TWI759752B - Composition for encapsulating organic light emitting diode device and display device - Google Patents

Abstract

Disclosed is a composition for encapsulating an organic light emitting diode device including a photocurable monomer and an initiator, wherein the photocurable monomer does not include a silicon-based photocurable monomer, the photocurable monomer includes an aromatic group-containing monomer represented by Chemical Formula 1, and a non-aromatic group-containing monomer, and the non-aromatic-group-containing monomer has di(meth)acrylate having a C8 to C20 alkylene group, di(meth)acrylate having a C1 to C7 alkylene group, or a combination thereof, and an organic light emitting diode display device manufactured therefrom:

Description

Compositions for encapsulating organic light emitting diode devices and display devices

The present invention relates to a composition for encapsulating an organic light emitting diode device and an organic light emitting diode display device manufactured therefrom.

The organic light emitting diode display device is a light emitting type display device and includes organic light emitting diodes. The organic light emitting diode device may deteriorate when it comes into contact with external moisture or oxygen, so the organic light emitting diode device should be sealed with an encapsulation composition. The organic light emitting diode device is encapsulated with a multilayer structure in which an inorganic barrier layer and an organic barrier layer are sequentially formed. The inorganic barrier layer is formed by plasma deposition, and the organic barrier layer may be plasma etched. Such etching may impair the encapsulation function of the organic barrier layer, and thus, the organic light emitting diode device may have poor light emitting characteristics and low reliability.

Meanwhile, the barrier layer may be formed by applying the composition for encapsulating the organic light emitting diode device by an ink jet printer. At this time, if the composition aggregates or has poor spreadability, the processability is reduced, and the thickness of the final barrier layer is not uniform, which may affect image quality when applied to a display device.

(Patent Document 1) Korean Patent Publication No. 2012-0115841

An embodiment provides a composition for encapsulating an organic light emitting diode device having a high refractive index and cure rate, improved spreadability, and a low plasma etch rate after curing.

Another embodiment provides an organic light emitting diode display device including an organic barrier layer fabricated from the composition for encapsulating an organic light emitting diode device according to an embodiment.

其中，在化學式1中， L¹ 到L⁴ 獨立地是O、S、CO、COO、NR¹ （其中R¹ 是氫或C1到C5烷基），或C1到C10伸烷基， Ar¹ 到Ar⁴ 獨立地是經取代或未經取代的C6到C20芳基，且 Z¹ 到Z⁴ 獨立地是氫、C1到C10烷基或由化學式2表示的基團，前提是Z¹ 到Z⁴ 中的至少一個是由化學式2表示的基團： （化學式2）

其中，在化學式2中， Y¹ 是O、S、CO、COO或NR¹ （其中R¹ 是氫或C1到C5烷基）， R² 是氫或C1到C5烷基， p和q獨立地是0到10的整數中的一個， k是0或1，且 *是與另一原子的連接位置； m1到m4獨立地是0或1，且 n1到n4獨立地是0或1，前提是n1到n4中的至少一個是1。A composition for encapsulating an organic light emitting diode device according to an embodiment includes a photocurable monomer and an initiator, wherein the photocurable monomer does not include a silicon-based photocurable monomer, and the photocurable monomer includes a chemical formula An aromatic group-containing monomer represented by 1 and an aromatic group-free monomer having a di(meth)acrylate having a C8 to C20 alkylene group, a C1 to C20 alkylene group C7 alkylene di(meth)acrylate, or a combination thereof: (Chemical formula 1)

wherein, in Chemical Formula 1, L ¹ to L ⁴ are independently O, S, CO, COO, NR ¹ (wherein R ¹ is hydrogen or C1 to C5 alkyl), or C1 to C10 alkylene, Ar ¹ to Ar ⁴ is independently a substituted or unsubstituted C6 to C20 aryl group, and Z ¹ to Z ⁴ are independently hydrogen, a C1 to C10 alkyl group, or a group represented by Chemical Formula 2, provided that Z ¹ to Z ⁴ At least one of is a group represented by Chemical Formula 2: (Chemical Formula 2)

wherein, in Chemical Formula 2, Y ¹ is O, S, CO, COO or NR ¹ (wherein R ¹ is hydrogen or C1 to C5 alkyl), R ² is hydrogen or C1 to C5 alkyl, and p and q are independently is one of the integers 0 to 10, k is 0 or 1, and * is the position of attachment to another atom; m1 to m4 are independently 0 or 1, and n1 to n4 are independently 0 or 1, provided that At least one of n1 to n4 is 1.

Ar ¹ to Ar ⁴ in Chemical Formula 1 may be independently substituted or unsubstituted phenyl, naphthyl, anthracenyl, phenanthrenyl, enyl, or triphenyl, and one or both of n1 to n4 Can be 1 and the rest can be 0.

One of Z ¹ to Z ⁴ in Chemical Formula 1 may be a group represented by Chemical Formula 2, and the other three may be independently hydrogen or C1 to C10 alkyl groups.

In Chemical Formula 2, Y ¹ may be O, S or COO, p may be 0, and q may be one of integers of 1 to 4.

In Chemical Formula 2, Y ¹ may be O, S or COO, p may be one of integers of 1 to 4, and q may be 0.

在以上化學式中，n是1到10的整數中的一個，

。The aromatic group-containing monomer represented by Chemical Formula 1 may include one or more of monomers represented by the following Chemical Formula:

In the above chemical formula, n is an integer from 1 to 10,

.

The di(meth)acrylate having the C8 to C20 alkylene may include octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate ) acrylate, undecanediol di(meth)acrylate, dodecanediol di(meth)acrylate, tridecanediol di(meth)acrylate, tetradecanediol di(meth)acrylate meth)acrylate, pentadecanediol di(meth)acrylate, or a combination thereof.

The di(meth)acrylate having the C1 to C7 alkylene may include ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylic acid ester, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, or a combination thereof.

The aromatic group-free monomer may further include a mono(meth)acrylate having a C8 to C20 alkyl group.

The mono(meth)acrylate having the C8 to C20 alkyl group may include decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate Tridecyl acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, or a combination thereof.

In the composition, the amount of the aromatic group-containing monomer represented by Chemical Formula 1 may be greater than or equal to 50 wt % based on the total weight of the photocurable monomer and the initiator.

In the composition, the amount of the initiator may be less than 10% by weight based on the total weight of the photocurable monomer and the initiator.

The composition for encapsulating the organic light emitting diode device may have a spreadability of 140% to 170% according to Equation 1 by the following experimental method: >Equation 1> Spreadability 1 = S2 / S1 x 100 In Equation 1, S1 is by dropping the composition for encapsulating the organic light emitting diode device in an amount of 13 picoliters into an ink jet printer and measuring the maximum particle size of the drop after 30 seconds have elapsed (unit: microns) average value obtained 3 times, and S2 is by dropping the composition for encapsulating the organic light emitting diode device in an amount of 13 picoliters into an ink jet printer and measuring the maximum particle size of the drop after 300 seconds have elapsed (Unit: micrometer) The average value of 3 measurements.

The composition for encapsulating the organic light emitting diode device may have a plasma etch rate of less than 10% as measured by the following experimental method according to Equation 2: >Equation 2> Plasma etch rate (%) = (T1-T2)/T1 x 100 In Equation 2, T1 is the initial height of the deposited layer measured by photocuring after depositing the composition, and T2 is the height of the deposited layer after it has undergone inductively coupled plasma (ICP) treatment using ICP power: 2500 watts; RE power: 300 watts; DC bias Pressure: 200 V; Ar flow: 50 standard cubic centimeters/min; Etching time: 1 minute; Pressure: 10 mTorr; ICP CVD system: BMR technology.

An organic light emitting diode display device according to another embodiment includes: an organic light emitting diode device; and a blocking stack formed on the organic light emitting diode device and including an inorganic blocking layer and an organic blocking layer, wherein the The organic barrier layer may be fabricated using the composition according to the embodiment.

In the barrier stack, the inorganic barrier layers and the organic barrier layers may be alternately stacked.

The composition for encapsulating an organic light emitting diode device according to the embodiment has an excellent photocuring rate and spreadability, thereby improving workability, and has a high refractive index, thereby even if it is formed on an organic light emitting diode Brightness values at the front and/or sides are also increased on inorganic films in bulk display devices. Furthermore, it is possible to implement an organic barrier layer that can improve the reliability of the device by protecting the organic light emitting diode device due to stronger plasma resistance after curing. In addition, the composition for encapsulating an organic light emitting diode device according to the embodiment has a low modulus and can be used in a flexible device.

With reference to the accompanying drawings, the present invention will be described in detail so that those skilled in the art to which the present invention pertains can be easily practiced by the embodiments. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and the same reference numerals are assigned to the same or similar elements throughout the specification.

In this specification, "substituted" in "substituted or unsubstituted" refers to the replacement of at least one hydrogen of a given functional group by: C1 to C10 saturated or unsaturated hydrocarbon group, C6 to C20 aromatic hydrocarbon group, C1 to C20 aromatic hydrocarbon group C10 alkoxy, C6 to C20 aryloxy, C7 to C20 arylalkoxy, halogen (chloro, fluoro, bromo, iodo), hydroxy, carboxyl, amino, nitro, cyano, or a combination thereof.

In the present specification, "(meth)propenyl" may refer to propenyl and/or methacryl.

In the present specification, the "aryl group" refers to a functional group in which all elements of the cyclic substituent have p orbitals, and these p orbitals form conjugation. Aryl groups contain monocyclic functional groups, non-fused polycyclic functional groups, or fused polycyclic functional groups. "Fused" refers to rings in which carbon atoms share adjacent pairs.

Aryl also includes biphenyl, terphenyl, or tetraphenyl, which is a form in which two or more aryl groups are linked by a sigma bond. In an embodiment, aryl may refer to phenyl, naphthyl, anthracenyl, phenanthryl, naphthyl, pyrenyl, or methylene.

Specific examples of C6 to C20 aryl groups may include substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, Substituted or unsubstituted naphthyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted methylene, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted perylene, and the like.

In this specification, "the composition for encapsulating an organic light emitting diode device" may be simply referred to as "encapsulation composition".

An organic electroluminescence unit (organic light emitting diode (OLED)) has a structure in which a functional organic material layer is interposed between an anode and a cathode, and is passed through holes injected into the anode and injected into the cathode. recombination of electrons to generate excitons with high energy. The formed excitons move to the ground state to generate light of a specific wavelength. Organic electroluminescent units have advantages such as self-luminescence, high-speed response, wide viewing angle, ultra-thin, high-definition, and durability. Due to these advantages, organic electroluminescence cells are used in backlights of liquid crystals and the like to obtain high-brightness light emission at a low voltage, and are expected to be thin flat display devices.

Organic electroluminescence (EL) devices can be extremely susceptible to moisture, the interface between the metal electric field and the organic EL layer can peel off under the influence of moisture, metals can oxidize and are highly resistant to corrosion, and organic materials themselves can be degraded by moisture and oxygen , and the device may not emit light due to oxidation of organic materials and/or electrode materials by outgassing generated from outside or inside, and may also exhibit reduced brightness. In order to solve this problem, methods of encapsulating organic EL devices with curable compositions have been developed. As a conventional encapsulation method, a method of molding with an acrylic resin or a method of preventing the organic EL device from getting wet by adding a hygroscopic material to the encapsulation resin of the organic EL device has been proposed.

The inventors of the present invention have made efforts to develop a composition for encapsulating an organic light emitting diode device having a high refractive index and a viscosity within a predetermined range to prevent pinholes when using inkjet printing The organic film is formed at a low viscosity to improve processability by preventing the organic film from spreading and to perform the organic film at a low plasma etching rate. Accordingly, the present invention was accomplished by confirming that the compositions according to the Examples as described below can achieve all the above-mentioned objects.

其中，在化學式1中， L¹ 到L⁴ 獨立地是O、S、CO、COO、NR¹ （其中R¹ 是氫或C1到C5烷基），或C1到C10伸烷基， Ar¹ 到Ar⁴ 獨立地是經取代或未經取代的C6到C20芳基，且 Z¹ 到Z⁴ 獨立地是氫、C1到C10烷基或由化學式2表示的基團，前提是Z¹ 到Z⁴ 中的至少一個是由化學式2表示的基團： （化學式2）

其中，在化學式2中， Y¹ 是O、S、CO、COO或NR¹ （其中R¹ 是氫或C1到C5烷基）， R² 是氫或C1到C5烷基， p和q獨立地是0到10的整數中的一個， k是0或1， *是與另一原子的連接位置； m1到m4獨立地是0或1，且 n1到n4獨立地是0或1，前提是n1到n4中的至少一個是1。Specifically, the composition for encapsulating an organic light emitting diode device according to an embodiment of the present invention includes a photocurable monomer and an initiator, wherein the photocurable monomer does not include a silicon-based photocurable monomer, the The photocurable monomer includes an aromatic group-containing monomer represented by Chemical Formula 1 and an aromatic group-free monomer having a bis(methyl group having a C8 to C20 alkylene group) ) acrylate, di(meth)acrylate with C1 to C7 alkylene, or a combination thereof: (Chemical formula 1)

wherein, in Chemical Formula 1, L ¹ to L ⁴ are independently O, S, CO, COO, NR ¹ (wherein R ¹ is hydrogen or C1 to C5 alkyl), or C1 to C10 alkylene, Ar ¹ to Ar ⁴ is independently a substituted or unsubstituted C6 to C20 aryl group, and Z ¹ to Z ⁴ are independently hydrogen, a C1 to C10 alkyl group, or a group represented by Chemical Formula 2, provided that Z ¹ to Z ⁴ At least one of is a group represented by Chemical Formula 2: (Chemical Formula 2)

wherein, in Chemical Formula 2, Y ¹ is O, S, CO, COO or NR ¹ (wherein R ¹ is hydrogen or C1 to C5 alkyl), R ² is hydrogen or C1 to C5 alkyl, and p and q are independently is one of the integers 0 to 10, k is 0 or 1, * is the position of attachment to another atom; m1 to m4 are independently 0 or 1, and n1 to n4 are independently 0 or 1, provided n1 At least one of n4 is 1.

The composition for encapsulating an organic light emitting diode device according to the embodiment may have a high refractive index, and may form an organic film capable of improving the luminance value at the front surface and/or the side surface even when formed on an inorganic film, And can have an appropriate viscosity for printing using ink jet etc. to provide good spreading of droplets and thus provide excellent processability. The thickness of the barrier layer made from the composition can be uniform and generally thin, the surface can be uniform, and the photocuring rate can also be increased to provide good processability. In addition, the cured film can have higher plasma resistance, and thus a low plasma etch rate, thereby improving the reliability of the device. Furthermore, the composition can also have a low modulus and thus it can be used in panels of flexible devices.

As described above, the photocurable monomer according to the embodiment is a non-silicon-based photocurable monomer that does not contain silicon (Si).

In the composition according to the embodiment, when a silicon-based photocurable monomer is used instead of the aromatic group-containing monomer represented by Chemical Formula 1, the di(meth)acrylate having C8 to C20 alkylene, and the When one of the C7 alkylene di(meth)acrylates, the spreadability of the composition may be poor or the modulus of the composition may be high, resulting in low flexibility problems.

Furthermore, in the composition according to the embodiment, when the silicon-based photocurable monomer is combined with the aromatic group-containing monomer represented by Chemical Formula 1, the di(meth)acrylate having a C8 to C20 alkylene and/or having When C1 to C7 alkylene di(meth)acrylates are additionally included together, the spreadability of the composition may be poor or the modulus of the composition may be higher, resulting in low flexibility problems.

In the present invention, an aromatic group-containing photocurable monomer represented by Chemical Formula 1, a di(meth)acrylate having a C8 to C20 alkylene group and a C1 to C7 alkylene group as the aromatic group-free monomer The di(meth)acrylate of the alkyl group and the initiator are each different compounds. The compounds may each comprise one or more materials.

Hereinafter, each component of the composition according to the embodiment is described in detail. ( A ) Aromatic group-containing photocurable monomer represented by Chemical Formula 1

The aromatic group-containing photocurable monomer represented by Chemical Formula 1 has the effects of increasing the refractive index of the encapsulation composition to 1.50 or more, preventing the organic film from being phase deposition and etching, as well as to provide the appropriate viscosity of the encapsulating composition. The monomer of Chemical Formula 1 may be contained alone or in a combination of two or more.

In Chemical Formula 1, L ¹ to L ⁴ may independently be O, S, CO, COO, NR ¹ (wherein R ¹ is hydrogen or a C1 to C5 alkyl group) or a C1 to C10 alkylene group, when m1 to m4 are each When it is 1, it exists as a linker, which is one of the groups. In embodiments, L ¹ to L ⁴ may independently be O, S, COO, or C1 to C4 alkylene. On the other hand, when m1 to ^m4 are each 0, L1 to L4 should be understood as ^a single bond, respectively.

In Chemical Formula 1, Ar ¹ to Ar ⁴ may independently be substituted or unsubstituted C6 to C20 aryl groups, wherein "aryl" is the same as described above.

For example, Ar ¹ to Ar ⁴ of Chemical Formula 1 may independently be substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted Substituted phenanthrenyl, substituted or unsubstituted methylene, substituted or unsubstituted triphenyl, and the like, but not limited thereto. In embodiments, Ar ¹ to Ar ⁴ of Chemical Formula 1 may independently be a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.

As described above, "substituted" refers to the replacement of at least one hydrogen of an aryl group by a C1 to C10 saturated or unsaturated hydrocarbyl group, a C6 to C20 aromatic hydrocarbyl group, a C1 to C10 alkoxy group, a C6 to C20 aryloxy group, C7 to C20 arylalkoxy, halogen (chloro, fluoro, bromo, iodo), hydroxy, carboxyl, amino, nitro, cyano, or a combination thereof.

Ar ¹ to Ar ⁴ of Chemical Formula 1 may also be present or absent when n1 to n4 are 0 or 1, respectively, but at least one of n1 to n4 is 1, and thus Chemical Formula 1 includes at least one aryl group. In an embodiment, one or both of n1 to n4 may be 1 and the others may be 0. That is, the compound represented by Chemical Formula 1 may have at least one aryl group, or may contain two aryl groups.

。Z ¹ to Z ⁴ in Chemical Formula 1 may independently be hydrogen, a C1 to C10 alkyl group, or a group represented by Chemical Formula 2, wherein at least one of Z ¹ to Z ⁴ is a group represented by Chemical Formula 2: (Chemical formula 2)

.

In Chemical Formula 2, Y ¹ , R ² , p, q, k and * are each the same as defined above.

The portion represented by Chemical Formula 2 is a portion that allows the compound represented by Chemical Formula 1 to be polymerized and cured by light through radical reaction. That is, Chemical Formula 2 corresponds to the photocurable part. Accordingly, the aromatic group-containing monomer represented by Chemical Formula 1 may contain at least one moiety represented by Chemical Formula 2 in the molecule. That is, at least one of Z ¹ to Z ⁴ in Chemical Formula 1 is a group represented by Formula 2. In an embodiment, one of Z ¹ to Z ⁴ in Chemical Formula 1 may be a group represented by Chemical Formula 2, and the other three may independently be hydrogen or C1 to C10 alkyl groups.

Y ¹ in Chemical Formula 2 may be a linking group such as O, S or COO when k is 1, and should be understood as a single bond when k is 0.

In an embodiment, p may be 0 and q may be one of the integers from 1 to 4, or in an embodiment, p may be one of the integers from 1 to 4, and q may be 0.

In an embodiment, R ² can be hydrogen or a C1 to C4 alkyl group such as methyl. In this specification, as shown below, when a specific chemical formula of the compound represented by Chemical Formula 1 is shown, even if only the chemical formula in which R ² is hydrogen or methyl is exemplified, those skilled in the art will understand that in the compound All compounds in which R2 is ^hydrogen or methyl are included within the scope of the present invention.

As described above, the compound represented by Chemical Formula 1 has at least one aryl group, two aryl groups, three aryl groups, or four aryl groups in the molecule. Furthermore, in each of the above cases, one photocurable moiety, two photocurable moieties, three photocurable moieties, or four photocurable moieties represented by Chemical Formula 2 may be included in the molecule. In an embodiment, the aromatic group-containing photocurable monomer represented by Chemical Formula 1 may include one photocurable moiety.

In an embodiment, the compound represented by Chemical Formula 1 may be a photocurable monomer having one or two aryl groups in a molecule and further including one photocurable moiety represented by Chemical Formula 2. In an embodiment, the compound represented by Chemical Formula 1 may be a photocurable monomer including one aryl group and one photocurable moiety represented by Chemical Formula 2 in the molecule. Alternatively, the compound represented by Chemical Formula 1 may be a photocurable monomer containing one aryl group and one photocurable moiety represented by Chemical Formula 2 in the molecule and two or more aryl groups (eg, two aryl groups) in the molecule. or three aryl groups) and a photocurable monomer of the photocurable moiety represented by Chemical Formula 2.

在以上化學式中，n是1到10的整數，

。As specific examples of the compound represented by Chemical Formula 1, the compound represented by the following Chemical Formula can be shown, but is not limited thereto, and the following compounds may be included alone or in a combination of two or more.

In the above chemical formula, n is an integer from 1 to 10,

.

The above chemical formula is exemplified by a specific compound containing an acrylate group or a methacrylate group as a photocurable moiety. However, as described above, for example, in the case of a compound having an acrylate group, a compound having a methacrylate group instead of an acrylic group (in which the rest of the compound has the same structure) can also serve as a type of The photocurable monomer represented by Chemical Formula 1 is contained. Furthermore, on the contrary, in the case of a compound having a methacrylate group, a compound having an acrylate group instead of a methacrylate group in which the rest of the compound has the same structure can also be represented by Chemical Formula 1 as a type of of photocurable monomers. In addition, the compound represented by Chemical Formula 1 includes all compounds containing a (meth)acrylate group, which is a structural isomer. For example, although only phenethyl 2-(meth)acrylate is mentioned as an example of the monomer represented by Chemical Formula 1, phenethyl 3-(meth)acrylate, phenylethyl 4-(meth)acrylate and the like may be included as examples of the monomer represented by Chemical Formula 1 contained in the composition of the present invention.

In the composition according to the embodiment, the amount of the aromatic group-containing monomer represented by Chemical Formula 1 may be greater than or equal to 50 wt % based on the total weight of the photocurable monomer and the initiator. For example, the amount of the aromatic group-containing monomer represented by Chemical Formula 1 may be greater than or equal to 51% by weight, such as greater than or equal to 52% by weight, such as greater than or equal to 55% by weight, such as greater than or equal to 60% by weight, such as greater than or equal to 62% by weight, such as greater than or equal to 63% by weight, such as greater than or equal to 65% by weight, such as greater than or equal to 68% by weight, such as greater than or equal to 70% by weight, such as greater than or equal to 72% by weight, such as greater than or equal to Equal to 75% by weight, such as greater than or equal to 77% by weight, such as greater than or equal to 80% by weight, such as greater than or equal to 85% by weight, but not limited thereto.

When the aromatic group-containing monomer represented by Chemical Formula 1 is included in the above amount range, the composition according to the embodiment may have desired refractive index, viscosity, photocuring rate, light transmittance, and the like, and be produced therefrom The organic film has a high plasma etch rate, and the modulus is greatly reduced, so the composition can be used as an organic barrier layer for flexible organic light emitting diode display devices, and at the same time, the composition can exhibit high brightness value . ( B ) Di ( meth ) acrylates with C8 to C20 alkylene

The composition according to the embodiment may include a di(meth)acrylate having a C8 to C20 alkylene group as a photocurable monomer having no aromatic group.

Di(meth)acrylates having C8 to C20 alkylene groups are included in the encapsulation composition, thereby increasing the crosslinking rate during curing of the organic film, thereby reducing the plasma etch rate of the organic barrier layer to improve the inclusion of the Reliability of organic light emitting diode display devices with organic barrier layers. When a di(meth)acrylate having an alkylene group having more than 20 carbon atoms is included in the composition according to the embodiment, the spreadability of the composition is poor, or the modulus of the composition is relatively high, Therefore flexibility may be reduced.

The di(meth)acrylate having a C8 to C20 alkylene group may be a non-silicon-based di(meth)acrylate that does not contain silicon.

The di(meth)acrylate having a C8 to C20 alkylene group may include a di(meth)acrylate having an unsubstituted C8 to C20 alkylene group between the (meth)acrylate groups. Herein, the number of carbon atoms in the alkylene group only means the number of carbon atoms in the alkylene group itself, excluding carbon in the di(meth)acrylate group.

在化學式3中， R³ 是C8到C20伸烷基，且 R⁴ 和R⁵ 獨立地是氫或甲基。In an embodiment, the di(meth)acrylate having a C8 to C20 alkylene group may be represented by Chemical Formula 3: (Chemical Formula 3)

In Chemical Formula 3, R ³ is a C8 to C20 alkylene group, and R ⁴ and R ⁵ are independently hydrogen or methyl.

For example, ^R3 can be a C8 to C15 alkylene, such as a C8 to C13 alkylene.

Examples of di(meth)acrylates having C8 to C20 alkylene groups may be octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate ester, undecanediol di(meth)acrylate, dodecanediol di(meth)acrylate, tridecanediol di(meth)acrylate, tetradecanediol di(meth)acrylate ) acrylate, pentadecanediol di(meth)acrylate, and the like, but not limited thereto.

In the composition according to the embodiment, the di(meth)acrylate having a C8 to C20 alkylene group as the monomer containing no aromatic group may be based on the total weight of the photocurable monomer and the initiator in the composition In an amount of less than or equal to about 42% by weight, for example, in an amount of less than or equal to about 40% by weight, such as less than or equal to about 38% by weight, such as less than or equal to about 35% by weight, such as less than or equal to about 32% by weight, such as less than or equal to about 30% by weight, such as less than or equal to about 28% by weight, such as less than or equal to about 25% by weight, such as less than or equal to about 22% by weight, or for example less than or equal to about 20% by weight, and for example greater than or equal to about An amount of 10% by weight, such as greater than or equal to about 12% by weight, or such as greater than or equal to about 15% by weight is included, but not limited thereto.

When the di(meth)acrylate having a C8 to C20 alkylene group is included in the above range, the encapsulation composition according to the embodiment can implement an organic barrier layer with a low plasma etch rate and a low mold after curing amount to provide a flexible display device, and can improve the spreadability of the composition encapsulating the organic light emitting diode device.

In an embodiment, the di(meth)acrylate having a C8 to C20 alkylene group may be included in an amount of about 15 wt % to 40 wt % based on the total weight of the photocurable monomer and initiator, such as about 20 wt % % to about 35% by weight.

Di(meth)acrylates having C8 to C20 alkylene may be included alone or together with the subsequently described di(meth)acrylates having C1 to C7 alkylenes as non-aromatic components in the composition based photocurable monomers. ( C ) Di ( meth ) acrylates with C1 to C7 alkylene

The composition according to the embodiment may include a di(meth)acrylate having a C1 to C7 alkylene group as an aromatic group-free photocurable monomer.

Similar to di(meth)acrylates with C8 to C20 alkylene groups, di(meth)acrylates with C1 to C7 alkylene groups are included in the encapsulation composition to reduce the plasma etch rate of the organic barrier layer, And improve the reliability of the organic light emitting diode display device including the organic barrier layer.

The di(meth)acrylate having a C1 to C7 alkylene group may be a non-silicon-based di(meth)acrylate that does not contain silicon.

The di(meth)acrylate having a C1 to C7 alkylene group may include a di(meth)acrylate having an unsubstituted C1 to C7 alkylene group between the (meth)acrylate groups. Herein, the number of carbon atoms in the alkylene group only means the number of carbon atoms in the alkylene group itself, excluding carbon in the di(meth)acrylate group.

在化學式4中， R⁶ 是C1到C7伸烷基，且 R⁷ 和R⁸ 獨立地是氫或甲基。In an embodiment, the di(meth)acrylate having a C1 to C7 alkylene group may be represented by Chemical Formula 4: (Chemical Formula 4)

In Chemical Formula 4, R ⁶ is a C1 to C7 alkylene group, and R ⁷ and R ⁸ are independently hydrogen or methyl.

For example, ^R6 can be a C1 to C7 alkylene, such as a C3 to C7 alkylene.

Examples of di(meth)acrylates having C1 to C7 alkylene groups may be ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, Butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, heptanediol di(meth)acrylate and the like, but not limited to this.

Similar to the di(meth)acrylate having an alkylene group of C8 to C20, when the di(meth)acrylate having an alkylene group having C1 to C7 is contained alone as an aromatic group-free monomer, it can be The photocurable monomers and initiators are included in the compositions according to the embodiments in an amount of less than or equal to about 42 wt %, such as less than or equal to about 40 wt %, such as less than or equal to about 38 wt %, such as less than or equal to about 35% by weight, such as less than or equal to about 32% by weight, such as less than or equal to about 30% by weight, such as less than or equal to about 28% by weight, such as less than or equal to about 25% by weight, such as less than or equal to about 22% % by weight or, for example, less than or equal to about 20% by weight, and for example, greater than or equal to about 10% by weight, such as greater than or equal to about 12% by weight, or for example, greater than or equal to about 15% by weight, are included in compositions according to embodiments , but not limited to this.

When the di(meth)acrylate having a C1 to C7 alkylene group is included in the range, the encapsulation composition according to the embodiment may implement an organic barrier layer having a low plasma etch rate and a low plasma etch rate after curing Modulus to provide flexible display devices and can improve the spreadability of compositions for encapsulating organic light emitting diode devices. In an embodiment, the di(meth)acrylate having a C1 to C7 alkylene group may be included in an amount of about 15 wt % to 40 wt % based on the total weight of the photocurable monomer and initiator, such as about 20 wt % % to about 35% by weight.

As described above, the aromatic-free monomers in the compositions according to the embodiments may comprise di(meth)acrylates having C8 to C20 alkylene and/or di(meth)acrylates having C1 to C7 alkylene (Meth)acrylate, wherein the two components may be contained in predetermined amounts in both cases when the two components are each present alone and when the two components are mixed, as long as they are not contained The total amount of aromatic-based monomers may be within a range of less than or equal to about 42% by weight based on the total weight of photocurable monomers and initiators in the composition according to the present invention. In other words, when only either of the two components is present, the one component may be included in less than or equal to about 42% by weight based on the total weight of the photocurable monomer and initiator, or when all of the components are present In the case of two components, the sum of the two components may be less than or equal to about 42 weight percent based on the total weight of the photocurable monomer and initiator. In this case, the mixing ratio of the two components is not particularly limited. In other words, when the two components are included together, the two components may be mixed in any weight ratio in the range between about 1:99 and about 99:1.

Both di(meth)acrylates having C1 to C7 alkylene groups and di(meth)acrylates having C8 to C20 alkylene groups and compounds represented by having diacrylates and by having dimethacrylates The compounds represented (which have the same structure of another region) all relate to the scope of the compounds according to the invention. Furthermore, all structural isomers thereof may relate to the scope of the compounds according to the present invention. ( D ) Mono ( meth ) acrylates with C8 to C20 alkyl groups

On the other hand, in addition to the above-described di(meth)acrylates having C8 to C20 alkylene and/or di(meth)acrylates having C1 to C7 alkylene, the encapsulation according to the embodiment The composition may further comprise a mono(meth)acrylate having a C8 to C20 alkyl group as an aromatic group-free photocurable monomer.

The photocuring rate of the encapsulating composition can be further improved by further including a mono(meth)acrylate having a C8 to C20 alkyl group in the encapsulating composition according to the embodiment. In addition, mono(meth)acrylates with C8 to C20 alkyl groups can increase the light transmittance of the organic barrier layer and also reduce the plasma etch rate.

The mono(meth)acrylate having a C8 to C20 alkyl group may be a non-silicon based mono(meth)acrylate that does not contain silicon.

The mono(meth)acrylate having a C8 to C20 alkyl group may be a mono(meth)acrylate containing, for example, a C8 to C16 alkyl group, and more desirably, a C8 to C12 alkyl group.

Examples of mono(meth)acrylates having C8 to C20 alkyl groups can be decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, deca (meth)acrylate Triesters, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, and the like, but not limited thereto.

The mono(meth)acrylate having a C8 to C20 alkyl group may be included in an amount of less than or equal to about 20% by weight, based on the total weight of the photocurable monomer and initiator in the compositions according to the embodiments, for example, in an amount of less than or equal to about 20% by weight. or equal to about 17% by weight, such as less than or equal to about 15% by weight, such as less than or equal to about 12% by weight, or for example less than or equal to about 10% by weight, and for example greater than or equal to about 1% by weight or such as greater than or equal to about 5% The amount of % by weight includes, but is not limited to. ( E ) Initiator

The initiator may include, but is not limited to, conventional photopolymerization initiators capable of photocuring reaction. For example, the photopolymerization initiator may include triazine-based, acetophenone-based, benzophenone-based, thioxanthone-based, benzoin-based, phosphorus-based or oxime-based initiators, or a mixture thereof. The initiators may be included alone or in a combination of two or more.

The phosphorus-based initiator may be diphenyl(2,4,6-trimethylbenzyl)phosphine oxide, benzyl(diphenyl)phosphine oxide, or a mixture thereof. For example, when a phosphorus-based initiator is used, the compositions of the present invention may exhibit better initiation performance for long wavelength UV.

In the encapsulation composition according to the embodiment, the amount of the initiator may be less than 10 wt % based on the total weight of the photocurable monomer and the initiator. For example, the initiator may be included in an amount less than or equal to 8% by weight, such as in an amount less than or equal to 7% by weight or, for example, less than or equal to 5% by weight, and such as greater than or equal to 0.5% by weight, such as greater than or equal to 1% by weight , such as greater than or equal to 2% by weight, such as or greater than or equal to 3% by weight, but not limited thereto. When the initiator is contained within the above range, photopolymerization can sufficiently occur during exposure, and it is possible to prevent a decrease in transmittance due to unreacted initiator remaining after photopolymerization.

The encapsulation composition according to the embodiment can be prepared by mixing all the components of (A) to (C) and (E), and in the embodiment, the component of (D) is further included. For example, the composition for encapsulating an organic light emitting diode device may be formed in a solvent-free type that does not contain a solvent.

The composition for encapsulating the organic light emitting diode device is a photocurable composition curable by irradiation at a UV wavelength of 10 mW/cm 2 to 500 mW/cm 2 for 1 second to 50 seconds.

As shown in examples to be described later, compositions for encapsulating organic light emitting diode devices according to embodiments have a refractive index greater than or equal to 1.50, eg, greater than or equal to 1.50 and less than or equal to 1.70, greater than or equal to 1.70 1.52 and less than or equal to 1.65 or more than or equal to 1.52 and less than or equal to 1.60 refractive index, so when having a refractive index within the range, the composition can be realized even when formed in an organic light emitting diode display device Organic films that also have higher brightness on the front and/or side surfaces while on the inorganic films in the middle. In particular, when the encapsulation composition according to the present invention is used for a hybrid protective layer in which organic films and inorganic films are alternately laminated, the composition can prevent a decrease in brightness even if light passing through the inorganic film is passing through the organic film The phenomenon.

Furthermore, the encapsulating composition according to the present invention has a viscosity of greater than or equal to 10 centipoise, such as about 12 centipoise to 30 centipoise, about 13 centipoise to about 25 centipoise, or about 13 centipoise to about 20 centipoise Therefore, the organic film can be formed with a uniform thickness when using inkjet printing, and the processability can also be improved by preventing the phenomenon that the organic film spreads due to excessively low viscosity.

In general, monomers with higher refractive index and particles with high refractive index can be used to increase the refractive index of the encapsulating composition. In this case, however, it is possible to increase the refractive index of the encapsulating composition, but the viscosity is excessively increased to prevent the problem in forming the organic film by the ink jet printing method. But the compositions according to the examples can satisfy both ranges of refractive index and viscosity, even without particles.

Along with increasing refractive index and viscosity, the encapsulation composition according to the present invention improves plasma resistance by reducing plasma etching rate, so that organic and inorganic films can be easily formed, and organic light emitting diode devices can be minimized pulp damage. The inorganic film can be formed by plasma deposition. When the organic film is plasma etched, the organic light emitting diode device may be damaged by external moisture and/or oxygen.

As shown in the examples to be described later, encapsulation compositions according to embodiments may have a plasma etch rate of less than or equal to 7%, such as less than or equal to 6.8%, less than or equal to 6.7%, less than or equal to 6.5%, A plasma etch rate of less than or equal to 6.2% or less than or equal to 6.0%. When the plasma etch rate is within the range, damage to the organic light emitting diode device can be minimized when it is deposited on the inorganic film at a thin film thickness.

Furthermore, the composition may have a photocuring rate of greater than or equal to 85%, such as greater than or equal to 88%, greater than or equal to 89%, or greater than or equal to 90%, such as 90% to 99% (specifically 91% to 97%) ) of the photocuring rate. Within the range, the organic film has a degree of cure high enough to block penetration of external moisture and/or oxygen to prevent damage to the organic light emitting diode device, so that reliability can be improved, and also reduce cure shrinkage stress sufficiently to provide A layer in which no displacement occurs, makes it possible to employ the organic film for encapsulating a device.

Furthermore, the composition may have a spreadability of 140% to 170% as will be known from the examples to be described later. Within the range, when the composition is printed by ink jet, the composition is well dispersed without clogging in order to improve processability and provide an organic barrier layer with a uniform surface.

Furthermore, after deposition on a silicon wafer and photocuring, the composition has low plasma resistance, which is a plasma etch rate of less than 10%. Within the range, the reliability of the organic light emitting diode device may be satisfactory in a package structure of the organic light emitting diode device in which an inorganic barrier layer formed of plasma and an organic barrier layer are sequentially formed.

After curing the composition, the modulus at 25±2°C can be less than or equal to about 6.5 GPa, and desirably from 0.01 GPa to 6.5 GPa. Within the range, the composition can be used in a flexible organic light emitting diode display device.

After curing, the composition may have a light transmittance of greater than or equal to 95%, such as 95% to 99%, within the range of which visibility is improved upon encapsulation of organic light emitting diode devices, wherein, for example, at a wavelength of 550 nanometers The transmittance is measured in the visible region of .

The composition for encapsulating organic light emitting diode devices can be used to encapsulate organic light emitting diode devices. Specifically, an organic barrier layer may be formed from the composition in an encapsulation structure in which an inorganic barrier layer and an organic barrier layer are sequentially formed. In particular, compositions for encapsulating organic light emitting diode devices can be used in flexible organic light emitting diode display devices.

Compositions for encapsulating organic light emitting diode devices can be used for detachment of encapsulated devices or due to gases or liquids in the surrounding environment such as oxygen and/or moisture and/or water vapor in the atmosphere and for handling electronic products. components that become defective due to penetration of chemical agents) as components of devices, especially display devices. For example, the device components may be lighting devices, metal sensor pads, microdisk lasers, electrochromic devices, photochromic devices, microelectromechanical systems, solar cells, integrated circuits, charge coupled devices, light emitting polymers or light-emitting diodes, but not limited thereto.

The organic light emitting diode display device of the present invention may include an organic barrier layer formed of the composition for encapsulating an organic light emitting diode device of an embodiment of the present invention. Specifically, an organic light emitting diode display device includes an organic light emitting diode device and a barrier stack, the barrier stack is formed on the organic light emitting diode device and includes an inorganic barrier layer and an organic barrier layer, and the barrier stack is formed on the organic light emitting diode device and includes an inorganic barrier layer and an organic barrier layer, and the The organic barrier layer is formed of the composition for encapsulating an organic light emitting diode device according to an embodiment of the present invention. Therefore, the reliability of the organic light emitting diode display device can be improved.

Hereinafter, an organic light emitting diode display device according to an embodiment of the present invention is described with reference to FIG. 1 . FIG. 1 is a cross-sectional view of an organic light emitting diode display device according to an embodiment of the present invention.

1, an organic light emitting diode display device 100 according to an embodiment of the present invention includes a substrate 10, an organic light emitting diode device 20 formed on the substrate 10, and an organic light emitting diode device 20 formed on the organic light emitting diode device 20 and including Barrier stack 30 of inorganic barrier layer 31 and organic barrier layer 32, wherein inorganic barrier layer 31 is in contact with organic light emitting diode device 20, and organic barrier layer 32 may be used for encapsulating organic light emitting diodes according to embodiments of the present invention The composition of the body device is formed.

The substrate 10 is not particularly limited as long as it is a substrate on which an organic light emitting diode device can be formed. For example, it may be made of materials such as transparent glass, plastic foil, silicon, or may be a metal substrate.

The organic light emitting diode device 20 is typically used in organic light emitting diode display devices and is not shown in FIG. 1 , but may include a first electrode, a second electrode, and be formed between the first electrode and the second electrode organic light-emitting film. The organic light emitting film may be sequentially stacked hole injection layers, hole transport layers, light emitting layers, electron transport layers or electron injection layers, but is not limited thereto.

The barrier stack 30 includes an organic barrier layer and an inorganic barrier layer, wherein the organic barrier layer and the inorganic barrier layer may have different components from each other to provide a function for encapsulating each organic light emitting diode device.

The inorganic barrier layer has a composition different from that of the organic barrier layer, and thus complements the effect of the organic barrier layer. The inorganic barrier layer may be formed of an inorganic material having excellent light transmittance and excellent moisture and/or oxygen barrier properties. For example, the inorganic barrier layer can be a metal, non-metal, intermetallic compound or alloy, non-intermetallic compound or alloy, metal or non-metal oxide, metal or non-metal fluoride, metal or non-metal nitride, metal or Non-metallic carbides, metallic or non-metallic oxynitrides, metallic or non-metallic borides, metallic or non-metallic boron oxides, metallic or non-metallic silicides, or mixtures thereof. The metal or non-metal can be silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi) , transition metals, lanthanide metals, and the like, but not limited thereto. Specifically, the inorganic barrier layer may be silicon oxide (SiO _x ), silicon nitride (SiN _x ), silicon oxynitride (SiO _x N _y ), ZnSe, ZnO, Sb ₂ O ₃ , AlO _x (eg, Al ₂ O ) ₃ ), In ₂ O ₃ , or SnO ₂ .

The inorganic barrier layer can be deposited by plasma processes, vacuum processes such as sputtering, chemical vapor deposition (CVD), plasma chemical vapor deposition (CVD), evaporation, sublimation, electron cyclotron resonance - Plasma chemical vapor deposition, and combinations thereof.

When the organic barrier layer and the inorganic barrier layer are alternately deposited, the planarization property of the inorganic barrier layer can be ensured and spreading defects of the inorganic barrier layer to another inorganic barrier layer can be prevented.

The organic barrier layer may be formed by a combination of coating, deposition, curing, and the like of the composition used to encapsulate the organic light emitting diode device. For example, a composition for encapsulating an organic light emitting diode device is coated at a thickness of 1 micron and irradiated by irradiating the composition at 10 mW/cm2 to 500 mW/cm2 for 1 to 50 seconds. cured.

The barrier stack includes organic barrier layers and inorganic barrier layers, wherein the total number of organic barrier layers and inorganic barrier layers is not limited. The total number of organic and inorganic barrier layers may vary depending on the level of resistance to transport of oxygen and/or moisture and/or water vapor and/or chemical materials. For example, the total number of organic barrier layers and inorganic barrier layers is less than or equal to 10 layers, such as 2 layers to 7 layers, specifically, 7 layers of inorganic barrier layers/organic barrier layers/inorganic barrier layers/organic barrier layers are formed in sequence Barrier Layer/Inorganic Barrier Layer/Organic Barrier Layer/Inorganic Barrier Layer.

In the barrier stack, organic barrier layers are deposited alternately with inorganic barrier layers. This is due to the effect on the organic barrier layer produced by the properties of the composition. As such, the organic and inorganic barrier layers may complement or enhance the effect in encapsulating the device.

Hereinafter, an organic light emitting diode display device of another embodiment of the present invention is described with reference to FIG. 2 . 2 is a cross-sectional view of an organic light emitting diode display device according to another embodiment of the present invention.

Referring to FIG. 2 , an organic light emitting diode display device 200 according to another embodiment of the present invention may include a substrate 10 , an organic light emitting diode device 20 formed on the substrate 10 , and an organic light emitting diode device 20 formed on the substrate 10 . The barrier stack 30 is formed thereon and includes an inorganic barrier layer 31 and an organic barrier layer 32, wherein the inorganic barrier layer 31 encapsulates the inner space 40 that accommodates the organic light emitting diode device 20, and the organic barrier layer 32 may be formed of a Compositions for encapsulating organic light emitting diode devices are formed. The organic light emitting diode display device 200 is substantially equivalent to an organic light emitting diode display device according to an embodiment of the present invention, except that the inorganic barrier layer does not contact the organic light emitting diode device.

Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples. These examples are merely examples for explaining the present invention, and the scope of the present invention is not limited thereto, and the scope of the present invention will be limited only by the claims appended to this specification. example

（E-3）由以下化學式表示的2-苯基-2-(苯硫基)丙烯酸乙酯（福騰）：

（E-4）由以下化學式表示的2-丙烯酸,2-(三苯基甲氧基)乙酯（SDI）：

（E-5）由以下化學式表示的3-丙烯酸苯氧基苄酯（福騰）：

（E-6）由以下化學式表示的2-甲基丙烯酸苯氧基乙酯（奧德裡奇公司（Aldrich Co.））（奧德裡奇）：

（E-7）由以下化學式表示的2-丙烯酸萘基硫代乙酯（福騰）：

（E-8）由以下化學式表示的2-(1-萘氧基)甲基丙烯酸乙酯（福騰）：

（ F ） 引發劑 ： 磷系引發劑 （ 德牢固 （ Darocure ） TPO ， 巴斯夫公司 （ BASF Co. ）） 實例 1 ： 製備用於封裝有機發光二極體裝置的組合物 The photocurable monomers and initiators used in the Examples and Comparative Examples described below are as follows: ( A ) Di ( meth ) acrylates with C8 to C20 alkylene groups : dodecanediol dimethacrylate (dodecanediol dimethacrylate; DDCDMA) (Sartomer) ( B ) mono ( meth ) acrylate with C8 to C20 alkyl groups : lauryl acrylate (LA) (Sartomer) ( C ) with C1 to C7 alkylene di ( meth ) acrylates : hexanediol diacrylate (HDDA) (sadoxane) (D) Trimethylolpropane triacrylate (TMPTA) ( Aldrich) ( E ) Aromatic group-containing photocurable monomer represented by Chemical Formula 1 (E-1) 2-phenylphenoxyethyl acrylate (Hitachi Chemical) (E-2 ) ethyl 2-(phenylthio)acrylate (Chemieliva) represented by the formula:

(E-3) Ethyl 2-phenyl-2-(phenylthio)acrylate (Forton) represented by the following chemical formula:

(E-4) 2-Acrylic acid, 2-(triphenylmethoxy)ethyl ester (SDI) represented by the following chemical formula:

(E-5) Phenoxybenzyl 3-acrylate (Forton) represented by the following formula:

(E-6) Phenoxyethyl 2-methacrylate represented by the following chemical formula (Aldrich Co.) (Aldrich):

(E-7) 2-Naphthylthioethyl acrylate (Forton) represented by the following chemical formula:

(E-8) 2-(1-Naphthyloxy)ethyl methacrylate (Forton) represented by the following chemical formula:

( F ) Initiator : Phosphorus - based initiator ( Darocure TPO , BASF Co. ) Example 1 : Preparation of a composition for encapsulating organic light-emitting diode devices

Combine 10 grams of (B) Lauryl Acrylate (LA) (Sadol), 17 grams of (C) Hexylene Glycol Diacrylate (HDDA) (Sadol), 70 grams of (E-8) 2- (1-Naphthyloxy)ethyl methacrylate (Forteng) and 3 grams of (F) Durban TPO were added to a 125 ml brown polypropylene bottle and mixed for 3 hours at room temperature using a shaker to provide the encapsulated combination thing. Examples 2 to 8 and Comparative Examples 1 to 3 : Preparation of Compositions for Encapsulating Organic Light Emitting Diode Devices

The encapsulation compositions according to Examples 2 to 8 and Comparative Examples 1 to 3 were each prepared according to the same procedure as in Example 1, except that the compositions were each prepared with the components and amounts shown in Table 1. Evaluation 1 : Evaluate the physical properties of the encapsulation composition

The viscosity, refractive index, and spreadability of the encapsulation compositions obtained from Examples 1 to 8 and Comparative Examples 1 to 3 were measured according to the following methods, and the results are shown in Table 1.

(1) Viscosity (unit: centipoise (cps)): measured at 25°C by a viscometer of a Brookfield DV-III+ rheometer (Brookfield) with spindle No. 40 at 10 rpm each encapsulation composition.

(2) Refractive index: Each encapsulation composition was measured by an Abbe 5 Abbe refractometer at 25°C.

(3) Spreadability (%): Using an ink jet printer (OMNIJET 300, Unijet), each encapsulation composition was dropped on the substrate in an amount of 13 picoliters, and the maximum particle size of one drop was measured after 30 seconds. diameter (S1, unit: micrometer), the measurement was repeated 3 times and averaged. The dripping speed is 2.5 m/s to 3.5 m/s. In addition, 13 picoliters of the encapsulation composition was dropped using an ink jet printer (OMNIJET 300, Unijet), and after 180 seconds, the measurement was repeated 3 times and the maximum particle size (S2, unit: micrometer) of one drop was averaged to give Spreadability is assessed according to Equation 1: >Equation 1> Spreadability (%) = S2 / S1 x 100. Evaluation 2 : Fabrication of Organic Encapsulation Layer and Evaluation of Physical Properties

The encapsulation compositions obtained from Examples 1 to 8 and Comparative Examples 1 to 3 were each spin-coated on a silicon wafer to provide an organic film, and the organic film was attached to a device on which an organic light emitting diode device was formed. panel, and the relative brightness was measured by the following method.

In addition, the encapsulation compositions obtained from Examples 1 to 8 and Comparative Examples 1 to 3 were each deposited on a silicon wafer with a predetermined thickness on a silicon wafer, and photocured to provide an organic encapsulation layer, and plasma was measured by the following method etch rate. The measured plasma etch rates and relative brightness are shown in Table 1 below.

(1) Relative brightness (%): The obtained organic film was attached to a panel on which the organic light emitting diode device was formed, and the front surface of the panel was set at 0°, and EZcontrast (Eldim) was used to measure 0° brightness at. In this case, the relative brightness (%) was calculated from D/C x 100, where C refers to the brightness of Comparative Example 1 and D refers to the brightness of the corresponding example or comparative example. This means that the brightness becomes higher as the relative brightness is higher. It is estimated that the brightness is higher when the relative brightness is greater than or equal to 105%.

(2) Plasma etching rate (%): measure each initial height (T1, unit: micrometer) of the organic encapsulation layer obtained, and use ICP-CVD with ICP (Inductively Coupled Plasma) power: 2500 watts; radio frequency ( radio frequency; RF) power: 300 watts; DC bias voltage: 200 V; AR flow rate: 50 standard cubic centimeters/min; etching time: 1 min; height (T2, in microns), and the plasma etch rate was estimated according to Equation 2. >Equation 2> Plasma Etch Rate (%) = (T1-T2)/T1 x 100 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) DDCDMA - - - 30 35 twenty two 27 - 85 47 47 (B) LA 10 - 17 12 - - - 15 - 50 - (C) HDDA 17 17 15 - - 15 15 19 - - 50 (D) TMPTA - - - - - - - - 12 - - (E-1) - - - 20 20 20 20 - - - - (E-2) - - - - - 40 - 20 - - - (E-3) - - - - - - 35 - - - - (E-4) - - - - - - - 3 - - - (E-5) - - - - 42 - - - - - - (E-6) - 10 - - - - - 20 - - - (E-7) - - 65 35 - - - 20 - - - (E-8) 70 70 - - - - - - - - - (F) TPO 3 3 3 3 3 3 3 3 3 3 3 Total (g) 100 100 100 100 100 100 100 100 100 100 100 refractive index 1.527 1.548 1.568 1.552 1.557 1.561 1.559 1.578 1.461 1.459 1.463 Relative brightness (%) 106 107 112 109 108 109 109 113 100 98 100 Viscosity 17.4 16.2 13.9 17.2 14.2 16.1 13.4 16.9 12.9 7.9 6.2 Plasma etch rate (%) 5.7 5.2 6.1 5.7 6.2 6.5 5.8 5.3 19 twenty three 15 Spreadability (%) 158 153 163 157 161 159 163 160 135 192 200

As depicted in Table 1, the aromatic group-containing di(meth)acrylate represented by Chemical Formula 1 and the di(meth)acrylate having a C8 to C20 alkylene group and/or having C1 according to an embodiment Encapsulation compositions according to Examples 1 to 8 of photocurable monomers to C7 alkylene di(meth)acrylates of aromatic-free monomers in refractive index, relative brightness, viscosity, plasma etching The compositions according to Comparative Example 1 to Comparative Example 3 are shown to be superior in all data of speed and spreadability.

Specifically, in terms of refractive index, all compositions according to Examples 1 to 8 exhibited refractive indices greater than 1.50, but all compositions according to Comparative Examples 1 to 3 exhibited refractive indices of less than 1.50.

In terms of relative brightness, referring to the 100% brightness of Comparative Example 1, the lowest relative brightness of Examples 1 to 8 was 106% of that of Example 1, and the other Examples showed higher relative brightness than this; on the other hand, Comparative Example 2 And Comparative Example 3 exhibits 100% or 98%, which is equivalent to or lower than the relative brightness in Comparative Example 1.

In terms of viscosity, the lowest viscosity of Example 7 was 13.4 centipoise, and the highest viscosity of Example 1 was 17.4 centipoise, demonstrating that all compositions of Examples 1-8 maintained a suitable viscosity range. On the other hand, in the compositions of Comparative Examples 1 to 3, the highest viscosity was 12.9 cps in Comparative Example 1, and the viscosities of Comparative Examples 2 and 3 were less than 10 cps, which was very low.

In terms of plasma etch rates, Examples 1 to 8 all exhibit low plasma etch rates of less than 10% (specifically, less than 7%), and Comparative Examples 1 to 3, on the other hand, exhibit greater than at least 15% high etch rate.

Finally, in terms of the spreadability of the compositions, the compositions of Examples 1 to 8 show a range from 158% to 160%, which has a good effect on the processability of organic films and prevents nozzles during inkjet printing Appropriate ranges for clogging and the like. On the other hand, the spreadability of Comparative Example 1 was 135%, which was significantly lower than that of the Examples, making it difficult to provide a uniform film possibly due to clogging of nozzles or non-spreading of droplets during inkjet printing. Meanwhile, in the case of Comparative Example 2 and Comparative Example 3, the spreadability was 190% or more, which was too high. In this case, it is difficult to provide an organic film having an appropriate thickness.

Thus, since the composition according to the embodiment includes the aromatic group-containing di(meth)acrylate represented by Chemical Formula 1 and the di(meth)acrylate having the C8 to C20 alkylene and/or the C1 to C7 alkylene The photocurable monomer of alkyl di(meth)acrylate without aromatic group di(meth)acrylate, so the provided composition for encapsulating organic light emitting diode device can have high refractive index high relative brightness, viscosity in the proper range, low plasma etch rate, and excellent spreadability.

While embodiments of the present invention have been described above, they are merely illustrative of the present invention, and it should be understood that the scope of the present invention is not limited thereby. Furthermore, simple modifications or changes to the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

10: Substrate 20: Organic Light Emitting Diode Devices 30: Barrier stack 31: Inorganic barrier layer 32: Organic barrier layer 40: Inner space 100, 200: Organic Light Emitting Diode Display Device

FIG. 1 is a cross-sectional view of an organic light emitting diode display device according to an embodiment. FIG. 2 is a cross-sectional view of an organic light emitting diode display device according to another embodiment.

10: Substrate

20: Organic Light Emitting Diode Devices

30: Barrier stack

31: Inorganic barrier layer

32: Organic barrier layer

100: Organic Light Emitting Diode Display Device

Claims (15)

A composition for encapsulating an organic light emitting diode device, comprising a photocurable monomer and an initiator, wherein the photocurable monomer does not include a silicon-based photocurable monomer, and the photocurable monomer includes a compound represented by Chemical Formula 1 Aromatic group-containing monomers and aromatic-group-free monomers, and the aromatic-group-free monomers include di(meth)acrylates with C8 to C20 alkylene extension, C1 to C7 extension Di(meth)acrylate of an alkyl group, or a combination thereof:

wherein, in Chemical Formula 1, L ¹ to L ⁴ are independently O, S, CO, COO, NR ¹ , or C1 to C10 alkylene, wherein R ¹ is hydrogen or C1 to C5 alkyl, and Ar ¹ to Ar ⁴ are independently unsubstituted phenyl, naphthyl, anthracenyl, phenanthryl,

group or triphenylene group, and Z ¹ to Z ⁴ are independently hydrogen, C1 to C10 alkyl, or a group represented by Chemical Formula 2, provided that at least one of Z ¹ to Z ⁴ is a group represented by Chemical Formula 2 group:

wherein, in Chemical Formula 2, Y ¹ is O, S, CO, COO or NR ¹ , wherein R ¹ is hydrogen or C1 to C5 alkyl, R ² is hydrogen or C1 to C5 alkyl, and p and q are independently one of the integers 0 to 10, k is 0 or 1, and * is the position of attachment to another atom; m1 to m4 are independently 0 or 1, and one or both of n1 to n4 is 1 and the rest is 0, provided that when two of n1 to n4 are ¹ and the rest are 0, and two of Z1 to ^Z4 are independently groups represented by Chemical Formula 2, each of which is linked to two Each of Ar ¹ to Ar ⁴ present. The composition for encapsulating an organic light emitting diode device as claimed in claim 1, wherein one of Z ¹ to Z ⁴ is a group represented by Chemical Formula 2, and the other three are independently hydrogen or C1 to C10 alkyl. The composition for encapsulating an organic light emitting diode device as claimed in claim 1, wherein Y ¹ of Chemical Formula 2 is O, S or COO, p is 0, and q is one of an integer of 1 to 4. The composition for encapsulating an organic light emitting diode device as claimed in claim 1, wherein Y ¹ of Chemical Formula 2 is O, S or COO, p is one of integers from 1 to 4, and q is 0. The composition for encapsulating an organic light emitting diode device according to claim 1, wherein the aromatic group-containing monomer represented by Chemical Formula 1 includes one or more of the monomers represented by the following chemical formula:

The composition for encapsulating an organic light emitting diode device according to claim 1, wherein the di(meth)acrylate having the C8 to C20 alkylene group comprises octanediol di(meth)acrylic acid ester, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, undecanediol di(meth)acrylate, dodecanediol di(meth)acrylate, Tridecanediol di(meth)acrylate, tetradecanediol di(meth)acrylate, pentadecanediol di(meth)acrylate, or a combination thereof. The composition for encapsulating an organic light emitting diode device according to claim 1, wherein the di(meth)acrylate having the C1 to C7 alkylene group comprises methyl glycol di(meth)acrylic acid Esters, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate base) acrylate, or a combination thereof. The composition for encapsulating an organic light emitting diode device of claim 1, wherein the photocurable monomer further comprises a mono(meth)acrylate having a C8 to C20 alkyl group. The composition for encapsulating an organic light emitting diode device as claimed in claim 8, wherein the mono(meth)acrylate having the C8 to C20 alkyl group comprises decyl (meth)acrylate, (meth)acrylate base) Undecyl acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate and hexadecyl (meth)acrylate one or more of the esters. The composition for encapsulating an organic light emitting diode device according to claim 1, wherein the amount of the aromatic group-containing monomer represented by Chemical Formula 1 is based on the photocurable monomer and the initiator The total weight is greater than or equal to 50% by weight. The composition for encapsulating an organic light emitting diode device according to claim 1, wherein the amount of the initiator is less than 10% by weight based on the total weight of the photocurable monomer and the initiator. The composition for encapsulating an organic light emitting diode device as claimed in claim 1, wherein the composition for encapsulating the organic light emitting diode device has 140% to 140% according to Equation 1 by the following experimental method 170% spreadability: <equation 1> Spreadability 1 = S2/S1 x 100 where, in equation 1, S1 is used for sealing by dropwise dispensing with an ink jet printer in a volume of 13 picoliters The composition of the organic light-emitting device and the average value in microns measured by measuring the maximum particle size of the droplets 3 times after 30 seconds, and S2 was measured by dropwise addition with an ink jet printer in a volume of 13 picoliters. The average value in micrometers measured in units of micrometers after sealing the composition of the organic light-emitting device and measuring the maximum particle size of the droplets 3 times after 300 seconds. The composition for encapsulating an organic light emitting diode device of claim 1, wherein the composition for encapsulating the organic light emitting diode device has a value of less than 10% Plasma Etch Rate: <Equation 2> Plasma Etch Rate (%)=(T1-T2)/T1 x 100 where, in Equation 2, T1 is the photocuring after depositing the composition to measure the initial height of the deposited layer, and T2 is the height of the deposited layer after it has undergone inductively coupled plasma treatment using inductively coupled plasma power: 2500 watts; RE power: 300 watts; DC bias: 200 volts ; Ar flow rate: 50 standard cubic centimeters per minute; Etching time: 1 minute; Pressure: 10 mTorr; Inductively coupled plasma chemical vapor deposition system: BMR technology. An organic light emitting diode display device, comprising: an organic light emitting diode device, and a blocking stack formed on the organic light emitting diode device and comprising an inorganic blocking layer and an organic blocking layer, and the organic blocking layer Comprising the composition of any one of claim 1 to claim 13. The organic light emitting diode display device of claim 14, wherein in the barrier stack, the inorganic barrier layers and the organic barrier layers are alternately stacked.

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