WO2018199705A1 - 밀봉재 조성물 - Google Patents

밀봉재 조성물 Download PDF

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Publication number
WO2018199705A1
WO2018199705A1 PCT/KR2018/004982 KR2018004982W WO2018199705A1 WO 2018199705 A1 WO2018199705 A1 WO 2018199705A1 KR 2018004982 W KR2018004982 W KR 2018004982W WO 2018199705 A1 WO2018199705 A1 WO 2018199705A1
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Prior art keywords
weight
parts
electronic device
organic electronic
compound
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PCT/KR2018/004982
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English (en)
French (fr)
Korean (ko)
Inventor
최국현
김준형
우유진
유미림
Original Assignee
주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2019558792A priority Critical patent/JP7020495B2/ja
Priority to CN201880028043.7A priority patent/CN110573565B/zh
Publication of WO2018199705A1 publication Critical patent/WO2018199705A1/ko

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    • 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
    • H10K50/842—Containers
    • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present application relates to a sealing material composition, an organic electronic device including the same, and a manufacturing method of the organic electronic device.
  • An organic electronic device refers to a device including an organic material layer that generates an exchange of electric charges using holes and electrons, and examples thereof include a photovoltaic device, a rectifier, Transmitters and organic light emitting diodes (OLEDs); and the like.
  • organic light emitting diodes have low power consumption, fast response speed, and are advantageous for thinning a display device or lighting, as compared with conventional light sources.
  • OLED has excellent space utilization, and is expected to be applied in various fields including various portable devices, monitors, notebooks, and TVs.
  • the present application can effectively block moisture or oxygen introduced into the organic electronic device from the outside to secure the life of the organic electronic device, and provides a sealing material composition excellent in storage stability during distribution and storage.
  • the present application relates to a sealant composition.
  • the sealant composition may be, for example, an encapsulant applied to encapsulating or encapsulating an organic electronic device such as an OLED.
  • the sealant composition of the present application may be applied to encapsulating or encapsulating the entire surface of the organic electronic device. Therefore, after the sealant composition is applied to the encapsulation, it may exist in the form of an organic layer that seals the entire surface of the organic electronic device.
  • the organic layer may be alternately stacked on the organic electronic device together with an inorganic protective film and / or an inorganic layer to be described later to form an encapsulation structure.
  • the present application relates to a sealing material composition for sealing an organic electronic device applicable to an inkjet process and a method for manufacturing the same, wherein the composition is discharged to a substrate using inkjet printing that can be patterned in a non-contact manner, It can be designed to have.
  • organic electronic device means an article or device having a structure including an organic material layer that generates an exchange of electric charge using holes and electrons between a pair of electrodes facing each other.
  • the photovoltaic device, a rectifier, a transmitter, and an organic light emitting diode (OLED) may be mentioned, but is not limited thereto.
  • the organic electronic device may be an OLED.
  • Exemplary sealant compositions are solvent-free photocurable sealant compositions and may include curable compounds, photoinitiators, photosensitizers, and thermal stabilizers.
  • the curable compound, the photoinitiator, the photosensitizer and the heat stabilizer may be included in the composition in a weight ratio of 90 to 98 parts by weight, 1 to 5 parts by weight, 0.01 to 3 parts by weight and 0.06 to 3 parts by weight, respectively.
  • 91 to 97 parts by weight, 1.5 to 4.5 parts by weight, 0.1 to 2 parts by weight and 0.1 to 2 parts by weight; 92 to 96 parts by weight, 2 to 4 parts by weight, 0.2 to 1.4 parts by weight and 0.2 to 1.4 parts by weight; 93 to 96 parts by weight, 2.5 to 3.5 parts by weight, 0.3 to 0.9 parts by weight and 0.3 to 0.9 parts by weight may be included in the composition.
  • the present application is to control the specific composition in a limited content range, before the sealant composition is applied on the organic electronic device, to suppress side reactions in the distribution and storage step, and to maintain the viscosity desired in the present application as a composition capable of ink jetting Storage stability can be maintained.
  • the curable compound may include at least one curable functional group.
  • the curable functional group may be, for example, at least one selected from oxetane group, glycidyl group, isocyanate group, hydroxy group, carboxyl group, amide group, epoxide group, sulfide group, acetal group and lactone group.
  • the curable functional group may be at least monofunctional or bifunctional or higher. The present application can implement excellent durability reliability, adhesive properties and moisture barrier properties by using the curable compound.
  • Exemplary curable compounds may include an epoxy compound and a compound having an oxetane group.
  • the compound having an oxetane group may be included in the range of 45 parts by weight to 145 parts by weight based on 100 parts by weight of the epoxy compound.
  • the compound having an oxetane group may be included in the range of 45 parts by weight to 145 parts by weight, 48 parts by weight to 144 parts by weight, 63 parts by weight to 143 parts by weight, or 68 parts by weight to 142 parts by weight based on 100 parts by weight of the epoxy compound. have.
  • the term "parts by weight” may mean a weight ratio between components.
  • the present application is capable of forming an organic layer in an inkjet method on an organic electronic device by controlling the specific composition and the content range described above, and the applied sealant composition has excellent spreadability within a short time and has excellent curing strength after curing.
  • the specific amount of the curable compound can achieve excellent storage stability, especially with the above-described photoinitiator, photosensitizer and heat stabilizer.
  • the sealant composition of the present application may have a contact angle to glass of 30 ° or less, 25 ° or less, 20 ° or less, or 12 ° or less.
  • the lower limit is not particularly limited, but may be 1 ° or 3 ° or more.
  • the present application can secure the spreadability within a short time in the inkjet coating by adjusting the contact angle to 30 ° or less, thereby forming an organic layer of a thin film.
  • the contact angle may be measured by applying a drop of the sealant composition on glass using a method of measuring the Sessile Drop, and measuring the average value after five application.
  • the curable compound including the epoxy compound and the compound having an oxetane group may be included in at least 70wt%, at least 75wt%, at least 80wt% or at least 85wt% or at least 89wt% in the total component of the sealant composition.
  • the upper limit is not particularly limited and may be 99 wt% or less, 95 wt% or less, or 93 wt% or less.
  • the epoxy compound may be at least one functional. That is, one or more epoxy functional groups may be present in the compound, and the upper limit is not particularly limited but may be 10 or less.
  • the epoxy compound implements an appropriate degree of crosslinking in the adhesive to achieve excellent heat resistance at high temperature and high humidity.
  • the epoxy compound may include a compound having a cyclic structure in the molecular structure and / or a linear or branched aliphatic compound. That is, the sealant composition of the present application may include at least one of a compound having a cyclic structure and a linear or branched aliphatic compound in the molecular structure as an epoxy compound, may be included together.
  • the compound having a cyclic structure in the molecular structure may have a ring constituent atom in the range of 3 to 10, 4 to 8 or 5 to 7 in the molecular structure and the cyclic structure in the compound at least 1 or at least 2, 10 It may be present below.
  • the linear or branched aliphatic compound is 20 parts by weight or more, less than 205 parts by weight, based on 100 parts by weight of the compound having a cyclic structure.
  • Sealant composition within the range of parts by weight to 204 parts by weight, 30 parts by weight to 203 parts by weight, 34 parts by weight to 202 parts by weight, 40 parts by weight to 201 parts by weight, 60 parts by weight to 200 parts by weight or 100 parts by weight to 173 parts by weight.
  • the present application by controlling the content range, the sealing material composition to have a suitable physical properties in the front seal the organic electronic device, to have a good curing strength after curing, and also to implement a good moisture barrier properties together.
  • the epoxy compound may have an epoxy equivalent in the range of 50 to 350 g / eq, 73 to 332 g / eq, 94 to 318 g / eq, or 123 to 298 g / eq.
  • the compound having an oxetane group may have a weight average molecular weight in the range of 150 to 1,000 g / mol, 173 to 980 g / mol, 188 to 860 g / mol, 210 to 823 g / mol or 330 to 780 g / mol.
  • the present application is to control the epoxy equivalent of the epoxy compound low, or by adjusting the weight average molecular weight of the compound having the oxetane group low, the viscosity of the composition is too high while improving the degree of completion of curing after the curing of the sealing material so that the inkjet process is impossible Can be prevented and at the same time can provide moisture barrier properties and excellent curing sensitivity.
  • the weight average molecular weight means a converted value with respect to standard polystyrene measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a column consisting of a metal tube having a length of 250 to 300 mm and an inner diameter of 4.5 to 7.5 mm is filled with 3 to 20 mm Polystyrene bead.
  • the weight average molecular weight can be indirectly measured according to the outflow time.
  • the amount separated from the column by size can be detected by plotting it with time.
  • the epoxy equivalent in this specification is the number of grams (g / eq) of resin containing 1 gram equivalent of epoxy group, and can be measured according to the method prescribed
  • the compound having an oxetane group may have a boiling point in the range of 90 to 300 ° C, 98 to 270 ° C, 110 to 258 ° C or 138 to 237 ° C.
  • the present application is to control the boiling point of the compound in the above range, to realize excellent printability even at high temperatures in the inkjet process, while excellent in water barrier property, the sealing material that can prevent damage to the device is suppressed out gas is suppressed It is possible to provide.
  • the boiling point may be measured at 1 atmosphere unless otherwise specified.
  • compounds having a cyclic structure in the molecular structure include 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate (EEC) and derivatives, dicyclopentadiene dioxides and derivatives, vinylcyclohexene Dioxides and derivatives, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) and derivatives may be exemplified, but is not limited thereto.
  • EEC 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate
  • dicyclopentadiene dioxides and derivatives vinylcyclohexene Dioxides and derivatives
  • 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) and derivatives
  • the compound containing the oxetane group is not limited in structure as long as it has the functional group, for example, OXT-221, CHOX, OX-SC, OXT101, OXT121, OXT221 or OXT212, manufactured by TOAGOSEI, or EHO, OXBP, OXTP or OXMA from ETERNACOLL can be exemplified.
  • linear or branched aliphatic epoxy compounds include aliphatic glycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol digly Include cylyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether or neopentylglycol diglycidyl ether It may be, but is not limited thereto.
  • the sealant composition may further include a photoinitiator.
  • the photoinitiator may be a cationic photopolymerization initiator.
  • cationic photo-polymerization initiator for example, aromatic sulfonium, aromatic iodonium, aromatic dia cation portion containing jonyum or aromatic ammonium and AsF 6 -, SbF 6 -, PF 6 -, or tetrakis (penta-fluorophenyl) may comprise a compound having an anion portion comprising a borate.
  • an onium salt or an organometallic salt-based ionization cation initiator or an organosilane or a latent sulfuric acid-based or non-ionized cationic photopolymerization initiator may be used.
  • Examples of the onium salt-based initiator include a diaryliodonium salt, a triarylsulfonium salt, an aryldiazonium salt, and the like. As the zero, iron arene and the like can be exemplified.
  • Examples of the organosilane-based initiator include o-nitrobenzyl triaryl silyl ether and triaryl silyl peroxide.
  • an acyl silane (acyl silane) and the like can be exemplified
  • the latent sulfuric acid-based initiator may be exemplified by ⁇ -sulfonyloxy ketone or ⁇ -hydroxymethylbenzoin sulfonate and the like, but is not limited thereto. .
  • the present application particularly relates to the use of sealing organic electronic devices in an inkjet manner and to the inclusion with the above-mentioned curable compounds, photosensitizers and thermal stabilizers, sulfonium salts as photoinitiators It may include.
  • the present application can achieve excellent storage stability by adjusting the content ratio between each composition in the specific composition combination.
  • the photoinitiator including the sulfonium salt may have at least one cyclic structure in a molecular structure.
  • the cyclic structure is a cyclic structure having a ring constituent atom in the range of 3 to 10, 4 to 8, or 5 to 7 in a molecular structure, and may be an aliphatic ring structure or an aromatic ring structure.
  • the sulfonium salt may include at least one or more aryl groups, for example, may include a phenyl group.
  • the aryl group may be optionally substituted with one or more substituents, and examples of the substituent include a halogen atom, hydroxy group, carboxyl group, thiol group, alkyl group, alkoxy group, alkenyl group, epoxy group, cyano group, carboxyl group, acryloyl group, Mercapto group substituted with an aromatic such as methacryloyl group, acryloyloxy group, methacryloyloxy group, aryl group or thiol phenol group and the like can be exemplified, but is not limited thereto.
  • substituents include a halogen atom, hydroxy group, carboxyl group, thiol group, alkyl group, alkoxy group, alkenyl group, epoxy group, cyano group, carboxyl group, acryloyl group, Mercapto group substituted with an aromatic such as methacryloyl group, acryloyloxy group, methacryloyloxy group, ary
  • the sulfonium salt may have at least one aryl group in which a mercapto group substituted with an aromatic group is present as a substituent.
  • the photoinitiator may be included in an amount of 0.1 to 15 parts by weight, 0.5 to 10 parts by weight, or 1 to 4 parts by weight based on 100 parts by weight of the total curable compound in the composition.
  • the present application includes the specific photoinitiator, thereby maintaining the long-term reliability of the composition together with the photosensitizer and the heat stabilizer.
  • the sealant composition may include a photosensitizer to compensate for the curability in the long wavelength active energy ray of 300nm or more.
  • the photosensitizer may be a compound that absorbs a wavelength in the range of 200 nm to 400 nm, 250 nm to 400 nm, 300 nm to 400 nm, 350 nm to 398 nm, or 375 nm to 397 nm.
  • the photosensitizer includes anthracene-based compounds such as anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl-9,10-dimethoxyanthracene; Benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3,3 Benzophenone compounds such as dimethyl-4-methoxybenzophenone and 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone; Acetophenone; Ketone compounds such as dimethoxy acetophenone, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and propanone; Perylene; Fluorenone compounds such
  • the content ratio of the photosensitizer to the content of the photoinitiator may be in the range of 0.1 to 0.8, 0.12 to 0.75, 0.13 to 0.72, 0.14 to 0.68, 0.15 to 0.63 or 0.16 to 0.58.
  • the present application by adjusting the content of the photosensitizer to the photoinitiator, while realizing a curing sensitivity synergistic action at the desired wavelength, while lowering the reliability of the composition due to problems such as phase separation in the relationship with the photoinitiator containing the sulfonium salt described above Can be prevented.
  • the sealant composition of the present application may include a heat stabilizer.
  • the heat stabilizer may be exemplified by a cresol compound, specifically 2,6-di-tert-Butyl-p-cresol and the like.
  • the thermal stabilizer may include a thiazine compound, a quinone compound, an amino alcohol, and the like, and specific examples thereof may include Phenothiazine (PTZ), Methylenequinones, 2-dimethyl amino methanol, or Mono methyl ether hydroquinone. .
  • the content ratio of the heat stabilizer to the content of the photoinitiator may be in the range of 0.12 to 0.78, 0.13 to 0.72, 0.15 to 0.68 or 0.16 to 0.53.
  • the present application by controlling the content of the thermal stabilizer for the photoinitiator, it is possible to maintain the inkjettable properties even during long-term distribution or storage while preventing the viscosity increase, gelation or curing reaction due to unnecessary heat energy in the above-described composition.
  • the sealant composition may further include a surfactant.
  • the sealant composition may include a surfactant, thereby providing a liquid ink having improved spreadability.
  • the surfactant may include a polar functional group, and the polar functional group may be present at the terminal of the compound structure of the surfactant.
  • the polar functional group may include, for example, a carboxyl group, a hydroxyl group, a phosphate salt or a sulfonate salt.
  • the surfactant may be a non-silicone-based surfactant or a fluorine-based surfactant.
  • non-silicone surfactant or the fluorine-based surfactant is applied together with the above-described curable compound to provide excellent coating properties on the organic electronic device.
  • the surfactant including the polar reactor since the affinity with other components of the sealant composition is high, an excellent effect in terms of adhesion may be realized.
  • hydrophilic fluorine-based surfactants or non-silicone-based surfactants may be used to improve the coating property on the substrate.
  • the surfactant may be a polymeric or oligomeric fluorine-based surfactant.
  • the surfactant may be a commercially available product, for example, Glide 100, Glide 110, Glide 130, Glide 460, Glide 440, Glide450 or RAD2500, Megaface F-251, F-281, of DaiNippon Ink & Chemicals (DIC), F-552, F554, F-560, F-561, F-562, F-563, F-565, F-568, F-570 and F-571 or Surflon S-111, S-112 by Asahi Glass , S-113, S-121, S-131, S-132, S-141 and S-145 or Fluorad FC-93, FC-95, FC-98, FC-129, FC-135 FC-170C, FC-430 and FC-4430 or BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK from
  • the surfactant may be included in an amount of 0.01 to 10 parts by weight, 0.05 to 10 parts by weight, 0.1 to 10 parts by weight, 0.5 to 8 parts by weight, or 1 to 4 parts by weight based on 100 parts by weight of the curable compound.
  • the present application allows the sealant composition to be applied to an inkjet method to form an organic layer of a thin film.
  • the sealant composition of the present application may further include a coupling agent.
  • This application can improve the adhesiveness with the to-be-adhered body of the sealing material composition, and the moisture permeability of hardened
  • the coupling agent may include, for example, a titanium coupling agent, an aluminum coupling agent, or a silane coupling agent.
  • the silane coupling agent 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethicone) Epoxy silane coupling agents such as methoxy) methylsilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptodecyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxys
  • the coupling agent may be included in an amount of 0.1 parts by weight to 10 parts by weight or 0.5 parts by weight to 5 parts by weight based on 100 parts by weight of the curable compound.
  • the present application can implement the effect of improving the adhesion by the coupling agent within the above range.
  • the sealant composition of the present application may include a moisture adsorbent as necessary.
  • moisture adsorbent may be used as a generic term for components that can adsorb or remove moisture or moisture introduced from the outside through physical or chemical reactions. That is, it means a moisture reactive adsorbent or a physical adsorbent, and mixtures thereof may also be used.
  • the specific kind of water adsorbent that can be used in the present application is not particularly limited, and, for example, in the case of the water reactive adsorbent, one kind or a mixture of two or more kinds of metal oxides, metal salts, or phosphorus pentoxide (P 2 O 5 ) may be mentioned.
  • a physical adsorbent zeolite, zirconia or montmorillonite may be mentioned.
  • the sealant composition of the present application may include a moisture adsorbent in an amount of 5 parts by weight to 100 parts by weight, 5 to 80 parts by weight, 5 parts by weight to 70 parts by weight, or 10 to 30 parts by weight with respect to 100 parts by weight of the curable compound. have.
  • the sealing material composition of the present application preferably by controlling the content of the moisture adsorbent to 5 parts by weight or more, the sealing material composition or its cured product can be made to exhibit excellent moisture and moisture barrier properties.
  • the present application may control the content of the moisture adsorbent to 100 parts by weight or less, to provide a sealing structure of the thin film.
  • the sealant composition may further include an inorganic filler, as needed.
  • the specific kind of filler that can be used in the present application is not particularly limited, and for example, one kind or a mixture of two or more kinds of clay, talc, alumina, calcium carbonate or silica may be used.
  • the sealant composition of the present application may include 0 to 50 parts by weight, 1 to 40 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight of an inorganic filler based on 100 parts by weight of the curable compound. have.
  • the present application by controlling the inorganic filler to preferably 1 part by weight or more, it is possible to provide a sealing structure having excellent moisture or moisture barrier properties and mechanical properties.
  • the present invention can provide a cured product exhibiting excellent moisture barrier properties even when formed into a thin film by controlling the inorganic filler content to 50 parts by weight or less.
  • the sealing material composition according to the present application may include various additives in a range that does not affect the effects of the above-described invention.
  • the sealant composition may include an antifoaming agent, a tackifier, an ultraviolet stabilizer, an antioxidant, or the like in an appropriate range of contents depending on the desired physical properties.
  • the sealant composition may be liquid at room temperature, for example about 25 ° C.
  • the sealant composition may be a liquid in the form of a solvent.
  • the sealant composition may be applied to encapsulating the organic electronic device, and specifically, may be applied to encapsulating the entire surface of the organic electronic device.
  • the sealing material composition may have a liquid form at room temperature, thereby sealing the device in such a manner that the composition is applied to the side surface of the organic electronic device.
  • the present application has a solvent-free form, thereby controlling the volatile organic compounds and / or moisture content.
  • the sealant composition of the present application may be an ink composition.
  • the sealant composition of the present application may be an ink composition capable of an inkjetting process.
  • the sealant composition of the present application may have a specific composition and physical properties to be inkjettable.
  • the sealant composition has a viscosity measured by Brookfield's DV-3 of 50 cPs or less, 1 to 46 cPs, or 5 to 5 at a temperature of 25 ° C., a torque of 90% and a shear rate of 100 rpm. It may be in the range of 44 cPs.
  • the present application by controlling the viscosity of the composition in the above range, it is possible to implement the inkjettable physical properties when applied to the organic electronic device, it is also possible to provide a sealing material of the thin film by excellent coating properties.
  • the sealant composition has a surface energy of 5mN / m to 45mN / m, 10mN / m to 40mN / m, 15mN / m to 35mN / m or 20mN / m to 30 after curing. It may be in the range of mN / m.
  • the surface energy may be measured by a method known in the art, for example, may be measured by the Ring Method method.
  • the present application can implement excellent coating properties within the surface energy range.
  • the surface energy can be measured using a Drop Shape Analyzer (DSA100 manufactured by KRUSS).
  • DSA100 Drop Shape Analyzer manufactured by KRUSS.
  • the surface energy is applied to the SiNx substrate with a thickness of about 50 ⁇ m and a coating area of 4 cm 2 (width: 2 cm, length: 2 cm) to form a sealing film (spin coater). After drying for about 10 minutes at room temperature in the atmosphere and UV-cured through a light amount of 4000mJ / cm 2 at an intensity of 1000mW / cm 2 .
  • the process of dropping deionized water having a known surface tension and dropping the contact angle was repeated five times to obtain an average value of the five obtained contact angle values.
  • the surface energy can be obtained by substituting the numerical value (Strom value) of the surface tension of the solvent by Owens-Wendt-Rabel-Kaelble method using the average value of the contact angles with respect to the deionized water and diiomethane obtained.
  • the sealant composition may have a light transmittance of 90% or more, 92% or more or 95% or more in the visible light region after curing.
  • the present application provides a high resolution, low power consumption, and long life organic electronic device by applying a sealant composition to a top emission organic electronic device.
  • the sealing composition of the present application may have a haze of 3% or less, 2% or less, or 1% or less after curing according to JIS K7105 standard test, and the lower limit is not particularly limited, but may be 0%.
  • the sealant composition may have excellent optical properties after curing.
  • the light transmittance or haze described above may be measured in the state of curing the sealant composition with an organic layer, and may be an optical property measured when the thickness of the organic layer is any one of 2 ⁇ m to 50 ⁇ m. .
  • the aforementioned moisture adsorbent or inorganic filler may not be included.
  • An exemplary organic electronic device 3 includes a substrate 31, as shown in FIG. An organic electronic device 32 formed on the substrate 31; And an organic layer 33 that seals the entire surface of the organic electronic device 32 and includes the sealant composition described above.
  • the organic electronic device may include a first electrode layer, an organic layer formed on the first electrode layer and including at least a light emitting layer, and a second electrode layer formed on the organic layer.
  • the first electrode layer may be a transparent electrode layer or a reflective electrode layer
  • the second electrode layer may also be a transparent electrode layer or a reflective electrode layer.
  • the organic electronic device may include a reflective electrode layer formed on the substrate, an organic layer formed on the reflective electrode layer and including at least a light emitting layer, and a transparent electrode layer formed on the organic layer.
  • the organic electronic device 23 may be an organic light emitting diode.
  • the organic electronic device according to the present application may be a top emission type, but is not limited thereto, and may be applied to a bottom emission type.
  • the organic electronic device may further include a protective film 35 that protects the electrode and the light emitting layer of the device.
  • the passivation layer 35 may be an inorganic passivation layer.
  • the protective film may be a protective layer by chemical vapor deposition (CVD), the material may be a known inorganic material, for example, silicon nitride (SiNx) may be used. In one example, silicon nitride (SiNx) used as the protective film may be deposited to a thickness of 0.01 ⁇ m 50 ⁇ m.
  • the organic electronic device 3 may further include an inorganic layer 34 formed on the organic layer 33.
  • the inorganic layer 34 is not limited in its material, and may be the same as or different from the above-described protective film.
  • the inorganic layer may be one or more metal oxides or nitrides selected from the group consisting of Al, Zr, Ti, Hf, Ta, In, Sn, Zn and Si.
  • the inorganic layer may have a thickness of 0.01 ⁇ m to 50 ⁇ m, or 0.1 ⁇ m to 20 ⁇ m, or 1 ⁇ m to 10 ⁇ m.
  • the inorganic layer of the present application may be an inorganic material without a dopant, or an inorganic material with a dopant.
  • the dopant that can be doped is one or more elements selected from the group consisting of Ga, Si, Ge, Al, Sn, Ge, B, In, Tl, Sc, V, Cr, Mn, Fe, Co, and Ni or the elements It may be an oxide of, but is not limited thereto.
  • the thickness of the organic layer may be in the range of 2 ⁇ m 20 ⁇ m, 2.5 ⁇ m 15 ⁇ m, 2.8 ⁇ m 9 ⁇ m.
  • the present application can provide a thin film of the organic electronic device by providing a thin thickness of the organic layer.
  • the organic electronic device 3 of the present application may include an encapsulation structure including the organic layer 33 and the inorganic layer 34 described above, and the encapsulation structure includes at least one organic layer and at least one inorganic layer.
  • the organic layer and the inorganic layer may be repeatedly stacked.
  • the organic electronic device may have a structure of a substrate / organic electronic device / protective film / (organic layer / inorganic layer) n, and n may be a number in the range of 1 to 100.
  • 1 is a cross-sectional view illustrating an example where n is 1;
  • the organic electronic device 3 of the present application may further include a cover substrate present on the organic layer 33.
  • the material of the substrate and / or the cover substrate is not particularly limited, and materials known in the art may be used.
  • the substrate or cover substrate may be a glass, a metal substrate or a polymer film.
  • the polymer film is, for example, polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyurethane film, ethylene-vinyl acetate film, ethylene -Propylene copolymer film, ethylene-ethyl acrylate copolymer film, ethylene-methyl acrylate copolymer film, polyimide film and the like can be used.
  • the encapsulation film 37 present between the cover substrate 38 and the substrate 31 on which the organic electronic device 32 is formed. It may further include.
  • the encapsulation film 37 may be applied to attach the substrate 31 on which the organic electronic device 32 is formed and the cover substrate 38.
  • the encapsulation film 37 may be an adhesive film or an adhesive film, but is not limited thereto. It is not.
  • the encapsulation film 37 may seal the entire surface of the encapsulation structure 36 of the organic layer and the inorganic layer, which are stacked on the organic electronic device 32.
  • the present application relates to a method for manufacturing an organic electronic device.
  • the manufacturing method comprises the steps of forming the organic layer 33 on the substrate 31 having the organic electronic device 32 formed thereon so that the above-mentioned sealing material composition seals the entire surface of the organic electronic device 32. It may include.
  • the organic electronic device 32 is a substrate 31, for example, to form a reflective electrode or a transparent electrode on the substrate 31, such as glass or a polymer film by vacuum deposition or sputtering, and the It can be prepared by forming an organic material layer on the reflective electrode.
  • the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer and / or an electron transport layer.
  • a second electrode is further formed on the organic material layer.
  • the second electrode may be a transparent electrode or a reflective electrode.
  • the manufacturing method of the present application may further include forming an inorganic passivation layer 35 on the first electrode, the organic material layer, and the second electrode formed on the substrate 31. Thereafter, the above-described organic layer 33 is applied to cover the organic electronic device 32 on the substrate 31. At this time, the step of forming the organic layer 33 is not particularly limited, and the inkjet printing, gravure coating, spin coating, screen printing or reverse offset of the sealant composition described above on the entire surface of the substrate 31. A process such as reverse offset may be used.
  • the manufacturing method also;
  • the method may further include irradiating light to the organic layer.
  • a curing process may be performed on the organic layer encapsulating the organic electronic device.
  • the curing process may be performed in, for example, a heating chamber or a UV chamber, and may be preferably performed in a UV chamber.
  • the composition may be irradiated with light to induce crosslinking.
  • Irradiating the light may include irradiating light having a wavelength range of 250 nm to 450 nm or 300 nm to 450 nm at a light amount of 0.3 to 6 J / cm 2 or a light amount of 0.5 to 5 J / cm 2 .
  • the manufacturing method of the present application may further include forming an inorganic layer 34 on the organic layer 33.
  • Forming the inorganic layer a method known in the art may be used, and may be the same as or different from the above-described protective film forming method.
  • the present application provides a sealant composition and an organic electronic device including the same, which effectively secures the life of the organic electronic device by effectively blocking moisture or oxygen introduced into the organic electronic device from the outside, and has excellent storage stability during distribution and storage. .
  • 1 and 2 are cross-sectional views illustrating an organic electronic device according to one example of the present invention.
  • Alicyclic epoxy compound (Celloxide 2021P from Daicel), aliphatic epoxy compound 1,4-butanediol diglycidyl ether (DE200, HAJIN CHEM TECH) as a curable compound at room temperature, and oxetane-containing curable compound (OXT- from TOAGOSEI) 212), photoinitiators with triphenylsulfonium salts (UV693 from TETRA CHEM), fluorine-based surfactants (F447 from DIC), photosensitizers (9,10-Dibutoxyanthracene) and thermal stabilizers 2,6-di-tert-Butyl-p -cresol (BHT from SIGMA aldrich) 20: 20: 54: 3: 1: 0.5: 0.5 (Celloxide2021P: DE200: OXT-212: UV693: F447: 9,10-Dibutoxyanthracene: 2,6-di-tert-But
  • the mixing container was prepared using a Planetary mixer (Kurabo, KK-250s) to prepare a uniform sealing composition ink.
  • a sealing material composition was prepared in the same manner as in Example 1 except that the content of the photoinitiator was changed to 1 part by weight and the content of the oxetane group-containing curable compound was 56 parts by weight.
  • a sealing material composition was prepared in the same manner as in Example 1, except that a photoinitiator having a diphenyl iodonium salt (TTA UV-694) was used as the photoinitiator.
  • TTA UV-694 a photoinitiator having a diphenyl iodonium salt
  • a sealing material composition was prepared in the same manner as in Example 1, except that 5 parts by weight of the thermal stabilizer and 49.5 parts by weight of the oxetane group-containing curable compound were changed.
  • a sealing material composition was prepared in the same manner as in Example 1, except that 5 parts by weight of the photosensitizer content and 49.5 parts by weight of the oxetane group-containing curable compound were changed.
  • a sealing material composition was prepared in the same manner as in Example 1, except that the content of the heat stabilizer was changed to 0.001 parts by weight.
  • a sealing material composition was prepared in the same manner as in Example 1, except that the content of the photosensitizer was changed to 3.2 parts by weight.
  • a sealing material composition was prepared in the same manner as in Example 1 except that the content of the heat stabilizer was changed to 3.5 parts by weight.
  • a sealing material composition was prepared in the same manner as in Example 1 except that the content of the photoinitiator was changed to 3.3 parts by weight and the content of the heat stabilizer was changed to 0.05 parts by weight.
  • the sealing material composition prepared in the Example and the comparative example was stored on condition of the following.
  • UV cut film green and yellowish
  • a container with a temperature of 25 ° C. to 35 ° C., moisture and oxygen of 1000 ppm or less.
  • Viscosity change was measured under these four conditions (Brookfield, Inc., using a con & plate at 25 ° C., 90% torque, and 100 rpm shear rate conditions). If the change is within ⁇ 10%, O, if the viscosity changes by more than ⁇ 10%, it is indicated by X.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Sealing Material Composition (AREA)
  • Polyethers (AREA)
  • Epoxy Resins (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
PCT/KR2018/004982 2017-04-28 2018-04-30 밀봉재 조성물 WO2018199705A1 (ko)

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CN201880028043.7A CN110573565B (zh) 2017-04-28 2018-04-30 封装组合物

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CN114874159B (zh) * 2022-04-15 2023-09-29 西安瑞联新材料股份有限公司 脂肪族环氧化合物及其组合物与应用

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