KR20140085262A - Filling agent for organic light emitting diode and organic light emitting diode apparatus comprising the same - Google Patents

Abstract

The present invention relates to a filler for an organic light emitting device which includes a multifunctional compound and a binder resin with a curable functional group on a branch chain. The filler for the organic light emitting device according to the embodiment of the present invention suppresses the generation and growth of a dark spot.

Description

TECHNICAL FIELD [0001] The present invention relates to a filler for an organic light emitting device, and an organic light emitting device including the filler for the organic light emitting device.

The present invention relates to a filler for an organic light emitting device and an organic light emitting device including the same. More particularly, the present invention relates to a filler for an organic light emitting device having a small amount of outgas, excellent barrier properties, and no dark spot, and an organic light emitting device including the filler.

The organic light emitting device may be manufactured by disposing another substrate on a substrate on which an organic light emitting diode (OLED) is deposited, and sealing the both substrates. However, the organic light emitting element is very weak in moisture, and the interface between the metal electric field and the organic EL layer may be peeled off by moisture, and the organic matter contained in the organic EL may be altered by moisture. Further, the resistance of the metal constituting the organic EL element may be increased by oxidation. For this reason, the organic light emitting device should include a filler capable of filling a space between the substrate and the substrate in addition to the sealing.

Conventionally, a small organic light emitting device for mobile use is filled with inert gas, which is a non-reactive gas, as a filler between a substrate on which a device is deposited and a substrate that covers the substrate. However, as the development is expanded to large-sized products such as TVs, if the inert gas is filled between the substrates as in the conventional method, warping due to the weight of the glass substrate may occur. Further, there is a problem that the entire panel and the organic light emitting device may be damaged due to an external impact.

According to Korean Patent Laid-Open Publication No. 2011-0126378, there is disclosed a laminate comprising a core particle, a cross-linking agent introduced into the surface of the core particle and having at least one SiH group, and at least one And a curing agent of a polyorganosiloxane having a phenoxy group and a phenoxy group. However, the presence of the crosslinking agent may cause damage to the display portion due to the residual crosslinking agent.

An object of the present invention is to provide a filler for organic light emitting devices capable of suppressing occurrence and growth of dark spots due to its low barrier property and low water permeability.

Another object of the present invention is to provide a filling agent for an organic light emitting device capable of suppressing the generation and growth of dark spots, because it is possible to encapsulate the organic light emitting element without causing physical and chemical adverse effects due to a low outgassing amount.

It is still another object of the present invention to provide a filler for an organic light emitting device capable of providing reliability over a long period of time by protecting the organic light emitting element from external impact.

The filler for an organic light emitting device, which is one aspect of the present invention, may contain a binder resin having a curable functional group in its side chain and a polyfunctional compound.

The organic light emitting device, which is another aspect of the present invention, may include a cured product of the filler for the organic light emitting device.

Disclosure of Invention Technical Problem [8] The present invention relates to an adhesive for a filler capable of suppressing the generation and growth of dark spots, because it has good barrier properties and low water permeability and low outgas generation, Lt; / RTI > The present invention also provides an adhesive film for a filler which can protect the organic light emitting element from external impact and provide reliability over a long period of time.

1 is a schematic cross-sectional view of an organic light emitting device according to one embodiment of the present invention.

The filler for an organic light emitting device, which is one aspect of the present invention, may contain a binder resin having a curable functional group in its side chain and a polyfunctional compound.

The binder resin may have a curing functional group in the side chain of the binder resin. Accordingly, the binder resin can form a filler by curing reaction with the polyfunctional compound. In addition, by increasing the cross-linking density at the time of curing, it is possible to provide a filler having high barrier properties that can block water or oxygen of the filler and excellent reliability.

The "side chain" may mean a branch portion connected to the main chain of the binder resin, preferably a branch portion excluding the most terminal in the longitudinal direction of the main chain.

The "curable functional group" may be a functional group capable of photo-curing or thermosetting. In an embodiment, the curable functional group may be a (meth) acrylate group, a vinyl group, or the like.

The curable functional group may be directly connected to the main chain of the binder resin as a side chain or may be connected to the side chain of the binder resin by a curable functional group-providing compound. The curable functional group-providing compound may include a compound having a reactive functional group capable of binding with the side chain of the binder resin and the curable functional group.

In an embodiment, the curable functional group-providing compound may include a compound having an isocyanate group and a (meth) acrylate group. For example, the curable functional group-providing compound may be (meth) acryloyloxyalkyl isocyanate.

The curable functional group may be 5-30% by weight, preferably 10-25% by weight, of the binder resin. Within the above range, it is possible to provide a cured site which is capable of completely reacting the hydroxyl group of the binder with the isocyanate group of the curable functional group and is capable of crosslinking.

The binder resin may include an aromatic hydrocarbon resin having an aromatic hydrocarbon group in the main chain or side chain of the binder resin. The aromatic hydrocarbon group can suppress the brittle phenomenon of the coating film by improving the film property of the adhesive film.

In an embodiment, the aromatic hydrocarbon group is an aryl group having 6-20 carbon atoms, an arylene group having 6-20 carbon atoms, an arylalkyl group having 7-21 carbon atoms, an arylalkylene group having 7-21 carbon atoms, an aryloxy group having 6-20 carbon atoms, Or an aryloxy group having 6 to 20 carbon atoms. For example, phenyl group, bisphenol A or F, naphthalene group and the like.

The weight average molecular weight of the binder resin may be 10,000 to 200,000 g / mol, preferably 20,000 to 100,000 g / mol. In the above range, the effect of suppressing the elution of the low-molecular substance and enhancing the elasticity of the filler to give the film strength and the barrier property can be obtained by excluding the low molecular substance.

The binder resin may have a glass transition temperature (Tg) of 0 to 90 캜, preferably 30 to 80 캜. Within this range, film rigidity can be ensured and an adhesive force capable of bonding to an organic light emitting device substrate through mixing with a low molecular weight material can be ensured.

The binder resin may include 30 to 90% by weight, preferably 40 to 80% by weight, of the filler. Within the above range, the coating film rigidity required for the OLED process can be secured.

The binder resin may include a polymer resin modified with a curable functional group.

In an embodiment, the binder resin may be prepared by reacting a polymer resin having a hydroxyl group in a side chain, a reactive functional group capable of reacting with the hydroxyl group of the polymer resin, and a curable functional group-containing compound having the curable functional group. For example, the reactive functional group may be an isocyanate group, but is not limited thereto.

In one embodiment, the polymer resin may include a non-(meth) acrylic resin that does not include a (meth) acrylic resin.

For example, the polymer resin may be at least one of a phenoxy resin, a phenol resin, a cresol resin, a phenol aralkyl resin, a triphenol methane resin and the like, but is not limited thereto.

The phenoxy resin may be represented by the following Formula 1:

≪ Formula 1 >

(Wherein n is an integer of 1-1000 and R is hydrogen, an alkyl group having 1-10 carbon atoms, a hydroxy group, a cycloalkyl group having 3-10 carbon atoms, an aryl group having 6-20 carbon atoms, a halogen, an amino group, or a mercapto group to be)

The phenolic resin may be represented by the following formula (2)

(2)

(Wherein n is an integer of 1-1000)

The cresol resin may be represented by the following Formula 3:

(3)

(Wherein n is an integer of 1-1000)

The phenol aralkyl resin may be represented by the following general formula (4)

≪ Formula 4 >

(Wherein n is an integer of 1-1000)

The triphenol methane resin may be represented by the following formula (5)

≪ Formula 5 >

(Wherein n is an integer of 1-1000)

The curable functional group-providing compound may be a non-carboxylic acid-based compound containing no carboxylic acid group. This is because the carboxylic acid group may cause a defective device upon contact with the organic light emitting device.

In an embodiment, the curable functional group-providing compound is a compound having an isocyanate group and a curable functional group, and may be (meth) acryloyloxyalkyl (e.g., an alkylene group having from 1 to 10 carbon atoms) isocyanate or a mixture containing , But is not limited thereto. (Meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, and the like.

The binder resin may be formed by reacting 80 to 95% by weight of the polymer resin and 5 to 20% by weight of the curable functional group-providing compound. Within the above range, the reaction can be promoted effectively, and the cured density ensuring the barrier property can be obtained.

The reaction between the polymer resin and the curable functional group-providing compound can be carried out in a conventional manner. In embodiments, the reaction may be carried out in the presence of a catalyst, but preferably in the presence of a catalyst for polymerization such as dibutyltin dilaurate (DBTDL). For example, the catalyst may be present at 10-400 ppm relative to the polymeric resin.

The reaction can be carried out at 30-50 DEG C for 4 hours to 20 hours, but is not limited thereto.

Preferably, the binder resin may include a phenoxy resin or an epoxy resin modified with (meth) acryloyloxyethyl isocyanate.

In an embodiment, the binder resin may comprise the following formula 6 in the side chain:

 (6)

- O - C (= O) -NH- (CH ₂ ) _n --O - C (= O) - C X = CH ₂

(Wherein * is a linking site for the main chain of the binder resin,

X is hydrogen or a methyl group,

and n is an integer of 1 to 2)

The polyfunctional compound may be included in the filler together with the binder resin to increase the tackiness, thereby allowing the filler to adhere well to the substrate, and after curing, increase the degree of crosslinking to improve the barrier property and reliability.

The polyfunctional compound may be a curable compound having a curable functional group. In an embodiment, the curable functional group may be a (meth) acrylate group, a vinyl group, or the like.

The polyfunctional compound may be bifunctional to hexafunctional having two or more, preferably 2-7, curable functional groups. In the above range, the cross-linking density of the filler can be increased through the curing reaction with the binder resin, thereby enhancing the barrier property and reliability.

The polyfunctional compound may comprise a polyfunctional monomer or oligomer thereof. In an embodiment, the polyfunctional compound may include at least one of urethane (meth) acrylate, epoxy (meth) acrylate, polyethylene glycol di (meth) acrylate and alkyl (meth) acrylate.

The polyfunctional compound may have a weight average molecular weight of 10,000 g / mol or less, preferably 500-5000 g / mol. Within this range, the final composition may be provided with tackiness.

The polyfunctional compound may include 5-60% by weight, preferably 10-50% by weight, more preferably 20-50% by weight, and most preferably 30-40% by weight of the filler. In the above range, it is possible to impart coating properties and tackiness to the final composition.

The weight ratio (A / B) of the binder resin (A) to the polyfunctional compound (B) in the filler may be 1-5, preferably 1.5-3.5.

The filler may further include an initiator.

The initiator may catalyze a curing reaction between the binder resin and the polyfunctional compound. In embodiments, the initiator may include one or more of a photocurable initiator, a thermoset initiator, and the like.

In an embodiment, the photoinitiator may comprise a triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime or mixtures thereof.

Examples of triazine derivatives include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxysti (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6- (Piperonyl) -6-triazine, 2,4- (trichloromethyl (4'-methoxystyryl) -6-triazine or mixtures thereof.

Examples of the acetophenone-based solvents include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloro 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2,2'-dichloroacetophenone, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, or mixtures thereof.

Examples of the benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-dichlorobenzo Phenone, 3,3'-dimethyl-2-methoxybenzophenone, or a mixture thereof.

Examples of thioxanthone include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone or And mixtures thereof.

The benzoin group may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or a mixture thereof.

Phosphorous can be bisbenzoylphenylphosphine oxide, benzoyldiphenylphosphine oxide or mixtures thereof.

The oxime system was prepared by reacting 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, or mixtures thereof.

In an embodiment, the thermal initiator is selected from the group consisting of azobisisobutyronitrile, azobis- (2,4-dimethyl) valeronitrile, octane oil peroxide, decanoyl peroxide, lauroyl peroxide, But are not limited to, oxides, triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime, or mixtures thereof.

The initiator may be included in the filler in an amount of 0.1 to 10% by weight, preferably 0.1 to 7% by weight, more preferably 1 to 7% by weight. In this range, a curing rate of 98% or more can be obtained and the remaining initiator can be prevented from remaining.

The filler may be formed of a composition for a filler including the binder resin, the polyfunctional compound, and the initiator. In embodiments, the filler can be prepared by coating the composition on a release film and drying. The drying may be performed at 80 DEG C for 10 minutes, but is not limited thereto.

The content of the binder resin, the polyfunctional compound and the initiator in the composition is as described above.

The binder resin may include 40-80 wt%, the polyfunctional compound may be 10-50 wt%, and the initiator may be 0.1-10 wt% based on the solids content of the composition.

The composition may further include a conventional solvent to improve the ease of coating the composition. In an embodiment, the solvent may be, but is not limited to, methyl ethyl ketone and the like.

The form of the filler is not limited, but may be in the form of a film. The film may be an adhesive film having adhesiveness for adhering the substrate.

The thickness of the film may be from 5 탆 to 30 탆, preferably from 10 탆 to 20 탆. In this range, it can be used as a filler in an organic light emitting device, and can be applied to various cases by varying the thickness of the film according to a gap.

The filler may have a low molecular weight after curing of 500 ppm or less, preferably 0-200 ppm. The 'low molecular weight' is a molecule having a weight average molecular weight of 500 to 5000 g / mol, and may be (meth) acrylate based monomer included in the process of producing the binder resin, but is not limited thereto.

The filler is a curable filler, preferably a curable adhesive film, which can be used as a filler of an organic light emitting device by being filled between a substrate including the organic light emitting device and the substrate and then cured.

The filler may have an outgassing amount of 500 ppm or less, preferably 300 ppm or less, and more preferably 0-200 ppm, at 15O < 0 > C and 30 minutes of collection after curing. In the above range, the effect on the organic light emitting element is minimized, and the effect of suppressing the generation and growth of dark spots can be obtained.

The filler has a water vapor permeability of 30 g / m ² · day or less, preferably 15 g / m ² · day or less, measured at 37.8 ° C. and 100% relative humidity for 24 hours, 10-20 g / m ² · day. Within this range, it is possible to obtain an effect of increasing the barrier property and preventing the movement of residual moisture and oxygen.

The outgassing amount and moisture permeability can be measured according to the following experimental examples.

The organic light emitting display device according to another aspect of the present invention may include a filler, particularly a cured product of the adhesive film, as a filler.

1 is a cross-sectional view schematically showing an organic light emitting device according to one embodiment of the present invention. As shown in FIG. 1, the organic light emitting device 100 includes a first substrate 110; A second substrate 120 disposed to face the first substrate 110; An organic light emitting diode (D) formed on the first substrate (110); And a filler 170 covering the organic light emitting device D and filling a space between the first substrate 110 and the second substrate 120.

Wherein the filler is in direct contact with a part or all of the surface of the organic light emitting device to protect the organic light emitting device from the external environment and is bonded to the first substrate and the second substrate, And serves to fill a space formed between one substrate and the second substrate.

The filler may comprise the filler, in particular a cured product of the adhesive film. In an embodiment, the filler may be prepared by pressing the adhesive film on the organic light emitting element under vacuum and curing. For example, the curing may include one or more of light curing, heat curing. In an embodiment, photo-curing may be performed at a light intensity of 1000 mJ or higher, and thermal curing may be performed at 100 ° C / 2 hr.

The filler may be used not only as a small but also as a filler in a panel including a large-sized organic light emitting device. In a conventional organic light emitting device, a space between a substrate and a substrate is filled with an inert gas. However, if the development is expanded to a large-sized product such as a TV, if the inert gas is filled between the substrates, the substrate may be warped due to the weight of the substrate, and the entire panel or the organic light emitting diode may be damaged due to an external impact.

On the other hand, even when applied to a large-sized organic light emitting device, the filler protects the panel or the organic light emitting device from external impact to maintain long-term stable light emission characteristics, thereby enhancing long-term reliability and suppressing generation and growth of dark spots due to good modulus and barrier characteristics can do.

In one embodiment, the filler has a water vapor permeability of 30 g / m ² .day or less, preferably 15 g / m ² .day or less, measured for 24 hours at 37.8 캜 and 100% relative humidity for a thickness of 20 탆 .

In another embodiment, the filling agent may have an outgassing amount of 500 ppm or less, preferably 200 ppm or less, at 150 ° C under 30 minutes of collection conditions.

The first substrate may be a transparent substrate. In an embodiment, the first substrate may be a flexible substrate or a non-flexible substrate. For example, the first substrate may be a glass substrate or a plastic substrate. The material of the plastic substrate may be an insulating organic material, for example, a silicone resin, a polyamide resin, an epoxy resin, a polyethersulfone resin, a polyacrylate resin, a polyetherimide resin, a polyethylene naphthalate resin, a polyethylene terephthalate resin , Polyphenyl sulfide resin, polyarylate resin, polyimide resin, polycarbonate resin, cellulose resin, and the like.

The organic light emitting device may be formed on the first substrate.

In the present specification, 'upper' is referred to as 'upper' with reference to the drawings, and may be lower depending on viewing time.

The organic light emitting device may include an organic light emitting device including an organic light emitting layer and a plurality of thin film transistors connected to the organic light emitting layers. And can be classified into a passive driving type and an active driving type depending on whether the driving of each organic light emitting element is controlled by a thin film transistor. The organic light emitting device of the present invention can be applied to both passive driving type and active driving type.

The second substrate opposes the first substrate and may cover the organic light emitting device in contact or non-contact manner. The second substrate may be formed of the same or different material as the first substrate. In an embodiment, the second substrate may be a glass substrate.

The organic light emitting device can be manufactured by a conventional method. For example, the composition for a filler is coated on a release film and dried to produce an adhesive film. An adhesive film is laminated on the substrate in a single layer or a plurality of layers, and another substrate on which the organic light emitting element is formed is joined so that the adhesive film and the organic light emitting element are in contact with each other. Then, an organic light emitting device filled with a filler can be manufactured by thermosetting or photo-curing.

The organic light emitting device may further include a sealing material 150.

The sealing material is attached only to the edge portions of the first substrate and the second substrate, respectively, without contacting the organic light emitting device, thereby sealing the space between the first substrate and the second substrate and preventing the permeation of moisture or oxygen from the outside . The sealing material may be an inorganic material such as an organic material including epoxy or the like and a frit that does not need to use a separate moisture absorbent, but is not limited thereto.

The organic light emitting device may include a conventional element included in a conventional organic light emitting device, for example, a buffer layer for improving the smoothness of the first substrate and blocking the penetration of impurities, an organic film of an organic light emitting element, .

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Manufacturing example : Binder resin manufacturing

A phenoxy resin (JER-4275, mitsubishi chemical) having a weight average molecular weight of 10,000 g / mol was dissolved in MEK (methyl ethyl ketone) in an amount of 40% by weight. 400 g of the obtained solution was added to a glass jacket reactor equipped with an agitator. 40 g of methacryloyloxyethyl isocyanate (MOI) and 200 ppm of dibutyltin dilaurate (DTBDL) were added thereto, followed by stirring at 40 ° C for 8 hours. After completion of the reaction, IR analysis revealed that the isocyanate peak of MOI completely disappeared. As a result, a MOI-modified phenoxy resin having a methacrylate group introduced into the side chain of the phenoxy resin was prepared.

Example : Phenoxy / ( Meta Acrylic hardening type Filler  Produce

A binder resin, a polyfunctional compound, an initiator, and a MEK solvent of Preparation Example were added in the amounts described in Table 1 (unit: parts by weight), and the mixture was homogeneously mixed to prepare a composition for a filler. The prepared composition was coated on a release type polyethylene terephthalate film with an applicator to form a coating film, followed by drying to remove the MEK solvent. A polyethylene terephthalate film having a thickness of 20 mu m was prepared.

Example 1 Example 2 Example 3 Example 4 Example 5 Binder resin The binder resin 30 25 30 25 25 Multifunctional
compound Urethane acrylate PU2100, Miwon Specialty Chemical 10 15 0 0 0 Polyethylene glycol dimethacrylate
(PEGDMA) NK ESTER 14G, SHIN-NAKAMURA CHEMICAL 0 0 10 15 0 Epoxy acrylate Miramer EA 2235, Miwon Specialty Chemical 0 0 0 0 15 solvent MEK
(Methyl ethyl ketone) - 57 57 57 57 57 Initiator TPO TPO, BASF 3 3 3 3 3

Comparative Example  1-2: Epoxy curing type Filler  Produce

The components described in Table 2 (parts by weight) were introduced and uniformly mixed to prepare an adhesive film composition for a filler. Then, an adhesive film for a filler was prepared in the same manner as in the above example.

division product name Comparative Example 1 Comparative Example 2 Liquid epoxy resin KDS8128 30 20 Solid epoxy resin EPPN-501HY 10 10 Phenoxy resin PKHH 10 20 Imidazole catalyst 2PZCNS-PW 3 3 solvent MEK 47 47

Comparative Example  3: Phenoxy  Hardened type Filler  Produce

Except that 25 parts by weight of a phenoxy resin having no methacrylate group introduced into its side chain, 15 parts by weight of a polyfunctional compound, 57 parts by weight of a solvent and 3 parts by weight of an initiator were used in place of the binder resin of the preparation example in Example 1 To prepare an adhesive film for a filler.

Experimental Example

The following properties of the filler thus prepared were evaluated and are shown in Table 3 below.

1. Tackiness (gf): Tackiness (tackiness) was measured with a probe tack tester (tacktoc-2000) using a specimen which was not cured and had thickness x width x length (20 m x 1 cm x 4 cm) ) Were measured. The measurement method was as described in ASTM D2979-71, where the tip of a clean probe was contacted with the adhesive film for 1.0 ± 0.01 seconds at a speed of 10 ± 0.1 mm / sec and a contact load of 9.79 ± 1.01 kPa, Tackiness.

2. Moisture permeability (g / m ² ㆍ day): Moisture permeability meter (PERMATRAN-W 3/33, MOCON) is used. After curing at 100 ° C for 2 hours, moisture permeability was measured for 24 hours at 37.8 ° C and 100% relative humidity using a moisture permeability meter (PERMATRAN-W 3/33, MOCON Co.) for 20 μm thick specimens .

3. Low Molecular Content (ppm): UV-cured film samples of 1000 mJ light intensity or 100 ° C for 2 hours are dissolved in ACN and analyzed by LC instrument to check for low molecular substances. Each low - molecular weight substance was LC - analyzed by concentration and calibrated.

As can be seen in the examples, the polymerized binder does not have residual low molecular weight residues such as monomers and does not affect the direct contact organic devices.

4. Outgassing amount (ppm): The composition for an adhesive film was applied on a glass substrate by spraying and cured under the condition of UV 1000 mJ light amount or 100 ° C for 2 hours. Then, 2 cm x 2 cm x 20 m (width x length x thickness) An organic protective layer specimen is obtained. For the specimen, use a GC / MS instrument (Perkin Elmer Clarus 600). As GC / MS, a helium gas (flow rate: 1.0 mL / min, average velocity = 32 cm / s) was used as a mobile phase using a DB-5MS column (length: 30 m, diameter: 0.25 mm, ), The split ratio is 20: 1, the temperature condition is kept at 40 ° C for 3 minutes, then the temperature is raised at a rate of 10 ° C / minute, and then the temperature is maintained at 320 ° C for 6 minutes. The outgas was 20 cm x 20 cm in glass size, the Tedlar bag was collected, the collection temperature was 150 ° C, the collection time was 30 minutes, the N ₂ purge flow rate was 300 mL / min and the adsorbent was Tenax GR (5% phenylmethylpolysiloxane ).

The sum of the integral values of the outgas components collected in the same amount of specimens is compared with each other, and the above conditions are summarized in Table 3 below.

division
Detail Collection conditions






Glass size: 20cm * 20cm Collecting container: Tedlar bag Collecting temperature: 120 ℃ Collection time: 30 min N2 purge flow rate: 300 mL / min Adsorbent: Tenax GR GC / MS conditions



Column DB-5MS? 30 m 0.25 mm 0.25 占 퐉
(5% phenylmethylpolysiloxane) Mobile phase He Flow 1.0 mL / min (Average velocity = 32 cm / s) Split Split ratio = 20: 1 method 40 캜 (3 min) -10 캜 / min? 320 캜 (6 min)

5. Dark spot evaluation: A transparent electrode was formed to a thickness of 0.1 탆 on a glass substrate by sputtering. A hole transport layer and an organic EL layer were sequentially formed on the transparent electrode in a thickness of 0.05 mu m. Further, on the top of the organic EL layer, a rear electrode having a thickness of 0.2 mu m was formed. After the film formation of these devices was completed, each sample formed as a sheet on the glass substrate 1 was transferred using a laminator. A non-water-permeable glass substrate was superimposed on the transferred glass substrate 1 and heat-pressed using a vacuum laminator. Thereafter, each sample was completely cured under the condition of a UV light of 1000 mJ or a temperature of 100 DEG C for 2 hours by a heat dryer. Thus, a panel was prepared, and the growth of dark spots was observed in an environment at 60 캜 and a relative humidity of 90% at a continuous point or the like. The case where a dark spot having a diameter of 100 占 퐉 or more after 1000 hours was not observed was evaluated as?, The case where a slightly dark spot was observed was evaluated as?, And the case where a dark spot was clearly observed was evaluated as X.

6. Simplicity of fairness evaluation: The cover release film of the film prepared in the example was peeled off and laminated on a slide glass of 2.6 cm * 7.6 cm to prepare a sample. The Scotch tape is attached to the base release film and peeled off to evaluate whether the base release film falls well. ? When the release film lamination using the release film lamination and the scotch tape was performed within 3 times,? When the release film was used three times or more, and X when the release film lamination was impossible or not possible.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Stickiness
(gf) 105 120 95 107 105 41 35 One Low molecular weight content
(ppm) 0 0 0 0 0 5500 2800 0 Outgas production
(ppm) 35 85 56 90 15 810 752 25 Water permeability
(g / m ² ㆍ day) 13 15 14 15 11 11 11 15 Dark Spot Rating ○ ○ ○ ○ ○ △ △ ○ Fairness ○ ○ ○ ○ ○ ○ ○ X

As shown in Table 4, the adhesive film for a filler of the present invention has good adhesiveness and can be easily adhered to a substrate. Also, the adhesive film for a filler of the present invention can be used as a highly reliable filler since a low molecular weight content, moisture permeability, and outgassing amount are low even after curing and dark spots do not occur.

On the other hand, the adhesive film for a filler of Comparative Example 1-2, which contains an epoxy curing compound known as a filler for ordinary organic light emitting devices, has a low content of low molecular weight, a high water vapor permeability, In addition, the adhesive film for a filler of Comparative Example 3 containing a phenoxy resin having no curable functional group has a poor film property and may cause a brittle phenomenon.

It is to be understood that the present invention is not limited to the above embodiments and drawings and that various changes and modifications may be made therein without departing from the spirit and scope of the present invention. As will be understood by those skilled in the art. Therefore, it should be understood that the above-described embodiments and drawings are to be considered in all respects as illustrative and not restrictive.

Claims (18)

A filler for an organic light emitting device comprising a binder resin having a curable functional group in a side chain and a polyfunctional compound.
The filler for an organic light emitting device according to claim 1, wherein the curable functional group comprises at least one of a (meth) acrylate group and a vinyl group.
The filler according to claim 1, wherein the curable functional group is contained in an amount of 5-30% by weight of the binder resin.
The filler for an organic light emitting device according to claim 1, wherein the binder resin is formed by reacting a polymer resin having a hydroxyl group with a (meth) acrylic compound having a reactive functional group.
5. The filler for an organic light emitting device according to claim 4, wherein the polymer resin comprises at least one of a phenoxy resin, a phenol resin, a cresol resin, a phenol aralkyl resin, and a triphenol methane resin.
5. The filler according to claim 4, wherein the (meth) acrylic compound comprises (meth) acryloyloxyalkyl isocyanate.
The filler for an organic light emitting device according to claim 4, wherein the binder resin is formed by a reaction of 80 to 95% by weight of the polymer resin and 5 to 20% by weight of the (meth) acrylic compound.
The filler according to claim 1, wherein the binder resin has a weight average molecular weight of 10,000 to 200,000 g / mol.
The organic electroluminescent device according to claim 1, wherein the polyfunctional compound is at least one compound selected from the group consisting of urethane (meth) acrylate, epoxy (meth) acrylate, polyethylene glycol di (meth) acrylate and alkyl Filler.
The filling agent for an organic light emitting device according to claim 1, wherein the filler further comprises an initiator.
The filler for an organic light emitting device according to claim 10, wherein the filler comprises 40-80 wt% of the binder resin, 10-50 wt% of the polyfunctional compound, and 0.1-10 wt% of the initiator.
The filler for an organic light emitting device according to claim 1, wherein the weight ratio (A / B) of the binder resin (A) to the polyfunctional compound (B) in the filler is 0.5-5.
The filling agent for an organic light emitting device according to claim 1, wherein the filler for organic light emitting devices has a film form.
14. The filler according to claim 13, wherein the film has a thickness of 5 to 30 mu m.
The filler for an organic light emitting device according to claim 1, wherein the filler has a water vapor permeability of 30 g / m ² · day or less, measured for 24 hours at 37.8 ° C. and 100% relative humidity with respect to a film thickness of 20 μm after curing.
The filler for an organic light emitting device according to claim 1, wherein the filler has an outgassing amount of 300 ppm or less after curing.
A first substrate; A second substrate disposed to face the first substrate; An organic light emitting device formed on the first substrate; And the filler covering the organic light emitting device and filling a space between the first substrate and the second substrate,
The organic light emitting device according to any one of claims 1 to 16, wherein the filler comprises a cured product of an adhesive film for a filler for an organic light emitting element.
18. The organic light emitting device according to claim 17, wherein the organic light emitting device further comprises a sealing material.

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