JP7020495B2 - Sealing material composition - Google Patents

Description

Mutual Citation with Related Application This application claims the benefit of priority under Korean Patent Application No. 10-2017-0055101 dated April 28, 2017, and all disclosed in the document of the Korean patent application. The content is included as part of this specification.

Technical Field This application relates to a sealing material composition, an organic electronic device including the sealing material composition, and a method for manufacturing the organic electronic device.

An organic electronic diode (OED) means a device including an organic material layer that generates an exchange of charges by utilizing holes and electrons, and examples thereof include a photocell device (photovoltaic diode) and a rectifier (rectifier). A rectifier), a transmitter, an organic light emitting diode (OLED), and the like can be mentioned.

Among the organic electronic devices, an organic light emitting diode (OLED: Organic Light Emitting Diode) consumes less power, has a faster response speed, and is advantageous for reducing the thickness of a display device or lighting as compared with an existing light source. In addition, OLED has excellent 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 OLED is the problem of durability. Organic materials and metal electrodes contained in OLEDs are very susceptible to oxidation due to external factors such as moisture. Therefore, products containing OLEDs are highly sensitive to environmental factors. As a result, various methods have been proposed for effectively blocking 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 water or oxygen flowing into an organic electronic device from the outside to secure the life of the organic electronic device and has excellent storage stability during distribution and storage. offer.

This application relates to a sealing material composition. The sealing material composition may be a sealing material applied to seal or encapsulate an organic electronic device such as, for example, an OLED. In one example, the sealing composition of the present application may be applied to seal or encapsulate the front surface of an organic electronic device. Therefore, after the sealant composition has been applied to encapsulation, it may exist in the form of an organic layer that seals the front surface of the organic electronic device. Further, the organic layer can be alternately laminated on the organic electronic device together with the inorganic protective film and / or the 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 element applicable to an inkjet process and a method for producing the same, wherein the composition utilizes inkjet printing capable of non-contact patterning. It can be designed to have appropriate physical properties when discharged onto a substrate.

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

An exemplary sealant composition is a solvent-free type photocurable sealant composition, which can include curable compounds, photoinitiators, photosensitizers and heat stabilizers. The curable compound, the photoinitiator, the photosensitizer and the heat stabilizer have 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. Can be included in the composition, and as yet another example, 91-97 parts by weight, 1.5-4.5 parts by weight, 0.1-2 parts by weight and 0.1-2 parts by weight; 92- 96 parts by weight, 2 to 4 parts by weight, 0.2 to 1.4 parts by weight and 0.2 to 1.4 parts by weight; 93 to 96 parts by weight, 2.5 to 3.5 parts by weight, 0.3 to 0.9 parts by weight and 0.3 to 0.9 parts by weight may be included in the composition. In this application, the particular composition is adjusted to a limited content range to suppress side reactions in the distribution and storage stages before the sealant composition is applied onto the organic electronic device. The desired viscosity can be maintained and its storage stability can be maintained as an ink jettable composition.

In a specific example of the present application, the curable compound may contain at least one curable functional group. The curable functional group may be, for example, one or more selected from an oxetane group, a glycidyl group, an isocyanate group, a hydroxy group, a carboxyl group, an amide group, an epoxide group, a sulfide group, an acetal group and a lactone group. .. The curable functional group may be at least monofunctional or bifunctional or higher. By using the curable compound, the present application can realize excellent durability reliability, adhesive property and moisture blocking property.

Exemplary curable compounds can include epoxy compounds and compounds with oxetane groups. In a specific example of the present application, the compound having an oxetane group may be contained 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 the components. In the present application, an organic layer can be formed 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 curing. In addition, the curable compound having the specific content can realize excellent storage stability, particularly together with the above-mentioned photoinitiator, photosensitizer and heat stabilizer.

In one example, the sealing composition of the present application may have a contact angle with respect to the 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, the spreadability can be ensured within a short time in the inkjet coating, whereby the organic layer of the thin film can be formed. In the present application, the contact angle may be measured by applying a drop of the sealing material composition onto glass using a sessile drop measuring method, and the average value is measured after 5 times of application. There may be.

In one example, the curable compound including the epoxy compound and the compound having an oxetane group is contained in 70 wt% or more, 75 wt% or more, 80 wt% or more and 85 wt% or more or 89 wt% or more in the whole component 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. 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 for an adhesive and realizes excellent heat resistance and durability at high temperature and high humidity.

In a specific example of the present application, the epoxy compound can include a compound having a ring structure in the molecular structure and / or a linear or branched aliphatic compound. That is, the sealing material composition of the present application can contain at least one of a compound having a ring-shaped structure in a molecular structure and a linear or branched aliphatic compound as an epoxy compound, and can also be contained together. .. In one example, the compound having a ring-shaped structure in the molecular structure may have ring-constituting atoms in the range of 3 to 10, 4 to 8 or 5 to 7 in the molecular structure, and the ring-shaped in the molecular structure. The structure may be 1 or more, 2 or more, and 10 or less. When the compound having a ring structure and the aliphatic compound having a linear or branched chain are contained together, the aliphatic compound having a linear or branched chain is 20 parts by weight with respect to 100 parts by weight of the compound having a ring structure. More 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 contained in the sealing material composition within the range of ~ 173 parts by weight. In the present application, by controlling the content range, the sealing material composition has physical characteristics suitable for front-sealing an organic electronic device, has excellent curing strength after curing, and has excellent moisture content. To be able to embody the barrier property 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. Further, the compound having an oxetane group may have a weight average molecular weight in the range of 150 to 1,000 g / mol, 173 to 980 g / mol, 188 to 860 g / mol, 210 to 823 g / mol or 330 to 780 g / mol. In this application, the viscosity of the composition is improved while improving the degree of completion of curing after curing of the sealing material by controlling the epoxy equivalent of the epoxy compound to be low or adjusting the weight average molecular weight of the compound having an oxetane group to be low. Can be prevented from becoming excessively high, making the epoxy process impossible, while at the same time providing moisture barrier and excellent curing sensitivity. In the present specification, the weight average molecular weight means a conversion value with respect to standard polystyrene measured by GPC (Gel Permeation Chromatography). 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 filled with polystyrene beads of 3-20 mm. When a diluted solution in which the substance to be measured is dissolved in a THF solvent is passed through the column, the weight average molecular weight can be indirectly measured according to the time of outflow. The amount separated by size from the column can be plotted and detected by time. Further, in the present specification, the epoxy equivalent is the number of grams (g / eq) of the resin containing 1 gram equivalent of the epoxy group, and can be measured by the method specified 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. In this application, by controlling the boiling point of the compound within the above range, while realizing excellent printability even at high temperatures in the inkjet process, it is excellent in moisture blocking property from the outside, outgas is suppressed, and damage to the device is inflicted. It is possible to provide a sealing material that can prevent the problem. Unless otherwise specified, the boiling point may be measured at 1 atm in the present specification.

In one example, the compounds having a ring structure within the molecular structure are 3,4-epoxycyclohexylmethyl 3', 4'-epoxycyclohexanecarboxylate (EEC) and derivatives, dicyclopentadiene dioxides and derivatives, vinylcyclohexenedi. Examples include, but are not limited to, oxides and derivatives, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) and derivatives.

In one example, the oxetane-containing compound is not limited in structure as long as it has the functional group, for example, OXT-221, CHOX, OX-SC, OXT101, OXT121, OXT221 or OXT212 of TOAGOSEI. , Or ETERNCOLL's EHO, OXBP, OXTP or OXMA can be exemplified. In addition, linear or branched aliphatic epoxy compounds include alifatic glycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and propylene glycol diglycidyl. It may include, but is not limited to, ethers, diethylene glycol diglycidyl ethers, butyl glycidyl ethers, 2-ethylhexyl glycidyl ethers or neopentyl glycol diglycidyl ethers.

In a specific example of the present application, the sealant composition may further comprise a photoinitiator. The photoinitiator may be a cationic photopolymerization initiator.

In the case of cationic photopolymerization initiators, materials known in the art can be used, for example, a cationic moiety containing aromatic sulfonium, aromatic iodinenium, aromatic diazonium or aromatic ammonium, and AsF ₆ ⁻ , SbF ₆ ⁻ , PF. A compound having a ₆ ^- or anionic moiety containing a tetrakis (pentafluorphenyl) borate can be included. Examples of the cationic photopolymerization initiator include an ionium salt-based ionized cation initiator, an organic silane, a latent sulfonic acid-based, and a non-ionic cation photopolymerization. Initiators can be used. Examples of the onium salt-based initiator include diallyliodonium salt, triarylsulfonium salt, and aryldiazonium salt, and examples of the organic metal salt-based initiator include iron allene. (Iron allene) and the like can be exemplified, and examples of the organic silane-based initiator include o-nitrobenzyl triaryl ether, triarylsilyl peroxide, and acyl silane. Etc., and examples of the latent sulfonic acid-based initiator include, but are not limited to, α-sulfonyloxyketone or α-hydroxymethylbenzoinsulfonate.

In one example, the application takes into account, in particular, its application to the application of sealing organic electronic devices in an inkjet manner and its inclusion with the curable compounds, photosensitizers and heat stabilizers described above. , A sulfonium salt can be included as a photoinitiator. In the present application, storage stability can be satisfactorily realized by adjusting the content ratio between each composition in the formulation of the specific composition.

The photoinitiator containing the sulfonium salt can have at least one or more ring-shaped structures in the molecular structure. The ring-shaped structure is a ring-shaped structure in which ring-constituting atoms are in the range of 3 to 10, 4 to 8 or 5 to 7 in the molecular structure, and may be an aliphatic ring structure or an aromatic ring structure. In a specific example of the present application, the sulfonium salt can contain at least one aryl group, for example, a phenyl group. The aryl group can be optionally substituted with one or more substituents, and the substituents include a halogen atom, a hydroxy group, a carboxyl group, a thiol group, an alkyl group, an alkoxy group, an alkenyl group, an epoxy group and a cyano group. Examples include, but are not limited to, aromatic-substituted mercapto groups such as carboxyl groups, acryloyl groups, methacryloyl groups, acryloyloxy groups, methacryloyloxy groups, aryl groups or thiolphenol groups. In one example, the sulfonium salt can have at least one aryl group in which an aromatically substituted mercapto group is present as the 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 with respect to 100 parts by weight of the total curable compound in the composition. The present application can maintain the long-term reliability of the composition together 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 contain a photosensitizer to supplement the curability in active energy rays having a long wavelength of 300 nm or more. The photosensitizer may be a compound that absorbs wavelengths 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 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 , 3,4,4-Tetra (t-butylperoxycarbonyl) benzophenone and other benzophenone compounds; acetophenone; dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, propanone, etc. Ketone compounds; perylene; fluorenone compounds such as 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone; thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro- Thioxanthone compounds such as 4-propyloxythioxanthone, isopropylthioxanthone (ITX), diisopropylthioxanthone; xanthone compounds such as xanthone and 2-methylxanthone; anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, t-butylanthraquinone, 2 , 6-Dichloro-9, 10-anthraquinone and other anthraquinone compounds; 9-phenylacrinedin, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinylpentane), 1, 3 -Acridin compounds such as bis (9-acridinyl) propane; dicarbonyl such as benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, 9,10-phenanthrenquinone Compounds; phosphinoxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 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-ji) Amino synergists such as ethylaminobenzal) cyclohexanone, 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclopentanone; 3,3-carbonylvinyl-7- (diethylamino) coumarin, 3-( 2-Benzothyazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10-carbonylbis [1,1,7,7-tetramethyl] Cmarin compounds such as -2,3,6,7-tetrahydro-1H, 5H, 11H-C1] -benzopyrano [6,7,8-ij] -quinolidine-11-one; 4-diethylaminochalcone, 4-azido It may be one or more selected from the group consisting of a chalcone compound such as benzalacetophenone; 2-benzoylmethylene; and 3-methyl-b-naphthiazolin.

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. In the present application, the content of the photosensitizer to the photoinitiator is adjusted to realize the effect of increasing the curing sensitivity at a desired wavelength, but the relationship with the above-mentioned photoinitiator containing a sulfonium salt is used. It is possible to prevent the reliability of the composition from being lowered due to a problem such as separation.

The sealing material composition of the present application may contain a heat stabilizer as described above. Examples of the heat stabilizer include cresol compounds, specifically 2,6-di-tert-butyl-p-cresol and the like. Further examples of the heat stabilizer include thiazine compounds, quinone compounds, aminoalcohols and the like, and specific examples thereof include phenothiazine (PTZ), methylenequinone, 2-dimethylaminomethanol or monomethylether hydroquinone. Can include. In a specific example 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 0.16. It may be in the range of 0.53. In this application, by adjusting the content of the heat stabilizer with respect to the photoinitiator, the viscosity increase, gelation or curing reaction due to unnecessary heat energy in the above-mentioned composition can be prevented, and the ink jet can be used for long-term distribution or storage. It is possible to maintain the physical properties that can be sought.

In a specific example of the present application, the sealing material composition may further contain 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 may comprise a polar functional group, which may be present at the end of the compound structure of the surfactant. The polar functional group can 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-silicone surfactant or a fluorine-based surfactant. The non-silicone or fluorosurfactant is applied together with the curable compounds described above to provide excellent coating properties on organic electronic devices. 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, it is possible to realize an excellent effect in terms of adhesive strength. In a specific example 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. Commercially available products can be used as the surfactant, for example, Glide 100, Glide 110, Glide 130, Glide 460, Glide 440, Glide 450 or RAD2500, DIC (DaiNippon Inc & Chemicals) of TEGO, Megaface. 281 -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 Ltd. -135, FC-170C, FC-430 and FC-4430 or Dupont's 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-DYNWET800, etc. You can use the one selected from the group.

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

The sealing composition of the present application may further contain a coupling agent. This application can improve the adhesion of the cured material of the sealing material composition to the adherend and the adhesion to the cured product. The coupling agent can include, for example, a titanium-based coupling agent, an aluminum-based coupling agent, and a silane coupling agent.

In the specific example of the present application, the silane coupling agent specifically includes 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane and 2-. (3,4-Epylcyclohexyl) Epoxy-based silane coupling agents such as 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 -Ureid-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 agents; acrylate-based silane coupling agents such as 3-acrylicoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyandiapropyltrimethoxysilane, bis (triethoxy). Crust-based silane coupling agents such as silylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; examples thereof include phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, and triazinesilane.

In the present application, the coupling agent may be contained 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 with respect to 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 may contain a water adsorbent, if necessary. The term "moisture adsorbent" may be used to collectively refer to components capable of adsorbing or removing moisture or moisture flowing in 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 the 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, a type such as a metal oxide, a metal salt, or phosphorus pentoxide (P ₂ O ₅ ) or A mixture of two or more is mentioned, and in the case of a physical adsorbent, zeolite, zirconia, montmorillonite and the like can be mentioned.

In the sealing material composition of the present application, the moisture adsorbent is added to 100 parts by weight of the curable compound by 5 parts by weight to 100 parts by weight, 5 to 80 parts by weight, 5 parts by weight to 70 parts by weight or 10 to 30 parts by weight. Can be included in the amount of parts. The sealing material composition of the present application is preferably capable of exhibiting excellent moisture and moisture blocking properties in the sealing material composition or a cured product thereof by controlling the content of the moisture adsorbent to 5 parts by weight or more. Further, the present application can provide a thin film sealing structure by controlling the content of the water adsorbent to 100 parts by weight or less.

In one example, the sealant composition may further contain an inorganic filler, if desired. The specific types of fillers that can be used in this application are 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 is inorganic in an amount of 0 to 50 parts by weight, 1 part by weight to 40 parts by weight, 1 part by weight to 20 parts by weight, or 1 to 10 parts by weight with respect to 100 parts by weight of the curable compound. It can contain a filler. 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. Further, by controlling the content of the inorganic filler to 50 parts by weight or less, the present invention can provide a cured product showing excellent moisture blocking properties even when formed of a thin film.

In addition to the above-mentioned composition, the sealing material composition according to the present application may contain various additives as long as it does not affect the effects of the above-mentioned invention. For example, the sealing material composition can be contained in an appropriate range depending on the physical characteristics for the purpose of an antifoaming agent, a tackifier, an ultraviolet stabilizer, an antioxidant and the like.

In one example, the sealant composition may be liquid at room temperature, eg, about 25 ° C. In a specific example of the present application, the sealing material composition may be a solvent-free liquid. The sealing material composition can be applied to seal an organic electronic device, and specifically, can be applied to seal the front surface of an 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 adjust the volatile organic compound and / or the 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 step. The sealing material composition of the present application can have a specific composition and physical characteristics so as to be capable of ink jetting.

Further, in a specific example of the present application, the sealing material composition has a viscosity of 50 cPs or less and 1 to 46 cPs measured by Brookfield's 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 the physical characteristics that can be ink-jetted at the time of application to the organic electronic device, and the coating property is improved to seal the thin film. Materials can be provided.

In one example, the sealing material composition has a surface energy 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 / m after curing. It may be within the range of m. The surface energy can be measured by a method known in the art, for example, by the Ring Method method. The present application can realize excellent coating properties within the above surface energy range.

In a specific example of the present application, the surface energy (γ ^surface , mN / m) can be calculated by γ ^surface = γ ^dispersion + γ ^polar . In one example, surface energy can be measured using a water drop analyzer (Drop Shape Analyzer, DSA100 product from KRUSS). For example, the surface energy is measured after the sealing material composition to be measured is applied 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) to form a sealing film (spin). (Coater), after drying in a nitrogen atmosphere at room temperature for about 10 minutes, UV curing is performed at an intensity of 1000 mW / cm ² through a light amount of 4000 mJ / cm ² . After curing, deionized water having a known surface tension is dropped on the film, and the process of determining the contact angle is repeated 5 times, and the average value of the obtained 5 contact angle values is obtained. Similarly, diiodomethane whose surface tension is known is dropped, and the process of obtaining the contact angle is repeated 5 times, and the average value of the numerical values of the obtained 5 contact angles is obtained. After that, the surface energy can be obtained by substituting the numerical value (Strom value) related to the surface tension of the solvent by the Owns-Wendt-Label-Kaelble method using the average value of the contact angles with respect to the deionized water and diiodomethane obtained. ..

Further, in the specific example of the present application, the sealing material composition may have a light transmittance of 90% or more, 92% or more or 95% or more in the visible light region after curing. Within the above scope, the present application applies a sealing material composition to a front light emitting organic electronic device to provide an organic electronic device having high resolution, low power consumption and longevity. Further, the sealing material 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%. You may. 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 with an organic layer, and the thickness of the organic layer may be any one of 2 μm to 50 μm. It may be an optical characteristic measured when the thickness is one. In the specific example of the present application, the above-mentioned moisture adsorbent or inorganic filler may not be contained in order to realize the optical properties.

The present application also relates to organic electronic devices. An exemplary organic electronic device 3 seals the substrate 31; the organic electronic element 32 formed on the substrate 31; the front surface of the organic electronic element 32; and the above-mentioned seal, as shown in FIG. The organic layer 33 containing the material composition can be included.

In a specific example of the present application, the 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 also 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. Can include 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 of a top emission type, but is not limited to this, and may be applied to a bottom emission type.

The organic electronic device may further include a protective film 35 that protects the electrode of the device and the light emitting layer. The protective film 35 may be an inorganic protective film. The protective film may be a protective layer by chemical vapor deposition (CVD), and a known inorganic material can be used as the material, for example, silicon nitrid (SiNx) can be used. In one example, silicon nitrid (SiNx) used as the protective film can be vapor-deposited to a thickness of 0.01 μm to 50 μm.

In a specific example of the present application, the organic electronic device 3 can 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 thickness of the inorganic layer may be 0.01 μm to 50 μm, 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 element, but is not limited to this.

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 electronic device by providing a thin organic layer.

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

In one example, the organic electronic device 3 of the present application can further include a cover substrate existing on the organic layer 33. The material of the substrate and / or the cover substrate is not particularly limited, and materials known in the art can be used. For example, the substrate or cover substrate may be glass, a metal substrate, or a polymer film. Examples of the polymer film include polyethylene terephthalate film, polytetrafluorethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyurethane film, ethylene-vinyl acetate film, and ethylene-propylene. A polymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, a polyimide film and the like can be used.

Further, as shown in FIG. 2, 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 element 32 is formed. Can be done. The sealing film 37 can be applied to an application for adhering the substrate 31 on which the organic electronic element 32 is formed and the cover substrate 38, and may be, for example, an adhesive film or an adhesive film, but is limited thereto. It's not a thing. The sealing film 37 can seal the front surface of the sealing structure 36 of the organic layer and the inorganic layer laminated on the organic electronic element 32.

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

In one example, the manufacturing method is a step of forming an organic layer 33 on a substrate 31 on which an organic electronic device 32 is formed so that the sealing material composition described above seals the front surface of the organic electronic device 32. Can be included.

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

Further, the manufacturing method can further include a step of irradiating the organic layer with light. In the present invention, the curing step can also be performed on the organic layer that encloses the organic electronic device, so that such a curing step can be carried out, for example, in a heating chamber or a UV chamber, preferably in a UV chamber. Can proceed.

In one example, the above-mentioned sealing material composition can be applied to form a front organic layer, and then the composition can be irradiated with light to induce cross-linking. Irradiating the light means irradiating light having a wavelength range of 250 nm to 450 nm or 300 nm to 450 nm with a light amount of 0.3 to 6 J / cm ² or a light amount of 0.5 to 5 J / cm ² . Can include.

Further, the manufacturing method of the present application can further include a step of forming the inorganic layer 34 on the organic layer 33. A method known in the art can be used for the step of forming the inorganic layer, and the method may be the same as or different from the method for forming the protective film described above.

In this application, a sealing material composition which can effectively block water or oxygen flowing into an organic electronic device from the outside to secure the life of the organic electronic device and has excellent storage stability during distribution and storage, and a sealing material composition. An organic electronic device including this is provided.

It is sectional drawing which shows the organic electronic apparatus by one example of this invention. It is sectional drawing which shows the organic electronic apparatus by one example of this 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
Aliphatic epoxy compounds (Cresolxide 2021P, Daicel), aliphatic epoxy compounds 1,4-butanidiol diglycidyl ether (DE200, HAJIN CHEM TECH), and oxetane group-containing curable compounds (TOAGOSEI) as curable compounds at room temperature. OXT-212), photoinitiator with triphenylsulfonium salt (UV693 from TETRA CHEM), fluorosurfactant (F447 from DIC), photosensitizer (9,10-dibutoxyantracene) and heat. Stabilizer 2,6-di-tert-butyl-p-cresol (BHT from SIGMA aldrich) 20:20:54: 3: 1: 0.5: 0.5 (Celloxide2021P: DE200: OXT-212: UV693) : F447: 9,10-dibutoxytoluene: 2,6-di-tert-butyl-p-cresol) was charged into the mixing vessel in a weight ratio.

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

Example 2
A sealing material composition was produced by the same method 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 produced 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 produced by the same method 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 by the same method as in Example 1 except that the content of the photosensitizer 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 4
A sealant composition was produced 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 sealant composition was produced 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 produced 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 sealant composition was produced in the same manner as in Example 1 except that the content of the photoinitiator was changed to 3.3 parts by weight and the content of the heat stabilizer was changed to 0.05 parts by weight.

Experimental Example 1-Evaluation of storage stability The sealing material compositions produced in Examples and Comparative Examples were stored under the following conditions.
1) Store in a container with a temperature of 25 ° C to 35 ° C, water and oxygen of 1,000 ppm or less in an N ₂ atmosphere and light blocking for 15 days. 2) A temperature of 45 ° C and light in an atmospheric atmosphere. Store for 15 days in a closed container 3) Store for 15 days in a container exposed to temperatures of 25 ° C to 35 ° C and yellow 4) UV cut film (green and yellow light) exposed to white fluorescent lamps Stored for 15 days in a container with a temperature of 25 ° C to 35 ° C and a moisture and oxygen content of 1,000 ppm or less.

Viscosity changes were measured under the above four conditions (measured using Brookfield, connect & plate at a temperature of 25 ° C., 90% torque and a shear rate of 100 rpm), and the viscosity immediately before storage and after 15 days of 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 Encapsulation structure 37 Encapsulation film 38 Cover substrate

Claims (15)

A solvent-free type photocurable sealing material composition.
Contains curable compounds, photoinitiators containing sulfonium salts, photosensitizers and heat stabilizers.
The curable compound, photoinitiator, photosensitizer and heat stabilizer have weight ratios 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. Included in
The curable compound includes an epoxy compound; a compound having an oxetane group (but not including an epoxy compound having an aromatic ring).
The viscosity measured at a temperature of 25 ° C., a torque of 90% and a shear rate of 100 rpm is 50 cPs or less .
The content ratio of the heat stabilizer to the content of the photoinitiator is 0.12 to 0.78.
Sealing material composition for encapsulating organic electronic devices for ink jetting. The curable compound contains at least one curable functional group.
The sealing material composition for encapsulating an organic electronic device according to claim 1. The curable functional group is one or more selected from a glycidyl group, an oxetane group, an isocyanate group, a hydroxy group, a carboxyl group, an amide group, an epoxide group, a sulfide group, an acetal group and a lactone group.
The sealing material composition for encapsulating an organic electronic device 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 device according to claim 2 or 3. Epoxy compounds include compounds having a ring structure within the molecular structure and / or linear or branched aliphatic compounds.
The sealing material composition for encapsulating an organic electronic device according to any one of claims 1 to 4. 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 ring structure.
The sealing material composition for encapsulating an organic electronic device according to claim 5. The compound having an oxetane group is contained in an amount of 45 parts by weight to 145 parts by weight with respect to 100 parts by weight of the epoxy compound.
The sealing material composition for encapsulating an organic electronic device according to any one of claims 1 to 6. The photoinitiator comprises a cationic photopolymerization initiator,
The sealing material composition for encapsulating an organic electronic device according to any one of claims 1 to 7. Photoinitiators containing sulfonium salts have at least one ring structure within the molecular structure.
The sealing material composition for encapsulating an organic electronic device according to any one of claims 1 to 8. The photosensitizer is a substance that absorbs wavelengths in the range of 200 nm to 400 nm.
The sealing material composition for encapsulating an organic electronic device according to any one of claims 1 to 9. Thermal stabilizers include 2,6-di-tert-butyl-p-cresol, phenothiazine (PTZ), methylenequinone, 2-dimethylaminomethanol or monomethylether hydroquinone.
The sealing material composition for encapsulating an organic electronic device according to any one of claims 1 to 10. The ratio of the photosensitizer content to the photoinitiator content is in the range of 0.1-0.8.
The sealing material composition for encapsulating an organic electronic device according to any one of claims 1 to 11. Further containing a surfactant,
The sealing material composition for encapsulating an organic electronic device according to any one of claims 1 to 12. With a substrate; with an organic electronic device formed on the substrate;
With an organic layer that seals the front surface of the organic electronic device and contains the sealing material composition for encapsulating the organic electronic device according to any one of claims 1 to 13.
Organic electronic devices including. The sealing material composition for encapsulating an organic electronic device according to any one of claims 1 to 13 is organic so as to seal the front surface of the organic electronic device on a substrate on which an organic electronic device is formed. A method of manufacturing an organic electronic device including a step of forming a layer.

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