KR102126059B1 - Composition for preventing bleeding of composition for encapsulating organic light emitting diode device and organic light emitting diode display comprising barrier prepared using the same - Google Patents

Abstract

(A) at least one of a fluorine-based leveling agent, a silicone-based leveling agent, (B) polyfunctional (meth)acrylate, (C) monofunctional (meth)acrylate, and (D) initiator, and the organic light emitting device The composition for blocking bleeding of a sealing composition has a contact angle with a glass plate of 6° or higher at 25° C., and provides an organic light emitting device display device comprising a composition for blocking bleeding of a composition for sealing an organic light emitting device and a barrier prepared therefrom. do.

Description

Organic light emitting device display device comprising a composition for blocking bleeding of an organic light emitting device encapsulation composition and a barrier made therefrom. SAME}

The present invention relates to an organic light emitting device display device comprising a composition for blocking bleeding of a composition for sealing an organic light emitting device and a barrier prepared therefrom. In more detail, the present invention blocks the bleeding of the composition for the organic layer among the organic light-emitting device encapsulation layer in the process of forming the organic light-emitting device encapsulation layer, thereby increasing the reliability between the organic light-emitting devices even if the interval between the organic light-emitting devices is narrowed, and the photocuring rate This excellent, low plasma etch rate can increase the reliability of the organic light-emitting device and / or organic light-emitting device encapsulation layer, an organic light-emitting device comprising a composition for blocking the bleeding of the composition for sealing an organic light-emitting device and a barrier prepared therefrom It is about the device.

The organic light emitting device display device is a display device that emits light by itself using an electroluminescence phenomenon, and includes an organic light emitting device. The organic light emitting device may degrade light emission characteristics when it comes into contact with external moisture and/or oxygen. Therefore, the organic light emitting device must be sealed with a sealing layer formed of a composition for sealing. The encapsulation layer may be composed of an inorganic layer alone or an organic layer alone, but one or more inorganic layers and one or more organic layers are alternately stacked in order to prevent damage to the organic light emitting device to external moisture and/or oxygen. It is generally formed into a structure. The organic layer may be formed by dropping and curing the composition for the organic layer on the surface of the inorganic layer by vapor deposition or inkjet.

Recently, in order to increase the area of the display area (display area) in the display device, the width of the bezel corresponding to the non-display area is narrowed, and thus, it is inevitable to relatively narrow the distance between the organic light emitting devices. Accordingly, referring to FIG. 3, when the organic layer is formed of the composition for encapsulating the organic light emitting device on the inorganic layer 31, bleeding of the composition 100 for encapsulating the organic light emitting device occurs, which may adversely affect the reliability of the organic light emitting device. have.

Accordingly, even if the gap between the organic light emitting elements is narrowed by blocking the bleeding of the composition for the organic layer, the reliability between the organic light emitting elements can be increased, and the reliability of the organic light emitting element and/or the organic light emitting element encapsulation layer is increased as it is formed in the organic light emitting element display device. It needs to be increased.

Background art of the present invention is disclosed in Korean Patent Publication No. 2011-0071039.

An object of the present invention is to provide a composition for blocking bleeding of a composition for sealing an organic light-emitting device, which can increase the reliability between the organic light-emitting devices even if the gap between the organic light-emitting devices is narrowed by preventing bleeding of the composition for sealing the organic light-emitting devices.

Another object of the present invention is to provide a composition for blocking bleeding of a composition for sealing an organic light-emitting device, which can form a barrier for blocking the bleeding of a composition for sealing an organic light-emitting device on the surface of an inorganic layer among the organic light-emitting device sealing layers.

Another object of the present invention is a composition for blocking the bleeding of the composition for encapsulating an organic light-emitting device, which has a high contact angle with respect to the inorganic layer and the organic layer of the organic light-emitting device encapsulation layer and has excellent repelling power with the composition for an organic layer and can prevent bleeding of the composition for an organic layer. Is to provide

Another object of the present invention is to provide a composition for blocking bleeding of a composition for encapsulating an organic light emitting device, which can increase the reliability of an organic light emitting device and/or an organic light emitting device encapsulation layer due to a high photocuring rate and a low plasma etch rate.

The composition for blocking bleeding of the composition for encapsulating the organic light emitting device of the present invention comprises (A) at least one of a fluorine-based leveling agent and a silicone-based leveling agent, (B) a polyfunctional (meth)acrylate, (C) a monofunctional (meth)acrylic Rate, and (D) the initiator, and the composition for blocking bleeding of the composition for encapsulating the organic light emitting device may have a contact angle with a glass plate of 6° or higher at 25°C.

The organic light emitting device display device of the present invention includes a substrate; An organic light emitting element formed on the substrate; An encapsulation layer encapsulating the organic light emitting device and including at least one inorganic layer and at least one organic layer; And a barrier formed on the outer circumferential surface of the organic layer or the outer circumferential surface of the encapsulation layer, and the barrier may be formed of a composition for blocking bleeding of the composition for encapsulating the organic light emitting device of the present invention.

The present invention provides a composition for blocking bleeding of an organic light emitting device encapsulating composition, which can increase the reliability between organic light emitting devices even if the gap between the organic light emitting devices is narrowed by preventing bleeding of the composition for encapsulating the organic light emitting device.

The present invention provided a composition for blocking bleeding of a composition for sealing an organic light emitting device, which can form a bleeding blocking layer on the surface of an inorganic layer among the organic light emitting device sealing layers.

The present invention provides a composition for blocking bleeding of a composition for sealing an organic light emitting device, which has a high contact angle with respect to the inorganic layer and an organic layer of the organic light emitting device encapsulation layer and has excellent repelling power with the composition for an organic layer, thereby preventing bleeding of the composition for an organic layer.

The present invention provides a composition for blocking bleeding of a composition for encapsulating an organic light-emitting device, which can increase the reliability of an organic light-emitting device and/or an organic light-emitting device encapsulation layer due to a high photocuring rate and a low plasma etch rate.

1 is a cross-sectional view of an organic light emitting diode display device according to an exemplary embodiment of the present invention.
2 is a top plan view of an organic light emitting display device according to an embodiment of the present invention.
Figure 3 is a cross-sectional view showing the bleeding of the composition for sealing an organic light emitting device.

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

In the present specification, “substituted” means, unless otherwise defined, one or more hydrogen atoms of the functional group are halogen (eg, F, Cl, Br or I), hydroxy group, nitro group, cyano group, imino group (=NH) , =NR, R are alkyl groups of C1 to C10), amino groups (-NH ₂ , -NH(R'), -N(R")(R"'), and R',R",R"' are each Independently C1 to C10 alkyl group), amidino group, hydrazine group, hydrazone group, carboxylic acid group, C1 to C20 alkyl group, C6 to C30 aryl group, C3 to C30 cycloalkyl group, C3 to C30 heteroaryl group, It means substituted with C2 to C30 heterocycloalkyl group.

"Aryl (aryl) group" as used herein refers to a functional group in which all elements of a cyclic substituent have p-orbitals, and these p-orbitals form a conjugate. Aryl groups include monocyclic, non-fused polycyclic or fused polycyclic functional groups. In this case, fusion means a ring shape in which carbon atoms divide adjacent pairs. The aryl group also includes a biphenyl group, a terphenyl group, or a quarterphenyl group, which is a form in which two or more aryl groups are connected through a sigma bond. The aryl group may mean a phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, chrysenyl group, or the like.

As used herein, “heteroaryl group” means a functional group which contains 1 to 3 hetero atoms selected from the group consisting of N, O, S, P, and Si in the aryl group, and the rest is carbon. Heteroaryl groups include those in which two or more heteroaryl groups are directly connected via sigma bonds. Heteroaryl groups include those in which two or more heteroaryl groups are fused to each other. When a heteroaryl group is fused, each ring may include 1 to 3 heteroatoms. The heteroaryl group may mean, for example, a pyridinyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, or the like.

More specifically, C6 to C30 aryl group and/or C3 to C30 heteroaryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl Group, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted p-terphenyl group, substituted or unsubstituted m-terphenyl group, substituted or unsubstituted Substituted chrysenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted perenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted Or an unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazoleyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazole Diary, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or Unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazole group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinoli Nyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazineyl group, substituted Or an unsubstituted benzthiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazineyl group, a substituted or unsubstituted phenothiazineyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted Dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.

As used herein, "(meth)acrylic" means acrylic and/or methacrylic.

In the present specification, "a composition for blocking bleeding of a composition for sealing an organic light-emitting device" may be simply referred to as a "composition for blocking bleeding".

In this specification, "plasma etch rate of cured product of a composition for blocking bleeding" or "plasma etch rate" measures an initial height (T1, unit: µm) of a barrier formed by photocuring a composition for blocking bleeding to a predetermined thickness, and preparing the above Inductively coupled plasma (ICP) power: 2500W, RF (radio frequency) power: 300W, DC bias: 200V, Ar flow: 50sccm, etching time: 1min, pressure: 10mtorr using ICP-CVD The height (T2, unit: µm) of the barrier after plasma treatment at is measured, and is a value calculated by Equation 2 below. At this time, the initial height (T1) of the barrier may be 1 μm to 10 μm: the lower the value calculated by Equation 2, the better the plasma resistance of the composition for blocking bleeding.

<Equation 2>

Plasma etch rate (%) of the cured product of the composition for blocking bleeding = (T1-T2)/T1 x 100.

Hereinafter, a composition for blocking bleeding according to an embodiment of the present invention will be described.

The composition for blocking bleeding according to an embodiment of the present invention includes (A) at least one of a fluorine-based leveling agent and a silicone-based leveling agent, (B) polyfunctional (meth)acrylate, (C) monofunctional (meth)acrylate, And (D) an initiator, wherein the composition for blocking bleeding may have a contact angle of 6° or more with respect to a glass plate at 25°C.

When the inventor of the present invention has the above contact angle range, a bleeding blocking barrier capable of preventing bleeding of the composition for encapsulating the organic light emitting element in the inorganic layer may be formed, and the barrier for the composition for organic layer and/or the inorganic layer is high. It was confirmed that the function as can be sufficiently performed. In the present invention, "barrier" may mean a dam formed at a predetermined width and a predetermined height on the outer peripheral surface of the organic layer on the surface of the inorganic layer. The “barrier” refers to a structure capable of preventing bleeding of the composition for encapsulating the organic light-emitting device of FIG. 3 due to its excellent repelling power to the composition for encapsulating the organic light-emitting device. The “barrier” will be described in more detail in the description of the organic light emitting diode display device of the exemplary embodiment of the present invention with reference to FIGS. 1 and 2 below. The composition for blocking bleeding may have a contact angle with respect to a glass plate of 6° to 45° at 25°C, more specifically 7° to 35°, and 7° to 25°.

The composition for blocking bleeding of the present invention can secure the above-mentioned contact angle by including the above-described components, has a high photocuring rate, and a low plasma etch rate, thereby increasing the reliability of the organic light emitting device and/or the organic light emitting device encapsulation layer. .

(A) Fluorine Leveling agent , Silicone Leveling agent More than 1

One or more of the fluorine-based leveling agent and the silicone-based leveling agent may allow the composition for blocking bleeding to have the contact angle range. The present invention confirmed that the photocuring rate and plasma resistance are excellent while securing the contact angle range by using the leveling agent described below.

In one embodiment, the fluorine-based leveling agent and the silicone-based leveling agent may not have one or more (meth)acrylate groups.

In another embodiment, the fluorine-based leveling agent and the silicone-based leveling agent have one or more (meth)acrylate groups, thereby curing the polyfunctional (meth)acrylate and monofunctional (meth)acrylate to further increase the photocuring rate. It can prevent the fluorine-based leveling agent and the release of the silicon-based leveling agent.

In one embodiment, the fluorine-based leveling agent may include a monofunctional or polyfunctional (meth)acrylate having an aliphatic hydrocarbon group substituted with one or more fluorine. The "aliphatic hydrocarbon group" is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 10 carbon atoms, 2 to 20 carbon atoms, preferably carbon number It may include an alkynyl group having 2 to 10 carbon atoms, but is not limited thereto. Preferably 2 to 20, more preferably 2 to 10 fluorine may be substituted. For example, the fluorine-based leveling agent may include at least one of hexafluoroisopropyl (meth)acrylate and heptafluorobutyl (meth)acrylate.

In another embodiment, the fluorine-based leveling agent includes fluorine, and may further include at least one of a hydrophilic group and a lipophilic group. For example, the fluorine-based leveling agent may include one or more of fluorine, oligomers containing hydrophilic groups and lipophilic groups, and oligomers having fluorine and lipophilic groups. In this regard, DIC's F-477, F554, and the like can be used as a trade name, but are not limited thereto. The hydrophilic group may be a hydroxyl group, a carboxylic acid group or a sulfonic acid group, but is not limited thereto. The lipophilic group may be an aliphatic hydrocarbon group, for example, an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an aromatic hydrocarbon group, for example, an aromatic hydrocarbon group having 3 to 20 carbon atoms, but is not limited thereto.

In one embodiment, the silicone-based leveling agent may include a polyether-modified (meth)acrylic functional polyalkylsiloxane. For example, the polyether-modified (meth)acrylic functional polyalkylsiloxane may be represented by Formula 1 below, but is not limited thereto.

<Formula 1>

(In the formula 1,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are, independently of each other, hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted A substituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 heteroaryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a halogen, a hydroxyl group, or an amino group,

R ₇ and R ₈ are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted A C6 to C20 heteroaryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a halogen, a hydroxyl group, an amino group, or the following Chemical Formula 1-1,

<Formula 1-1>

(In Formula 1-1, * is a linking site to Si in Formula 1,

R ₉ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkylether group, or a substituted or unsubstituted C6 to C20 arylene group,

R ₁₀ is hydrogen or a methyl group)

At least one of R ₇ and R ₈ is Formula 1-1).

Preferably, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently a substituted or unsubstituted C1 to C20 alkyl group, more preferably a substituted or unsubstituted C1 to C5 alkyl group , Most preferably a methyl group. Preferably, R ₇ and R ₈ are each of Formula 1-1.

For example, BYK UV-3500, BYK UV-3530 (above, BYK), X-22-164AS, X-22-2445 (above, Shin-Etsu) can be used as a silicone leveling agent.

At least one of the fluorine-based leveling agent and the silicone-based leveling agent may be included in 0.001 parts by weight to 20 parts by weight, for example, 0.01 parts by weight to 15 parts by weight, more preferably 0.2 to 10 parts by weight, in 100 parts by weight of the composition for blocking bleeding. have. In the above range, the contact angle range of the present invention can be secured, and the light curing rate and plasma resistance can be excellent. In one embodiment, at least one of the fluorine-based leveling agent and the silicone-based leveling agent is 0.001 part to 20 parts by weight of 100 parts by weight of the total weight of (A), (B), (C) and (D), for example 0.01 parts by weight to 15 parts by weight, for example, 0.2 parts by weight to 10 parts by weight may be included.

(B) Multifunctional ( Met ) Acrylate

The polyfunctional (meth)acrylate may be included in the composition for blocking bleeding to increase the photo-curing rate, and also improve plasma resistance when combined with the leveling agent.

The polyfunctional (meth)acrylate may include two or more functional groups, for example, one or more of the bifunctional to six functional (meth)acrylates. The polyfunctional (meth)acrylate may include one or more of silicone-free non-silicone polyfunctional (meth)acrylate and silicone-containing polyfunctional polyfunctional (meth)acrylate.

The non-silicone-based polyfunctional (meth)acrylate may include one or more of silicone-free bifunctional to six-functional (meth)acrylates. For example, the non-silicone-based polyfunctional (meth)acrylate may increase the photocuring rate of the composition for blocking bleeding, increase the light transmittance after curing, and lower the viscosity of the composition for blocking bleeding due to low viscosity at 25°C. Through this, the composition for blocking bleeding can easily form a barrier on an organic light emitting device or an inorganic layer encapsulating the organic light emitting device by a method such as inkjet.

In one embodiment, the non-silicone-based polyfunctional (meth)acrylate is a non-aromatic system that does not contain an aromatic group, and a non-silicone-based bifunctional (meth)acrylate containing a substituted or unsubstituted long chain alkylene group. It can contain. In this case, the composition for blocking bleeding can easily form a barrier on an organic light emitting device or an inorganic layer encapsulating the organic light emitting device by a method such as inkjet.

Specifically, the non-silicone-based bifunctional (meth)acrylate may be a di(meth)acrylate having a substituted or unsubstituted C1 to C20 alkylene group. More specifically, the non-silicone-based bifunctional (meth)acrylate may include di(meth)acrylate having an alkylene group of C1 to C15 unsubstituted between (meth)acrylate groups. At this time, the number of carbon atoms in the alkylene group means only the number of carbon atoms in the alkylene group itself, excluding the carbon in the di(meth)acrylate group. The non-silicone-based bifunctional (meth)acrylate can be represented by the following formula (2):

<Formula 2>

(In the formula 2,

R ₁₂ and R ₁₃ are each independently hydrogen or a methyl group,

R ₁₁ is a substituted or unsubstituted C1 to C20 alkylene group).

The composition for blocking bleeding of the present invention may include a non-silicone-based bifunctional (meth)acrylate represented by Chemical Formula 2 to further increase the photo-curing rate, and may have a lower viscosity to facilitate deposition and the like. For example, in Formula 2, R ₁₁ may be an unsubstituted C8 to C12 alkylene group. More specifically, the non-silicone-based bifunctional (meth)acrylate includes octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, and undecanedioldi(meth)acrylate , Dodecane diol (meth) acrylate.

The non-silicone-based polyfunctional (meth)acrylate may be included alone or in combination of two or more of the compositions for blocking bleeding.

The non-silicone-based polyfunctional (meth)acrylate is included in 20 parts by weight to 80 parts by weight, for example, 25 parts by weight to 75 parts by weight, more preferably 30 parts by weight to 65 parts by weight, among 100 parts by weight of the composition for blocking bleeding Can. In one example, the non-silicone-based polyfunctional (meth)acrylate is 20 parts by weight to 80 parts by weight, for example, 25 parts by weight of 100 parts by weight of the total weight of (A), (B), (C) and (D) Part to 75 parts by weight, for example, may be included as 30 parts by weight to 65 parts by weight. In the above range, the photocuring rate of the composition for blocking bleeding may be improved, a light transmittance may be high, and a barrier having a low plasma etch rate may be implemented.

The silicone-based polyfunctional (meth)acrylate may include silicone-containing bifunctional to hexafunctional (meth)acrylate. The silicone polyfunctional (meth)acrylate may also have a synergistic effect in contact angle by being included together with the leveling agent. For example, the silicone-based polyfunctional (meth)acrylate may include a silicone-based bifunctional (meth)acrylate. The silicone-based bifunctional (meth)acrylate may include at least one substituted or unsubstituted C6 to C30 aryl group linked to a silicon atom. Through this, the composition for blocking bleeding has a high resistance to plasma, and thus a barrier with a low plasma etch rate can be implemented.

The silicone-based bifunctional (meth)acrylate may be represented by Formula 3 below.

<Formula 3>

(In the formula 3,

R ₁₄ , R ₁₅ are independently of each other, a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C30 alkylene ether group, *-N(R')-(R" )-*(* is the linking site of the element, R'is hydrogen, or a substituted or unsubstituted C1 to C30 alkyl group, R" is a substituted or unsubstituted C1 to C20 alkylene group), a substituted or unsubstituted C6 To C30 arylene group, substituted or unsubstituted C7 to C30 arylalkylene group, or *-(R')-O-** (where * is a linkage to O in Formula 3, ** is Formula 3 In the linking site to Si, R'is a substituted or unsubstituted C1 to C30 alkylene group),

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ are each independently hydrogen, hydroxyl group, halogen, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 Heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 alkyl ether group, *-N(R')(R")(* is an element linkage site, R 'And R" are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkyl group), a substituted or unsubstituted C1 to C30 alkylsulfide group, a substituted or unsubstituted C6 to C30 aryl group, a substitution Or an unsubstituted C2 to C30 heteroaryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group,

One or more of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ is a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

R ₁₆ and R ₁₇ are each independently hydrogen or a methyl group,

n is 0 To 30 or an average value of n is 0 to 30).

The "single bond" means that Si and O are directly connected in Formula 3 (Si-O).

Specifically, in Chemical Formula 3, R ₁₄ , R ₁₅ may be independently of each other, a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C1 to C30 alkylene ether group. . Specifically, in Chemical Formula 3, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 alkyl ether group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 heteroaryl group, or substituted or unsubstituted C7 To C30 is an arylalkyl group, and one or more of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , and X ₆ may be a substituted or unsubstituted C6 to C30 aryl group.

More specifically, in Formula 3, R ₁₄ and R ₁₅ may each independently be a single bond, or a substituted or unsubstituted C1 to C20 alkylene group. In this case, there may be an effect of lowering the plasma etch rate.

More specifically, in Formula 3, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ are each independently a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C10. It is an aryl group, and one or more of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , and X ₆ may be a substituted or unsubstituted C6 to C10 aryl group. More specifically, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ are each independently a methyl group, ethyl group, propyl group, butyl group, pentyl group, phenyl group, biphenyl group, or naphthyl group. And ₁ , ₂ , ₃ or ₆ of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ may be a phenyl group or a naphthyl group. In this case, there may be an effect of lowering the plasma etch rate.

More specifically, n may be an integer from 1 to 5. In this case, there may be an effect of lowering the plasma etch rate. More specifically, the silicone-based bifunctional (meth)acrylate may be represented by any one of the following Chemical Formulas 4 to 9:

<Formula 4>

<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

The silicone-based polyfunctional (meth)acrylate may be included in a composition for blocking bleeding alone or by mixing two or more kinds.

The silicone-based polyfunctional (meth)acrylate may be included in 0 to 40 parts by weight, for example, 0 to 35 parts by weight, out of 100 parts by weight of the composition for blocking bleeding. In one example, the silicone-based polyfunctional (meth)acrylate is 0 parts by weight to 40 parts by weight, for example, 0 parts by weight to 100 parts by weight of the total weight of (A), (B), (C) and (D) It may be included as 35 parts by weight, 0.1 parts by weight to 35 parts by weight. In the above range, the photocuring rate of the composition for blocking bleeding may be improved, a light transmittance may be high, and a barrier having a low plasma etch rate may be implemented.

The silicone-based bifunctional (meth)acrylate can be produced by a conventional method. For example, the silicone-based bifunctional (meth)acrylate extends the carbon chain and the siloxane compound in which a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group is connected to one or more silicon atoms. It can be prepared by reacting a compound (eg, allyl alcohol), followed by reacting (meth)acryloyl chloride, but is not limited thereto. Alternatively, the silicone-based bifunctional (meth)acrylate includes a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group connected to at least one silicon atom and a (meth)acryloyl chloride It may be prepared by reacting, but is not limited thereto.

The polyfunctional (meth)acrylate may be included in 10 parts by weight to 80 parts by weight, for example, 30 parts by weight to 80 parts by weight, and 30 parts by weight to 65 parts by weight among 100 parts by weight of the composition for blocking bleeding. In the above range, the contact angle range of the present invention can be secured, and the light curing rate and plasma resistance can be excellent. In one embodiment, the polyfunctional (meth)acrylate is 10 parts by weight to 80 parts by weight, for example, 30 parts by weight to 100 parts by weight of the total weight of (A), (B), (C) and (D) 80 parts by weight, for example, may be included as 30 parts by weight to 65 parts by weight.

(C) Monofunctional ( Met ) Acrylate

Monofunctional (meth)acrylate is included in the composition for blocking bleeding, so that the photocuring rate of the composition for blocking bleeding can be increased.

The monofunctional (meth)acrylate may include at least one of an aromatic monofunctional (meth)acrylate having an aromatic group and a non-aromatic monofunctional (meth)acrylate having no aromatic group. These may be included alone or in combination of two or more.

Both the aromatic monofunctional (meth)acrylate and the aforementioned silicone polyfunctional (meth)acrylate have aromatic groups, and when used together, the compatibility in the composition for blocking bleeding is more excellent.

The aromatic monofunctional (meth)acrylate may include monofunctional (meth)acrylate having a substituted or unsubstituted aromatic group. Here, the'aromatic group' means a polycyclic aromatic group including a monocyclic or fused form, or a single ring connected by a sigma bond. For example, the aromatic group is a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C7 to C50 arylalkyl group, a substituted or unsubstituted C3 to C50 heteroaryl group, a substituted or unsubstituted C3 to C50 It may mean one or more of the heteroaryl alkyl group. More specifically, the aromatic group is phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, anthracenyl, phenanthrenyl, chrysenyl, triphenylenyl, tetrasenyl, pyrenyl, benzopyrenyl, pentacenyl, coronenyl , Ovalenyl, Coranulenyl, Benzyl, Pyridinyl, Pyrazinyl, Pyrimidinyl, Pyridazinyl, Triazinyl, Quinolinyl, Isoquinolinyl, Quinoxalinil, Acridinyl, Quinazolinyl, Sin Nolinyl, phthalazinyl, thiazolyl, benzothiazolyl, isoxazolyl, benzisoxazolyl, oxazolyl, benzoxazolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, purinyl, thiophenyl, It may be one or more of benzothiophenyl, furanyl, benzofuranyl, and isobenzoprenyl.

For example, the aromatic monofunctional (meth)acrylate can be represented by the following formula (10):

<Formula 10>

(In the formula 10,

R ₁₈ is hydrogen or a methyl group,

s is an integer from 0 to 10,

R ₁₉ is a substituted or unsubstituted C6 to C50 aryl group or a substituted or unsubstituted C6 to C50 aryloxy group).

For example, R ₁₉ is a phenylphenoxyethyl group, phenoxyethyl group, benzyl group, phenyl group, phenylphenoxy group, phenoxy group, phenylethyl group, phenylpropyl group, phenylbutyl group, methylphenylethyl group, propylphenylethyl group, methoxyphenylethyl group , Cyclohexylphenylethyl group, chlorophenylethyl group, bromophenylethyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, propylphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group, biphenyl group, terphenyl ) Group, quaterphenyl group, anthracenyl group, naphthalenyl group, triphenylenyl group, methylphenoxy group, ethylphenoxy group, methylethylphenoxy group, methoxyphenyloxy group, propylphenoxy group, cyclohexyl group Phenoxy group, chlorophenoxy group, bromophenoxy group, biphenyloxy group, terphenyloxy group, quaterphenyloxy group, anthracenyloxy group, naphthalenyloxy group, tree It may be a phenylenyloxy (triphenylenyloxy) group.

Specifically, the aromatic monofunctional (meth)acrylate is 2-phenylphenoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyl (meth)acrylate, phenoxy(meth)acrylate, 2 -Ethylphenoxy(meth)acrylate, benzyl(meth)acrylate, 2-phenylethyl(meth)acrylate, 3-phenylpropyl(meth)acrylate, 4-phenylbutyl (meth)acrylate, 2-( 2-methylphenyl)ethyl (meth)acrylate, 2-(3-methylphenyl)ethyl (meth)acrylate, 2-(4-methylphenyl)ethyl (meth)acrylate, 2-(4-propylphenyl)ethyl (meth) )Acrylate, 2-(4-(1-methylethyl)phenyl)ethyl (meth)acrylate, 2-(4-methoxyphenyl)ethyl (meth)acrylate, 2-(4-cyclohexylphenyl)ethyl (Meth)acrylate, 2-(2-chlorophenyl)ethyl (meth)acrylate, 2-(3-chlorophenyl)ethyl (meth)acrylate, 2-(4-chlorophenyl)ethyl (meth)acrylate , 2-(4-bromophenyl)ethyl (meth)acrylate, 2-(3-phenylphenyl)ethyl (meth)acrylate, 4-(biphenyl-2-yloxy)butyl (meth)acrylate, 3-(biphenyl-2-yloxy)butyl (meth)acrylate, 2-(biphenyl-2-yloxy)butyl (meth)acrylate, 1-(biphenyl-2-yloxy)butyl (meth) )Acrylate, 4-(biphenyl-2-yloxy)propyl (meth)acrylate, 3-(biphenyl-2-yloxy)propyl (meth)acrylate, 2-(biphenyl-2-yloxy) )Propyl (meth)acrylate, 1-(biphenyl-2-yloxy)propyl (meth)acrylate, 4-(biphenyl-2-yloxy)ethyl (meth)acrylate, 3-(biphenyl-) 2-yloxy)ethyl (meth)acrylate, 2-(biphenyl-2-yloxy)ethyl (meth)acrylate, 1-(biphenyl-2-yloxy)ethyl (meth)acrylate, 2- (4-benzylphenyl)ethyl (meth)acrylate, 1-(4-benzylphenyl)ethyl (meth)acrylate, or one or more of these structural isomers. That is, the (meth)acrylate mentioned in the present invention corresponds to an example, but is not limited thereto, and further, the present invention includes all acrylates in a structural isomer relationship. For example, although only 2-phenylethyl (meth)acrylate is mentioned as an example of the present invention, the present invention includes both 3-phenylethyl (meth)acrylate and 4-phenyl (meth)acrylate.

The non-aromatic monofunctional (meth)acrylate may be a monofunctional (meth)acrylate having a substituted or unsubstituted C1 to C20 alkyl group. Specifically, the non-aromatic monofunctional (meth)acrylate is a monofunctional (meth)acrylate having an unsubstituted linear C1 to C20 alkyl group, and more specifically, an unsubstituted straight chain C10 to C20. It may be a monofunctional (meth)acrylate having an alkyl group. For example, non-aromatic monofunctional (meth)acrylates include decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl ( Meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, arachidyl (meth) Acrylate, but is not limited thereto.

Monofunctional (meth)acrylate may be included in 10 parts by weight to 60 parts by weight, for example, 15 parts by weight to 55 parts by weight of 100 parts by weight of the composition for blocking bleeding. In the above range, the contact angle range of the present invention can be secured, and the light curing rate and plasma resistance can be excellent. In one embodiment, the monofunctional (meth)acrylate is 10 parts by weight to 60 parts by weight, for example, 15 parts by weight to 100 parts by weight of the total weight of (A), (B), (C) and (D) It may be included as 55 parts by weight.

(D) Initiator

The initiator is to form a barrier by curing the polyfunctional (meth)acrylate and monofunctional (meth)acrylate, and may include a conventional photopolymerization initiator without limitation. The initiator may cure at least one of a fluorine-based leveling agent and a silicone-based leveling agent.

The initiator may include, but is not limited to, one or more of a triazine-based initiator, acetophenone-based initiator, benzophenone-based initiator, thioxanthone-based initiator, benzoin-based initiator, phosphorus-based initiator, and oxime-based initiator. For example, phosphorus-based initiators include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, benzyl(diphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4, 4-trimethylpentyl)phosphine oxide or mixtures thereof. For example, when using a phosphorus-based initiator, the composition of the present invention may show better initiation performance at long wavelength UV. The initiator may be included alone or in combination of two or more.

The initiator may be included in 1 part to 10 parts by weight of 100 parts by weight of the composition for blocking bleeding, for example, 2 parts to 8 parts by weight. In the above range, the composition for blocking bleeding may sufficiently undergo photopolymerization during exposure. In addition, the unreacted initiator remaining after photopolymerization can be reduced, and the light transmittance of the barrier can be further improved. Specifically, the initiator may be included in 1 part by weight to 10 parts by weight, for example, 2 parts by weight to 8 parts by weight of 100 parts by weight of the total of (A), (B), (C), and (D).

The composition for blocking bleeding may further include conventional additives known to those skilled in the art. The additive may include at least one of a heat stabilizer, a UV absorber, an antioxidant, and a pigment, but is not limited thereto.

The composition for blocking bleeding may have a surface tension of 20 mN/m to 50 mN/m at 25°C, for example, 20 mN/m to 35 mN/m, and 20 mN/m to 31 mN/m. In the above range, there may be a flow control effect of the composition for sealing an organic light emitting device.

The contact angle of the composition for encapsulating the organic light emitting device on the cured product of the composition for blocking bleeding may be 6° to 45°, more specifically 7° to 35°. In the above range, the repulsive force of the cured bleeding blocking composition and the organic light emitting device encapsulating composition is large, thereby preventing bleeding of the organic light emitting device encapsulating composition. The "organic light emitting device encapsulation composition" may mean a composition for a display encapsulant described in Korean Patent Publication No. 2016-0150256. This will be described in detail below.

The composition for blocking bleeding may have a photocuring rate of 88% or more, for example, 88% to 100%. In addition, the composition for blocking bleeding may have a light transmittance of 93% or more at a wavelength of 380 nm to 700 nm after curing, for example, 93.5% to 100%. In addition, the composition for blocking bleeding may have an etch rate of the barrier by plasma after curing of 30% or less, for example, 25% or less, for example, 0.1% to 20%. Reliability of the organic light emitting device may be significantly increased in a range of the photocuring rate, light transmittance, and etching rate by plasma.

The composition for blocking bleeding may have a viscosity of 5 cps to 40 cps or 10 cps to 30 cps at 25±2° C. (23° C. to 27° C.). The composition for blocking bleeding in the above range may facilitate the formation of a barrier, and may be advantageous in performing methods such as vapor deposition and inkjet when forming the barrier.

The composition for blocking bleeding is formed by mixing (A) a fluorine-based leveling agent, at least one of a silicone-based leveling agent, (B) polyfunctional (meth)acrylate, (C) monofunctional (meth)acrylate and (D) initiator. can do. The composition for blocking bleeding may be formed in a solvent-free type that does not contain a solvent. For example, when the composition for blocking bleeding is a solvent-free type, the weight percentage is (A) at least one of a fluorine-based leveling agent and a silicone-based leveling agent, (B) polyfunctional (meth)acrylate, (C) monofunctional (meth) )Acrylates and (D) initiators.

The composition for blocking bleeding is a photocurable composition, which may be cured by irradiation for 1 second to 100 seconds at 10 mW/cm ² to 500 mW/cm ² at UV wavelength, but is not limited thereto.

Hereinafter, the organic light emitting device display device of the present invention will be described.

The organic light emitting device display device of the present invention may include a barrier formed of the composition for blocking bleeding of the present invention. The barrier has excellent repelling power to the inorganic layer and the organic layer of the organic light emitting device encapsulation layer, and thus can be easily formed in a predetermined range of thickness and height on the organic light emitting device encapsulation layer, and has excellent repulsive power with the composition for encapsulating the organic light emitting device, thereby providing an organic layer. The bleeding of the composition can be prevented. In addition, since the barrier has a low plasma etch rate, the reliability of the organic light emitting device and/or the organic light emitting device encapsulation layer may be improved.

An organic light emitting diode display device according to an exemplary embodiment of the present invention will be described with reference to FIGS. 1 and 2.

Referring to FIG. 1, an organic light emitting diode display device includes a substrate 10; An organic light emitting element 20; An encapsulation layer 30 including an inorganic layer 31 and an organic layer 32; And a barrier 40.

1 and 2, the barrier 40 is formed on the surface of the inorganic layer 31 and on the outer peripheral surface of the organic layer 32.

Although not illustrated in FIGS. 1 and 2, the barrier 40 may form at least a portion of the non-display area of the organic light emitting diode display device. Preferably, the barrier 40 is formed to directly contact the inorganic layer 31 and the organic layer 32, respectively.

The barrier 40 is formed of a composition for blocking bleeding of the present invention and is easily formed to have a predetermined range and thickness on an inorganic layer. When the organic layer is formed, the barrier prevents bleeding of the composition for encapsulating the organic light emitting device, thereby increasing the reliability of the organic light emitting device even if the gap between the organic light emitting device and the adjacent organic light emitting device is narrowed.

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

The organic light emitting device 20 is commonly used in an organic light emitting device display device and is not shown in FIG. 1, but includes an organic light emitting film formed between a first electrode, a second electrode, and a first electrode and a second electrode. The light emitting layer may be a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, or an electron injection layer sequentially stacked, but is not limited thereto.

The encapsulation layer 30 may include a stacked structure in which the inorganic layer 31 and the organic layer 32 are alternately stacked. The inorganic layer and the organic layer have different components constituting each layer, so that the organic light emitting device can be sealed.

The inorganic layer has a different component from the organic layer, and thus the effect of the organic layer can be supplemented. The inorganic layer may be formed of an inorganic material having excellent light transmittance and excellent moisture and/or oxygen barrier properties. For example, the inorganic layer may be a metal, nonmetal, intermetallic compound or alloy, nonmetallic compound or alloy, metal or nonmetal oxide, metal or nonmetal fluoride, metal or nonmetal nitride, metal or nonmetal carbide, metal or nonmetal It can be an oxynitride of, a boride of a metal or non-metal, an oxyboride of a metal or a non-metal, a silicide of a metal or a non-metal, or a mixture thereof. Metals or nonmetals are silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition Metal, lanthanide metal, and the like, but are not limited thereto. Specifically, the inorganic barrier layer is AlOx, In ₂ O ₃ , including silicon oxide (SiOx), silicon nitride (SiNx), silicon oxygen nitride (SiOxNy), ZnSe, ZnO, Sb ₂ O ₃ , Al ₂ O _3, etc. It can be SnO ₂ . The inorganic layer may be deposited by a plasma process, a vacuum process, such as sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma vapor deposition, and combinations thereof.

When the organic layer is alternately deposited with the inorganic layer, the smoothing property of the inorganic layer is secured, and defects in the inorganic layer can be prevented from propagating to another inorganic layer.

The organic layer may be formed by deposition of an organic light emitting device encapsulating composition, inkjet, screen printing, spin coating, blade coating, curing alone or a combination thereof. For example, the composition for sealing an organic light emitting device may be coated to a thickness of 1 μm to 50 μm, and cured by irradiating at 10 mW/cm ² to 500 mW/cm ² for 1 to 100 seconds.

The composition for encapsulating the organic light emitting device may include the composition for display encapsulant described in Korean Patent Publication No. 10-2016-0150256. The content described in Korean Patent Publication No. 10-2016-0150256 is the application of the inventor of the present application, and the content described therein can be regarded as described herein.

For example, the composition for encapsulating an organic light emitting device includes a photocurable monomer and a photopolymerization initiator, and the photocurable monomer includes a monomer having no aromatic hydrocarbon group; And a monomer having two or more substituted or unsubstituted phenyl groups represented by Chemical Formula 1, and the photocurable monomer includes 5 to 45% by weight of the monomer having two or more substituted or unsubstituted phenyl groups. , The photo-curable monomer may include 55 to 95% by weight of the monomer having no aromatic hydrocarbon group:

<Formula 11>

(In the formula (11), A is a substituted or unsubstituted hydrocarbon containing two or more phenyl groups or a substituted or unsubstituted heteroatom-containing hydrocarbon containing two or more phenyl groups,

Z ¹ , Z ² are each independently Formula 12,

a and b are each an integer from 0 to 2, and a+b is an integer from 1 to 4:

<Formula 12>

(In the above formula 12, * is a connection to the carbon of A in the formula 1,

X is a single bond, O, or S,

Y is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms,

R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms,

c is 0 or 1).

The monomer having two or more substituted or unsubstituted phenyl groups may be at least one of mono(meth)acrylate and di(meth)acrylate.

The mono (meth) acrylate may be represented by the formula (13).

<Formula 13>

(In the formula 13, R ² is hydrogen or a methyl group, R ³ is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R ⁴ is Hydrocarbons containing two or more substituted or unsubstituted phenyl groups or heteroatom-containing hydrocarbons containing two or more substituted or unsubstituted phenyl groups).

The di(meth)acrylate may be represented by Formula 14 below:

<Formula 14>

(In the formula (14), R ⁵ , R ⁹ are each independently hydrogen or a methyl group, R ⁶ , R ⁸ are each independently substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, R ⁷ is a substituted or unsubstituted hydrocarbon containing two or more phenyl groups, or a substituted or unsubstituted heteroatom-containing hydrocarbon containing two or more phenyl groups).

Monomers having no aromatic hydrocarbon group include mono(meth)acrylate having an amine group, di(meth)acrylate having a substituted or unsubstituted C1 to C20 alkylene group, di(meth)acrylate having an ethylene oxide group, and ethylene oxide Tri(meth)acrylate having a group and trimethylolpropane tri(meth)acrylate.

The encapsulation layer includes an organic layer and an inorganic layer, but the total number of organic and inorganic layers is not limited. 1 shows a case in which one inorganic layer and one organic layer are alternately formed, but is not limited thereto. For example, the total number of organic and inorganic layers can be varied depending on the level of permeation resistance to oxygen and/or moisture and/or water vapor and/or chemicals. For example, the total number of the organic layer and the inorganic layer may be 10 layers or less, for example, 2 to 7 layers, and specifically, an inorganic layer/organic layer/inorganic layer/organic layer/inorganic layer/organic layer/inorganic layer It may be formed in seven layers in order.

The height of the first layer of the inorganic layer may be 100 mm 2 to 2000 mm 2, for example, 500 mm 2 to 2000 mm 2. The height of the first layer of the organic layer may be 1 μm to 50 μm, for example, 5 μm to 50 μm.

The height of the barrier may be the same or higher than the height of the organic layer to be formed. Alternatively, the height of the barrier may be smaller than the height of the organic layer to be formed among the encapsulation layers.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is provided as a preferred example of the present invention and cannot be interpreted as limiting the present invention by any means.

The specific specifications of the components used in Examples and Comparative Examples are as follows.

(A) Fluorine leveling agent or silicone leveling agent

(A1) 1,1,1,3,3,3-Hexafluoroisopropyl acrylate (Aldrich)

(A2) 1,1,1,3,3,3-Hexafluoroisopropyl methacrylate (Aldrich)

(A3) 2,2,3,3,4,4,4-heptafluorobutyl methacrylate (Aldrich)

(A4) BYK UV-3500 (BYK): Polyether modified acryl functional polydimethylsiloxane

(A5) BYK UV-3530 (BYK): Polyether modified acryl functional polydimethylsiloxane

(A6) F-477 (DIC): Oligomer with fluoro, hydrophilic and lipophilic group

(A7) F-554 (DIC): Oligomer with fluoro and lipophilic group

(A8) X-22-164AS (Shin-Etsu)

(A9) X-22-2445 (Shin-Etsu)

(A10) BYK-323 (BYK): Aralkyl modified polymethylsiloxane

(A11) BYK-3560 (BYK): Polyacrylate copolymer

(B) polyfunctional (meth)acrylate

(B1) 1,12-dodecanediol diacrylate (Sartomer)

(B2) 2-Propenoic acid, 2-methyl-1,1'-[(1,1,5,5-tetramethyl-3,3-diphenyl-1,5-trisiloxanediyl)di-3,1-propanediyl] ester

(C) Monofunctional (meth)acrylate

(C1) 2-phenylphenoxyacrylate (M1142, Miwon Corporation),

(C2) lauryl acrylate (Sartomer)

(D) initiator: Darocur TPO (BASF)

Example Comparative example

(A), (B), (C), (D) according to the contents of Table 1 and Table 2 (unit: parts by weight) below into a 125 ml brown polypropylene bottle, and mixed at room temperature for 3 hours using a shaker To prepare a composition for blocking bleeding.

The following properties were measured for the composition for blocking bleeding prepared in Examples and Comparative Examples, and the results are shown in Tables 1 and 2.

Method for evaluating physical properties

(1) Viscosity (unit: cps): The bleeding blocking composition of Examples and Comparative Examples was measured with a viscosity meter LV DV-II Pro (Brookfield) at 25°C with a spindle number (No. spindle) 40.

(2) Light curing rate (unit: %): For the composition for blocking bleeding of Examples and Comparative Examples, using FT-IR (NICOLET 4700, Thermo Co.), 1635 cm ^-1 vicinity (C = C), 1720 cm ^-1 vicinity ( The intensity of the absorption peak at C=O) is measured. A composition for blocking bleeding was applied on a glass substrate by spin coating and irradiated with 100 mW/cm ² for 10 seconds to cure UV, thereby obtaining a specimen of 20 cm×20 cm×3 μm (width x length x thickness). Obtain a cured film and, FT-IR (NICOLET 4700, Thermo Co.) is used in the vicinity of 1635cm ^-1 (C = C), 1720cm ^-1 measured intensity of the absorption peak in the vicinity of the (C = O) a. The photocuring rate is calculated according to the following equation 1.

<Equation 1>

Light curing rate (%)= ｜1-(A/B)｜ x 100

(In the above formula 1, A is the ratio of the intensity of the absorption peak at around 1635 cm ^-1 to the intensity of the absorption peak at around 1720 cm ^-1 for the cured film,

B is the ratio of the intensity of the absorption peak at around 1635 cm ^-1 to the intensity of the absorption peak at around 1720 cm ^-1 for the composition for blocking bleeding).

(3) Plasma etch rate (unit: %): The bleeding blocking compositions of Examples and Comparative Examples were coated and photocured to a predetermined thickness to measure the height of the cured product (T1, 1 μm to 10 μm). After ICP power: 2500W, RF power: 300W, DC bias: 200V, Ar flow: 50sccm, ethching time: 1min, pressure: 10mtorr, the plasma was treated with the cured product and the height of the cured product (T2, unit:㎛) It was measured. The etch rate of the cured product by plasma was calculated by Equation 2.

<Equation 2>

Plasma etch rate (%) of cured product of the composition for blocking bleeding = (T1-T2)/T1 x 100

(4) Contact angle of the composition for encapsulating the organic light-emitting device on the cured product of the composition for blocking bleeding (unit:°): The composition for bleeding blocking of Examples and Comparative Examples was coated on a glass substrate by spin coating, and 100 mW/cm ² for 10 seconds. It was irradiated for a while to undergo UV curing to obtain a cured product of the composition for blocking bleeding.

The composition for sealing the organic light emitting device is prepared as follows.

In a 3000 ml reactor equipped with a cooling tube and a stirrer, 300 ml of dichloromethane was added, 200 g of 4-hydroxybutyl acrylate and 168 g of triethylamine were added, the temperature in the flask was lowered to 0°C, and 278 g of p-toluenesulfonyl chloride The solution dissolved in 500 ml of dichloromethane was added dropwise and stirred for 2 hours. After stirring for an additional 5 hours, the residual solvent was removed by distillation. 300 g of the obtained compound was placed in 1000 ml of acetonitrile, 220 g of potassium carbonate and 141 g of 2-phenylphenol were added and stirred at 80°C. The residual solvent and the reaction residue were removed to obtain a compound of Formula 15 (molecular weight 296.36) having an HPLC purity of 93%.

<Formula 15>

90 parts by weight of dodecanediol dimethacrylate, 10 parts by weight of the compound of formula (15) prepared above, and 5 parts by weight of phosphorus initiator Darocure TPO were mixed to prepare a composition for sealing an organic light emitting device.

1 drop of the composition for encapsulation of the prepared organic light emitting device was dropped on the cured product. It was measured by a contact angle measuring method at 25°C for 1 drop with a contact angle meter of 26G needle. Less than 5° was not measured due to the characteristics of the device, so when measurement was impossible, it was collectively marked as less than 5°.

(5) Contact angle (unit:°) on the glass plate: Measured by the contact angle measuring method for 1 drop of the composition for blocking bleeding with a 26G needle contact angle meter at 25°C on the cleaned glass plate for the bleeding blocking compositions of Examples and Comparative Examples. Did. Less than 5° was not measured due to the characteristics of the device, so when measurement was impossible, it was collectively marked as less than 5°.

(6) Surface tension (unit: mN/m): Pt ring type, Circum=5.966cm, R/r=48.5 using a surface tension meter of SEO at 25°C for the compositions for blocking bleeding of Examples and Comparative Examples It was measured.

(7) Evaluation of the bleeding blocking ability of the composition for blocking bleeding: The bleeding blocking compositions of Examples and Comparative Examples were length x width (5 cm x 1 cm, thickness of 20 μm of coating solution, width of 200 μm of coating solution) using an inkjet printer. The barrier of FIG. 2 was formed by coating in a ring-opened rectangular shape of size and curing to 2000 mJ. When the composition for sealing the organic light emitting device prepared in (4) was completely filled in the barrier, it was measured by a method of confirming by observing whether or not bleeding of the composition for sealing occurs outside the rectangle. If there was no bleeding, it was evaluated as "o" if there was "x" bleeding. In the case of bleeding, the reliability of the organic light emitting device is deteriorated and cannot be used.

Example One 2 3 4 5 6 7 8 9 10 11 (A1) 2 2 2 10 10 10 - - - - (A2) - - - - - - 2 10 - - - (A3) - - - - - - - - 2 10 - (A4) - - - - - - - - - - 0.2 (A5) - - - - - - - - - - - (A6) - - - - - - - - - - - (A7) - - - - - - - - - - - (A8) - - - - - - - - - - - (A9) - - - - - - - - - - - (A10) - - - - - - - - - - - (A11) - - - - - - - - - - - (B1) 62 42 48 54 34 40 62 54 62 54 63.8 (B2) - - 28 - - 28 - - - - - (C1) 33 33 19 33 33 19 33 33 33 33 33 (C2) - 20 - - 20 - - - - - - (D) 3 3 3 3 3 3 3 3 3 3 3 total 100 100 100 100 100 100 100 100 100 100 100 (One) 19.5 15.2 20.5 16.3 12.1 16.9 20.2 16.6 20.1 16.4 21.5 (2) 91.2 92.4 92.5 93.1 92.7 92.8 91.1 92.1 91 91.3 91.8 (3) 6.1 6.3 6.8 7.3 7.2 7.8 6.2 6.9 * * 6.1 (4) 9.3 10.1 9.8 13.2 13.3 12.9 9.6 13.4 9.2 13.8 13.9 (5) 8.9 12.1 9.2 10.1 12.7 11 8.7 12.9 9.1 12.9 30.7 (6) 30.3 30.1 30.2 27.6 27.4 27.7 30.5 27.9 29.2 27.1 21.8 (7) x x x x x x x x x x x

Example Comparative example 12 13 14 15 16 17 18 19 20 One 2 3 (A1) - - - - - - - - - - - - (A2) - - - - - - - - - - - - (A3) - - - - - - - - - - - - (A4) 10 - - - - - - - - - - - (A5) - 0.2 10 - - - - - - - - - (A6) - - - 0.5 - - - - - - - - (A7) - - - - 0.5 - - - - - - - (A8) - - - - - 0.01 0.5 - - - - - (A9) - - - - - - - 0.01 0.5 - - - (A10) - - - - - - - - - - 0.5 - (A11) - - - - - - - - - - - 0.5 (B1) 54 63.8 54 63.5 63.5 63.99 63.5 63.99 63.5 63 63.5 63.5 (B2) - - - - - - - - - - - - (C1) 33 33 33 33 33 33 33 33 33 34 33 33 (C2) - - - - - - - - - - - - (D) 3 3 3 3 3 3 3 3 3 3 3 3 total 100 100 100 100 100 100 100 100 100 100 100 100 (One) 23.8 21.3 22.9 21.2 21.5 21.1 21 21.1 21.2 20 21.3 21.1 (2) 92.1 92.5 92.7 92.1 91.9 90.9 91.1 91.8 91.7 91.5 90.2 91.2 (3) 6.8 6.2 6.7 6.3 6.2 * * * * 6.2 * * (4) 15.2 23.8 25.1 9.7 12.5 14.8 32.2 15.6 20.4 Less than 5 Less than 5 Less than 5 (5) 13.6 16.2 20.5 21.3 17.5 10.1 7.2 8.7 6.6 Less than 5 degrees 5 5.9 (6) 20.9 30.1 29.2 22.9 21.6 30.1 24.2 24.7 22.6 ** 29.6 32.1 (7) x x x x x x x x x o o o

* In Tables 1 and 2,'*' indicates that plasma etch rate was not measured.

* In Table 2 above,'**' indicates that the surface tension was not measured.

As shown in Table 1 and Table 2, the composition for blocking bleeding of the composition for encapsulating the organic light-emitting device of the present invention blocks the bleeding of the composition for encapsulating the organic light-emitting device, thereby improving the reliability between the organic light-emitting devices even if the interval between the organic light-emitting devices is narrowed. Can be increased. In addition, the composition of the present invention has a high photo-curing rate and a low plasma etch rate, thereby increasing the reliability of the organic light emitting device and/or the organic light emitting device encapsulation layer.

On the other hand, Comparative Example 1, which does not contain a leveling agent, Comparative Example 2 and Comparative Example 3, which do not contain the leveling agent of the present invention even if a leveling agent is included, could not obtain the effect of the present invention.

Simple modifications or changes of 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.

Claims (19)

(A) One or more of fluorine-based leveling agent and silicon-based leveling agent, (B) polyfunctional (meth)acrylate, (C) monofunctional (meth)acrylate and (D) initiator, for sealing organic light emitting device As a composition for blocking bleeding of the composition,
The composition for blocking bleeding of the composition for encapsulating the organic light emitting device has a contact angle of 6° or more with respect to a glass plate at 25° C., a composition for blocking bleeding of the encapsulation layer for an organic light emitting device.
The composition for blocking bleeding of an organic light emitting device encapsulation layer according to claim 1, wherein the contact angle of the composition for sealing an organic light emitting device on the photocured product of the composition for blocking bleeding is 6° to 45°.
The composition for blocking bleeding of claim 1, wherein the composition for blocking bleeding has a viscosity of 5cp to 40cp at 25±2°C.
The composition for blocking bleeding of a composition for encapsulating organic light-emitting devices according to claim 1, wherein the fluorine-based leveling agent comprises a monofunctional or polyfunctional (meth)acrylate having an aliphatic hydrocarbon group substituted with one or more fluorine. .
According to claim 4, The fluorine-based leveling agent is hexafluoroisopropyl (meth) acrylate, one or more of heptafluorobutyl (meth) acrylate, blocking the bleeding of the composition for sealing an organic light emitting device Dragon composition.
According to claim 1, The fluorine-based leveling agent is to have one or more of a hydrophilic group, a lipophilic group, a composition for blocking bleeding of the composition for sealing an organic light emitting device.
The method of claim 6, wherein the hydrophilic group is a hydroxyl group, a carboxylic acid group or a sulfonic acid group,
The lipophilic group is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, a composition for blocking bleeding of a composition for sealing an organic light emitting device.
The composition for blocking bleeding of a composition for sealing an organic light emitting device according to claim 1, wherein the silicone-based leveling agent comprises a polyether-modified (meth)acrylic functional polyalkylsiloxane.
According to claim 8, wherein the polyether-modified (meth) acrylic functional polyalkylsiloxane is to include the following formula (1), composition for blocking bleeding of the composition for sealing an organic light emitting device:
<Formula 1>

(In the formula 1,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are, independently of each other, hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted A substituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 heteroaryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a halogen, a hydroxyl group, or an amino group,
R ₇ and R ₈ are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted A C6 to C20 heteroaryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a halogen, a hydroxyl group, an amino group, or the following Chemical Formula 1-1,
<Formula 1-1>

(In Formula 1-1, * is a linking site to Si in Formula 1,
R ₉ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkylether group, or a substituted or unsubstituted C6 to C20 arylene group,
R ₁₀ is hydrogen or a methyl group)
At least one of R ₇ and R ₈ is Formula 1-1).
According to claim 1, One or more of the fluorine-based leveling agent, the silicon-based leveling agent is contained in 0.001 parts by weight to 20 parts by weight of 100 parts by weight of the composition for blocking bleeding, blocking the bleeding of the composition for sealing an organic light emitting device Dragon composition.
The method of claim 1, wherein the polyfunctional (meth) acrylate comprises a non-silicone-based polyfunctional (meth) acrylate,
The non-silicone-based polyfunctional (meth)acrylate comprises a substituted or unsubstituted C1 to C20 di(meth)acrylate having an alkylene group, a composition for blocking bleeding of an organic light emitting device sealing composition.
The composition for blocking bleeding of a composition for encapsulating an organic light emitting device according to claim 11, wherein the polyfunctional (meth)acrylate further comprises a silicone-based difunctional (meth)acrylate represented by the following Chemical Formula 3:
<Formula 3>

(In the formula 3,
R ₁₄ , R ₁₅ are independently of each other, a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C30 alkylene ether group, *-N(R')-(R" )-*(* is the linking site of the element, R'is hydrogen, or a substituted or unsubstituted C1 to C30 alkyl group, R" is a substituted or unsubstituted C1 to C20 alkylene group), a substituted or unsubstituted C6 To C30 arylene group, substituted or unsubstituted C7 to C30 arylalkylene group, or *-(R')-O-** (where * is a linkage to O in Formula 3, ** is Formula 3 In the linking site to Si, R'is a substituted or unsubstituted C1 to C30 alkylene group),
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ are each independently hydrogen, hydroxyl group, halogen, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 Heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 alkyl ether group, *-N(R')(R") (* is an element linkage site, R 'And R'are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkyl group), a substituted or unsubstituted C1 to C30 alkylsulfide group, a substituted or unsubstituted C6 to C30 aryl group, a substitution Or an unsubstituted C2 to C30 heteroaryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group,
At least one of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , and X ₆ is a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
R ₁₆ and R ₁₇ are each independently hydrogen or a methyl group,
n is 0 To 30 or an average value of n is 0 to 30).
According to claim 1, The monofunctional (meth) acrylate will include an aromatic monofunctional (meth) acrylate, the composition for blocking bleeding of the composition for sealing an organic light emitting device.
The composition for blocking bleeding of a composition for sealing an organic light emitting device according to claim 12, wherein the monofunctional (meth)acrylate further comprises a non-aromatic monofunctional (meth)acrylate.
According to claim 1, 100% by weight of the total composition for blocking bleeding of the encapsulation layer of the organic light emitting device
(A) 0.001 part by weight to 20 parts by weight of at least one of the fluorine-based leveling agent and the silicone-based leveling agent,
The (B) polyfunctional (meth) acrylate 10 parts by weight to 80 parts by weight,
The (C) monofunctional (meth)acrylate 10 parts by weight to 60 parts by weight,
The (D) initiator containing 1 part by weight to 10 parts by weight of the composition for blocking bleeding of the composition for sealing an organic light emitting device.
Board; An organic light emitting element formed on the substrate; An encapsulation layer encapsulating the organic light emitting device and including at least one inorganic layer and at least one organic layer; And a barrier formed on the outer peripheral surface of the organic layer or the outer peripheral surface of the encapsulation layer,
The barrier comprises a barrier formed of a composition for blocking bleeding of the composition for encapsulating any one of claims 1 to 15, an organic light emitting device display device.
The organic light emitting diode display device of claim 16, wherein the barrier has a plasma etch rate of 30% or less of the cured product of the composition for blocking bleeding according to Equation 2 below:
<Equation 2>
Plasma etch rate (%) of the cured product of the composition for blocking bleeding = (T1-T2)/T1 x 100.
(In Equation 2 above,
T1 is the initial height of the barrier (unit: μm)
T2 is plasma treated at the barrier inductively coupled plasma (ICP) power: 2500W, radio frequency (RF) power: 300W, DC bias: 200V, Ar flow: 50sccm, etching time: 1min, pressure: 10mtorr The height of the barrier after (in µm).
The display device of claim 16, wherein the barrier is formed on the surface of the inorganic layer.
The method of claim 16, wherein the organic layer comprises a photocurable monomer and a photopolymerization initiator, the photocurable monomer, a monomer that does not have an aromatic hydrocarbon group; And a monomer having two or more substituted or unsubstituted phenyl groups represented by Chemical Formula 1, and the photocurable monomer includes 5 to 45% by weight of the monomer having two or more substituted or unsubstituted phenyl groups. , The photo-curable monomer is an organic light-emitting device display device comprising a monomer that does not have the aromatic hydrocarbon group in 55% to 95% by weight:
<Formula 11>

(In the formula 11, A is a substituted or unsubstituted hydrocarbon containing two or more phenyl groups or a substituted or unsubstituted heteroatom-containing hydrocarbon containing two or more phenyl groups,
Z ¹ , Z ² are each independently the following formula (12),
a and b are each an integer from 0 to 2, and a+b is an integer from 1 to 4:
<Formula 12>

(In the above formula 12, * is a connection to the carbon of A in the formula 1,
X is a single bond, O, or S,
Y is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms,
R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms,
c is 0 or 1).

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