡＣ回転マグネトロンスパッタリングなど）、蒸着法（例えば、抵抗加熱蒸着、電子ビーム蒸着、イオンビーム蒸着、プラズマ支援蒸着など）、熱ＣＶＤ法、触媒化学気相成長法（Ｃａｔ－ＣＶＤ）、容量結合プラズマＣＶＤ法（ＣＣＰ－ＣＶＤ）、光ＣＶＤ法、プラズマＣＶＤ法（ＰＥ－ＣＶＤ）、エピタキシャル成長法、原子層成長（ＡＬＤ）法、反応性スパッタ法等の化学蒸着法等によって層形成することが好ましい。 The gas barrier layer is not particularly limited, but for example, in the case of an inorganic gas barrier layer such as silicon monoxide, silicon dioxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, etc., the inorganic material is sputtered (e.g. , magnetron cathode sputtering, planar magnetron sputtering, bipolar AC planar magnetron sputtering, bipolar AC rotating magnetron sputtering, etc.), vapor deposition methods (e.g., resistance heating evaporation, electron beam evaporation, ion beam evaporation, plasma assisted deposition, etc.), thermal CVD method, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD (CCP-CVD), optical CVD, plasma CVD (PE-CVD), epitaxial growth, atomic layer deposition (ALD), reaction It is preferable to form the layer by a chemical vapor deposition method such as a chemical sputtering method.
　さらに、ポリシラザン、オルトケイ酸テトラエチル（ＴＥＯＳ）などの無機前駆体を含む塗布液を支持体上に塗布した後、真空紫外光の照射などにより改質処理を行い、無機ガスバリアー層を形成する方法や、樹脂基材への金属めっき、金属箔と樹脂基材とを接着させる等のフィルム金属化技術などによっても、無機ガスバリアー層は形成される。 Furthermore, there is a method in which a coating solution containing an inorganic precursor such as polysilazane or tetraethyl orthosilicate (TEOS) is applied onto a support, and then a modification treatment is performed by irradiation with vacuum ultraviolet light to form an inorganic gas barrier layer. The inorganic gas barrier layer can also be formed by film metallization techniques such as metal plating on a resin base material, bonding of a metal foil and a resin base material, and the like.
　また、無機ガスバリアー層は、有機ポリマーを含む有機層を含んでいてもよい。すなわち、無機ガスバリアー層は、無機材料を含む無機層と有機層との積層体であってもよい。 Additionally, the inorganic gas barrier layer may include an organic layer containing an organic polymer. That is, the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.
　有機層は、例えば、有機モノマー又は有機オリゴマーを樹脂基材に塗布し、層を形成し、続いて、例えば、電子ビーム装置、ＵＶ光源、放電装置、又はその他の好適な装置を使用して重合及び必要に応じて架橋することにより形成することができる。また、例えば、フラッシュ蒸発及び放射線架橋可能な有機モノマー又は有機オリゴマーを蒸着した後、有機モノマー又は有機オリゴマーからポリマーを形成することによっても形成することができる。コーティング効率は、樹脂基材を冷却することにより改善され得る。 The organic layer can be formed by, for example, applying an organic monomer or an organic oligomer to a resin substrate to form a layer, followed by polymerization using, for example, an electron beam device, a UV light source, an electrical discharge device, or other suitable device. It can also be formed by crosslinking, if necessary. It can also be formed, for example, by flash evaporation and vapor deposition of radiation crosslinkable organic monomers or organic oligomers followed by formation of polymers from organic monomers or organic oligomers. Coating efficiency can be improved by cooling the resin substrate.
　有機モノマー又は有機オリゴマーの塗布方法としては、例えば、ロールコーティング（例えば、グラビアロールコーティング）、スプレーコーティング（例えば、静電スプレーコーティング）等が挙げられる。また、無機層と有機層との積層体の例としては、例えば、国際公開第２０１２／００３１９８号、国際公開第２０１１／０１３３４１号に記載の積層体などが挙げられる。 Examples of methods for applying the organic monomer or organic oligomer include roll coating (eg, gravure roll coating), spray coating (eg, electrostatic spray coating), and the like. Examples of the laminate of an inorganic layer and an organic layer include the laminates described in International Publication No. 2012/003198 and International Publication No. 2011/013341.
　無機層と有機層との積層体である場合、各層の厚さは同じでもよいし、異なっていてもよい。無機層の厚さは、好ましくは３～１０００ｎｍの範囲内、より好ましくは１０～３００ｎｍの範囲内である。有機層の厚さは、好ましくは１００ｎｍ～１００μｍの範囲内、より好ましくは１～５０μｍの範囲内である。 In the case of a laminate of an inorganic layer and an organic layer, the thickness of each layer may be the same or different. The thickness of the inorganic layer is preferably within the range of 3 to 1000 nm, more preferably within the range of 10 to 300 nm. The thickness of the organic layer is preferably within the range of 100 nm to 100 μm, more preferably within the range of 1 to 50 μm.
　以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、下記実施例において、特記しない限り、操作は室温（２５℃）で行われた。また、特記しない限り、「％」及び「部」は、それぞれ、「質量％」及び「質量部」を意味する。 The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. In addition, in the following examples, unless otherwise specified, operations were performed at room temperature (25° C.). Further, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively.
［モノマー］
　封止用組成物の調製に使用するモノマーは以下のとおりである。また、各モノマーのＨＯＭＯ、ＬＵＭＯ値を後述する方法により算出し、下記表Ｉに示した。さらに、アッベ屈折計により、２５℃におけるD線の屈折率（nd25）を各モノマーについて算出し下記表Ｉに示した。 [monomer]
The monomers used to prepare the encapsulating composition are as follows. Further, the HOMO and LUMO values of each monomer were calculated by the method described later and are shown in Table I below. Further, the D-line refractive index (nd25) at 25° C. was calculated for each monomer using an Abbe refractometer and is shown in Table I below.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
［封止用組成物１～２８の調製］
　各モノマーを下記表IIに示す種類及び質量部となるように窒素環境下で秤量した。
　さらに、光重合開始剤として、リン系開始剤（ＩＧＭ社製、Ｏｍｎｉｒａｄ　８１９）５質量部、増感剤として２－イソプロピルチオキサントン（Ｍｅｒｃｋ社製）０．５質量部を褐色瓶へ入れ、６５℃のホットプレート上で３時間撹拌し、各封止用組成物１～２８を得た。 [Preparation of sealing compositions 1 to 28]
Each monomer was weighed in a nitrogen environment so that the types and parts by weight were shown in Table II below.
Furthermore, 5 parts by mass of a phosphorus initiator (manufactured by IGM, Omnirad 819) as a photopolymerization initiator and 0.5 parts by mass of 2-isopropylthioxanthone (manufactured by Merck) as a sensitizer were placed in a brown bottle, and the mixture was heated at 65°C. The mixture was stirred on a hot plate for 3 hours to obtain each of the sealing compositions 1 to 28.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
［屈折率ｎ及び消衰係数ｋ］
　窒素環境下にて、５０ｍｍ×５０ｍｍの寸法を有するガラス基板上に厚さ１００ｎｍとなるように封止用組成物の塗膜を作製した。この塗膜に、窒素環境下で、３００ｍＷ／ｃｍ２条件で積算光量が１．５Ｊ／ｃｍ２になるように３９５ｎｍの波長の紫外線（ＩＳＴ社製　ＭＺ　２４０ｍｍ　３９５ｎｍ　ＵＶＬＥＤ）を照射して、塗膜を硬化させ、測定サンプルとした。測定サンプルを堀場ＪＹＯＢＩＮ－ＹＶＯＮ社製　ＵＶＳＥＬ／ＦＵＶ－ＦＧＭＳによる分光エリプソメトリーにより２５０ｎｍ～８００ｎｍにおける屈折率と消衰係数を測定し、封止用組成物の硬化膜の３８０ｎｍにおける屈折率ｎ、３８０ｎｍにおける消衰係数ｋを求め、下記表IIIに示した。
　さらに、３８０ｎｍにおける屈折率ｎに対する３８０ｎｍにおける消衰係数ｋの比率ｋ／ｎを求め、下記表IIIに示した。 [Refractive index n and extinction coefficient k]
A coating film of the sealing composition was formed to a thickness of 100 nm on a glass substrate having dimensions of 50 mm x 50 mm in a nitrogen environment. This coating film was irradiated with ultraviolet rays with a wavelength of 395 nm (MZ 240 mm 395 nm UVLED manufactured by IST) under a nitrogen environment at 300 mW/cm 2 conditions so that the cumulative light amount was 1.5 J/cm 2 . was cured and used as a measurement sample. The refractive index and extinction coefficient of the measurement sample at 250 nm to 800 nm were measured by spectroscopic ellipsometry using UVSEL/FUV-FGMS manufactured by Horiba JYOBIN-YVON, and the refractive index n at 380 nm and the refractive index n at 380 nm of the cured film of the sealing composition were measured. The extinction coefficient k was determined and shown in Table III below.
Furthermore, the ratio k/n of the extinction coefficient k at 380 nm to the refractive index n at 380 nm was determined and shown in Table III below.
［平均二重結合数］
　平均二重結合数は、各モノマーに含まれる二重結合の数をｄ、全モノマーの合計質量を１にしたときの、各モノマーの質量比率ｗを用いて以下のように計算し、下記表IIIに示した。
　平均二重結合数＝ｄ１×ｗ１＋ｄ２×ｗ２＋・・・
　（ｄ及びｗの添字はモノマーの番号を表す。） [Average number of double bonds]
The average number of double bonds is calculated as follows using the mass ratio w of each monomer when the number of double bonds contained in each monomer is d and the total mass of all monomers is 1. Shown in III.
Average number of double bonds = d1 x w1 + d2 x w2 +...
(The d and w subscripts represent the monomer numbers.)
［ＨＯＭＯ及びＬＵＭＯのエネルギー準位］
　化学構造の情報から、ＨＵＬＩＮＫＳ社製のＧａｕｓｓｉａｎソフトウェアを用いて、各モノマーのＨＯＭＯ、ＬＵＭＯ（単位：ｅＶ）を得た。計算においては、汎関数としてＢ３ＬＹＰを用いた。各モノマーのＨＯＭＯ、ＬＵＭＯ値は表IIに示した。得られた各モノマーのＨＯＭＯの値とＬＵＭＯの値から、ＨＯＭＯの平均値と、ＬＵＭＯの平均値を以下の式によって算出し、ＨＯＭＯの平均値及びＬＵＭＯの平均値からギャップ（Ｇａｐ）を計算し、下記表IIIに示した。
　ＨＯＭＯの平均値＝ＨＯＭＯ１×ｗ１＋ＨＯＭＯ２×ｗ２＋・・・
　ＬＵＭＯの平均値＝ＬＵＭＯ１×ｗ１＋ＬＵＭＯ２×ｗ２＋・・・
　前記式において、ｗは前記した各モノマーの質量比率を表す。また、ｗ、ＨＯＭＯ及びＬＵＭＯの添え字はモノマーの番号を表す。
　Ｇａｐ（単位：ｅＶ）＝ＬＵＭＯの平均値－ＨＯＭＯの平均値 [HOMO and LUMO energy levels]
From the chemical structure information, the HOMO and LUMO (unit: eV) of each monomer were obtained using Gaussian software manufactured by HULINKS. In the calculation, B3LYP was used as a functional. The HOMO and LUMO values of each monomer are shown in Table II. From the obtained HOMO value and LUMO value of each monomer, calculate the average value of HOMO and the average value of LUMO using the following formula, and calculate the gap (Gap) from the average value of HOMO and the average value of LUMO. , as shown in Table III below.
Average value of HOMO=HOMO1×w1+HOMO2×w2+...
Average value of LUMO = LUMO1×w1+LUMO2×w2+...
In the above formula, w represents the mass ratio of each monomer described above. Furthermore, the subscripts w, HOMO, and LUMO represent the monomer numbers.
Gap (unit: eV) = LUMO average value - HOMO average value
［有機ＥＬ素子の作製］
（１）基板の準備
　フィルム基板として、１５μｍのポリイミドフィルムを準備した。さらに、このポリイミドフィルムに、フィルム基材用のガスバリアー層（ＳｉＯ２膜：２５０ｎｍ／ＳｉＮｘ膜：５０ｎｍ／ＳｉＯ２膜：５００ｎｍ（上層／中間層／下層））をプラズマＣＶＤ法で成膜した。 [Production of organic EL element]
(1) Preparation of substrate A 15 μm polyimide film was prepared as a film substrate. Furthermore, a gas barrier layer for the film base material (SiO 2 film: 250 nm/SiNx film: 50 nm/SiO 2 film: 500 nm (upper layer/middle layer/lower layer)) was formed on this polyimide film by plasma CVD.
（２）第１電極の形成
　前記基板の一方の面に、第１電極（金属層）として下記条件でＡｌ膜を形成した。形成した第１電極の厚さは１５０ｎｍであった。なお、第１電極の厚さは、接触式表面形状測定器（ＤＥＣＴＡＫ）により測定した値である。
　Ａｌ膜は、真空蒸着装置を用い、真空度１×１０－４Ｐａまで減圧した後、タングステン製の抵抗加熱用るつぼを使用して形成した。 (2) Formation of first electrode An Al film was formed as a first electrode (metal layer) on one surface of the substrate under the following conditions. The thickness of the first electrode formed was 150 nm. Note that the thickness of the first electrode is a value measured using a contact type surface profile measuring device (DECTAK).
The Al film was formed using a tungsten resistance heating crucible after reducing the pressure to a degree of vacuum of 1×10 −4 Pa using a vacuum evaporation device.
（３）有機ＥＬ層の形成
　まず、真空蒸着装置内の蒸着用るつぼの各々に、有機機能層の各層を構成する下記に示す材料を各々素子作製に最適の量で充填した。蒸着用るつぼは、モリブデン製又はタングステン製の抵抗加熱用材料で作製されたものを用いた。 (3) Formation of organic EL layer First, each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the materials listed below constituting each layer of the organic functional layer in amounts optimal for device fabrication. The crucible for vapor deposition was made of a resistance heating material made of molybdenum or tungsten.
（３－１）正孔注入層の形成
　真空度１×１０－４Ｐａまで減圧した後、下記化合物Ａ－１の入った蒸着用るつぼに通電して加熱し、蒸着速度０．１ｎｍ／秒で第１電極（金属層側）上に蒸着し、厚さ１０ｎｍの正孔注入層を形成した。 (3-1) Formation of hole injection layer After reducing the pressure to a degree of vacuum of 1 × 10 -4 Pa, electricity was applied to the deposition crucible containing the following compound A-1 to heat it at a deposition rate of 0.1 nm/sec. A hole injection layer having a thickness of 10 nm was formed by vapor deposition on the first electrode (metal layer side).
（３－２）正孔輸送層の形成
　次に、下記化合物Ｍ－２の入った蒸着用るつぼに通電して加熱し、蒸着速度０．１ｎｍ／秒で正孔注入層上に蒸着し、厚さ３０ｎｍの正孔輸送層を形成した。 (3-2) Formation of hole transport layer Next, the following compound M-2 is heated by applying electricity to the crucible for deposition, and the compound M-2 is deposited on the hole injection layer at a deposition rate of 0.1 nm/sec. A hole transport layer with a thickness of 30 nm was formed.
（３－３）発光層の形成
　次に、下記化合物ＢＤ－１及び下記化合物Ｈ－１を、化合物ＢＤ－１が７質量％の濃度になるように蒸着速度０．１ｎｍ／秒で共蒸着し、厚さ１５ｎｍの青色発光を呈する発光層（蛍光発光層）を形成した。
　次に、下記化合物ＧＤ－１、下記化合物ＲＤ－１及び下記化合物Ｈ－２を、化合物ＧＤ－１が２０質量％、ＲＤ－１が０．５質量％の濃度になるように蒸着速度０．１ｎｍ／秒で共蒸着し、厚さ１５ｎｍの黄色を呈する発光層（リン光発光層）を形成した。 (3-3) Formation of light-emitting layer Next, the following compound BD-1 and the following compound H-1 were co-evaporated at a deposition rate of 0.1 nm/sec so that the concentration of compound BD-1 was 7% by mass. A light-emitting layer (fluorescent light-emitting layer) exhibiting blue light emission and having a thickness of 15 nm was formed.
Next, the following compound GD-1, the following compound RD-1, and the following compound H-2 were deposited at a vapor deposition rate of 0.0. Co-evaporation was performed at a rate of 1 nm/sec to form a yellow light emitting layer (phosphorescent light emitting layer) with a thickness of 15 nm.
（３－４）電子輸送層の形成
　その後、電子輸送材料として下記化合物Ｔ－１の入った加熱ボートを通電し、Ａｌｑ３（トリス（８－キノリノール））よりなる電子輸送層を、発光層上に形成した。この際、蒸着速度を０．１～０．２ｎｍ／秒の範囲内とし、厚さを３０ｎｍとした。 (3-4) Formation of electron transport layer After that, electricity is applied to a heating boat containing the following compound T-1 as an electron transport material to form an electron transport layer made of Alq 3 (tris(8-quinolinol)) on the light emitting layer. was formed. At this time, the deposition rate was set within the range of 0.1 to 0.2 nm/sec, and the thickness was set to 30 nm.
（３－５）電子注入層（金属親和性層）の形成
　次に、電子注入材料として下記化合物Ｉ－１の入った加熱ボートに通電して加熱し、Ｌｉｑよりなる電子注入層を、電子輸送層上に形成した。この際、蒸着速度を０．０１～０．０２ｎｍ／秒の範囲内とし、厚さを２ｎｍとした。なお、この電子注入層は金属親和性層の機能を果たす。
　以上により、白色に発光する有機ＥＬ層を形成した。 (3-5) Formation of electron injection layer (metal affinity layer) Next, a heating boat containing the following compound I-1 as an electron injection material is heated by applying electricity to form an electron injection layer made of Liq. formed on the layer. At this time, the deposition rate was set within the range of 0.01 to 0.02 nm/sec, and the thickness was set to 2 nm. Note that this electron injection layer functions as a metal affinity layer.
Through the above steps, an organic EL layer that emits white light was formed.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
（４）第２電極の形成
　さらに、Ｍｇ／Ａｇ混合物（Ｍｇ：Ａｇ＝１：９（ｖｏｌ比））を厚さ１０ｎｍで蒸着して第２電極と、その取り出し電極を形成した。 (4) Formation of second electrode Further, a Mg/Ag mixture (Mg:Ag=1:9 (vol ratio)) was deposited to a thickness of 10 nm to form a second electrode and its extraction electrode.
（５）キャッピング層の形成
　その後、元の真空槽内に移送し、第２電極上に、α－ＮＰＤ（４，４′－ビス〔Ｎ－（１－ナフチル）－Ｎ－フェニルアミノ〕ビフェニル）を蒸着速度０．１～０．２ｎｍ／秒の範囲内で厚さが４０ｎｍとなるまで蒸着し、光取り出し改良を目的とするキャッピング層を形成した。 (5) Formation of capping layer After that, it is transferred to the original vacuum chamber, and α-NPD (4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl) is deposited on the second electrode. was deposited to a thickness of 40 nm at a deposition rate of 0.1 to 0.2 nm/sec to form a capping layer for the purpose of improving light extraction.
（６）第１封止層の形成
　次に、前記で作製した有機ＥＬ素子の発光部を覆う第１封止層として、プラズマＣＶＤ法により厚さ５００ｎｍの窒化珪素（ＳｉＮｘ）、ビッカース硬度ＨＶ９００）を形成した。 (6) Formation of first sealing layer Next, as a first sealing layer covering the light emitting part of the organic EL element produced above, silicon nitride (SiNx) with a thickness of 500 nm (Vickers hardness HV900) was formed by plasma CVD method. was formed.
（７）第２封止層の形成
　次に、前記で調製した封止用組成物１について、窒素環境下にてインクジェットヘッド（コニカミノルタ社製　ＫＭ１０２４ｉ－ＭＨＥ－Ｄ）へ充填した。そして、前記第１封止層まで形成した有機ＥＬ素子を窒素環境下にてインクジェット法を用いて封止用組成物１を塗布厚みが１０μｍなるように塗布した。その後、３００ｍＷ／ｃｍ２条件で積算光量が１．５Ｊ／ｃｍ２になるように３９５ｎｍの波長の紫外線（ＩＳＴ社製　ＭＺ　２４０ｍｍ　３９５ｎｍ　ＵＶＬＥＤ）を照射して、第２封止層を形成した。 (7) Formation of second sealing layer Next, the sealing composition 1 prepared above was filled into an inkjet head (KM1024i-MHE-D manufactured by Konica Minolta) in a nitrogen environment. Then, the organic EL element formed up to the first sealing layer was coated with the sealing composition 1 using an inkjet method in a nitrogen environment so that the coating thickness was 10 μm. Thereafter, a second sealing layer was formed by irradiating ultraviolet light with a wavelength of 395 nm (MZ 240 mm 395 nm UVLED manufactured by IST) under 300 mW/cm 2 conditions so that the cumulative light amount was 1.5 J/cm 2 .
（８）第３封止層の形成
　次に、第２封止層上に第３封止層として、プラズマＣＶＤ法により厚さ５００ｎｍの窒化珪素（ＳｉＮｘ）、ビッカース硬度ＨＶ９００）を形成し、第１～第３封止層が形成された評価用の有機ＥＬ素子１を得た。 (8) Formation of third sealing layer Next, silicon nitride (SiNx) with a thickness of 500 nm (Vickers hardness HV900) is formed as a third sealing layer on the second sealing layer by plasma CVD method. An organic EL element 1 for evaluation in which the first to third sealing layers were formed was obtained.
［有機ＥＬ素子２～２８の作製］
　前記有機ＥＬ素子１の作製において、前記第２封止層の形成における封止用組成物１を下記表に示すとおりにそれぞれ変更した以外は同様にして、評価用の有機ＥＬ素子２～２８を作製した。 [Production of organic EL elements 2 to 28]
In producing the organic EL element 1, organic EL elements 2 to 28 for evaluation were prepared in the same manner except that the sealing composition 1 in forming the second sealing layer was changed as shown in the table below. Created.
［評価］
＜折り曲げた後の信頼性試験（発光効率）＞
　得られた評価用の有機ＥＬ素子のサンプルを発光させ、発光効率（ｌｍ／Ｗ単位）を測定し、初期発光効率とした。その後、評価サンプルをクラムシェル型　繰り返し折り曲げ試験機（ＹＵＡＳＡ社製　Ｔｅｎｓｉｏｎ－Ｆｒｅｅ(R)　Ｆｏｌｄｉｎｇ　Ｃｌａｍｓｈｅｌｌ－ｔｙｐｅ　卓上型耐久試験機）を用いて、Ｒ＝２．５ｍｍの折り曲げ半径で常温環境にて２０万回繰り返し折り曲げを行った。その後、評価サンプルの発光効率（ｌｍ／Ｗ単位）を測定し、折り曲げ後発光効率とした。
　初期発光効率に対する折り曲げ後発光効率の変化率％を評価し、以下の評価基準で判定した。ランク２～４を合格とした。
　（評価基準）
　ランク１：８０％未満
　ランク２：８０％以上９０％未満
　ランク３：９０％以上９５％未満
　ランク４：９５％以上 [evaluation]
<Reliability test after bending (luminous efficiency)>
The obtained sample of the organic EL element for evaluation was allowed to emit light, and the luminous efficiency (lm/W unit) was measured, which was taken as the initial luminous efficiency. Thereafter, the evaluation sample was bent for 20 minutes at room temperature with a bending radius of R = 2.5 mm using a clamshell-type repeated folding tester (Tension-Free(R) Folding Clamshell-type tabletop durability tester manufactured by YUASA). Folding was repeated 10,000 times. Thereafter, the luminous efficiency (lm/W unit) of the evaluation sample was measured, and the luminous efficiency was defined as the luminous efficiency after bending.
The percent change in luminous efficiency after bending with respect to the initial luminous efficiency was evaluated and determined based on the following evaluation criteria. Ranks 2 to 4 were considered passing.
(Evaluation criteria)
Rank 1: Less than 80% Rank 2: 80% or more and less than 90% Rank 3: 90% or more and less than 95% Rank 4: 95% or more
＜折り曲げ後の折りぐせ（耐折性試験後の膜変形評価）＞
　フィルム基板として、１５μｍのポリイミドフィルムを準備した。さらに、このポリイミドフィルムに、前記した（６）第１封止層の形成、（７）第２封止層の形成、（８）第３封止層の形成と同様の方法で封止層を形成し、評価用サンプルとした。
　評価用サンプルを、ポリイミドフィルム側が凸になるようにＲ＝２．０ｍｍの屈曲半径で折り曲げた。折り曲げた状態で固定し、８５℃の環境に７２時間保持した。評価用サンプルを取り出し、接触式膜厚測定器（Ｂｒｕｋｅｒ社　ｄｅｋｔａｋ　ＸＴ）で第３封止層側の表面形状プロファイルを測定した。膜が変形している場合、凹凸の形状が観察され、凸形状の最大高さ、凹形状の最大深さを評価し、以下の評価基準で判定した。ランク２～４を合格とした。
　（評価基準）
　ランク１：最大高さ又は最大深さが５μｍ以上
　ランク２：最大高さ又は最大深さが３μｍ以上５μｍ未満
　ランク３：最大高さ又は最大深さが１μｍ以上３μｍ未満
　ランク４：最大高さ又は最大深さが１μｍ未満 <Folding after bending (membrane deformation evaluation after folding durability test)>
A 15 μm polyimide film was prepared as a film substrate. Furthermore, a sealing layer was formed on this polyimide film in the same manner as (6) forming the first sealing layer, (7) forming the second sealing layer, and (8) forming the third sealing layer. It was formed into a sample for evaluation.
The evaluation sample was bent with a bending radius of R=2.0 mm so that the polyimide film side was convex. It was fixed in a bent state and kept in an environment of 85° C. for 72 hours. A sample for evaluation was taken out, and the surface shape profile on the third sealing layer side was measured using a contact film thickness measuring device (Dektak XT, manufactured by Bruker). When the film was deformed, an uneven shape was observed, and the maximum height of the convex shape and the maximum depth of the concave shape were evaluated, and the evaluation was made based on the following evaluation criteria. Ranks 2 to 4 were considered passing.
(Evaluation criteria)
Rank 1: Maximum height or maximum depth is 5 μm or more Rank 2: Maximum height or maximum depth is 3 μm or more and less than 5 μm Rank 3: Maximum height or maximum depth is 1 μm or more and less than 3 μm Rank 4: Maximum height or Maximum depth less than 1μm
＜比誘電率＞
　窒素環境下にて、１００ｍｍ×１００ｍｍの寸法を有する離型性フィルム基板上に、厚さ５０μｍの封止用組成物の塗膜を作製した。この塗膜に、窒素環境下で、３００ｍＷ／ｃｍ２条件で積算光量が１．５ｍＪ／ｃｍ２になるように３９５ｎｍの波長の紫外線（ＩＳＴ社製　ＭＺ　２４０ｍｍ　３９５ｎｍ　ＵＶＬＥＤ）を照射して、塗膜を硬化させた。得られた硬化膜を離型性フィルムから剥離し、次いで両面にＡｇ膜をスパッタリング法により成膜して測定サンプルとした。測定サンプルはインピーダンス測定装置（：Ｓｏｌａｒｔｒｏｎ製１２６０９６）により周波数１００ｋＨｚ、ＡＣ　０．１（Ｖ）でインピーダンス測定し、比誘電率を測定した。比誘電率が２．９未満を合格、２．９以上を不合格とした。 <Relative dielectric constant>
A coating film of the sealing composition having a thickness of 50 μm was produced on a releasable film substrate having dimensions of 100 mm×100 mm in a nitrogen environment. This coating film was irradiated with ultraviolet rays with a wavelength of 395 nm (MZ 240 mm 395 nm UVLED manufactured by IST) under a nitrogen environment at 300 mW/cm 2 conditions so that the cumulative light amount was 1.5 mJ/cm 2 . hardened. The obtained cured film was peeled off from the release film, and then Ag films were formed on both sides by sputtering to prepare a measurement sample. The impedance of the measurement sample was measured using an impedance measuring device (126096 manufactured by Solartron) at a frequency of 100 kHz and AC 0.1 (V), and the relative dielectric constant was measured. A dielectric constant of less than 2.9 was considered a pass, and a dielectric constant of 2.9 or more was judged a fail.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　上記結果に示されるように、本発明の封止用組成物は、比較例の封止用組成物に比べて、折り曲げた状態での信頼性試験後の見栄えが良好で、かつ、折り曲げ信頼性試験後の発光効率に優れ、また、比誘電率が低い封止膜が得られることが分かる。 As shown in the above results, the encapsulating composition of the present invention has a better appearance after the reliability test in the folded state and has better bending reliability than the encapsulating composition of the comparative example. It can be seen that a sealing film with excellent luminous efficiency after the test and a low dielectric constant can be obtained.
　本発明は、折り曲げた状態での信頼性試験後の見栄えが良好で、かつ、折り曲げ信頼性試験後の発光効率に優れ、比誘電率の低い封止膜が得られる電子デバイス封止用組成物、電子デバイス封止膜及び電子デバイス封止膜の形成方法に利用できる。 The present invention provides a composition for encapsulating electronic devices that provides a sealing film that has a good appearance after a reliability test in a folded state, has excellent luminous efficiency after a reliability test after being folded, and has a low dielectric constant. , it can be used for an electronic device sealing film and a method for forming an electronic device sealing film.

Claims (12)

  1. 　光重合性モノマー及び光重合開始剤を含有する電子デバイス封止用組成物であって、
    　光重合性モノマーとして、（メタ）アクリレートを含有し、
    　窒素環境下で波長３９５ｎｍの紫外線を１．５Ｊｃｍ－２照射して硬化したとき、
    　形成される電子デバイス封止膜の、波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内であり、かつ、当該電子デバイス封止膜の、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である電子デバイス封止用組成物。     An electronic device encapsulation composition containing a photopolymerizable monomer and a photopolymerization initiator,
    Contains (meth)acrylate as a photopolymerizable monomer,
    When cured by irradiating 1.5 Jcm -2 of ultraviolet light with a wavelength of 395 nm in a nitrogen environment,
    The refractive index of the formed electronic device sealing film at a wavelength of 380 nm is within the range of 1.45 to 1.56, and the extinction coefficient of the electronic device sealing film at a wavelength of 380 nm is 50× A composition for encapsulating an electronic device having a molecular weight within the range of 10 −5 to 200×10 −5 .
  2. 　前記屈折率が、１．５０～１．５３の範囲内である請求項１に記載の電子デバイス封止用組成物。 The composition for encapsulating an electronic device according to claim 1, wherein the refractive index is within the range of 1.50 to 1.53.
  3. 　前記消衰係数が、１２５×１０－５～２００×１０－５の範囲内である請求項１に記載の電子デバイス封止用組成物。 The composition for encapsulating an electronic device according to claim 1, wherein the extinction coefficient is within the range of 125×10 −5 to 200×10 −5 .
  4. 　前記屈折率ｎと前記消衰係数ｋが、下記の関係を満たす請求項１に記載の電子デバイス封止用組成物。
    　ｋ／ｎ≧１００×１０－５     The composition for encapsulating an electronic device according to claim 1, wherein the refractive index n and the extinction coefficient k satisfy the following relationship.
    k/n≧100× 10-5
  5. 　前記電子デバイス封止用組成物に含有される前記光重合性モノマーの平均二重結合数が、５以下である請求項１に記載の電子デバイス封止用組成物。 The composition for encapsulating an electronic device according to claim 1, wherein the photopolymerizable monomer contained in the composition for encapsulating an electronic device has an average number of double bonds of 5 or less.
  6. 　前記電子デバイス封止用組成物に含有される前記光重合性モノマーの最高被占分子軌道（ＨＯＭＯ）及び最低空分子軌道（ＬＵＭＯ）のエネルギー準位が、下記の関係を満たす請求項１に記載の電子デバイス封止用組成物。
    　５．９ｅＶ≦ＬＵＭＯ－ＨＯＭＯ≦６．５ｅＶ     According to claim 1, the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the photopolymerizable monomer contained in the electronic device encapsulation composition satisfy the following relationship. Composition for encapsulating electronic devices.
    5.9eV≦LUMO-HOMO≦6.5eV
  7. 　光重合性モノマー及び光重合開始剤を含有する電子デバイス封止用組成物を硬化して電子デバイスを封止する電子デバイス封止膜であって、
    　前記光重合性モノマーとして、（メタ）アクリレートを含有し、
    　前記電子デバイス封止膜の波長３８０ｎｍにおける屈折率が、１．４５～１．５６の範囲内であり、かつ、
    　前記電子デバイス封止膜の、波長３８０ｎｍにおける消衰係数が、５０×１０－５～２００×１０－５の範囲内である電子デバイス封止膜。     An electronic device sealing film that seals an electronic device by curing an electronic device sealing composition containing a photopolymerizable monomer and a photopolymerization initiator,
    The photopolymerizable monomer contains (meth)acrylate,
    The refractive index of the electronic device sealing film at a wavelength of 380 nm is within the range of 1.45 to 1.56, and
    The electronic device sealing film has an extinction coefficient within the range of 50×10 −5 to 200×10 −5 at a wavelength of 380 nm.
  8. 　電子デバイスを封止する電子デバイス封止膜であって、
    　窒化ケイ素、酸化ケイ素又は酸窒化ケイ素を含有する第１封止層と、
    　請求項１から請求項６までのいずれか一項に記載の電子デバイス封止用組成物を用いた第２封止層と、を有する電子デバイス封止膜。     An electronic device sealing film that seals an electronic device,
    a first sealing layer containing silicon nitride, silicon oxide or silicon oxynitride;
    An electronic device sealing film comprising a second sealing layer using the electronic device sealing composition according to any one of claims 1 to 6.
  9. 　前記第２封止層上に、窒化ケイ素、酸化ケイ素又は酸窒化ケイ素を含有する第３封止層を有する請求項８に記載の電子デバイス封止膜。 The electronic device sealing film according to claim 8, further comprising a third sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride on the second sealing layer.
  10. 　請求項１から請求項６までのいずれか一項に記載の電子デバイス封止用組成物を用いて、電子デバイス封止膜を形成する方法であって、
    　電子デバイス上に気相法により第１封止層を形成する工程と、
    　前記第１封止層上に前記電子デバイス封止用組成物を塗布することにより第２封止層を形成する工程と、を備える電子デバイス封止膜形成方法。     A method of forming an electronic device sealing film using the electronic device sealing composition according to any one of claims 1 to 6, comprising:
    forming a first sealing layer on the electronic device by a vapor phase method;
    A method for forming an electronic device sealing film, comprising: forming a second sealing layer by applying the electronic device sealing composition on the first sealing layer.
  11. 　前記第２封止層上に、気相法により第３封止層を形成する工程を備える請求項１０に記載の電子デバイス封止膜形成方法。 The electronic device sealing film forming method according to claim 10, comprising the step of forming a third sealing layer on the second sealing layer by a vapor phase method.
  12. 　インクジェット法により前記第２封止層を形成する請求項１０に記載の電子デバイス封止膜形成方法。 The electronic device sealing film forming method according to claim 10, wherein the second sealing layer is formed by an inkjet method.
PCT/JP2023/027397 2022-07-29 2023-07-26 Composition for electronic device sealing, electronic device sealing film, and method for forming electronic device sealing film WO2024024841A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019140003A (en) * 2018-02-13 2019-08-22 パナソニックＩｐマネジメント株式会社 Ultraviolet curable resin composition, organic EL light emitting device manufacturing method, and organic EL light emitting device
JP2021128938A (en) * 2020-02-13 2021-09-02 三星エスディアイ株式会社Samsung SDI Co., Ltd. Composition for sealing organic light-emitting element, and organic light-emitting element display device including organic layer formed from the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019140003A (en) * 2018-02-13 2019-08-22 パナソニックＩｐマネジメント株式会社 Ultraviolet curable resin composition, organic EL light emitting device manufacturing method, and organic EL light emitting device
JP2021128938A (en) * 2020-02-13 2021-09-02 三星エスディアイ株式会社Samsung SDI Co., Ltd. Composition for sealing organic light-emitting element, and organic light-emitting element display device including organic layer formed from the same

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