JP2020518952A - Sealing material composition - Google Patents

Abstract

The present application relates to a sealant composition, an organic electronic device including the same, and a method for manufacturing the organic electronic device. The present invention effectively shuts off moisture or oxygen that flows into the organic electronic device from the outside, thereby improving the life of the organic electronic device. And a sealing material composition having excellent storage stability during distribution and storage.

Description

Mutual reference with related applications This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0055101, dated April 28, 2017, and discloses all the documents disclosed in the document of the Korean patent application. The content is included as part of this specification.

TECHNICAL FIELD The present application relates to a sealing material composition, an organic electronic device including the same, and a method for manufacturing the organic electronic device.

An organic electronic device (OED) refers to a device including an organic material layer that generates an alternating charge by utilizing holes and electrons, and examples thereof include a photovoltaic device and a rectifier. Rectifiers, transmitters, organic light emitting diodes (OLEDs), and the like.

Among the organic electronic devices, an organic light emitting diode (OLED) has lower power consumption and faster response speed than existing light sources, and is advantageous for thinning a display device or lighting. Further, the OLED is excellent in space utilization and is expected to be applied in various fields including various portable devices, monitors, notebook computers and televisions.

The most important problem in the commercialization and expansion of applications of OLEDs is durability. Organic materials and metal electrodes contained in the OLED are very susceptible to oxidation due to external factors such as moisture. Therefore, products containing OLEDs are highly sensitive to environmental factors. Accordingly, various methods have been proposed to effectively block the permeation of oxygen or moisture from the outside into an organic electronic device such as an OLED.

The present application provides a sealing material composition that can effectively block moisture or oxygen that flows into an organic electronic device from the outside to ensure the life of the organic electronic device and has excellent storage stability during distribution and storage. provide.

The present application relates to a sealant composition. The sealing material composition may be, for example, an encapsulating material applied to encapsulating or encapsulating an organic electronic device such as an OLED. In one example, the sealant composition of the present application can be applied to seal or encapsulate the front surface of an organic electronic device. Therefore, after the sealing material composition is applied for encapsulation, it may be in the form of an organic layer that seals the front surface of the organic electronic device. In addition, the organic layer may be alternately laminated on an organic electronic device together with an inorganic protective film and/or an inorganic layer described later to form a sealing structure.

In a specific example of the present application, the present application relates to a sealing material composition for encapsulating an organic electronic device applicable to an inkjet process and a method for producing the same, wherein the composition uses inkjet printing capable of non-contact patterning. Then, it may be designed to have appropriate physical properties when ejected onto the substrate.

As used herein, the term "organic electronic device" refers to an article or device having a structure that includes a layer of organic material between a pair of electrodes facing each other that utilizes holes and electrons to generate an alternating charge. Examples include, but are not limited to, photovoltaic devices, rectifiers, transmitters, organic light emitting diodes (OLEDs), and the like. In one example of the present application, the organic electronic device may be an OLED.

An exemplary sealant composition is a solventless type photocurable sealant composition, which can include a curable compound, a photoinitiator, a photosensitizer, and a heat stabilizer. The curable compound, the photoinitiator, the photosensitizer and the heat stabilizer are 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. And 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; 96 parts by weight, 2-4 parts by weight, 0.2-1.4 parts by weight and 0.2-1.4 parts by weight; 93-96 parts by weight, 2.5-3.5 parts by weight, 0.3- It can be included in the composition at 0.9 parts by weight and 0.3 to 0.9 parts by weight. In the present application, the specific composition is controlled in a limited content range to suppress side reactions during the distribution and storage steps before the sealing material composition is applied on the organic electronic device. The desired viscosity can be maintained to maintain its storage stability as an injectable composition.

In an embodiment of the present application, the curable compound may include at least one or more curable functional groups. The curable functional group may be, for example, one or more 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 more. The present application can realize excellent durability reliability, adhesive property and moisture barrier property by using the curable compound.

Exemplary curable compounds can include epoxy compounds and compounds having oxetane groups. In an embodiment of the present application, the compound having an oxetane group may be included in the range of 45 parts by weight to 145 parts by weight with respect to 100 parts by weight of the epoxy compound. The compound having an oxetane group is 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 with respect to 100 parts by weight of the epoxy compound. Can be included in. As used herein, the term "parts by weight" means the weight ratio between each component. The present application is capable of forming an organic layer on an organic electronic device by an inkjet method by controlling the specific composition and its content range, and the applied sealing material composition spreads excellently within a short time. It is possible to provide an organic layer having properties and having excellent curing strength after being cured. In addition, the specific content of the curable compound may realize excellent storage stability, especially with the photoinitiator, the photosensitizer, and the heat stabilizer.

In one example, the sealing material composition of the present application may have a contact angle with 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. In the present application, by adjusting the contact angle to 30° or less, it is possible to secure the spreadability in a short time in inkjet coating, and thus it is possible to form a thin organic layer. In the present application, the contact angle may be measured by applying one drop of the sealing material composition on glass using a Sessile Drop measuring method, or by measuring the average value after applying 5 times. It may be.

In one example, the curable compound including the epoxy compound and the compound having an oxetane group is contained in an amount of 70 wt% or more, 75 wt% or more, 80 wt% or more 85 wt% or more, or 89 wt% or more in the entire components of the sealing material composition. obtain. The upper limit is not particularly limited, and may be 99 wt% or less, 95 wt% or less, or 93 wt% or less.

In one example, the epoxy compound may be at least monofunctional or more. That is, one or more or two 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 realizes an appropriate degree of cross-linking in the adhesive and realizes excellent heat resistance and durability at high temperature and high humidity.

In the embodiments of the present application, 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 sealing material composition of the present application may include at least one of a compound having a cyclic structure in the molecular structure and a linear or branched aliphatic compound as an epoxy compound, or may include them together. .. In one example, the compound having a cyclic structure in the molecular structure may have 3 to 10, 4 to 8 or 5 to 7 ring-constituting atoms in the molecular structure. There may be 1 or more or 2 or more and 10 or less structures. When the compound having a cyclic structure and the linear or branched aliphatic compound are included together, the linear or branched aliphatic compound is 20 parts by weight based on 100 parts by weight of the compound having a cyclic structure. Above, 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. ˜173 parts by weight may be included in the sealant composition. The present application controls the content range so that the sealing material composition has suitable physical properties when front-sealing an organic electronic device, has excellent curing strength after curing, and has excellent moisture content. Make it possible to embody barrier properties together.

In one example, the epoxy compound can have an epoxy equivalent in the range of 50-350 g/eq, 73-332 g/eq, 94-318 g/eq or 123-298 g/eq. The weight average molecular weight of the compound having an oxetane group may be 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 controls the epoxy equivalent of the epoxy compound to be low, or adjusts the weight average molecular weight of the compound having an oxetane group to be low, thereby improving the degree of completion of curing after curing the sealing material, while increasing the viscosity of the composition. Can be prevented from becoming too high and making the ink jet process impossible, and at the same time, a moisture barrier property and excellent curing sensitivity can be provided. In the present specification, the weight average molecular weight means a conversion value with respect to standard polystyrene measured by GPC (Gel Permeation Chromatograph). In one example, a column consisting of a metal tube having a length of 250-300 mm and an inner diameter of 4.5-7.5 mm is packed with 3-20 mm polystyrene beads. When a diluted solution obtained by dissolving the substance to be measured in a THF solvent is passed through the column, the weight average molecular weight can be indirectly measured depending on the flow-out time. The amount separated from the column according to size can be detected by plotting with time. In addition, in this 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 by the method defined in JIS K 7236.

Further, 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 realizes excellent printability even at high temperature in an inkjet process by controlling the boiling point of the compound within the above range, has an excellent moisture barrier property from the outside, suppresses outgas, and damages applied to the device. It is possible to provide a sealing material that can prevent the above. In this specification, the boiling point may be measured at 1 atm, unless otherwise specified.

In one example, compounds having a cyclic structure within the molecular structure include 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate (EEC) and derivatives, dicyclopentadiene dioxide and derivatives, vinylcyclohexenediene. Examples thereof include oxides and derivatives, 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate) and derivatives, but are not limited thereto.

In one example, the compound containing the oxetane group is not limited in its structure as long as it has the functional group, and examples thereof include OXT-221, CHOX, OX-SC, OXT101, OXT121, OXT221 or OXT212 manufactured by TOAGOSEI. , Or EHO, OXBP, OXTP or OXMA manufactured by ETERACOLL. In addition, the linear or branched aliphatic epoxy compound is an aliphatic glycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, propylene glycol diglycidyl ether. It may include, but is not limited to, ether, diethylene glycol diglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether or neopentyl glycol diglycidyl ether.

In embodiments of the present application, the sealant composition may further include a photoinitiator. The photoinitiator may be a cationic photopolymerization initiator.

In the case of the cationic photopolymerization initiator, materials known in the art can be used, and examples thereof include a cation moiety containing aromatic sulfonium, aromatic iodonium, aromatic diazonium or aromatic ammonium, AsF ₆ ⁻ , SbF ₆ ⁻ , PF. ₆ ^-, or it may include tetrakis (pentafluorophenyl) compound having an anion portion including borate. Further, as the cationic photopolymerization initiator, an onium salt or organometallic salt-based ionized cationic initiator or an organic silane or a latent sulfonic acid-based or non-ionized cationic photopolymerization is used. Initiators can be used. Examples of the onium salt-based initiator include diaryliodonium salt, triarylsulfonium salt, aryldiazonium salt, and the like. Examples of the organometallic salt initiator include iron allene. (Iron arene) and the like, and examples of the organic silane-based initiator include o-nitrobenzyl triaryl silyl ether, triaryl silyl peroxide, or acyl silane. Examples of the latent sulfonic acid-based initiator include α-sulfonyloxy ketone and α-hydroxymethyl benzoin sulfonate, but are not limited thereto.

In one example, the present application is particularly considered when it is applied to the use of sealing an organic electronic device by an ink jet method and is included together with the above-mentioned curable compound, photosensitizer and heat stabilizer. A sulfonium salt may be included as a photoinitiator. In the present application, the storage stability can be favorably realized by adjusting the content ratio between the respective compositions in the composition of the specific composition.

The photoinitiator containing the sulfonium salt may have at least one ring structure in the molecular structure. The ring structure is a ring structure having 3 to 10 ring atoms, 4 to 8 ring atoms or 5 to 7 ring atoms in the molecular structure, and may be an aliphatic ring structure or an aromatic ring structure. In an embodiment of the present application, the sulfonium salt may include at least one or more aryl groups, for example, a phenyl group. The aryl group may be optionally substituted with one or more substituents, and as the substituent, a halogen atom, a hydroxy group, a carboxyl group, a thiol group, an alkyl group, an alkoxy group, an alkenyl group, an epoxy group, a cyano group, Examples thereof include, but are not limited to, a carboxyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an aryl group, or an aromatic-substituted mercapto group such as a thiolphenol group. In one example, the sulfonium salt may have at least one aryl group having an aromatic-substituted mercapto group 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 entire curable compound in the composition. The present application can maintain long-term reliability of the composition with the photosensitizer and the heat stabilizer by including the specific photoinitiator.

In a specific example of the present application, the sealing material composition may include a photosensitizer in order to complement the curability in active energy rays having a long wavelength 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, 350 nm to 398 nm or 375 nm to 397 nm.

The photosensitizer is an anthracene-based compound such as anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 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-dimethyl-4-methoxybenzophenone, 3 Benzophenone compounds such as 3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; acetophenone; dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, propanone, etc. Perylene; 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone and other fluorenone compounds; thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro- Thioxanthone compounds such as 4-propyloxythioxanthone, isopropylthioxanthone (ITX) and diisopropylthioxanthone; xanthone compounds such as xanthone and 2-methylxanthone; anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, t-butylanthraquinone, 2 Anthraquinone compounds such as 6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3 Acridine compounds such as bis(9-acridinyl)propane; benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione, dicarbonyl such as 9,10-phenanthrenequinone Compounds; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Methyl-4-(dimethylamino)benzoate , Ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate and other benzoate compounds; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6 -Bis(4-di Amino synergists such as ethylaminobenzal)cyclohexanone, 2,6-bis(4-diethylaminobenzal)-4-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 -3,6,7-Tetrahydro-1H,5H,11H-C1]-benzopyrano[6,7,8-ij]-quinolidin-11-one and other coumarin-based compounds; 4-diethylaminochalcone, 4-azide It may be one or more selected from the group consisting of chalcone compounds such as benzalacetophenone; 2-benzoylmethylene; and 3-methyl-b-naphthothiazoline.

In a specific example of the present application, the content ratio of the photosensitizer to the content of the photoinitiator is 0.1 to 0.8, 0.12 to 0.75, 0.13 to 0.72, 0.14 to. It may be in the range of 0.68, 0.15 to 0.63 or 0.16 to 0.58. The present application realizes an effect of increasing the curing sensitivity at a desired wavelength by adjusting the content of the photosensitizer with respect to the photoinitiator, and yet, in view of the relationship with the photoinitiator containing the sulfonium salt, It is possible to prevent the reliability of the composition from being lowered due to problems such as separation.

The sealant composition of the present application can include a heat stabilizer, as described above. The heat stabilizer can be exemplified by a cresol compound, and specific examples thereof include 2,6-di-tert-butyl-p-cresol. Examples of the heat stabilizer include thiazine compounds, quinone compounds, amino alcohols, and the like, and specific examples thereof include phenothiazine (PTZ), methylenequinone, 2-dimethylaminomethanol, or monomethyletherhydroquinone. Can be included. In an embodiment of the present application, the content ratio of the heat stabilizer to the content of the photoinitiator is 0.12 to 0.78, 0.13 to 0.72, 0.15 to 0.68 or 0.16 to. It may be in the range of 0.53. The present application controls the content of the heat stabilizer with respect to the photoinitiator to prevent viscosity increase, gelation or curing reaction due to unnecessary heat energy in the above-described composition, and to prevent ink from being used for long-term distribution or storage. It is possible to maintain the physical properties that can be applied.

In an embodiment of the present application, the sealing material composition may further include a surfactant. The sealing material composition can be provided as a liquid ink having improved spreadability by containing a surfactant. In one example, the surfactant can include a polar functional group, and the polar functional group can be 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 or a sulfonate. Further, in the specific example of the present application, the surfactant may be a non-silicon-based surfactant or a fluorine-based surfactant. The non-silicon-based surfactant or the fluorine-based surfactant is applied together with the curable compound described above to provide excellent coating properties on the organic electronic device. In addition, in the case of a surfactant containing a polar reactive group, since it has a high affinity with other components of the sealing material composition, an excellent effect can be realized in terms of adhesive force. In the embodiments of the present application, a hydrophilic fluorosurfactant or a non-silicone surfactant can be used to improve the coating property on the substrate.

Specifically, the surfactant may be a polymer type or oligomer type fluorine-based surfactant. As the surfactant, a commercially available product can be used, and examples thereof include Glide 100, Glide 110, Glide 130, Glide 460, Glide 440, Glide 450 or RAD2500 manufactured by TEGO Co., Ltd. 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 manufactured by Asahi Glass Co., Ltd. -112, S-113, S-121, S-131, S-132, S-141 and S-145 or Fluorad FC-93, FC-95, FC-98, FC-129, FC manufactured by Sumitomo 3M Limited. -135, FC-170C, FC-430 and FC-4430 or DuPont Zonyl FS-300, FSN, FSN-100 and FSO and BYK 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-DYNWET800. Those selected from the group can be used.

The surfactant is 0.01 to 10 parts by weight, 0.05 to 10 parts by weight, 0.1 parts by weight to 10 parts by weight, and 0.5 to 8 parts by weight with respect to 100 parts by weight of the curable compound. Alternatively, it may be included in an amount of 1 to 4 parts by weight. Within the above content range, the present application enables the sealant composition to be applied in an inkjet method to form a thin organic layer.

The sealant composition of the present application may further include a coupling agent. INDUSTRIAL APPLICABILITY The present application can improve the adhesion of the cured product of the sealing material composition to the adherend and the adhesion to 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 the specific examples of the present application, specific examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, and 2-glycidyloxypropyltriethoxysilane. Epoxy-based silane coupling agents such as (3,4-epoxycyclohexyl)ethyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyl. Mercapto-based silane coupling agents such as trimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N- Amino-based silane coupling agents such as methylaminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; 3 -Ureido-based silane coupling agents such as ureidopropyltriethoxysilane, vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styryl-based silanes such as p-styryltrimethoxysilane Coupling agent; acrylate-based silane coupling agent such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agent such as 3-isocyanatepropyltrimethoxysilane; bis(triethoxy) Sulfidic silane coupling agents such as silylpropyl)disulfide and bis(triethoxysilylpropyl)tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane and the like.

In the present application, the coupling agent may be included in an amount of 0.1 to 10 parts by weight, or 0.5 to 5 parts by weight, based on 100 parts by weight of the curable compound. In the present application, the effect of improving the adhesion by adding the coupling agent can be realized within the above range.

The sealing material composition of the present application can optionally include a moisture adsorbent. The term "moisture adsorbent" may be used as a general term to mean a component capable of adsorbing or removing moisture or moisture flowing from the outside through a physical or chemical reaction or the like. That is, it means a water-reactive adsorbent or a physical adsorbent, and a mixture thereof can also be used.

The specific type of water adsorbent that can be used in the present application is not particularly limited, and for example, in the case of a water-reactive adsorbent, one kind of metal oxide, metal salt or phosphorus pentoxide (P ₂ O ₅ ) or Examples of the physical adsorbent include zeolite, zirconia, and montmorillonite.

The sealing material composition of the present application contains a water adsorbent in an amount of 5 parts by weight to 100 parts by weight, 5 parts by weight to 80 parts by weight, 5 parts by weight to 70 parts by weight or 10 to 30 parts by weight based on 100 parts by weight of the curable compound. It can be included in parts quantity. In the sealing material composition of the present application, preferably, the content of the water adsorbent is controlled to 5 parts by weight or more, so that the sealing material composition or the cured product thereof can exhibit excellent moisture and moisture barrier properties. In addition, the present application can control the content of the water adsorbent to 100 parts by weight or less to provide a thin film sealing structure.

In one example, the sealant composition may further include an inorganic filler, if desired. The specific type 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 such as clay, talc, alumina, calcium carbonate or silica can be used.

The sealing material composition of the present application contains 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 material based on 100 parts by weight of a curable compound. A filler can be included. The present application can control the inorganic filler to preferably 1 part by weight or more to provide a sealing structure having excellent moisture or moisture barrier properties and mechanical properties. In addition, the present invention can provide a cured product that exhibits excellent moisture barrier properties even when formed into a thin film by controlling the content of the inorganic filler to 50 parts by weight or less.

The sealing material composition according to the present application may include various additives in addition to the above-described configuration, as long as the effects of the above-described invention are not affected. For example, the sealant composition may include a defoaming agent, a tackifier, a UV stabilizer, an antioxidant, and the like in an appropriate range depending on the desired physical properties.

In one example, the sealant composition may be liquid at ambient temperature, eg, about 25°C. In embodiments of the present application, the sealant composition may be liquid in a solventless form. The sealing material composition may be applied to seal an organic electronic device, and specifically, may be applied to seal a front surface of the organic electronic device. In the present application, since the sealing material composition has a liquid form at room temperature, the device can be sealed by a method of applying the composition to the side surface of the organic electronic device. In addition, the present application can control the volatile organic compound and/or water content by having a solvent-free form.

Further, the sealing material composition of the present application may be an ink composition. The sealing material composition of the present application may be an ink composition capable of an ink jetting process. The sealant composition of the present application can have certain compositions and physical properties so that it can be ink jettable.

Further, in a specific example of the present application, the sealing material composition has a viscosity of 50 cPs or less, 1 to 46 cPs, measured by a Brookfield DV-3 at a temperature of 25° C., a torque of 90% and a shear rate of 100 rpm. Alternatively, it may be in the range of 5 to 44 cPs. In the present application, by controlling the viscosity of the composition within the above range, it is possible to realize ink-jettable physical properties at the time of being applied to an organic electronic device, and to improve the coating property to seal a thin film. Material can be provided.

In one example, the sealant composition has a surface energy of the cured product after curing of 5 mN/m to 45 mN/m, 10 mN/m to 40 mN/m, 15 mN/m to 35 mN/m or 20 mN/m to 30 mN/. It may be in the range of m. The surface energy can be measured by a method known in the art, for example, the Ring Method method. In the present application, excellent coating properties can be realized within the surface energy range.

In the example of the present application, the surface energy (γ ^surface , mN/m) can be calculated as γ ^surface =γ ^dispersion +γ ^polar . In one example, surface energy can be measured using a water drop analyzer (Drop Shape Analyzer, KRUSS DSA100 product). For example, the surface energy is measured by applying the sealant composition to be measured to a SiNx substrate with a thickness of about 50 μm and a coating area of 4 cm ² (width: 2 cm, length: 2 cm) and after forming a sealing film (spin). coater), after drying about 10 minutes at room temperature under an atmosphere of nitrogen, to UV curing through light quantity of 4000 mJ / cm ² at an intensity of 1000 mW / cm ^2. After curing, deionized water having a known surface tension was dropped on the film, and the process of determining the contact angle was repeated 5 times to obtain the average value of the obtained 5 contact angle values. Similarly, the process of dropping diiodomethane having a known surface tension and determining the contact angle thereof is repeated 5 times, and the average value of the obtained five contact angle values is determined. After that, the surface energy can be calculated by substituting the numerical value (Strom value) related to the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method by using the obtained average value of the contact angles for deionized water and diiodomethane. ..

Further, in a specific example of the present application, the sealing material composition may have a light transmittance in a visible light region of 90% or more, 92% or more, or 95% or more after curing. Within the above range, the present application applies the sealing material composition to a top emitting organic electronic device to provide an organic electronic device with high resolution, low power consumption and longevity. In addition, the sealant composition of the present application may have a haze of 3% or less, 2% or less, or 1% or less according to the JIS K7105 standard test after curing, and the lower limit is not particularly limited, but is 0%. May be. Within the haze range, the sealant composition can have excellent optical properties after curing. In the present specification, the above-mentioned light transmittance or haze may be measured in a state where the sealing material composition is cured in an organic layer, and the thickness of the organic layer is 2 μm to 50 μm. It may be an optical characteristic measured when the thickness is one. In the embodiment of the present application, the water adsorbent or the inorganic filler may not be included in order to realize the optical characteristics.

The present application also relates to organic electronic devices. As shown in FIG. 1, the exemplary organic electronic device 3 includes a substrate 31, an organic electronic element 32 formed on the substrate 31, a front surface of the organic electronic element 32, and the above-described seal. And an organic layer 33 containing the material composition.

In a specific example of the present application, an organic electronic device includes 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. Can be included. The first electrode layer may be a transparent electrode layer or a reflective electrode layer, and the second electrode layer may be a transparent electrode layer or a reflective electrode layer. More specifically, the organic electronic device includes 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 formed on the organic layer. And layers.

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 film 35 for protecting the electrodes and the light emitting layer of the device. The protective film 35 may be an inorganic protective film. The protective film may be a protective layer formed by chemical vapor deposition (CVD), and the material thereof may be a known inorganic material, for example, 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 embodiment 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 protective film described above. 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 inorganic layer may have a thickness of 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 a dopant-free inorganic material or a dopant-containing inorganic material. 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. Alternatively, it may be an oxide of the above element, but is not limited thereto.

In one example, the thickness of the organic layer may be in the range of 2 μm to 20 μm, 2.5 μm to 15 μm, 2.8 μm to 9 μm. The present application can provide a thin organic layer to provide a thin-film organic electronic device.

The organic electronic device 3 of the present application may include a sealing structure including the organic layer 33 and the inorganic layer 34 described above, and the sealing structure includes at least one organic layer and at least one inorganic layer. And an organic layer and an inorganic layer can be repeatedly laminated. For example, the organic electronic device may have a structure of substrate/organic electronic device/protective film/(organic layer/inorganic layer) n, and n may be a number in the range of 1 to 100. .. FIG. 1 is a cross-sectional view exemplifying a case where n is 1.

In one example, the organic electronic device 3 of the present application may further include a cover substrate 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 can be used. For example, the substrate or the cover substrate may be 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. A polymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film or a polyimide film can be used.

In addition, the organic electronic device 3 of the present application further includes a sealing film 37 existing between the cover substrate 38 and the substrate 31 on which the organic electronic device 32 is formed, as shown in FIG. You can The encapsulation film 37 may be applied to the application of 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, but is not limited thereto. Not a thing. The sealing film 37 may seal the front surface of the above-described organic layer and inorganic layer sealing structure 36 stacked on the organic electronic device 32.

The present application also relates to a method of manufacturing an organic electronic device.

In one example, the manufacturing method includes forming an organic layer 33 on the substrate 31 having the organic electronic device 32 formed thereon so that the sealing material composition seals the front surface of the organic electronic device 32. Can be included.

In the above, the organic electronic device 32 may be formed by forming a reflective electrode or a transparent electrode as a substrate 31 on the substrate 31 such as glass or polymer film by a method such as vacuum deposition or sputtering, and forming an organic layer on the reflective electrode. It can be manufactured by forming a layer of material. 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. Next, 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 protective film 35 on the first electrode, the organic material layer, and the second electrode formed on the substrate 31. Then, the above-mentioned organic layer 33 is applied on the substrate 31 so as to cover the front surface of the organic electronic device 32. At this time, the step of forming the organic layer 33 is not particularly limited, and the sealing material composition may be applied to the front surface of the substrate 31 by inkjet printing (Inkjet), gravure coating, spin coating, screen printing or reverse printing. A process such as offset coating (Reverse Offset) can be used.

In addition, the manufacturing method may further include irradiating the organic layer with light. In the present invention, the curing process may be performed on the organic layer that seals the organic electronic device, and thus the curing process may be performed, for example, in a heating chamber or a UV chamber, and preferably in a UV chamber. Can be advanced.

In one example, the above-mentioned sealant composition may be applied to form a front organic layer, and then the composition may be irradiated with light to induce crosslinking. Irradiating the light, the irradiation with light having a wavelength range of 250nm~450nm or 300nm~450nm area zones in quantity of light amount or 0.5~5J / cm ² of 0.3~6J / cm ² Can be included.

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

The present application effectively seals out moisture or oxygen that flows into an organic electronic device from the outside, can ensure the life of the organic electronic device, and has excellent storage stability during distribution and storage. An organic electronic device including the same is provided.

1 is a cross-sectional view showing an organic electronic device according to one example of the present invention. 1 is a cross-sectional view showing an organic electronic device according to one 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
An alicyclic epoxy compound (Celloxide 2021P manufactured by Daicel Co., Ltd.), a 1,4-butanediol diglycidyl ether aliphatic compound (DE200, HAJIN CHEM TECH) as a curable compound at room temperature, and a curable compound containing an oxetane group (TOAGOSEI company) OXT-212), a photoinitiator having a triphenylsulfonium salt (UV693 from TETRA CHEM), a fluorosurfactant (F447 from DIC), a photosensitizer (9,10-dibutoxyanthracene) and heat. Stabilizer 2,6-di-tert-butyl-p-cresol (BHT from SIGMA aldrich) was added to 20:20:54:3:1:0.5:0.5 (Celloxide 2021P:DE200:OXT212:UV693). :F447:9,10-dibutoxyanthracene:2,6-di-tert-butyl-p-cresol) was added to the mixing vessel.

A uniform sealing material composition ink was manufactured by using a planetary mixer (Kurabo, KK-250s) in the mixing container.

Example 2
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 changed to 56 parts by weight.

Comparative Example 1
A sealant composition was prepared in the same manner as in Example 1, except that a photoinitiator having a diphenyliodonium salt (TTA UV-694) was used as the photoinitiator.

Comparative example 2
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 5 parts by weight and the content of the oxetane group-containing curable compound was changed to 49.5 parts by weight.

Comparative Example 3
A sealing material composition was produced in the same manner as in Example 1, except that the content of the photosensitizer was changed to 5 parts by weight and the content of the curable compound containing an oxetane group was changed to 49.5 parts by weight.

Comparative Example 4
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 part by weight.

Comparative Example 5
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.

Comparative Example 6
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.

Comparative Example 7
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 part by weight.

Experimental Example 1-Evaluation of Storage Stability The sealing material compositions produced in Examples and Comparative Examples were stored under the following conditions.
1) Under a N ₂ atmosphere, a temperature of 25° C. to 35° C., moisture and oxygen are 1,000 ppm or less, and stored for 15 days in a light-shielded container 2) Under an atmosphere of air, a temperature of 45° C. and light 15 days for storage in a container in which light is blocked 3) Store for 15 days in a container where the temperature of 25°C to 35°C and yellow are exposed 4) UV exposure film (green and yellow light) that is exposed to a white fluorescent lamp Is stored for 15 days in a container with a temperature of 25°C to 35°C and moisture and oxygen of 1,000 ppm or less.

The change in viscosity was measured under the above four conditions (measured at a temperature of 25° C., a torque of 90% and a shear rate of 100 rpm using a cone & plate manufactured by Brookfield), and the viscosity immediately before storage and after 15 days storage When the change in viscosity was within ±10%, it was indicated by O, and when it exceeded ±10% and the viscosity changed, it was indicated by X.

3 Organic Electronic Device 31 Substrate 32 Organic Electronic Element 33 Organic Layer 34 Inorganic Layer 35 Protective Film 36 Sealing Structure 37 Sealing Film 38 Cover Substrate

Claims (16)

A solventless photocurable sealant composition,
A curable compound, a photoinitiator containing a sulfonium salt, a photosensitizer and a heat stabilizer,
The curable compound, the photoinitiator, the photosensitizer and the heat stabilizer are 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. A sealing material composition for encapsulating an organic electronic element, which is included in 1. The curable compound contains at least one or more curable functional groups,
The sealing material composition for encapsulating an organic electronic element according to claim 1. The curable functional group is one or more selected from glycidyl group, oxetane group, isocyanate group, hydroxy group, carboxyl group, amide group, epoxide group, sulfide group, acetal group and lactone group,
The sealing material composition for encapsulating an organic electronic element according to claim 2. The curable compound contains at least two or more curable functional groups,
The sealing material composition for encapsulating an organic electronic element according to claim 2 or 3. The curable compound includes an epoxy compound; and a compound having an oxetane group,
The sealing material composition for encapsulating an organic electronic element according to claim 1. The epoxy compound includes a compound having a cyclic structure in the molecular structure and/or a linear or branched aliphatic compound.
The sealing material composition for encapsulating an organic electronic element according to claim 5. The linear or branched aliphatic compound is contained in an amount of 20 parts by weight or more and less than 205 parts by weight with respect to 100 parts by weight of the compound having a cyclic structure.
The sealing material composition for encapsulating an organic electronic element according to claim 6. The compound having an oxetane group is included in an amount of 45 to 145 parts by weight based on 100 parts by weight of the epoxy compound.
The sealing material composition for encapsulating an organic electronic element according to claim 5. The photoinitiator includes a cationic photopolymerization initiator,
The sealing material composition for encapsulating an organic electronic element according to any one of claims 1 to 8. The photoinitiator containing a sulfonium salt has at least one ring structure in the molecular structure,
The sealing material composition for encapsulating an organic electronic element according to any one of claims 1 to 9. The photosensitizer is a substance that absorbs a wavelength in the range of 200 nm to 400 nm,
The sealing material composition for encapsulating an organic electronic element according to claim 1. Thermal stabilizers include 2,6-di-tert-butyl-p-cresol, phenothiazine (PTZ), methylenequinone, 2-dimethylaminomethanol or monomethyletherhydroquinone,
The sealing material composition for encapsulating an organic electronic element according to any one of claims 1 to 11. The content ratio of the photosensitizer to the content of the photoinitiator is within the range of 0.1 to 0.8,
The sealing material composition for encapsulating an organic electronic element according to claim 1. Further comprising a surfactant,
The sealing material composition for encapsulating an organic electronic element according to any one of claims 1 to 13. A substrate; an organic electronic device formed on the substrate;
An organic layer that seals the front surface of the organic electronic device and contains the organic electronic device sealing material composition according to any one of claims 1 to 14.
Organic electronic devices including. The organic electronic device sealing material according to any one of claims 1 to 14 is formed on a substrate on which an organic electronic device is formed so that the organic electronic device is sealed so as to seal the front surface of the organic electronic device. A method of manufacturing an organic electronic device comprising the steps of forming a layer.

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