KR101251121B1 - Composition for encapsulating organic light emitting display, adhesive film, preparation method thereof and organic light emitting display - Google Patents

Abstract

The present invention relates to a composition for encapsulating an organic light emitting display device, an adhesive film, and an organic light emitting display device. The composition of the present invention can be effectively applied as an encapsulant of an organic light emitting display device by providing a cured product having excellent electrical conductivity, thermal conductivity, moisture barrier properties, and adhesive properties. The composition of the present invention is particularly useful as an encapsulant of a dual plate type organic light emitting display device having excellent electrical connection reliability and heat dissipation, and wherein the light emitting portion and the driving portion are present on separate substrates.

Thermosetting resin, conductive filler, curing agent, organic light emitting display device, dual plate type

Description

Composition for encapsulating organic light emitting display device, adhesive film, manufacturing method and organic light emitting display device {Composition for encapsulating organic light emitting display, adhesive film, preparation method

The present invention relates to a composition for encapsulating an organic light emitting display device, an adhesive film, a method of manufacturing the same, and an organic light emitting display device.

An organic light emitting display (OLED) has a lower power consumption, a faster response speed, and a thinner thickness than an existing display (eg, LCD or PDP). As described above, the organic light emitting diode display has advantages of excellent portability and space utilization, and thus is expected to be applied to various portable devices, monitors, notebooks, and TVs.

In the commercialization of the organic light emitting display device and the expansion of its use, the main problems are durability and electrical problems. That is, since the organic light emitting material, the metal electrode, and the like included in the organic light emitting display are very easily oxidized by moisture or the like, they are much more sensitive to environmental factors than the conventional display. Accordingly, in the case of the organic light emitting diode display, it is necessary to effectively block oxygen, moisture, or the like penetrating from the outside. In addition, as an electrical problem, when a large area is considered in connection with the expansion of the use of the organic light emitting diode display, there is a problem in that the luminous efficiency varies depending on the location depending on the difference in resistance generated.

In order to solve the above-mentioned electrical problem, a technique has been proposed in which a driving circuit is wired to a lower plate in a display device, a light emitting element is deposited on the upper plate, and then the driving circuit and the light emitting element are connected by a plurality of electrical connection means. (Korean Patent Publication No. 2004-0079169, etc.). In such a system, a method of bonding the edges of the upper plate and the lower plate with a sealant is adopted, and the electrical connection between the light emitting element of the upper plate and the drive circuit of the lower plate is made only of physical connection.

However, the organic light emitting display device having the above structure has a disadvantage that is very vulnerable to physical shock, heat dissipation is not easy, and durability is also weak.

An object of the present invention is to provide a composition for encapsulating an organic light emitting display device, an adhesive film, a method of manufacturing the same, and an organic light emitting display device.

The present invention provides a composition for encapsulating an organic light emitting display device including a thermosetting resin and a conductive filler as a means for solving the above problems.

The present invention as another means for solving the above problems, a base film or a release film; And an adhesive layer formed on the base film or the release film and containing the composition according to the present invention.

The present invention as another means for solving the above problems, the first step of coating a coating liquid containing a composition according to the invention on a base film or a release film; And

It provides a method for producing an adhesive film comprising a second step of drying the coating solution coated in the first step.

According to another aspect of the present invention, there is provided a device including: a first substrate on which a driving circuit is formed; A second substrate disposed spaced apart from the first substrate and having an organic light emitting element formed on a surface of the first substrate; And

An organic light emitting display device is formed between the first substrate and the second substrate to encapsulate the organic light emitting device, and includes an encapsulation portion containing a cured product of the composition according to the present invention.

The composition or adhesive film of the present invention can provide a cured product excellent in electrical conductivity, thermal conductivity, moisture barrier properties, and adhesive properties. Accordingly, the composition or the adhesive film of the present invention can be effectively applied as an encapsulant of an organic light emitting display (OLED).

In particular, the composition or adhesive film according to the present invention has excellent electrical connection reliability and heat dissipation, and has a dual plate type organic light emitting display device (DPOLED) in which a light emitting part and a driving part (eg, a transistor array part) exist on separate substrates; Dual Plate type OLED) is applied as the encapsulation material, it can exhibit an excellent effect.

The present invention relates to a composition for encapsulating an organic light emitting display device including a thermosetting resin and a conductive filler.

The composition of the present invention is an organic light emitting display (OLED), particularly a dual plate type organic light emitting display (DPOLED) having a light emitting part and a driving part (eg, a transistor array part) on a separate substrate. It can be effectively applied as an encapsulant of type OLED).

Hereinafter, the composition for encapsulating an organic light emitting display device according to the present invention will be described in detail.

The composition of this invention contains a thermosetting resin as a base resin. The kind of thermosetting resin that can be used in the present invention is not particularly limited as long as it includes a functional group capable of forming a matrix by thermosetting. The kind of functional group which is contained in a thermosetting resin in this invention and can form a matrix by thermosetting is not specifically limited, For example, glycidyl group, an isocyanate group, a hydroxyl group, or a carboxyl group etc. are mentioned.

In the present invention, the content of the functional group included in the thermosetting resin is not particularly limited. In one aspect of the present invention, two or more, preferably three or more functional groups capable of thermosetting may be included in the resin in order to effectively implement desired adhesive properties and curing properties. In addition, the upper limit of the functional group content is not particularly limited, and may be appropriately adjusted in the range of, for example, 10 or less.

The specific kind of thermosetting resin which can be used by this invention is not specifically limited. For example, in one aspect of the present invention, the thermosetting resin may be a resin having a linear or branched structure including the aforementioned functional group, and specifically, an isocyanate resin, an acrylic resin, a polyester resin or an epoxy resin. Among them, it is preferable to use an epoxy resin, but is not limited thereto.

The specific kind of epoxy resin is not specifically limited above. That is, in the present invention, an aromatic or aliphatic, which may be cured to exhibit adhesive properties, and contains at least one epoxy functional group (glycidyl group); Alternatively, linear or branched epoxy resins can be used without limitation. In one aspect of the present invention, an epoxy resin having an epoxy equivalent of 180 g / eq to 1,000 g / eq can be used as containing two or more functional groups. Examples of such epoxy resins include cresol novolac epoxy resins, bisphenol A epoxy resins, bisphenol A novolac epoxy resins, phenol novolac epoxy resins, tetrafunctional epoxy resins, biphenyl epoxy resins, and triphenol methane types. A kind or mixture of an epoxy resin, an alkyl modified triphenol methane epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, or a dicyclopentadiene modified phenol type epoxy resin is mentioned. If the average epoxy equivalent of the epoxy resin is less than 180 g / eq, the crosslinking density is too high after curing, there is a fear that the adhesive performance is lowered, if it exceeds 1,000 g / eq, the glass transition temperature (Tg) may be too low There is.

In one aspect of the present invention, the thermosetting resin may be introduced with one or more silicone-based reactive moieties, and the silicone-based reactive moiety may include one or more functional groups selected from the group consisting of alkoxy groups, hydroxy groups and glycidyl groups. . As described above, when the thermosetting resin is composed of a hybrid resin containing a silicone-based reactive moiety, the adhesive properties of the composition of the present invention with a glass substrate or the like can be further improved. In addition, in the present invention, by controlling the functional group contained in the silicone-based reactive moiety to react with the moisture penetrating from the outside to form a matrix, the moisture barrier properties of the composition of the present invention can be further improved. .

Specifically, in the present invention, the thermosetting resin to which the silicone-based reactive moiety is introduced may be represented by, for example, the following Chemical Formula 1 or 2.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, X represents A- or Am-, A represents the above-mentioned thermosetting resin, m represents a linker connecting the thermosetting resin and the silicon atom, and R ₁ to R ₆ each independently Hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkynyl, glycidyl or halogen, a represents an integer of 1 to 5, each of which is the same as each other when R ₄ and R ₆ are plural Which may be different, at least one of R ₁ to R ₃ represents a hydroxy group or an alkoxy group, and at least one of R ₄ to R ₆ represents a hydroxy group or an alkoxy group.

Alkyl or alkoxy in the definition of Chemical Formula 1 or 2 may represent alkyl or alkoxy having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and specifically methyl, ethyl, Methoxy or ethoxy.

In addition, in the definition of Chemical Formula 1 or 2, alkenyl or alkynyl may represent alkenyl or alkynyl having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms. It may be ethenyl, ethynyl.

In addition, in the definition of Formula 1 or 2, halogen may represent fluorine, chlorine or bromine, preferably chlorine or bromine.

In addition, in the definition of Formula 1 or 2, alkyl, alkoxy, alkenyl or alkynyl may be substituted by one or more substituents, and examples of the substituents include hydroxy group, glycidyl group or 1 to 12 carbon atoms, preferably Is 1-8, More preferably, 1-4 alkyl or alkoxy etc. are mentioned.

In one embodiment of the present invention, the reactive moiety included in the compound of Formula 2 may be, for example, a functional group capable of condensation reaction, addition reaction or hydrosilylation reaction (eg, hydrogen, halogen, alkoxy group, vinyl group, etc.). It may be prepared by reacting a silane, siloxane or polysiloxane containing each other.

Examples of the silane compound which can be used at this time include tetramethoxy silane, tetraethoxy silane, methyltrimethoxy silane, methyltriethoxy silane, 3- (meth) acryloxypropyltrimethoxy silane, and 3- (meth) ) Acryloxypropyltriethoxy silane, vinyltrimethoxy silane, vinyltriethoxy silane, methyldichlorosilane, methyldimethoxy silane, methyldiethoxy silane, methyldi (n-propoxy) silane, methyldi (i- Propoxy) silane, methyldi (n-butoxy) silane, methyldi (sec-butoxy) silane, dimethyldichlorosilane, dimethyldimethoxy silane, dimethyldiethoxy silane, dimethyldi (n-propoxy) silane, dimethyl Di (i-propoxy) silane, dimethyldi (n-butoxy) silane, dimethyldi (sec-butoxy) silane, chlorodimethylsilane, methoxydimethyl silane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethyl Silane, Aoidotrimethylsilane, Methoxytrimethyl Silane, Ethoxy Dimethyl silane, n-propoxytrimethyl silane, i-propoxytrimethyl silane, n-butoxytrimethyl silane, sec-butoxytrimethyl silane, t-butoxytrimethyl silane, chlorovinyldimethyl silane, methoxyvinyldimethyl silane or Ethoxy vinyl dimethyl silane, and the like, and examples of the siloxane or polysiloxane include, but are not limited to, condensates of the silane compounds.

In the present invention, a method of obtaining the reactive moiety included in the compound of Formula 2 by reacting the compound as described above is not particularly limited, and general hydrolysis, condensation reaction or addition reaction in the art may be used. For example, the above-described compounds may be mixed in a suitable solvent, hydrolyzed and condensed in the presence of a base and water, or subjected to an addition reaction using a catalyst such as a platinum group catalyst, thereby being included in the compound of Formula 2 Reactive residues can be prepared.

In the thermosetting resin of the present invention, the silicone-based reactive moiety may be linked directly to the thermosetting resin chain or by an appropriate linker (-m-). At this time, the type of linker that can be applied is not particularly limited, and for example, a single bond, alkylene (ex. Methylene, ethylene of 1 to 12, preferably 1 to 8, more preferably 1 to 4) Or propylene and the like); Alkenylene or alkynylene having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms; -O-; Or -S- and the like.

In the present invention, the method of introducing the silicone-based reactive moiety into the thermosetting resin is not particularly limited, and examples thereof include silicone-based reactive moieties (ex. Silane, siloxane or polysilic acid); And thermosetting resins such as isocyanate resins, acrylic resins, polyester resins, epoxy resins, and the like, and each of the functional groups capable of reacting with each other is introduced and hybridized by reacting them under appropriate conditions.

In the present invention, the content of the silicone-based reactive moiety introduced into the thermosetting resin is not particularly limited, and is 5 parts by weight to 100 parts by weight, preferably 10 parts by weight to 80 parts by weight, more preferably 100 parts by weight of the thermosetting resin. Preferably, it may be 25 parts by weight to 50 parts by weight. If the amount of the silicone-based reactive residue is less than 5 parts by weight, the effect of improving the adhesive properties or the water barrier property may be insignificant. If it exceeds 100 parts by weight, physical properties such as film formability may be lowered.

The composition of this invention contains a conductive filler with the above-mentioned thermosetting resin. In the present invention, the conductive filler may be dispersed in a curing matrix made of a thermosetting resin, to impart electrical and thermal conductivity to the cured product, and in some cases, may serve to suppress the rate of penetration of moisture from the outside. In the present invention, in consideration of the desired electrical conductivity, a filler having an appropriate conductivity can be selected and used. For example, a conductive filler having an electrical resistance of 1 ohm-cm or less can be used. If the electrical resistance exceeds 1 ohm-cm, the desired conductivity may not be imparted to the cured product, or an excessive amount of filler may be added thereto, resulting in deterioration of other physical properties such as formability and adhesiveness. There is. In addition, in the present invention, the lower the electric resistance of the conductive filler can exhibit the excellent electrical properties of the cured product, the lower limit is not particularly limited. . The kind of the specific conductive filler that can be used in the present invention is not particularly limited, and examples thereof include carbon-based fillers such as carbon black, carbon nanotubes or graphite; Oxide fillers such as tin-doped indium oxide (ITO), antimony-doped zinc oxide (AZO), antimony-doped tin oxide (ATO), InO, ZnO, TiO ₂ , SnO, RuO ₂ , IrO ₂ or zirconia; Metal or metal alloy fillers such as gold, silver, nickel, copper, tantalum, palladium, silver / copper alloys or silver / palladium alloys; Or polyaniline, polyacetylene, polypyrrole, polyparaphenylene, polythiophene, polydienylene, polyphenylene vinylene, polyphenylene sulfide or polysulfurite One kind or a mixture of two or more kinds of conductive polymers such as polysulfurnitride may be used. In the present invention, in order to increase the efficiency of securing anisotropic conductivity, a conductive material in which one or more kinds of the aforementioned conductive fillers form a shell is used on the surface of a core composed of a polymer or the like as the conductive filler. It may be. In the present invention, a mixture of one or more of the various conductive materials may be used without limitation. Preferably, carbon-based, polymer-based, or oxide-based fillers having low oxidation problems may be used, but are not limited thereto. In addition, the size of the conductive filler in the present invention is also not particularly limited, and may be appropriately selected in consideration of the dispersibility of the filler, the possibility of aggregation and the moldability of the composition. In the present invention, for example, the average particle diameter of the conductive filler may be in the range of 1 nm to 100 μm.

The content of the conductive filler in the present invention may vary depending on the conductivity to be secured, but is included in an amount of 1 part by weight to 20 parts by weight, preferably 3 parts by weight to 10 parts by weight, based on 100 parts by weight of the above-mentioned thermosetting resin. Can be. If the content is less than 1 part by weight, the electrical connection reliability of the cured product may be deteriorated. If the content is more than 20 parts by weight, the film formability and adhesiveness may be deteriorated.

The composition of this invention may further contain a hardening | curing agent with the above-mentioned component. Such a curing agent may induce a reaction of the curing reactor of the thermosetting resin, and for example, the cured product may be cured between the upper and lower plates of the organic light emitting diode display to perform adhesion, support, and conduction functions.

In this invention, the specific kind of the said hardening | curing agent is suitably selected according to the kind of functional group contained in a thermosetting resin, The specific kind is not specifically limited. For example, when a thermosetting resin is an epoxy resin, the normal hardening | curing agent for epoxy resins can be used in this invention. Examples of such curing agents include, but are not limited to, various amine compounds, imidazole compounds, phenol compounds, phosphorus compounds, and / or acid anhydride compounds. When the curable functional group is a hydroxyl group or a carboxyl group, one or more kinds of isocyanate compounds, epoxy compounds, aziridine compounds or metal chelate compounds may be used as the curing agent, but the present invention is not limited thereto.

In the composition of the present invention, for example, when the thermosetting resin is an epoxy resin, the curing agent may be included in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the thermosetting resin. have. However, the content of the curing agent is only one aspect of the present invention, in the present invention may vary the content of the curing agent in accordance with the type and content of the thermosetting resin or the matrix structure to be implemented.

The composition of the present invention may further comprise a binder resin together with the aforementioned components. The binder resin may play a role of improving the moldability in the case of molding a film using the composition of the present invention.

The kind of the binder resin that can be used in the present invention is not particularly limited as long as it is compatible with the thermosetting resin and the like and can exhibit the above-described action. Specific examples of binder resins that can be used include phenoxy resins, acrylate resins, high molecular weight epoxy resins, ultra high molecular weight epoxy resins, high polarity functional group-containing rubbers, and high polarity functional group-containing reactive rubbers. One kind or a mixture of two or more kinds may be included, but is not limited thereto.

The content of the binder resin in the present invention is not particularly limited as it is controlled depending on the physical properties of the desired composition. For example, in the present invention, when the thermosetting resin has a sufficiently large molecular weight and shows good film formability, the binder resin may not be added. In one aspect of the present invention, the binder resin may be included in an amount of about 100 parts by weight or less, preferably 90 parts by weight or less, and more preferably about 70 parts by weight or less based on 100 parts by weight of the above-mentioned thermosetting resin. have. When the content of the binder resin exceeds 100 parts by weight, there is a fear that a problem occurs in terms of compatibility with other components of the composition.

The composition of the present invention may further comprise a suitable curing accelerator, if necessary. The kind of hardening accelerator which can be used by this invention is not specifically limited, It can select suitably according to the kind of thermosetting resin used. For example, when the thermosetting resin of this invention is an epoxy resin, as a hardening accelerator, tertiary amines, imidazole, or quaternary ammonium salt etc. can be used, specifically, 2-methylimidazole Or a mixture of two or more kinds such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole or 1-cyanoethyl-2-phenylimidazolium trimellitate can be used. have. In the composition of the present invention, the content of such a curing accelerator is not particularly limited, for example, 5 wt% or less, preferably 0.05 wt% to 3 wt%, more preferably based on the total amount of the thermosetting resin and the curing agent. Preferably in an amount of 0.2% to 3% by weight. When the content is more than 5% by weight, there is a risk that the storage stability is lowered or the pot life is difficult to control.

The composition of the present invention may further suitably further include a sol-gel reaction catalyst, if necessary, in order to further improve its moisture barrier properties. The sol-gel reaction catalyst may further improve the water blocking performance of the cured product by promoting a reaction between a functional group (eg, an alkoxy group or a hydroxyl group) of a silicone-based reactive moiety introduced into the thermosetting resin and moisture penetrating from the outside. The kind of the sol-gel reaction catalyst that can be used in the present invention is appropriately selected according to the functional group contained in the aforementioned silicone-based reactive moiety, and the specific kind thereof is not particularly limited. In the present invention, for example, as a catalyst having a relatively high reaction rate, one or more kinds of tin octanoate, trifluoroacetic acid, or titanium tetraispropoxide or the like As a catalyst which can be mixed and has a relatively moderate reaction rate, acetic acid, formic acid, titanium tetrakis (2-ethylhexoxide), One or more mixtures of aluminum chelate and aluminum alkoxide may be used, and as a relatively slow reaction catalyst, dibutyltin dilaurate, methyl trifluoroacetate (methyl trifluoroacetate) or ethyl trifluoroacetate, such as one or more than one It is, but is not limited to this.

In the present invention, the content of the sol-gel reaction catalyst is appropriately selected depending on the desired physical properties, and is not particularly limited. In the present invention, for example, 0.1 parts by weight to 10 parts by weight, preferably 1 parts by weight to 5 parts by weight of the sol-gel reaction catalyst may be used based on 100 parts by weight of the thermosetting resin. If the content is less than 0.1 part by weight, the effect of improving the water barrier performance due to the addition of the sol-gel reaction catalyst may be insignificant. If the content exceeds 10 parts by weight, no further acceleration effect may occur or the physical properties of the cured product may be lowered. There is.

However, the content of the sol-gel reaction catalyst is only one embodiment of the present invention. That is, in the present invention, the content of the sol-gel reaction catalyst may be freely changed according to the type and content of the functional group (ex. Alkoxy group or hydroxy group) in the inorganic component included in the silicon-based reactive moiety. For example, in one aspect of the present invention, when the thermosetting resin is an epoxy resin and the silicone-based reactive moiety is an alkoxy siloxane, about 5 parts by weight to 25 parts by weight of a sol gel reaction catalyst may be used based on 100 parts by weight of the alkoxy siloxane. Can be.

The composition of the present invention, in addition to the above components, in the range that does not affect the effect of the invention, a filler for improving the durability of the cured product, a plasticizer for improving the mechanical strength, heat resistance and light resistance, etc. Additional additives such as coupling agents, plasticizers, ultraviolet stabilizers, and antioxidants may be included.

The present invention further includes a base film or a release film (hereinafter, may be referred to as "first film"); And

It is related with the adhesive film formed on the said base film or a release film, and containing the adhesive layer containing the composition which concerns on this invention.

The adhesive film of the present invention may further include a base film or a release film (hereinafter, sometimes referred to as "second film" or "cover film") formed on the adhesive layer.

In the adhesive layer of the adhesive film of the present invention, the composition of the present invention, for example, may be contained in the form of a dried, semi-cured or cured product.

1 and 2 are views showing cross-sectional views of an adhesive film according to one aspect of the present invention.

As shown in FIG. 1, the adhesive film of the present invention may include an adhesive layer 22 formed on the base film or the release film 21. In another aspect of the present invention, the adhesive film may include an additional base film or release film 23 formed on the adhesive layer 22, as shown in FIG. However, the adhesive film shown in the drawings is only an aspect of the present invention. For example, the adhesive film of the present invention may have a form of a single adhesive layer formed only of a cured product of the composition of the present invention without a supporting substrate, and in some cases, an adhesive layer is formed on both sides of one base film or a release film. It may be configured in the form of a double-sided adhesive film.

The specific kind of the first film 21 used in the present invention is not particularly limited, and for example, a general polymer film in this field may be used. In the present invention, for example, polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyurethane Films, ethylene-vinyl acetate films, ethylene-propylene copolymer films, ethylene-ethyl acrylate copolymer films, ethylene-methyl acrylate copolymer films, polyimide films and the like can be used. In addition, an appropriate release treatment may be performed on one side or both sides of the base film or the release film of the present invention. Alkyd-based, silicone-based, fluorine-based, unsaturated ester-based, polyolefin-based, wax-based, etc. may be used as an example of the release agent used in the release treatment of the base film, and among these, it is preferable to use an alkyd-based, silicone-based, or fluorine-based release agent in terms of heat resistance. Preferred, but not limited to.

In the present invention, the thickness of the first film as described above is not particularly limited and may be appropriately selected depending on the application to be applied. For example, in the present invention, the thickness of the first film may be about 10 μm to 500 μm, preferably about 20 μm to 200 μm. If the thickness is less than 10 μm, deformation of the base film may occur easily during the manufacturing process. If the thickness is more than 500 μm, the economy is inferior.

In the adhesive film of the present invention, the thickness of the adhesive layer 22 formed on the first film 21 is not particularly limited, and may be appropriately selected in consideration of the application of the film. The adhesive layer included in the adhesive film of the present invention may be, for example, about 5 μm to 200 μm, preferably about 10 μm to 100 μm. When the thickness is less than 5 μm, for example, when the adhesive film of the present invention is used as an encapsulant such as an organic light emitting display device, embedding property and processability may decrease, and when it exceeds 200 μm, economical efficiency is inferior.

Moreover, the kind of said 2nd film used by this invention is not specifically limited, either. For example, in the present invention, as the second film, the same or different kind as the first film may be used in the category exemplified in the above-described first film. In addition, the second film may also be used by performing an appropriate release treatment. In the present invention, the thickness of the second film is also not particularly limited. In the present invention, for example, the thickness of the second film may be set in the same manner as the first film, or may be set to a thickness relatively thinner than the first film in terms of processability and the like.

In this invention, the method of manufacturing such an adhesive film is not specifically limited. In the present invention, for example, the first step of coating a coating liquid comprising the composition according to the invention described above on a base film or a release film; And a second step of drying the coating liquid coated in the first step. In the manufacturing method of the present invention, a third step of additionally compressing the base film or the release film on the coating liquid dried in the second step may be further performed.

The first step of the present invention is to prepare a coating solution by dissolving or dispersing the composition according to the present invention in a suitable solvent, and coating it on a substrate or a release film. In this process, the content of the thermosetting resin included in the coating solution takes into account the type of resin used (ex. Liquid resin or solid resin), the content of the conductive filler, the equivalent ratio with the curing agent, the adhesiveness, the moisture barrier property, and the film formability. To be controlled appropriately. In the present invention, the molecular weight of the thermosetting resin is not particularly limited, but if the molecular weight is excessively high or low, the viscosity of the coating liquid or the formability of the film may be deteriorated, so that it can be suitably controlled in consideration of this.

In addition, when the binder resin is included in the coating solution, the content of the binder resin also needs to be adjusted in consideration of film formability or impact resistance. For example, in the present invention, when the thermosetting resin is an epoxy resin (ex. Bisphenol-based epoxy resin), and a liquid resin having an epoxy equivalent of about 200 g / eq is used, in order to obtain suitable film formability, the molecular weight is about It is preferable to include a binder resin (ex. Phenoxy resin) of about 50,000 g / mol in an amount of about 5% to 50% by weight in the total solids. In addition to the above components, if the viscosity of the coating liquid is too low or high, the film formability may be deteriorated. Therefore, it is necessary to appropriately adjust the molecular weight of the binder resin, the amount of use thereof, the type of solvent, the amount of use thereof, and the like. In addition, when the content of the solvent contained in the coating solution is excessively increased, it may take a long time to dry, so it is preferable to minimize the amount of the solvent used.

In addition, when the curing agent is included in the coating liquid, the content thereof is not particularly limited to vary depending on the curing functional group of the thermosetting resin, and may be appropriately controlled in consideration of the curing rate, crosslinking degree, and storage stability. For example, in the present invention, when the thermosetting resin is an epoxy resin and the curing agent is an imidazole compound, the curing agent may be included in an amount of 1% by weight to 10% by weight relative to the thermosetting resin.

In addition, in the present invention, from the viewpoint of improving the dispersibility of the conductive filler in the coating liquid, a ball mill, bead mill, three rolls, or a high speed grinder may be used alone or in combination. Can also be used. Examples of the material of the ball and the beads include glass, alumina, zirconium, and the like, and in view of dispersibility of the particles, a ball or bead of a zirconium material is preferable.

The kind of solvent for manufacture of the coating liquid of this invention as mentioned above is not specifically limited. However, when the drying time of the solvent is excessively long or when it is necessary to dry at a high temperature, a problem may arise in terms of workability or durability of the adhesive film, and therefore it is preferable to use a solvent having a volatilization temperature of 100 ° C or lower. In the present invention, in consideration of film formability, a small amount of a solvent having a volatilization temperature of the above range or more can be mixed and used. Examples of the solvent that can be used in the present invention include methyl ethyl ketone (MEK), acetone, toluene, dimethylformamide (DMF), methyl cellosolve (MCS), tetrahydrofuran (THF) or N-methylpyrrolidone (NMP) and the like, or a mixture of two or more thereof, but is not limited thereto.

The method of applying the coating liquid to the base film or the release film in the first step of the present invention is not particularly limited, for example, knife coat, roll coat, spray coat, gravure coat, curtain coat, comma coat or lip Known methods such as coats and the like can be used without limitation.

The second step of the present invention is to dry the coating solution coated in the first step, to form an adhesive layer. That is, in the second step of the present invention, the adhesive layer can be formed by heating and removing the solvent by heating the coating liquid applied to the film. At this time, the drying conditions are not particularly limited, for example, the drying may be performed for 1 to 10 minutes at a temperature of 70 ℃ to 200 ℃.

In the method for producing an adhesive film of the present invention, after the second step, a third step of pressing an additional base film or a release film (second film) on the adhesive layer formed on the film may be further performed.

The third step of the present invention may be carried out by coating an additional release film or base film (cover film or second film) on the dried adhesive layer by hot roll lamination or pressing process after coating on the film. At this time, the third step may be carried out by a hot roll lamination method in view of the possibility and efficiency of the continuous process, wherein the process is about 0.1 kgf / cm ² to 10 at a temperature of about 10 ℃ to 100 ℃ It can be carried out at a pressure of kgf / cm ² .

The present invention also provides a display device comprising: a first substrate having a driving circuit (eg, a thin film transistor array unit) formed thereon; A second substrate disposed spaced apart from the first substrate and having an organic light emitting element formed on a surface of the first substrate; And

The present invention relates to an organic light emitting display device formed between the first substrate and the second substrate and encapsulating the organic light emitting element, and including an encapsulation portion containing a cured product of the composition of the present invention.

The cured product of the composition according to the present invention not only exhibits excellent optical properties, adhesive properties and moisture barrier properties, but also particularly excellent in characteristics such as electrical connection reliability and thermal conductivity, and thus applies a signal to the organic light emitting device and the device as described above. A driving circuit (for example, a thin film transistor array unit) capable of being applied to a dual plate type organic light emitting display device formed on a separate substrate can significantly improve the durability, electrical connection reliability, and the like.

Moreover, the composition or adhesive film of this invention has the advantage that the manufacturing process can be simplified and process cost can be reduced compared with the former.

Hereinafter, the organic light emitting diode display as described above will be described with reference to the accompanying drawings. 3 is a diagram schematically illustrating an organic light emitting display device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to 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 to the following examples.

Example 1

200 g of silane-modified epoxy resin (KSR-177, Kukdo Chemical Co., Ltd.), 30 g of carbon black (HIBLACK 41Y, Evonik Co.), and phenoxy resin (YP-55, Kukdo Chemical Co., Ltd.) at room temperature in the reactor. ) 125 g were added, and 400 g of methyl ethyl ketone was further added as a solvent. Subsequently, the inside of the reactor was replaced with nitrogen, the resin solution was stirred for 2 hours, then the conductive filler was dispersed for 1 hour using a ball mill, and further 1-cyanoethyl-2-phenylimida as a curing agent. 4 g of sol (2PZCN, manufactured by Shikoku Chemical Co., Ltd.) were added thereto, and the mixture was further stirred for 1 hour. Thereafter, the prepared solution was filtered with a mesh having a pore size of 50 μm to remove foreign substances to prepare a coating solution. Subsequently, the coating liquid was applied to a base film (RS-21G, SKC (manufactured)) having a thickness of 38 μm with a comma coater, dried at a temperature of 120 ° C. for 1 minute in a drier, and an adhesive film having a thickness of 5 μm was applied. Produced. Thereafter, using a laminator (manufactured by Fujisok Co., Ltd.) to the prepared adhesive film, a cover film of the same material as the base film was laminated to prepare an adhesive film.

Example 2

200 g of silane-modified epoxy resin (KSR-177, Kukdo Chemical Co., Ltd.), 30 g of carbon black (KETJENBLACK EC300J, Mitsubishi Chemical Co., Ltd.) and phenoxy resin (YP-55, Kukdo Chemical Co., Ltd.) at room temperature in the reactor. ) 125 g were added, and 400 g of methyl ethyl ketone was added as a solvent. The inside of the reactor was replaced with nitrogen, the solution was stirred for 2 hours, and then the filler was dispersed for 1 hour using a ball mill. Subsequently, 4 g of 2-phenyl imidazole (2PZ, Shikoku Chemical Co., Ltd.) was added as a hardening | curing agent, and it stirred further for 1 hour. Thereafter, the solution was filtered through a mesh having a pore size of 50 μm to remove foreign substances to obtain a coating solution, and then an adhesive film was prepared in the same manner as in Example 1.

Comparative Example 1

200 g of bisphenol A type epoxy resin (DER331, Nippon Kayaku Co., Ltd.), 4 g of 2-phenyl imidazole (2PZ, Shikoku Kasei Co., Ltd.) and phenoxy resin (YP-55, Kukdo Chemical Co., Ltd.) )) 125 g were added, and 400 g of methyl ethyl ketone was further added as a solvent. Thereafter, the inside of the reactor was replaced with nitrogen, and the resin solution was stirred for 2 hours. The stirred solution was filtered through a mesh having a pore size of 50 μm to remove foreign materials to obtain a coating solution, and then an adhesive film was prepared in the same manner as in Example 1.

The performance of the adhesive films prepared in the examples and comparative examples was evaluated by the method shown below.

1. Electrical resistivity measurement

The electrical resistivity of the prepared film was measured by applying a voltage of 1,000 V using a HIOKI 3802-50 Digital Hitester as a measuring instrument, and contacting both ends of a 10 μm thick cured film, The resistance value in the film thickness direction was measured.

2. Thermal conductivity measurement

As the films prepared in Examples and Comparative Examples, 10 films having a thickness of 10 μm were laminated to prepare specimens having a thickness of 100 μm, and then Kyoto Kyotos QTM-500 was used as a measuring device under the condition of Current 0.063A2. Thermal conductivity was measured.

3. lighting rating

In order to confirm the electrical connection reliability of the films manufactured in Examples and Comparative Examples, an organic light emitting display device having a structure designed such that the organic light emitting element and the driving circuit are separated on the upper plate and the lower plate, respectively, the adhesive film prepared in the Examples and Comparative Examples Encapsulated by, and the electricity was applied to confirm whether the lighting, the evaluation criteria at this time are as follows.

○: On average, over 90% of the five light emitting elements

(Triangle | delta): When an average of 40% or more and less than 90% are lit in all five light emitting elements

X: When less than 40% of all five light emitting elements light up

4. Calcium Test

In order to investigate the moisture barrier properties of the adhesive films of Examples and Comparative Examples, a calcium test was conducted. Specifically, 9 spots of calcium (Ca) were deposited on a glass substrate having a size of 100 mm × 100 mm in a size of 8 mm × 8 mm and a thickness of 100 nm, and a cover on which the adhesive films of Examples and Comparative Examples were transferred were transferred. The glass was heat-pressed at 80 ° C. for 1 minute using a vacuum press at each calcium vapor deposition point. Thereafter, after curing at 100 ° C. for 2 hours in a high temperature dryer, the sealed calcium (Ca) specimens were cut into 10 mm × 10 mm sizes, respectively. After the obtained specimens were left at a temperature of 80 ° C. and 90% R.H. in a constant temperature and humidity chamber, the degree of discoloration by the oxidation reaction was evaluated based on the following criteria.

○: When no discoloration occurs after 500 hours

(Triangle | delta): after 500 hours, when the transparent area is less than 50% of a total area

X: after 500 hours, when the transparent area is 50% or more of the total area

5. Adhesion Test

Two glass plates 20 mm × 40 mm in size and 3 mm thick were orthogonal, cut into 5 mm in diameter, heated and pressed at 200 kg for 1 minute at a temperature of 80 ° C. using the adhesive films of Examples and Comparative Examples. It hardened | cured for 2 hours at the temperature of 100 degreeC. Then, the adhesion of the adhesive film in the prepared specimen was measured using a tensile tester.

As described above, the test results conducted were summarized in Table 1 below.

[Table 1]

Electric resistance (Ω) Thermal conductivity
(W / mK) Evaluation Calcium test Adhesion
(Kgf / cm ² ) Example 1 300 0.4 ○ ○ 11 Example 2 50 0.5 ○ ○ 12 Comparative Example 1 Not measurable 0.1 × △ 14

As shown in Table 1, in the case of the adhesive film according to the present invention, while showing an equivalent adhesive strength compared to Comparative Example 1 corresponding to the existing epoxy-based encapsulant, it exhibits excellent thermal conductivity and electrical resistance, and also excellent water blocking properties And electrical connection reliability.

1 and 2 show cross-sectional views of an adhesive film according to one aspect of the present invention.

3 is a schematic diagram illustrating a schematic structure of an organic light emitting diode display according to an exemplary embodiment of the present invention.

≪ Description of reference numerals &

21, 23: base film or release film 22: adhesive layer

30: organic light emitting display

31: lower plate 32: upper plate

33: driving circuit 34: organic light emitting element

35: encapsulation

Claims (20)

An organic light emitting display encapsulation composition comprising a hybrid resin and a conductive filler containing a silicone-based reactive moiety containing at least one selected from the group consisting of an alkoxy group, a hydroxy group and a glycidyl group. The composition of claim 1, wherein the hybrid resin is an isocyanate resin, an acrylic resin, a polyester resin, or an epoxy resin. The epoxy resin of claim 2, wherein the epoxy resin is a cresol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol A novolac epoxy resin, a phenol novolac epoxy resin, a tetrafunctional epoxy resin, a biphenyl epoxy resin, or triphenol methane. A composition for encapsulating an organic light emitting display device which is at least one selected from the group consisting of an epoxy resin, an alkyl modified triphenol methane epoxy resin, a naphthalene epoxy resin, a dicyclopentadiene epoxy resin and a dicyclopentadiene modified phenol epoxy resin. delete The composition of claim 1, wherein the hybrid resin is represented by Formula 1 or 2 below: [Formula 1]

[Formula 2]

In Formulas 1 and 2, X represents A- or Am-, wherein A represents a thermosetting resin, m represents a linker connecting the thermosetting resin and the silicon atom, and R ₁ to R ₆ each independently, Hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkynyl, glycidyl or halogen, a represents an integer from 1 to 5, each of which is the same or different from each other when R ₄ and R ₆ are plural; Wherein at least one of R ₁ to R ₃ represents a hydroxy group or an alkoxy group, and at least one of R ₄ to R ₆ represents a hydroxy group or an alkoxy group. The composition of claim 1, wherein the conductive filler has an electrical resistance of 1 ohm-cm or less. The composition of claim 1, wherein the conductive filler is at least one selected from the group consisting of a carbon filler, an oxide filler, a metal filler, a metal alloy filler, and a polymer filler. The method of claim 1, wherein the conductive filler is carbon black, carbon nanotubes, graphite, ITO, AZO, ATO, InO, ZnO, TiO ₂ , SnO, RuO ₂ , IrO ₂ , zirconia, gold, silver, nickel, copper, tantalum With palladium, silver / copper alloy, silver / palladium alloy, polyaniline, polyacetylene, polypyrrole, polyparaphenylene, polythiophene, polydienylene, polyphenylenevinylene, polyphenylene sulfide and polysulfurnitride At least one organic light emitting display device composition for sealing selected from the group consisting of. The composition of claim 1, wherein the conductive filler is included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the hybrid resin. The composition of claim 1, further comprising a curing agent. The organic compound according to claim 10, wherein the curing agent is at least one selected from the group consisting of amine compounds, imidazole compounds, phenol compounds, phosphorus compounds, acid anhydride compounds, isocyanate compounds, epoxy compounds, aziridine compounds, and metal chelate compounds. Composition for encapsulating a light emitting display device. The composition of claim 1, further comprising a binder resin. The organic light emitting display device of claim 12, wherein the binder resin is at least one selected from the group consisting of a phenoxy resin, an acrylate resin, a high molecular weight epoxy resin, an ultra high molecular weight epoxy resin, a high polar functional group-containing rubber, and a high polar functional group-containing reactive rubber. Composition for sealing. The composition of claim 1, further comprising a sol-gel reaction catalyst. Base film or release film; And an adhesive layer formed on the base film or the release film and containing the composition according to any one of claims 1 to 3 or 5 to 14. The adhesive film according to claim 15, further comprising a base film or a release film formed on the adhesive layer. The adhesive film of claim 15, wherein the adhesive layer has a thickness of 5 µm to 200 µm. A first step of coating a coating liquid comprising a composition according to any one of claims 1 to 3 or 5 to 14 on a base film or a release film; And Method for producing an adhesive film comprising a second step of drying the coating solution coated in the first step. The method of manufacturing an adhesive film according to claim 18, further comprising performing a third step of pressing the base film or the release film onto the adhesive layer formed through the second step. A first substrate on which a driving circuit is formed; A second substrate disposed spaced apart from the first substrate and having an organic light emitting element formed on a surface of the first substrate; And It is formed between the said 1st board | substrate and a 2nd board | substrate, and encapsulates the said organic light emitting element, and contains the hardened | cured material of the composition in any one of Claims 1-3 or 5-14. An organic light emitting display device including an encapsulation unit.

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