KR20140024936A - Composition comprising an organic-inorganic hybrid compound, adhesive film and organic light emitting display - Google Patents

Abstract

The present invention relates to a composition including an organic-inorganic hybrid compound, an adhesive film, and an organic light emitting display device. The composition according to the present invention has a high adhesion property, a high optical property, and a high waterproof property in a curing process. For example, the composition is efficiently applied to a sealing material for increasing the durability of the organic light emitting display device. Also, according to the present invention, manufactured is the organic light emitting display device which secures a required lifetime property. A structural problem like heat discharge and impact resistance of the device is overcome without using existing glass can, getter, and metal can. The sealing process of the organic light emitting display device is simplified.

Description

Composition comprising an organic-inorganic hybrid compound, adhesive film and organic light emitting display}

The present invention relates to a composition comprising an organic-inorganic hybrid compound, an adhesive film, and an organic light emitting display.

OLED (Organic Light Emitting Display) has lower power consumption, faster response time, and thinner characteristics than conventional display devices (eg, LCD or PDP). As described above, the organic light emitting display device is expected to be used in various fields including portable devices, monitors, notebooks, and televisions since it has advantages of portability and space utilization.

In commercialization of an organic light emitting display device and enlargement of use thereof, the most important problem is a durability problem. That is, since the organic light emitting material and the metal electrode included in the organic light emitting device are easily oxidized by moisture or the like, they are much more sensitive to environmental factors than conventional display devices. Accordingly, various methods have been proposed in order to effectively block penetration of oxygen or moisture from the outside of the organic light emitting diode display.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a structure of a known organic light emitting display device (Patent Documents 1 to 4, etc.).

1, a conventional organic light emitting display includes a glass can including a getter (or a moisture absorbent) 14 for sealing an organic light emitting layer 13 formed on a substrate 11 made of a glass or a polymer film, (Or a metal can) 15 with an adhesive (ex. UV curing type adhesive) 12. In such a structure, a cavity or protrusion of a certain depth is required to mount the getter or the moisture absorbent. In addition, since the glass can used in the existing apparatus can be easily broken by mechanical impact, the overall impact resistance of the apparatus is very low, and in the case of the metal can, there is a problem that it is difficult to secure workability in response to the enlargement of the display apparatus. In addition, in the organic light emitting display device having a getter or can structure as shown in FIG. 1, the heat emission is not easy and the front emission capable of increasing the light efficiency is also impossible.

(Patent Document 1) U.S. Patent No. 6,226,890 (Patent Document 2) U.S. Patent No. 6,808,828 (Patent Document 3) Japanese Patent Application Laid-Open No. 2000-145627 (Patent Document 4) Japanese Laid-Open Patent Application No. 2001-252505

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and it is an object of the present invention to provide a composition, an adhesive film, and an organic light emitting display using the same, which can exhibit excellent moisture barrier properties, optical characteristics, And an object of the present invention is to provide a device.

The present invention provides, as means for solving the above problems, an organic component having at least one functional group capable of thermosetting or photo-curing; And an inorganic or organic compound having at least one functional group selected from an alkoxy group and a hydroxy group.

As another means for solving the above-mentioned problems, the present invention provides a substrate film or a release film; And

There is provided an adhesive film comprising an adhesive layer formed on the base film or the release film and containing the composition according to the present invention.

Another aspect of the present invention is a substrate processing apparatus comprising: a substrate; An organic light emitting device formed on the substrate; A sealing layer covering a front surface of the organic light emitting device and including a cured product of the composition according to the present invention; And

And a cover substrate formed on the sealing layer.

The present invention relates to an organic component having at least one functional group capable of thermosetting or photo-curing; And an inorganic compound having at least one functional group selected from an alkoxy group and a hydroxy group.

The composition of the present invention can exhibit excellent adhesive properties and optical properties while having excellent moisture barrier properties, for example, when applied to an encapsulating material or an adhesive member of an organic light emitting diode (OLED).

Hereinafter, the composition of the present invention will be described in more detail.

The composition of the present invention comprises an organic component containing a functional group capable of forming a matrix through thermosetting or photo-curing; (For example, a sol-gel reaction or a condensation reaction) with moisture that can be introduced from the outside to form a crosslinked structure, whereby a complex of an inorganic component containing a functional group capable of suppressing the penetration of the moisture into the matrix ≪ / RTI >

The type of the functional group contained in the organic component of the organic-inorganic hybrid compound of the present invention is not particularly limited as long as it can perform a thermosetting reaction or a photo-curing reaction. Examples of such functional groups include a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group and the like which are capable of being thermally cured, and examples thereof include an alkenyl group, an alkynyl group and an acrylate group.

The content of the functional group contained in the organic component is not particularly limited. In one aspect of the present invention, the thermosetting or photo-curable functional groups may be contained in the organic component in an amount of 2 or more, preferably 3 or more, in order to effectively realize the desired moisture barrier properties and the like. The upper limit of the functional group content is not particularly limited, and can be appropriately adjusted, for example, in a range of 10 or less.

The specific kind of the organic component including the above-mentioned curable functional group is not particularly limited. For example, in one aspect of the present invention, the organic component includes the above-mentioned functional group, and may be an acrylic resin, a polyester resin, or an epoxy resin, and among them, it is preferable to use an epoxy resin, Do not.

The specific kind of the epoxy resin is not particularly limited. That is, in the present invention, an aromatic or aliphatic, linear or branched epoxy resin containing at least one epoxy functional group (glycidyl group) which can be cured to exhibit adhesive properties can be used without limitation. In one embodiment of the present invention, an epoxy resin having an epoxy equivalent of 180 to 1,000, which contains two or more functional groups, can be used. Examples of such an epoxy resin include cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol A novolac epoxy resin, phenol novolak epoxy resin, tetrafunctional epoxy resin, biphenyl type epoxy resin, An epoxy resin, an alkyl-modified triphenolmethane epoxy resin, a naphthalene-type epoxy resin, a dicyclopentadiene-type epoxy resin, or a dicyclopentadiene-modified phenol-type epoxy resin. If the average epoxy equivalent of the epoxy resin is less than 180, the crosslinking density after curing becomes too high to lower the adhesive performance. If the average epoxy equivalent is more than 1,000, the glass transition temperature (Tg) may be excessively low.

In one aspect of the present invention, in addition to the glycidyl group, the above-mentioned other functional group capable of photo-curing or thermosetting may be introduced into the epoxy resin.

At this time, the method for introducing the functional group is not particularly limited. For example, the functional group capable of reacting with the glycidyl group contained in the epoxy resin and the other functional group capable of photo- A method of reacting the compound with the epoxy resin may be used.

At this time, the specific kind of the compound which reacts with the epoxy resin is not particularly limited and may be suitably selected as necessary. For example, in order to introduce an alkenyl group, an alkynyl group, or an acrylate group capable of photo-curing into an epoxy resin, it is preferable to contain 1 to 5, preferably 1 to 2, photocurable groups per molecule, A compound having a functional group capable of reacting with a functional group contained in the epoxy resin can be used. Examples of the functional group capable of reacting with the epoxy resin include a hydroxyl group and a carboxyl group. Specific examples of the compound usable in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) (Meth) acrylate, 2-hydroxypropyleneglycol (meth) acrylate, 2-hydroxypropyleneglycol (meth) acrylate, (Meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropyl acid, 4- (meth) acryloyloxybutyric acid, acrylic acid doublet, itaconic acid, maleic acid and maleic anhydride. , But is not limited thereto.

The type of the compound capable of introducing a thermosetting functional group into the epoxy resin is not particularly limited. For example, a functional group capable of reacting with the functional group of the epoxy resin and a thermosetting functional group (ex , A hydroxyl group, an isocyanate group, a carboxyl group, etc.). In the present invention, when introducing a functional group using such a compound, the reaction conditions, the amount of introduction and the like are not particularly limited and can be suitably controlled according to the intended use.

On the other hand, the inorganic component of the organic-inorganic hybrid compound of the present invention is an inorganic component containing a sol-gel reaction catalyst or a functional group capable of reacting with moisture, which will be described later. Specific examples of the sol-gel reaction catalyst or the functional group capable of reacting with moisture as described above include an alkoxy group and a hydroxy group. Specific examples of the inorganic component containing such a functional group include silane, siloxane, and polysiloxane. Although not particularly limited, it is preferable that the inorganic component contains two or more reactors such as the above-mentioned alkoxy or hydroxyl group.

Specifically, in the present invention, the inorganic component may be a silane compound represented by the following formula (1) or a siloxane or polysiloxane represented by the following formula (2).

[Chemical Formula 1]

(2)

In the formulas (1) and (2), X represents A- or Am-, A represents an organic component capable of thermally curing or photo-curing and at least one functional group capable of curing, m represents a linker connecting organic components, R ₁ to R ₆ each independently represent hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkynyl or halogen, a represents an integer of 1 to 5, and when R ₄ and R ₆ are plural, At least one of R ₁ to R ₃ represents an alkoxy or hydroxy group, and at least one of R ₄ to R ₆ represents an alkoxy or a hydroxy group.

In the definition of the formula 1 or 2, alkyl or alkoxy 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 Methoxy, ethoxy or ethoxy.

In the definition of the above 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, May be ethenyl, ethynyl.

Furthermore, in the definition of the above formula (1) or (2), the halogen may represent fluorine, chlorine or bromine, and preferably represents chlorine or bromine.

The alkyl, alkoxy, alkenyl or alkynyl in the above-mentioned formula (1) or (2) may be substituted with one or more substituents. Examples of the substituent include a hydroxy group or a C1- , More preferably 1 to 4 alkyl or alkoxy, and the like.

In one aspect of the present invention, the compound of formula (2) may be, for example, a silane containing a functional group capable of condensation reaction, addition reaction or hydrosilylation reaction (e.g., hydrogen, halogen, alkoxy group, A siloxane or a polysiloxane.

Examples of the silane compound that can be used in this case include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (Meth) acrylates such as acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi (n-propoxy) (Propoxy) silane, dimethyl di (n-butoxy) silane, dimethyl di (sec-butoxy) silane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Di (i-propoxy) silane, dimethyl di (n-butoxy) silane, dimethyl di (sec- butoxy) silane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethyl Silane, aoiodotrimethylsilane, methoxytrimethylsilane, ethoxylate Propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, chlorovinyldimethylsilane, methoxyvinyldimethylsilane, or Ethoxyvinyldimethylsilane, and the like. Examples of the siloxane or polysiloxane include condensates of the above-mentioned silane compounds and the like, but the present invention is not limited thereto.

In the present invention, a method of reacting such a compound to obtain the compound of Formula 2 is not particularly limited, and general hydrolysis, condensation reaction or addition reaction in this field may be used. For example, the compound of formula 2 may be prepared by mixing the compounds described above in an appropriate solvent, hydrolyzing and condensing them in the presence of a base and water, or carrying out an addition reaction using a catalyst such as a platinum group catalyst .

In the organic-inorganic hybrid compound of the present invention, the aforementioned organic and inorganic components may be directly connected to each other or may be connected by an appropriate linker (m in the formulas (1) and (2)). The type of linker that can be used is not particularly limited and includes, for example, a single bond, alkylene having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms (e.g., -CH ₂ -); 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 combining the organic component and the inorganic component by bonding them together is not particularly limited and includes, for example, silane, siloxane or polysilicic acid used as an inorganic component; And an epoxy resin, an acrylic resin or a polyester resin, which are used as an organic component, are reacted with each other by reacting them under appropriate conditions.

At this time, the content of the inorganic component to be introduced into the organic component is 5 parts by weight to 100 parts by weight, preferably 10 parts by weight to 80 parts by weight, more preferably 25 parts by weight To 50 parts by weight.

If the content of the inorganic component is less than 5 parts by weight, the moisture barrier properties of the cured product produced by the composition of the present invention may be deteriorated. If the content is more than 100 parts by weight, the film formability may deteriorate.

In one aspect of the present invention, the above-mentioned organic-inorganic hybrid compound may be a compound represented by the following general formula (3).

(3)

In the above formula (3), R represents hydrogen, hydroxy, alkyl, alkoxy, alkenyl or alkynyl, each R may be the same as or different from each other, R ₄ to R ₆ are as defined in formula , p is an integer of 1 to 3, and q is an integer of 1 to 3.

In the definition of the formula (3), alkyl or alkoxy may represent alkyl or alkoxy having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, specifically methyl, ethyl, methoxy or Lt; / RTI >

In the definition of the above formula (3), alkenyl or alkynyl may represent alkenyl or alkynyl having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 4 carbon atoms, Ethenyl, ethynyl.

In one aspect of the present invention, the substituent R in Formula 3 may be alkyl, preferably alkyl having 1 to 4 carbon atoms, more preferably methyl or ethyl.

Examples of the organic or inorganic hybrid compound may include those sold under the trade names Compoceran E200, E201, E202 or E222 (arakawa chem.).

The composition of the present invention may further comprise a curing agent capable of reacting with the thermosetting or photo-curable functional group included in the compound together with the above-mentioned organic-inorganic hybrid compound to form a matrix.

The specific kind of the curing agent is appropriately selected depending on the kind of thermosetting or photocurable functional group contained in the complex compound, and the specific kind is not particularly limited.

For example, when the curable functional group is epoxy, conventional curing agents for epoxy resins may be used in the present invention. Examples of such a curing agent 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 case where the curable functional group is an acrylate group, an alkenyl group or an alkynyl group, the curing agent may be a polyfunctional acrylate, an aromatic ketone, a thio group-containing aromatic ketone, an alkoxy group-containing aromatic ketone, Ketone or phosphine oxide compounds, but are not limited thereto.

For example, when the organic component of the organic-inorganic hybrid compound is an epoxy group, the composition of the present invention may contain 0.1 to 20 parts by weight, preferably 1 to 20 parts by weight, of the imidazole-based curing agent per 100 parts by weight of the organic- By weight to 10 parts by weight.

However, the content of the curing agent is only an embodiment of the present invention. In the present invention, the content of the curing agent may be variously changed according to the kind and content of the curable functional group contained in the complex compound, or the matrix structure to be implemented.

The composition of the present invention may further include a sol-gel reaction catalyst in addition to the above-mentioned components. The sol-gel reaction catalyst accelerates the reaction between the functional group (e.g., an alkoxy group) of the inorganic component contained in the organic-inorganic hybrid compound and the water permeated from the outside, and the water permeation inhibiting performance of the cured product prepared by the composition of the present invention Can be improved. The kind of the sol-gel reaction catalyst that can be used in the present invention is appropriately selected depending on the functional group of the inorganic component contained in the above-mentioned complex compound, and the specific kind thereof is not particularly limited. In the present invention, for example, a catalyst having a relatively high reaction rate may be used as a catalyst, such as tin octanoate, trifluoroacetic acid, titanium tetraisopropoxide, Acetic acid, formic acid, titanium tetrakis (2-ethylhexoxide), and the like, which can be used as a catalyst and have a relatively moderate reaction rate, Aluminum chelate and aluminum alkoxide may be used. As the catalyst having a relatively low reaction rate, there may be used dibutyltin dilaurate, methyl trifluoroacetate (methyl trifluoroacetate) and ethyl trifluoroacetate, or the like, It is, but is not limited to this.

In the present invention, the content of the sol-gel reaction catalyst is not particularly limited as it is appropriately selected depending on the physical properties of the desired cured product. In the present invention, for example, 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, of a sol-gel reaction catalyst may be used based on 100 parts by weight of the organic-inorganic hybrid compound. If the content is less than 0.1 parts by weight, the increase in the reaction rate with water due to the addition of the sol-gel reaction catalyst may be insignificant. If the content is more than 10 parts by weight, further acceleration effect may not occur or the physical properties of the cured product may deteriorate .

However, the content of the sol-gel reaction catalyst is only an aspect of the present invention. That is, in the present invention, the content of the sol-gel reaction catalyst can be freely changed according to the kind and content of functional groups (eg, alkoxy group or hydroxyl group) in the inorganic component contained in the organic-inorganic hybrid compound. For example, in one aspect of the present invention, when the organic component of the organic-inorganic hybrid compound is a bisphenol-type epoxy resin and the inorganic component is a composite compound having an alkoxysiloxane, the amount of the alkoxysilane, About 5 to 25 parts by weight of a sol-gel reaction catalyst may be used.

The composition of the present invention may further comprise a binder resin having compatibility with the above-mentioned organic-inorganic hybrid compound together with the aforementioned components.

The binder resin may serve to improve the moldability of the composition in the case of forming 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 above-mentioned complex compound and can exhibit the above-mentioned effects. Specific examples of the binder resin that can be used include phenoxy resins, acrylate resins, high molecular weight epoxy resins, ultrahigh molecular weight epoxy resins, high polarity functional group-containing rubbers, and high polarity functional group-containing reactive rubbers But is not limited to, a mixture of two or more species.

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 organic-inorganic hybrid compound has a sufficiently large molecular weight and exhibits good film formability, the binder resin may not be added. In one embodiment of the present invention, the binder resin is used in an amount of about 100 parts by weight or less, preferably 90 parts by weight or less, more preferably about 70 parts by weight or less, based on 100 parts by weight of the above- . When the content of the binder resin exceeds 100 parts by weight, there is a possibility of causing a problem in terms of compatibility with the organic / inorganic hybrid compound.

The composition of the present invention may further contain, in addition to the above-mentioned components, a plasticizer for improving the durability of the cured product, a plasticizer for improving mechanical strength, heat resistance and light resistance, Coupling agents, plasticizers, ultraviolet stabilizers, and antioxidants.

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

And an adhesive layer formed on the base film or the release film and including an adhesive layer containing the composition according to the present invention.

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

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

2 and 3 are cross-sectional views of an adhesive film according to an embodiment of the present invention.

The adhesive film of the present invention may include an adhesive layer 22 formed on a base film or a release film 21, as shown in Fig. In another aspect of the present invention, as shown in Fig. 3, it may include an additional base film or release film 23 formed on the adhesive layer 22. However, the adhesive film shown in the drawings is only an aspect of the present invention. The adhesive film of the present invention may have, for example, the 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 may be formed on both sides of one base film or release film , Or in the form of a double-sided adhesive film.

The specific kind of the first film used in the present invention is not particularly limited, and for example, general polymer films in this field can be used. In the present invention, for example, the above-mentioned substrate or release film may be a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film, Film, an ethylene-vinyl acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film. In addition, a suitable mold release treatment may be performed on one or both sides of the base film or release film of the present invention. Examples of the releasing agent used in the releasing treatment of the base film include an alkyd type, a silicone type, a fluorine type, an unsaturated ester type, a polyolefin type, a wax type and the like. Among them, the use of an alkyd type, a silicone type or a fluorine type releasing agent But is not limited thereto.

The type of the second film (hereinafter also referred to as " cover film ") used in the present invention is not particularly limited. For example, in the present invention, as the second film, the same or a different kind as the first film may be used in the category exemplified in the first film described above. In addition, the second film may also be used by performing appropriate mold release processing.

In the present invention, the thickness of the base film or the release film as described above is not particularly limited, and can be appropriately selected according to the application to which it is 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 mu m, the base film may be easily deformed during the manufacturing process. If the thickness exceeds 500 mu m, the economical efficiency is lowered.

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 to be the same as that of the first film, or may be set to a relatively thin thickness as compared with the first film in terms of processability and the like.

The thickness of the adhesive layer included in the adhesive film of the present invention is not particularly limited and may be suitably selected in consideration of the application to which the film is applied. The adhesive layer included in the adhesive film of the present invention may be, for example, about 5 m to 200 m, and preferably about 10 m to 100 m. When the thickness is less than 5 mu m, for example, when the adhesive film of the present invention is used as an encapsulating material for an organic light emitting display or the like, there is a fear that the filling property and the processability are lowered, and when it exceeds 200 mu m, the economical efficiency is lowered.

In this invention, the method of manufacturing such an adhesive film is not specifically limited. In the present invention, for example, a first step of coating a coating solution containing the composition according to the present 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. The manufacturing method of the present invention may further include a third step of further pressing the base film or the release film on the coating liquid dried in the second step.

The first step of the present invention is a step of preparing a coating solution by dissolving or dispersing the above-mentioned composition according to the present invention in a suitable solvent. In this process, the content of the organic / inorganic hybrid compound contained in the coating liquid needs to be appropriately controlled in accordance with the desired moisture barrier property and film formability. In the present invention, for example, it is preferable that the content of the inorganic component in the organic / inorganic hybrid compound is adjusted to be about 5 wt% to about 50 wt% based on the total solid content of the coating solution. If the content is less than 5% by weight, the moisture barrier properties of the cured product may be deteriorated. If the content is more than 50% by weight, the film formability may deteriorate. Also, 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, impact resistance, and the like. For example, in the present invention, when the inorganic compound is an alkoxysiloxane-based compound and the organic component is an epoxy resin having an epoxy equivalent of about 300 g / eq, the organic-inorganic hybrid compound has a molecular weight of about 50000 g / mol It is preferable that an in-binder resin (e.g., phenoxy resin) is included in the total solid content in an amount of about 5% by weight to 50% by weight. In addition to the above components, if the viscosity of the coating liquid is excessively 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 the binder resin used, If the content of the solvent contained in the coating liquid is excessively increased, it may take a long time for drying, so that the amount of the solvent used is preferably minimized.

When a filler is contained in the coating solution, a ball mill, a bead mill, a three roll, or a high-speed grinder may be used alone or in combination for the purpose of improving dispersibility It is possible. Examples of materials for the balls and beads include glass, alumina, and zirconium, and balls and beads made of zirconium are preferable in terms of dispersibility of the particles.

The type of the solvent for preparing the coating liquid of the present invention is not particularly 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, a small amount of a solvent having a volatilization temperature higher than the above range may be mixed and used in consideration of film formability and the like. Examples of the solvent usable in the present invention include methyl ethyl ketone (MEK), acetone, toluene, dimethylformamide (DMF), methylcellosolve (MCS), tetrahydrofuran (THF) (NMP), and the like, but is not limited thereto.

In the first step of the present invention, the method of applying the coating solution to the base film or release film is not particularly limited, and examples thereof include a knife coat, a roll coat, a spray coat, a gravure coat, a curtain coat, a comma coat, Known methods such as coating and the like can be used without limitation.

The second step of the present invention is a step of drying the coating liquid coated in the first step to form an adhesive layer. That is, in the second step of the present invention, the coating liquid applied to the film is heated to dry and remove the solvent, whereby an adhesive layer can be formed. In this case, the drying conditions are not particularly limited, and for example, the drying can be performed at a temperature of 70 to 200 캜 for 1 to 10 minutes.

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

The third step of the present invention can be performed by coating a film and then pressing a further release film or a base film (cover film or second film) on the dried adhesive layer by a hot roll laminate or a pressing process. At this time, the third step is, in the likelihood and efficiency of the side of the continuous process may be carried out by hot roll lamination, where the process is at a temperature of about 10 ℃ to 100 ℃ about 0.1 kgf / cm ² to 10 kgf / cm < ² >.

The invention also provides a substrate; An organic light emitting device formed on the substrate; A sealing layer covering a front surface of the organic light emitting device and including a cured product of the composition according to the present invention; And

And an organic light emitting diode (OLED) including a cover substrate formed on the sealing layer.

The cured product of the composition of the present invention has excellent moisture barrier properties as described above and is excellent in optical characteristics and can be applied as an encapsulant or a bonding material for an organic light emitting display device to exhibit excellent properties.

In addition, the cured product of the composition of the present invention exhibits excellent transparency and can be preferably applied to devices designed in a top emission or bottom emission mode.

Since the composition or the adhesive film of the present invention does not require the use of a getter or the like as compared with the conventional method, there is an advantage that the manufacturing process can be simplified and the process cost can be reduced. In addition, There is an advantage that it can be used irrespective of the method, and an excellent mechanical durability can be imparted to the finally produced organic light emitting display device and the like.

Hereinafter, the organic light emitting diode display will be described with reference to the accompanying drawings. FIG. 4 illustrates an organic light emitting display according to an embodiment of the present invention.

In order to manufacture the organic light emitting diode display of the present invention, for example, a transparent electrode is first formed on a glass or polymer film 31 used as a substrate by vacuum evaporation or sputtering, and a hole transport layer And the organic light emitting element 33 are formed. Then, an electrode layer is further formed on the organic light emitting element 33 thus formed. Then, an adhesive layer (encapsulation layer) 32 formed from the composition of the present invention is formed on the organic light emitting element 33 of the substrate 31 which has undergone the above-described processes. The method for forming the adhesive layer 32 is not particularly limited. For example, the adhesive layer formed of the composition of the present invention may be transferred onto the organic light emitting element 33 formed on the substrate 31 in advance, (E.g., a glass or polymer film) 34 that has been placed thereon can be formed by heating, pressing, or the like. In this step, for example, when the adhesive layer 32 is transferred onto the cover substrate 34, the substrate or the release film formed on the film is peeled off using the above-mentioned adhesive film of the present invention, , It may be transferred onto the organic light emitting element 33 by using a vacuum press or a vacuum laminator. In this process, if the curing reaction of the adhesive film is performed over a certain range, the adhesion or adhesion of the sealing material 32 may decrease, so it is preferable to control the process temperature to about 100 캜 or less and the process time to be within 5 minutes Do. Similarly, a vacuum press or a vacuum laminator can be used when the cover substrate 34 onto which the adhesive layer 32 is transferred is heated and pressed against the organic light emitting element. The temperature condition at this stage can be set as described above, and the process time is preferably 10 minutes or less.

Further, in the present invention, an additional curing process of the adhesive layer in which the device is pressed can be performed. This curing process (final curing) can be performed in, for example, a heating chamber or a UV chamber. The heating conditions at the time of the final curing can be appropriately selected in consideration of the stability of the organic light emitting device. For example, it is preferable that the final curing process is performed at a temperature of 100 ° C or less as in the case of the above transferring conditions.

However, the manufacturing process described above is only an aspect for manufacturing the organic light emitting display device of the present invention, and the process sequence, process conditions, and the like can be freely modified. For example, in the present invention, the adhesive layer 32 containing the composition of the present invention is first transferred to the organic light emitting element 33 on the substrate 31 in the order of the pressing and sealing steps, Or the like.

The composition of the present invention has excellent moisture barrier properties, is excellent in optical properties, and can be applied as an encapsulant or a bonding material for an organic light emitting display device to exhibit excellent durability and the like. In addition, the composition of the present invention can be effectively applied regardless of device design modes such as front emission or back emission. Further, since the composition or the adhesive film of the present invention does not require the use of a getter or a metal can in the construction of the organic light emitting display device, the manufacturing process can be simplified and the process cost can be reduced, It can be used irrespective of the designing method of the semiconductor device, and has an advantage that excellent mechanical durability can be imparted.

1 is a view showing an embodiment of a structure of a conventional organic light emitting diode display.
2 and 3 are views showing an embodiment of the adhesive film of the present invention.
4 is a view showing an embodiment of an organic light emitting diode display according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited by the following examples.

Example  One

To the reactor at room temperature, 200 g of an organic-inorganic hybrid compound (Compoceran E201, ARAKAWA Chem (JP)), 4 g of 1-cyanoethyl-2-phenylimidazole (2PZCN, Shikoku Kasei) Chemistry), and 400 g of methyl ethyl ketone was added as a solvent. The reactor was then purged with nitrogen and the mixture was stirred for 2 hours. Then, 4 g of tin octanoate as a sol-gel catalyst was further added to the mixture, and further stirred for 1 hour. Subsequently, the prepared solution was filtered with a mesh having a pore size of 50 microns to remove the foreign material, thereby obtaining a coating solution. The prepared coating liquid was applied to a base film (RS-21G, SKC) having a thickness of 38 μm using a comma coater and dried at 120 ° C. for 1 minute in a high-temperature drier to obtain an adhesive layer having a thickness of 20 μm. Then, the same cover film as that of the base film was laminated on the adhesive layer of the produced adhesive film using a laminator (manufactured by Fuji Soec Co., Ltd.) to produce an adhesive film for an organic light emitting display, An organic light emitting display device as shown was manufactured.

Example  2

200 g of an organic-inorganic hybrid compound (Compoceran E202, ARAKAWA Chem (JP)), 4 g of 2-phenylimidazole (2PZ, Shikoku Kasei) and 125 g of phenoxy resin (YP-55, Kukdo Chemical Co., Ltd.) , And then 400 g of methyl ethyl ketone (MEK) was added as a solvent. Subsequently, the interior of the reactor was replaced with nitrogen, and the solution in the reactor was stirred for 2 hours. Subsequently, 3 g of a sol-gel catalyst, tin octanoate, was added to the reactor and further stirred for 1 hour. Then, the prepared solution was filtered with a mesh having a pore size of 50 microns to remove the foreign matter to prepare a coating solution. Thereafter, the organic light emitting display was manufactured through the same procedure as in Example 1.

Comparative Example  One

200 g of bisphenol A type epoxy resin (DER331, Japanese explosive), 4 g of 2-phenylimidazole (2PZ, Shikoku Kasei) and 125 g of phenoxy resin (YP-55, Kuko Chemical) were charged into a reactor at room temperature, , 400 g of methyl ethyl ketone (MEK) was added. Subsequently, the inside of the reactor was replaced with nitrogen, and the solution in the reactor was stirred for 2 hours. The solution was then screened with a mesh having a pore size of 50 microns to prepare a coating solution. An organic light emitting display was manufactured in the same manner as in Example 1 using the prepared coating solution.

Test Example  1. Calcium test

A calcium test was performed using the adhesive film or the organic light emitting display device manufactured as described above. Specifically, in the case of the adhesive film according to the present invention and the organic light emitting diode display manufactured using the above, the penetration of the moisture into the inside is suppressed by reacting with the moisture introduced from the outside. Therefore, it is difficult to accurately compare the cut-off characteristics with the plane-direction moisture measurement method which assumes a steady state flow. Therefore, in order to measure the durability of the device, the calcium test was carried out in the following manner. Specifically, after nine places of deposition (9 spots) of calcium (Ca) on a glass substrate (100 mm x 100 mm) at a predetermined size (8 mm x 8 mm) and a thickness (100 nm) The cover glass onto which the adhesive film was transferred was heated and pressed at 80 DEG C for 1 minute by using a vacuum press on each spot. The specimen was then cured for 2 hours at a temperature of 100 DEG C in a high temperature drier, and then each sealed Ca (Ca) specimen of size 10 mm x 10 mm was cut. The cut specimens were allowed to stand in a thermo-hygrostat chamber at a temperature of 80 ° C and a relative humidity of 90%, and the degree of transparency by the oxidation reaction of calcium (Ca) was compared and evaluated according to the following criteria.

&Amp; cir &: No transparency occurred after 500 hours in the constant temperature and humidity chamber

[Delta]: When the transparency area after 500 hours in the constant temperature and humidity chamber is less than 50% of the total area

×: When the transparency area after 500 hours in the constant temperature and humidity chamber is 50% or more of the total area

Test Example  2. Light transmittance  Measure

In order to confirm whether the composition according to the present invention is suitable for the whole luminous design, the light transmittance was measured by the following method. Specifically, the adhesive films prepared in Examples and Comparative Examples were cured between protective films, and the protective films were removed. The specimens were measured for transmittance based on JIS K 7105 (model name: HR-100, manufactured by Murakami Color Research Laboratory, ) To measure the light transmittance.

Test Example  3. Adhesion measurement

In order to examine the interfacial properties between the adhesive layer and the substrate, which are the main paths of moisture penetration from the outside, when the adhesives prepared in Examples and Comparative Examples were applied as encapsulants for organic light emitting devices, Using the adhesive film produced in the example, the adhesive force was measured after compression and curing. Specifically, two glass plates having a predetermined size (20 mm x 40 mm) and a thickness (3 mm) were orthogonally cut and then cut into a size of 5 mm in diameter. Then, the prepared specimens were heated and pressed at 80 DEG C for 1 minute using the adhesive films prepared in Examples and Comparative Examples, and then further cured at 100 DEG C for 2 hours to prepare specimens. Then, the adhesive strength of the prepared specimen was measured using a tensile tester.

The results of the tests performed as described above are summarized in Table 1 below.

Calcium test Light transmittance (%) Adhesion (Kg / cm ² ) Example 1 ○ 91 15 Example 2 ○ 90 13 Comparative Example 1 △ 92 14

As shown in Table 1, in the case of the embodiment including the organic-inorganic hybrid compound according to the present invention, compared with an epoxy-based composition commonly used as an encapsulating material for existing optical elements, , It is possible to remarkably suppress moisture penetration from the outside.

11: substrate 12: adhesive or sealant
13: Organic light emitting element 14: Desiccator (desiccant, desiccant)
15: Glass or metal can
21: base film or release film 22: adhesive layer
23: Cover film
31: substrate 32: adhesive layer or sealing layer
33: organic light emitting element 34: cover substrate

Claims (17)

Board;
An organic light emitting device formed on the substrate;
An organic-inorganic composite compound comprising an organic component having at least one functional group capable of thermosetting or photocuring and an inorganic component having at least one functional group selected from an alkoxy group and a hydroxy group; And an encapsulation layer covering the entire surface of the organic light emitting device, wherein an adhesive layer comprising a composition comprising a binder resin, which is a phenoxy resin or an acrylate resin, is formed by heat pressing. And
An organic light emitting display device comprising a cover substrate formed on the encapsulation layer. The organic light emitting display device according to claim 1, wherein the functional group capable of thermosetting or photocuring is a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group, an alkenyl group, an alkynyl group or an acrylate group. The organic light emitting display device according to claim 1, wherein the organic component is an acrylic resin, a polyester resin, or an epoxy resin. The epoxy resin of claim 3, 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. An organic light emitting display device which is 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. The organic light emitting display device according to claim 1, wherein the inorganic component is silane, siloxane or polysiloxane. The organic light emitting display device according to claim 1, wherein the inorganic component is a compound represented by the following Chemical Formula 1 or a compound represented by the following Chemical Formula 2.
[Chemical Formula 1]

(2)

In the general formulas (1) and (2), X represents A- or Am-, A represents an organic component having at least one thermosetting or photocurable functional group, m represents a linker connecting organic components, R ₁ And R ₆ are each independently hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkynyl or halogen, a is an integer of 1 to 5, and when R ₄ and R ₆ are plural, And at least one of R ₁ to R ₃ represents an alkoxy or hydroxy group, and at least one of R ₄ to R ₆ represents an alkoxy or a hydroxy group. The organic light emitting display device of claim 1, wherein the organic-inorganic complex compound is a compound represented by Formula 3 below:
(3)

And R ₄ to R ₆ are each independently selected from the group consisting of hydrogen, hydroxy, alkyl, alkoxy, alkoxy, alkenyl or alkynyl, Alkenyl, alkynyl or halogen, and when R ₄ and R ₆ are plural, each may be the same or different, and at least one of R ₄ to R ₆ represents an alkoxy or hydroxy group, and p represents an integer of 1 to 3 , And q is an integer of 1 to 3. The organic light emitting display device of claim 1, wherein the composition further comprises a curing agent. The curing agent according to claim 8, wherein the curing agent is an amine compound, an imidazole compound, a phenol compound, a phosphorus compound, an acid anhydride compound, an isocyanate compound, an epoxy compound, an aziridine compound, a metal chelate compound, a polyfunctional acrylate, an aromatic ketone And an organic light emitting display device comprising a thi-group containing aromatic ketone, an alkoxy group containing aromatic ketone, a hydroxyl group containing aromatic ketone or a phosphine oxide compound. The organic light emitting display device of claim 1, wherein the composition further comprises a sol-gel reaction catalyst. The sol-gel reaction catalyst according to claim 10, wherein the sol-gel reaction catalyst is tin octanoate, trifluoroacetic acid, titanium tetraisopropoxide, acetic acid, formic acid, titanium tetrakis (2-ethylhexoxide), aluminum chelate, aluminum alkoxide, dibutyl An organic light emitting display device which is tin dilaurate, methyl trifluoroacetate or ethyl trifluoroacetate. The organic light emitting display device of claim 10, wherein the composition comprises 0.1 to 10 parts by weight of a sol-gel reaction catalyst based on 100 parts by weight of an organic-inorganic composite compound. The organic light emitting display device of claim 1, wherein the composition comprises a binder resin in an amount of 100 parts by weight or less based on 100 parts by weight of the organic-inorganic composite compound. The organic light emitting display device of claim 1, wherein the organic light emitting display device is a top emission type or a bottom emission type. An organic-inorganic hybrid compound containing an inorganic component having at least one functional group selected from an alkoxy group and a hydroxyl group and having at least one functional group capable of thermosetting or photo-curing; And a binder resin, and heating and pressing the cover substrate onto which the adhesive layer including the composition molded in the form of a film is transferred, so as to cover the entire surface of the organic light emitting device with the adhesive layer on the organic light emitting device formed on the substrate Gt; a < / RTI > organic light emitting display device. The method of claim 1, wherein the hot pressing is 100? A method of manufacturing an organic light emitting display device which is performed within 10 minutes at the following temperature. The method of manufacturing an organic light emitting display device according to claim 2, further comprising a main curing step of curing the adhesive layer after hot pressing.

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