KR20210056752A - Ink composition - Google Patents

Abstract

The present application relates to an ink composition and an organic electronic device including the same. More specifically, the present invention provides an ink composition which can effectively block moisture or oxygen flowing into the organic electronic device from the outside to secure lifespan of the organic electronic device, can realize a front light emitting-type organic electronic device, can be applied to an ink jet method, can provide a thin-type display, and can effectively prevent interference of an electromagnetic field due to a low dielectric constant.

Description

Ink composition {INK COMPOSITION}

The present application relates to an ink composition, an organic electronic device including the same, and a method of manufacturing the organic electronic device.

An organic electronic device (OED) refers to a device including an organic material layer that generates an exchange of charges using holes and electrons, and examples thereof include a photovoltaic device, a rectifier, and And a transmitter and an organic light emitting diode (OLED).

Among the organic electronic devices, an organic light emitting diode (OLED) consumes less power than a conventional light source, has a faster response speed, and is advantageous in reducing the thickness of a display device or lighting. In addition, OLED has excellent space utilization and is expected to be applied in various fields ranging from various portable devices, monitors, notebooks, and TVs.

In the commercialization and expansion of OLED use, the most important problem is the durability problem. Organic materials and metal electrodes included in OLEDs are very easily oxidized by external factors such as moisture. Therefore, products containing OLED are highly sensitive to environmental factors. Accordingly, various methods have been proposed to effectively block the penetration of oxygen or moisture from the outside into an organic electronic device such as OLED.

As an example, a technology for forming a passivation film by repeatedly stacking an organic layer and an inorganic layer on the entire surface of an organic electronic device is well known. However, forming an organic layer of a thin film according to the thinning of the OLED is a major research task. Even if an organic layer is formed, since the organic layer of a thin film causes an interference problem of an electromagnetic field, a method to solve this problem is being studied.

This application effectively blocks moisture or oxygen flowing into the organic electronic device from the outside to secure the lifespan of the organic electronic device, enables the implementation of a top emission type organic electronic device, and can be applied by an inkjet method, A display can be provided, and an ink composition that effectively prevents interference of an electromagnetic field due to a low dielectric constant, and an organic electronic device including the same.

The present application relates to an ink composition. The ink composition may be, for example, an encapsulant or encapsulant composition applied to encapsulating or encapsulating an organic electronic device such as an OLED. In one example, the ink composition of the present application may be applied to encapsulating or encapsulating the entire surface of an organic electronic device. Accordingly, after the ink composition is applied to encapsulation, it may exist in the form of an organic layer sealing the entire surface of the organic electronic device. In addition, the organic layer may be stacked on the organic electronic device together with a protective film and/or an inorganic layer to be described later to form an encapsulation structure.

In a specific example of the present application, the present application relates to an ink composition for encapsulating an organic electronic device applicable to an inkjet process, and the composition is designed to have appropriate physical properties when discharged onto a substrate using inkjet printing capable of non-contact patterning. I can.

In the present specification, the term "organic electronic device" refers to an article or device having a structure including an organic material layer that generates an exchange of charges using holes and electrons between a pair of electrodes facing each other, for example Examples include, but are not limited to, a photovoltaic device, a rectifier, a transmitter, and an organic light-emitting diode (OLED). In one example of the present application, the organic electronic device may be an OLED.

Exemplary ink compositions may be photocurable or thermosetting compositions. The ink composition includes an epoxy compound, an oxetane compound, and a cyclic olefin compound. The cyclic olefin-based compound may be included in the range of 5 to 35% by weight. The lower limit of the content may be, for example, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 13% by weight, 15% by weight, 18% by weight, or 23% by weight or more, and the upper limit May be, for example, 33% by weight, 28% by weight, 25% by weight, 23% by weight, 18% by weight, 15% by weight or 13% by weight or less. The present application can effectively prevent interference between circuits by lowering the dielectric constant as well as forming an organic layer of a thin film through the combination of the specific composition of the ink composition. In general, there are various methods in the same industry to lower the dielectric constant, but this is separate from the implementation of ink jetting properties, and the implementation of low dielectric constant and moisture barrier properties while maintaining the ink jetting properties is a problem of the present application.

In a specific example of the present application, the ink composition may have a dielectric constant of 2.8 or less, 2.7 or less, 2.65 or less, or 2.6 or less under conditions of 100 kHz to 400 kHz and 25° C. after curing into a thin film having a thickness of 20 μm or less. . The lower limit of the dielectric constant is not particularly limited, and may be 0.01 or 0.1. In general, the dielectric constant decreases as the thickness increases, but the present application may have the dielectric constant range even though the thickness of the thin film is 20 μm or less. The lower limit of the thickness may be, for example, 1 μm or 3 μm, and the ink composition of the present application may have the dielectric constant range of the present application even if cured to the lower limit of the thickness range. After curing, the ink composition of the present application may be adjusted to a low dielectric constant within the above range.

In the present application, as described above, the ink composition may include a cyclic olefin-based compound. The cyclic olefin-based compound may have, for example, 3 to 15, 4 to 14, 5 to 13, 6 to 12, or 7 to 11 ring members in the molecular structure. The cyclic olefin-based compound may be an aliphatic cyclic compound, and may be a polymer having at least one unsaturated group and polymerized by the unsaturated group. The cyclic olefin-based compound may be a homopolymer or a copolymer compound. The cyclic olefin-based compound may be included in the range of 5 to 70 parts by weight based on 100 parts by weight of the epoxy compound. Illustratively, the lower limit of the content may be 8 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 40 parts by weight, or 52 parts by weight or more, and the upper limit is For example, it may be 65 parts by weight, 60 parts by weight, 55 parts by weight, 50 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 25 parts by weight, or 18 parts by weight or less. In one example, the cyclic olefin-based compound may have a weight average molecular weight in the range of 300 to 30,000 g/mol. The lower limit of the weight average molecular weight may be 400 g/mol, 450 g/mol, 500 g/mol, 600 g/mol, 700 g/mol, 750 g/mol, or 800 g/mol or more, and the upper limit is 20,000 g /mol, 10,000 g/mol, 5,000 g/mol, 3,000 g/mol, 1,000 g/mol, or 900 g/mol or less. In addition, the cyclic olefin-based compound may be monocyclic, but is not limited thereto, and may be a bicyclic or tricyclic compound. Exemplary cyclic olefin-based compounds may include norbornene-based compounds, cyclopentadiene compounds, or dicyclopentadiene compounds. The present application not only can lower the dielectric constant in the above specific composition formulation, but also has ink jetting properties and can implement excellent curing sensitivity and optical properties after curing.

In one example, the epoxy compound may be at least monofunctional or bifunctional or more. That is, 1 or 2 or more epoxy functional groups may be present in the compound, and the upper limit may be 10 or less, although it is not particularly limited. In one example, the monofunctional epoxy compound to be described later among the epoxy compounds may be monofunctional, the linear or branched polyfunctional aliphatic compound may be bifunctional or higher, and the alicyclic compound may be monofunctional or bifunctional or higher. The epoxy compound implements an appropriate degree of crosslinking in the ink composition to realize excellent heat resistance durability at high temperature and high humidity.

In the embodiments of the present application, the epoxy compound may further include an alicyclic compound and/or a linear or branched polyfunctional aliphatic compound. That is, the ink composition of the present application may further include at least one of an alicyclic compound and a linear or branched polyfunctional aliphatic compound as an epoxy compound, or may be included together. In one example, the alicyclic compound may have 3 to 10, 4 to 8, or 5 to 7 cyclic atoms in the molecular structure, and 1 or more, 2 or more, or 10 or less cyclic structures may exist in the compound. When the alicyclic compound and the linear or branched polyfunctional aliphatic compound are included together, the linear or branched aliphatic compound is 15 parts by weight or more, less than 205 parts by weight, 20 parts by weight, based on 100 parts by weight of the alicyclic compound More than, less than 205 parts by weight, 23 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 It may be included in the ink composition in the range of to 173 parts by weight. The present application is to control the content range, so that the ink composition can prevent damage to the device when sealing the organic electronic device entirely, have appropriate properties that can be ink jetted, have excellent curing strength after curing, and have excellent It makes it possible to implement moisture barrier properties together.

In one example, the epoxy compound of the present application 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. In addition, the oxetane compound and/or the epoxy compound has a weight average molecular weight of 150 to 1,000 g/mol, 173 to 980 g/mol, 188 to 860 g/mol, 210 to 823 g/mol, 330 to 780 g/mol, 350 to 495 g May be in the range of /mol. The present application is intended to prevent the inkjet process from becoming impossible due to excessively high viscosity of the composition while improving the curing completion degree after curing of the sealing material by controlling the epoxy equivalent of the epoxy compound to be low or by adjusting the weight average molecular weight of the compound to be low. And, at the same time, moisture barrier properties and excellent curing sensitivity can be provided. In the present specification, the weight average molecular weight refers to a value converted to standard polystyrene measured by GPC (Gel Permeation Chromatograph). In one example, 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 beads. When the diluted solution in which the substance to be measured is dissolved in a THF solvent is passed through a column, the weight average molecular weight can be indirectly measured according to the time outflow. The amount separated by size from the column can be detected by plotting by time. In addition, in the present specification, the epoxy equivalent is the number of grams (g/eq) of a resin containing 1 gram equivalent of an epoxy group, and can be measured according to the method specified in JIS K 7236.

The epoxy compound may further include a linear monofunctional compound having 7 or more carbon atoms. In the present application, the monofunctional compound may be included in an amount of 25 to 81 parts by weight based on 100 parts by weight of the total epoxy compound in the composition. The lower limit of the content of the monofunctional compound may be, for example, 28 parts by weight or more, 33 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, 53 parts by weight or more, or 70 parts by weight or more, and the upper limit of the content is, for example , 80.5 parts by weight or less, 73 parts by weight or less, 65 parts by weight or less, 55 parts by weight or less, 48 parts by weight or less, 43 parts by weight or less, or 38 parts by weight or less. The ink composition of the present application may further include not only the monofunctional epoxy compound, but also the aforementioned alicyclic compound or a linear or branched polyfunctional aliphatic compound, as the epoxy compound, all of the epoxy compounds included in the composition When calculated as 100, the monofunctional epoxy compound may be included in the weight ratio. The present application can effectively prevent interference between circuits by lowering the dielectric constant as well as forming an organic layer of a thin film through the combination of the specific composition of the ink composition.

In one example, the type of the linear monofunctional compound having 7 or more carbon atoms is a compound having one epoxy group, and is not particularly limited. For example, the monofunctional compound is a compound having a straight chain structure and may not have a branched chain structure or a cyclic structure. In addition, the monofunctional compound may not contain an aromatic structure as an aliphatic compound. In addition, the monofunctional compound is a type of epoxy compound and includes a cyclic ether group, but may not include an ether group in the molecular structure. That is, the monofunctional compound of the present application may not contain an ether group except for a cyclic ether group. The linear structure may have 7 to 30, 8 to 25, 9 to 20, or 10 to 15 carbon atoms. The present application can implement the coating properties of the ink composition, curing properties after curing, and properties of low dielectric constant by adjusting the ink composition to the above specific composition formulation. Hereinafter, in the present specification, the linear monofunctional compound having 7 or more carbon atoms may be referred to as a monofunctional compound or a monofunctional epoxy compound.

In a specific example of the present application, the oxetane compound is 10 to 155 parts by weight, 11 to 150 parts by weight, 12 parts by weight to 145 parts by weight, 13 parts by weight to 144 parts by weight, 14 parts by weight based on 100 parts by weight of the epoxy compound It may be included in the range of parts to 143 parts by weight or 15 parts by weight to 142 parts by weight. In specific embodiments, the upper limit of the content may be 130 parts by weight, 100 parts by weight, 80 parts by weight, 60 parts by weight, 40 parts by weight, 30 parts by weight, 20 parts by weight, or 18 parts by weight or less. The term "parts by weight" in the present specification may mean a weight ratio between each component. In this application, by controlling the content ratio of the composition, an organic layer can be formed on an organic electronic device by an inkjet method, and the applied ink composition has excellent spreadability within a short time, and an organic layer having excellent curing strength after curing is formed. Can provide.

In one example, the oxetane compound 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 a sealing material capable of preventing damage to the device by controlling the boiling point of the compound within the above range, implementing excellent printability even at high temperatures in the inkjet process, excellent moisture barrier properties from the outside, and suppressing outgassing. It is possible to provide. In the present specification, the boiling point may be measured at 1 atmosphere unless otherwise specified.

In the specific examples of the present application, the types of the epoxy compound and the oxetane compound described above are not particularly limited.

In one example, the alicyclic epoxy compound is 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (EEC) and derivatives, dicyclopentadiene dioxide and derivatives, vinylcyclohexene dioxide and derivatives, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) and derivatives may be exemplified, but are not limited thereto. In addition, the linear or branched polyfunctional aliphatic epoxy compound is aliphatic glycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether or neopentyl glycol diglycidyl ether It may include, but is not limited thereto.

In one example, the structure of the oxetane compound is not limited as long as it has the functional group, for example, OXT-221, CHOX, OX-SC, OXT101, OXT121, or OXT212 from TOAGOSEI, or EHO from ETERNACOLL, OXBP, OXTP or OXMA can be exemplified.

In addition, in one example, the linear monofunctional compound having 7 or more carbon atoms is 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxy-9-decene, 1,2-epoxyeicosane, 1,2-epoxyhexadecane, or 1,2-epoxyoctadecane may be included, but is not limited thereto.

In the embodiment of the present application, the ink composition may further include a photoinitiator. The photoinitiator may be an ionic photoinitiator. In addition, the photoinitiator may be a compound that absorbs a wavelength in the range of 200 nm to 400 nm. In the present application, by using the photoinitiator, excellent curing properties can be implemented in the specific composition of the present application.

In one example, the photoinitiator may be a cationic photoinitiator. Can be used a known material in the art for 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 a compound having an anionic moiety including tetrakis (pentafluorophenyl) borate. In addition, as the cationic photoinitiator, an onium salt or an organometallic salt-based ionized cationic initiator or an organic silane or latent sulfonic acid-based or non-ionized cationic photopolymerization initiator may be exemplified . Examples of the onium salt-based initiator include a diaryliodonium salt, a triarylsulfonium salt, or an aryldiazonium salt. Initiation of an organometallic salt series As the zero, iron arene, etc. may be exemplified, and examples of the organosilane-based initiator include o-nitrobenzyl triaryl silyl ether, triaryl silyl peroxide. Alternatively, acyl silane may be exemplified, and the latent sulfuric acid-based initiator may include α-sulfonyloxy ketone or α-hydroxymethylbenzoin sulfonate, but is not limited thereto. .

In one example, the ink composition of the present application may include a photoinitiator including a sulfonium salt as a photoinitiator in the above-described specific composition so as to be suitable for use in sealing an organic electronic device by an inkjet method. Although the ink composition according to the above composition is directly sealed on the organic electronic device, the amount of outgassing is small, so that chemical damage to the device can be prevented. In addition, the photoinitiator containing a sulfonium salt is also excellent in solubility and can be suitably applied to an inkjet process.

In a specific example of the present application, the photoinitiator may be included in an amount of 1 to 15 parts by weight, 3 to 14 parts by weight, or 7 to 13.5 parts by weight based on 100 parts by weight of the epoxy compound. The present application can minimize physical and chemical damage to the device due to the characteristics of the ink composition of the present application directly applied to the organic electronic device by adjusting the content range of the photoinitiator.

In the specific example of the present application, the ink composition may further include a surfactant. In one example, the surfactant may include a polar functional group, and the polar functional group may be present at the end of the compound structure of the surfactant. The polar functional group may include, for example, a carboxyl group, a hydroxy group, a phosphate, an ammonium salt, a carboxylate group, a sulfate or sulfonate. In addition, in the exemplary embodiment of the present application, the surfactant may be a non-silicone surfactant or a fluorine surfactant. The non-silicone-based surfactant or fluorine-based surfactant is applied together with the above-described epoxy compound and oxetane compound to provide excellent coating properties on organic electronic devices. On the other hand, in the case of a surfactant including a polar reactive group, an excellent effect in terms of adhesion can be realized because the affinity with other components of the above-described ink composition is high. In a specific example of the present application, a hydrophilic fluorine-based surfactant or a non-silicone-based surfactant may be used in order to improve the inkjet coating property of the substrate.

Specifically, the surfactant may be a polymeric or oligomeric fluorine-based surfactant. The surfactant may be a commercial product, for example, TEGO's Glide 100, Glide110, Glide 130, Glide 460, Glide 440, Glide450 or RAD2500, DIC (DaiNippon Ink & Chemicals) Megaface F-251, F-281, 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 from Asahi Glass , S-113, S-121, S-131, S-132, S-141 and S-145 or Sumitomo SriM's Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 and FC-4430 or DuPont Zonyl FS-300, FSN, FSN-100 and FSO and BYK's BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK -359, BYK-361N, BYK-381, BYK-388, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYKETOL-AQ, BYK-DYNWET 800, etc. Can be used.

The surfactant is 0.1 parts by weight to 10 parts by weight, 0.05 parts by weight to 10 parts by weight, 0.1 parts by weight to 10 parts by weight, 0.5 parts by weight to 8 parts by weight, or 1 to 4 parts by weight based on 100 parts by weight of the epoxy compound. Can be included. Within the above content range, the present application allows the ink composition to be applied to an ink jet method to form a thin organic layer.

In a specific example of the present application, the ink composition may further include a photosensitizer to supplement curability in a long wavelength active energy ray of 300 nm 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, or 350 nm to 395 nm.

The photosensitizers include anthracene 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 dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and propanone; Perylene; Fluorenone compounds, such as 9-fluorenone, 2-chloro-9-prorenone, and 2-methyl-9-fluorenone; Thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone (ITX), diisopropyl thioxanthone, etc. Thioxanthone compounds; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane, etc. Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione, and 9,10-phenanthrenequinone; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; Benzoate compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, 2,6-bis(4-diethylaminobenzal)-4- Amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3 -Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzo Coumarin compounds such as pyrano[6,7,8-ij]-quinolizin-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; 2-benzoylmethylene; And 3-methyl-b-naphthothiazoline.

The photosensitizer may be included in a range of 28 parts by weight to 40 parts by weight, 31 parts by weight to 38 parts by weight, or 32 parts by weight to 36 parts by weight, based on 100 parts by weight of the photoinitiator. In the present application, by adjusting the content of the photosensitizer, while implementing the effect of increasing the curing sensitivity at a desired wavelength, it is possible to prevent the photosensitizer from dissolving in the inkjet coating and thus lowering the adhesion.

The ink composition of the present application may further include a coupling agent. The present application can improve the adhesion of the ink composition to the adherend of the cured product or the moisture permeability of the cured product. The coupling agent may include, for example, a titanium-based coupling agent, an aluminum-based coupling agent, or a silane coupling agent.

In a specific example of the present application, as the silane coupling agent, specifically, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dime Epoxy-based silane coupling agents such as oxy)methylsilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, Amino-based silane coupling agents such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; Ureide-based silane coupling agents such as 3-ureidepropyltriethoxysilane, vinyl-based silane coupling agents such as vinyl trimethoxysilane, vinyl triethoxysilane, and vinylmethyldiethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; Acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; Isocyanate-based silane coupling agents such as 3-isocyanate propyltrimethoxysilane, bis(triethoxysilylpropyl) disulfide, and sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide; Phenyl trimethoxysilane, methacryloxypropyl trimethoxysilane, imidazole silane, triazine silane, etc. are mentioned.

In the present application, 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 epoxy compound. The present application may implement an effect of improving adhesion by adding a coupling agent within the above range.

In one example, the ink composition may further include an inorganic filler, if necessary. The specific type of the filler that can be used in the present application is not particularly limited, and for example, one type of clay, talc, alumina, calcium carbonate, or silica, or a mixture of two or more types may be used.

The ink 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 epoxy compound. have. The present application may provide a sealing structure having excellent moisture or moisture barrier properties and mechanical properties by controlling the inorganic filler to preferably 1 part by weight or more. In addition, the present invention can provide a cured product exhibiting excellent moisture barrier properties even when formed as a thin film by controlling the inorganic filler content to 50 parts by weight or less.

The ink composition of the present application may further include a moisture adsorbent, if necessary. The term “moisture adsorbent” may be used as a generic term for a component capable of adsorbing or removing moisture or moisture introduced from the outside through a physical or chemical reaction. That is, it means a chemically reactive adsorbent or a physical adsorbent, and a mixture thereof may also be used.

The specific type of moisture adsorbent that can be used in the present application is not particularly limited, and for example, in the case of a chemically reactive adsorbent, one or more mixtures of _{metal oxides, metal salts, or phosphorus pentoxide (P 2} O _{5) may be mentioned.} And, in the case of a physical adsorbent, zeolite, zirconia, montmorillonite, etc. are mentioned.

The ink composition of the present application contains a moisture adsorbent, based on 100 parts by weight of the epoxy compound, 5 parts by weight to 150 parts by weight, 5 to 110 parts by weight, 5 parts by weight to 90 parts by weight, 10 to 50 parts by weight, 12 to 38 parts by weight Alternatively, it may be included in an amount of 14 to 23 parts by weight. In the ink composition of the present application, by controlling the content of the moisture adsorbent to be preferably 5 parts by weight or more, the ink composition or a cured product thereof may exhibit excellent moisture and moisture barrier properties. In addition, the present application may control the content of the moisture adsorbent to 150 parts by weight or less, thereby providing a thin film encapsulation structure while having inkjet-able physical properties by being blended with the above-described composition.

In addition, the moisture adsorbent has an average particle diameter of 10 to 15000 nm, 30 nm to 10000 nm, 50 nm to 8000 nm, 80 nm to 5 μm, 90 nm to 3 μm, 95 nm to 980 nm, or 98 nm to 495 nm. Can be. In the present specification, the particle diameter may be measured by a known method with a D50 particle size analyzer. The moisture adsorbent having a size in the above range can effectively block moisture intruding from the outside by properly controlling the reaction rate with moisture, and also, in ink jetting, excellent fairness can be implemented by preventing agglomeration of the adsorbent.

As described above, the ink composition of the present application may be an ink composition applied to an inkjet process. However, controlling the viscosity of the ink composition in the inkjet process and implementing a composition having inkjettable physical properties through it may correspond to a very detailed operation. However, since the aforementioned moisture adsorbent is included in the composition in the form of particles, for example, the adsorbent is agglomerated in the composition or dispersibility is poor, resulting in a problem that the nozzle is clogged in the ink jetting process or uniform ink jetting is impossible. do. However, the present application provides an ink composition having the above-described specific composition, so that even if the moisture adsorbent is included, the ink jetting process may be smoothly possible.

In addition to the above-described configuration, various additives may be included in the ink composition according to the present application within a range that does not affect the effects of the above-described invention. For example, the ink composition may contain a defoaming agent, a tackifier, an ultraviolet stabilizer, or an antioxidant in an appropriate range depending on the desired physical properties.

In one example, the ink composition may be liquid at room temperature, for example, 25°C. In a specific example of the present application, the ink composition may be a liquid in a solvent-free form. The ink composition may be applied to encapsulating an organic electronic device, and specifically, may be applied to encapsulating the entire surface of an organic electronic device. The ink composition of the present application may have a specific composition and physical properties to enable ink jetting.

In one example, the ink composition of the present application may have a contact angle with respect to glass of 15° or less, 12° or less, 10° or less, or 8° or less. The lower limit is not particularly limited, but may be 1° or 3° or more. According to the present application, by adjusting the contact angle to be 15° or less, spreadability can be secured within a short time in inkjet coating, and accordingly, a thin organic layer can be formed. In the present application, the contact angle may be measured by applying a drop of the ink composition on the glass using the Sessile Drop measurement method, and may be measured by measuring an average value after applying 5 times.

In addition, the ink composition of the present application may be an ink composition. The ink composition of the present application may be an ink composition capable of an ink jetting process. The ink composition of the present application may have a specific composition and physical properties to enable ink jetting.

In addition, in a specific example of the present application, the ink composition has a viscosity of 50 cPs or less, 1 to 46 cPs, or 5 to 50 cPs or less, as measured by Brookfield's DV-3, 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. In the present application, by controlling the viscosity of the composition within the above range, it is possible to implement inkjettable physical properties at the time of application to an organic electronic device, and to provide an encapsulant of a thin film by improving coating properties.

The present application also relates to an organic electronic device. An exemplary organic electronic device 3, as shown in Fig. 1, includes a substrate 31; An organic electronic device 32 formed on the substrate 31; And an organic layer 33 including the above-described ink composition and sealing the entire surface of the organic electronic device 32.

In a specific example of the present application, the organic electronic device may include a first electrode layer, an organic layer formed on the first electrode layer and including at least an emission 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, and the second electrode layer may also be a transparent electrode layer or a reflective electrode layer. More specifically, the organic electronic device may include a reflective electrode layer formed on a 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.

In the present application, the organic electronic device 23 may be an organic light emitting diode.

In one example, 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 layer 35 for protecting the electrode and the emission layer of the device. The protective layer 35 may be an inorganic protective layer. The protective layer may be a protective layer by chemical vapor deposition (CVD), and the material may be the same as or different from the following inorganic layer, and a known inorganic material may be used. For example, the protective layer may be made of silicon nitride (SiNx). In one example, silicon nitride (SiNx) used as the protective layer may be deposited to a thickness of 0.01 μm to 50 μm.

In the specific example of the present application, the organic electronic device 3 may further include an inorganic layer 34 formed on the organic layer 33. The material of the inorganic layer 34 is not limited, and may be the same as or different from the above-described protective layer. In addition, the inorganic layer 34 may be formed in the same manner as the protective layer 35. In one example, 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 thickness of the inorganic layer may be 0.01 μm to 50 μm or 0.1 μm to 20 μm or 1 μm to 10 μm. In one example, the inorganic layer of the present application may be an inorganic material without a dopant or an inorganic material including a dopant. The dopant that may 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 element It may be an oxide of, but is not limited thereto.

In one example, the thickness of the organic layer may be in the range of 20 μm or less, 2 μm to 20 μm, 2.5 μm to 15 μm, and 2.8 μm to 9 μm. The present application may provide a thin organic electronic device by providing a thin 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. For example, the organic electronic device may have a structure of a substrate/organic electronic device/protective layer/(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 when n is 1.

In one example, 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 a material known in the art may be used. For example, the substrate or the cover substrate may be a glass, a metal substrate, or a polymer film. Polymer films are, 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 -A propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film may be used.

In addition, the organic electronic device 3 of the present application, as shown in FIG. 2, is an 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 for attaching the substrate 31 on which the organic electronic device 32 is formed and the cover substrate 38, and may be, for example, an adhesive film or an adhesive film that is solid at room temperature. However, it is not limited thereto. The encapsulation film 37 may seal the entire surface of the encapsulation structure 36 of the organic and inorganic layers stacked on the organic electronic device 32.

In addition, the present application relates to a method of manufacturing an organic electronic device.

In one example, the manufacturing method includes forming an organic layer 33 such that the above-described ink composition seals the entire surface of the organic electronic device 32 on a substrate 31 having an organic electronic device 32 formed thereon. It may include.

In the above, the organic electronic device 32 is a substrate 31, for example, a reflective electrode or a transparent electrode is formed on a substrate 31 such as glass or a polymer film by vacuum deposition or sputtering, and the It can be manufactured by forming an organic material layer on the reflective electrode. The organic material layer may include a hole injection layer, a hole transport layer, an emission layer, an electron injection layer, and/or an electron transport layer. Subsequently, 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 a protective layer 35 on the first electrode, the organic material layer, and the second electrode formed on the substrate 31. Then, the above-described organic layer 33 is applied on the substrate 31 to cover the organic electronic device 32 entirely. At this time, the step of forming the organic layer 33 is not particularly limited, and inkjet printing, gravure coating, spin coating, screen printing, or reverse offset by applying the above-described ink composition on the entire surface of the substrate 31 A process such as coating (Reverse Offset) may be used.

The manufacturing method is also; It may further include the step of irradiating light to the organic layer. In the present invention, the curing process may be performed on the organic layer encapsulating the organic electronic device, such a curing process) may be performed in, for example, a heating chamber or a UV chamber, and preferably may be performed in a UV chamber.

In one example, after the above-described ink composition is applied to form the front organic layer, 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 0.5 to 5 J/cm ² .

In addition, the manufacturing method of the present application may further include forming the inorganic layer 34 on the organic layer 33. The step of forming the inorganic material layer may be performed by a method known in the art, and may be the same as or different from the above-described method for forming a protective layer.

This application effectively blocks moisture or oxygen flowing into the organic electronic device from the outside to secure the lifespan of the organic electronic device, enables the implementation of a top emission type organic electronic device, and can be applied by an inkjet method, A display can be provided, and an ink composition that effectively prevents interference of an electromagnetic field due to a low dielectric constant, and an organic electronic device including the same.

1 and 2 are cross-sectional views illustrating an organic electronic device according to an example of the present invention.

Hereinafter, the present invention will be described in more detail through examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited by the examples presented below.

Example 1

As an epoxy compound at room temperature, an alicyclic epoxy compound (Daicel's Celloxide 2021P), a monofunctional epoxy compound (1,2-Epoxydecane), an oxetane compound (TOAGOSEI's OXT-212), a cyclic olefin compound (KOLON's SU-90, CAS69430-35-9) and a photoinitiator (Irgacure 290 from BASF) were mixed in a weight ratio of 25:50:10:10:5 (Celloxide2021P: 1,2-Epoxydecane: OXT-212: SU-90: Irgacure 290), respectively It was put into the container.

A uniform ink composition was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Example 2

As an epoxy compound at room temperature, an alicyclic epoxy compound (Daicel's Celloxide 2021P), a monofunctional epoxy compound (1,2-Epoxydecane), an oxetane compound (TOAGOSEI's OXT-212), a cyclic olefin compound (KOLON's SU-90, CAS69430-35-9) and photoinitiator (Irgacure 290 from BASF) were mixed in a weight ratio of 20:45:10:20:5 (Celloxide2021P: 1,2-Epoxydecane: OXT-212: SU-90: Irgacure 290), respectively An ink composition was prepared in the same manner as in Example 1, except that it was put into a container.

Example 3

As an epoxy compound at room temperature, an alicyclic epoxy compound (Daicel's Celloxide 2021P), a monofunctional epoxy compound (1,2-Epoxydecane), an oxetane compound (TOAGOSEI's OXT-212), a cyclic olefin compound (KOLON's SU-90, CAS69430-35-9) and photoinitiator (Irgacure 290 from BASF) were mixed in a weight ratio of 15:40:10:30:5 (Celloxide2021P: 1,2-Epoxydecane: OXT-212: SU-90: Irgacure 290), respectively An ink composition was prepared in the same manner as in Example 1, except that it was put into a container.

Comparative Example 1

As an epoxy compound at room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel), a monofunctional epoxy compound (1,2-Epoxydecane), an oxetane compound (OXT-212 from TOAGOSEI), and a photoinitiator (Irgacure 290 from BASF) were each 40 It was added to the mixing container in a weight ratio of :45:10:5 (Celloxide2021P: 1,2-Epoxydecane: OXT-212: Irgacure 290).

A uniform ink composition was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Comparative Example 2

As an epoxy compound at room temperature, alicyclic epoxy compounds (Daicel's Celloxide 2021P), monofunctional epoxy compounds (1,2-Epoxydecane), oxetane compounds (TOAGOSEI's OXT-212), and a photoinitiator (BASF's Irgacure 290) were each 20 :20:55:5 (Celloxide2021P: 1,2-Epoxydecane: OXT-212: Irgacure 290) was added to the mixing container in a weight ratio.

A uniform ink composition was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Comparative Example 3

As an epoxy compound at room temperature, an alicyclic epoxy compound (Daicel's Celloxide 2021P), a monofunctional epoxy compound (1,2-Epoxydecane), an oxetane compound (TOAGOSEI's OXT-212), a cyclic olefin compound (KOLON's SU-90, CAS69430-35-9) and photoinitiator (Irgacure 290 from BASF) were mixed in a weight ratio of 10:35:10:40:5 (Celloxide2021P: 1,2-Epoxydecane: OXT-212: SU-90: Irgacure 290), respectively It was put into the container.

A homogeneous composition was prepared using the mixing vessel using a Planetary mixer (Kurabo, KK-250s).

Physical properties in Examples and Comparative Examples were evaluated in the following manner.

1. Measurement of permittivity

An Al plate (conductive plate) was deposited at 500Å on the cleaned bare glass. Ink-jet coating the ink compositions prepared in Examples and Comparative Examples on the deposited Al plate surface, and ^{curing the coated composition with an amount of light of 1000 mJ/cm 2} through an LED UV lamp to form an organic layer having a thickness of 8 μm. I did. On the organic layer, an Al plate (conductive plate) was deposited at 500Å again.

Thereafter, the capacitance value of the Al plate was measured at 100 kHz and 25° C. using an Agilent 4194A measuring instrument. Through the measured values, the dielectric constant of the organic layer was calculated using the following calculation formula.

C = εr · εo · A/D (C: Capacitance of Al plate, εr: dielectric constant of organic layer, εo: vacuum dielectric constant, A: area of Al plate, D: distance between two Al plates)

In the present application, the dielectric constant is a relative value (ratio) to the dielectric constant in the vacuum when the dielectric constant in the vacuum is 1.

2. Measurement of curing sensitivity

The ink compositions prepared in Examples and Comparative Examples were irradiated with UV of 1J/cm ^{2 with an intensity of 1000 mW/cm 2} , and then the tack free time of the adhesive was measured. First, the ink composition is spin-coated, applied to a thickness of 10 μm, and cured. Immediately after curing, the time until the tacky feeling disappears when the surface of the sealing material is touched and there is no smearing of the sealing material is defined as tack free time, and is measured. If the tack free time was less than 1 second, it was classified as O, if it was less than 1 minute, it was classified as β, and if it was more than 5 minutes, it was classified as X.

permittivity Hardening sensitivity Example 1 2.77 O Example 2 2.64 O Example 3 2.56 O Comparative Example 1 2.84 O Comparative Example 2 3.35 O Comparative Example 3 - X

3: organic electronics
31: substrate
32: organic electronic device
33: organic layer
34: inorganic layer
35: shield
36: bag structure
37: encapsulation film
38: cover substrate

Claims (20)

An ink composition comprising an epoxy compound, an oxetane compound, and a cyclic olefin compound, wherein the cyclic olefin compound is included in a range of 5 to 35% by weight. The ink composition according to claim 1, wherein the ink composition has a dielectric constant of 2.8 or less under conditions of 100 kHz to 400 kHz and 25° C. after curing into a thin film having a thickness of 20 μm or less. The ink composition according to claim 1, wherein the cyclic olefin-based compound has a ring constituent atom in the range of 3 to 15 in the molecular structure. The ink composition according to claim 1, wherein the cyclic olefin-based compound is an aliphatic cyclic compound. The ink composition according to claim 1, wherein the cyclic olefin-based compound is a homopolymer or a copolymer compound. The ink composition of claim 1, wherein the cyclic olefin-based compound is contained within a range of 5 to 70 parts by weight based on 100 parts by weight of the epoxy compound. The ink composition according to claim 1, wherein the cyclic olefin-based compound has a weight average molecular weight in the range of 300 to 30,000 g/mol. The ink composition of claim 1, wherein the epoxy compound comprises an alicyclic compound or a linear or branched polyfunctional aliphatic compound. The ink composition according to claim 8, wherein the alicyclic compound has a ring constituent atom in the range of 3 to 10 in the molecular structure. The ink composition according to claim 8, wherein the linear or branched polyfunctional aliphatic compound is contained within a range of 15 parts by weight or more and less than 205 parts by weight based on 100 parts by weight of the alicyclic compound. The ink composition according to claim 1, wherein the epoxy compound comprises a linear monofunctional compound having 7 or more carbon atoms. The ink composition of claim 11, wherein the monofunctional compound is contained within a range of 25 to 81 parts by weight based on 100 parts by weight of the total epoxy compound in the composition. The ink composition of claim 1, wherein the oxetane compound is contained within a range of 10 parts by weight to 155 parts by weight based on 100 parts by weight of the epoxy compound. The ink composition according to claim 1, wherein the epoxy compound or the oxetane compound has a weight average molecular weight in the range of 150 to 1,000 g/mol. The ink composition according to claim 1, further comprising an ionic photoinitiator. The ink composition of claim 15, wherein the photoinitiator is contained in an amount of 1 to 15 parts by weight based on 100 parts by weight of the epoxy compound. The ink composition according to claim 1, which is in a solvent-free form. Board; An organic electronic device formed on a substrate; And an organic layer comprising the ink composition according to claim 1 and sealing the entire surface of the organic electronic device. The organic electronic device of claim 18, wherein the organic layer has a thickness of 20 μm or less. A method of manufacturing an organic electronic device comprising the step of forming an organic layer on a substrate having an organic electronic device formed thereon so that the ink composition of claim 1 seals the entire surface of the organic electronic device.

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