KR101676520B1 - Composition for encapsulation of oled device and oled display prepared using the same - Google Patents

Abstract

(C) an organosilicon compound containing an Si-H group, and (D) an organosilicon compound containing an unsaturated group-containing organopolysiloxane (A) having an unsaturated group-containing organopolysiloxane (B) And a display device for an organic light emitting diode manufactured using the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for encapsulating an organic light emitting device, and an organic light emitting diode display using the same. BACKGROUND ART [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for encapsulating an organic light emitting device and an organic light emitting diode display using the same.

OLEDs (organic light emitting diodes) can emit blue, red, and green light emitting materials in a light emitting portion, and display white light by combining light emitting portions that display different colors. The organic light emitting device is very vulnerable to external moisture and / or oxygen, and therefore must be encapsulated with an encapsulating material of a packaging or encapsulated structure. The sealing material may be formed of a sealing composition including a light transmitting resin so that light emitted from the light emitting portion can pass through the outside, and a silicone composition may be used as the sealing composition.

The silicone composition is crosslinked and cured by hydrosilylation of an unsaturated group-containing polysiloxane such as a vinyl group and an organosilicon compound having an Si-H group to form an encapsulant. Platinum or other metal compounds are used as catalysts in the hydrosilylation reaction. However, in the silicone composition employing the hydrosilylation reaction, the hydrosilylation reaction proceeds slowly even at room temperature, so that the storage stability of the silicone composition may deteriorate. To solve this problem, an organosilicon compound having an unsaturated group-containing polysiloxane and an Si- Is a two-component type which is mixed with each other when it is stored in a separate container and used for actual sealing purposes, the processability may be deteriorated, and the process may not be applicable when a process using a silicone composition is required for a long time.

Related prior arts include Korean Patent Publication No. 2005-0021054 entitled " Organic electroluminescent device and its manufacturing method ".

A problem to be solved by the present invention is to provide a composition for encapsulating an organic luminescent device which contains a mixture of silicone compounds employing a hydrosilylation reaction and has high storage stability.

Another object of the present invention is to provide a composition for encapsulating an organic luminescent element which comprises a mixture of a silicone compound employing a hydrosilylation reaction and is excellent in long-term reliability.

Another object to be solved by the present invention is to provide a composition for encapsulating an organic luminescent device which comprises a mixture of silicone compounds employing a hydrosilylation reaction and has a low rate of change in viscosity and a low rate of permeability change even after storage for a long period of time.

Another object to be solved by the present invention is to provide a composition for encapsulating an organic light emitting device, which comprises a mixture of silicone compounds employing a hydrosilylation reaction and improves the processability and economy in a one-pack form.

(B) an unsaturated group of the following formula (1) and an organopolysiloxane containing an epoxy group, (C) an organosilicon compound containing an Si-H group, and an organopolysiloxane containing (D) a platinum catalyst of formula (15): < EMI ID =

≪ Formula 1 >

^{_{(R 21 SiO 3/2)}} a (R 22 SiO 3/2) b (R 23 R 24 SiO 2/2) c

(Wherein R ²¹ , R ²² , R ²³ , R ²⁴ , a, b and c are as defined in the following description)

≪ Formula 15 >

(Wherein X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , Y ₁ , Y ₂ and Y ₃ are as defined in the following description).

The organic light emitting diode display of the present invention includes a substrate, an organic light emitting diode formed on the substrate, a barrier stack formed on the organic light emitting diode and including an inorganic encapsulation layer and an organic encapsulation layer, And may be formed from a composition for encapsulating an organic light emitting element.

The present invention provides a composition for encapsulating an organic light emitting device containing a mixture of silicone compounds employing a hydrosilylation reaction and having high storage stability.

The present invention provides a composition for encapsulating an organic luminescent element which comprises a mixture of silicone compounds employing a hydrosilylation reaction and has excellent long-term reliability.

The present invention provides a composition for encapsulating an organic light emitting device, which comprises a mixture of silicone compounds employing a hydrosilylation reaction and has a low rate of change in viscosity and a low rate of change in permeability even after storage for a long period of time.

The present invention provides a composition for encapsulating an organic luminescent element which comprises a mixture of silicone compounds employing a hydrosilylation reaction and improves the processability and economy in a one-pack type.

1 is a cross-sectional view of an OLED display device according to an embodiment of the present invention.
2 is a cross-sectional view of an OLED display device according to another embodiment of the present invention.

The present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

The term " on "or " on" of another structure in this specification includes both the structure immediately above another structure and the structure interposed therebetween. On the other hand, a structure referred to as "directly on" or "directly above "

As used herein, the term " unsaturated group-containing organopolysiloxane "means a silicone compound having at least one unsaturated group and" unsaturated group and epoxy group-containing organopolysiloxane "means silicone having at least one unsaturated group and at least one epoxy group, Quot; Si-H group-containing organosilicon compound "means a silicon compound having at least one functional group (i.e., Si-H group) in which hydrogen atoms are bonded to silicon atoms, and" unsaturated group & - carbon double bond or triple bond, and may mean, for example, a (meth) acryl group, a vinyl group, or the like.

Hereinafter, the composition for encapsulating an organic luminescent element of the present invention will be described with reference to an embodiment of the present invention.

(B) an organopolysiloxane containing an unsaturated group and an epoxy group, (C) an organosilicon compound containing an Si-H group, and (C) an organopolysiloxane containing an unsaturated group, (D) a platinum catalyst.

A mixture of an organopolysiloxane containing an unsaturated group (A) and an organosilicon compound (C) containing an Si-H group may undergo crosslinking and / or curing at room temperature slowly even if the curing temperature is not reached, After storage for a predetermined period of time relative to the initial viscosity of the composition, the viscosity of the composition may be increased to lower the storage stability of the composition. Therefore, a mixture of (A) an organopolysiloxane containing an unsaturated group and (C) a Si-H-containing organosilicon compound should be used in a two-component type. However, the unsaturated group-containing organopolysiloxane (B) and the epoxy group-containing organopolysiloxane (B) according to an embodiment of the present invention have a temperature lower than the curing temperature of the mixture of the organopolysiloxane containing (A) the unsaturated group and the organosilicon compound , The crosslinking reaction is inhibited, whereby the storage stability of the composition is enhanced and the composition can be used as a one-component composition.

Specifically, the total number of moles of the unsaturated groups in the organopolysiloxane (A) containing an unsaturated group and the epoxy-containing organopolysiloxane (A) and the number of moles of Si-H in the organosilicon compound containing an Si-H group 2 to 1: 0.5: 1, specifically 0.9: 1 to 1.1: 1. The organic sealing layer for sealing an organic light emitting element can be formed within the above range, the storage stability of the composition can be enhanced, The organic light emitting device can have long term reliability.

(B) The organopolysiloxane may be an organopolysiloxane containing at least one unsaturated group and at least one epoxy group in a molecule. Specifically, (B) the organopolysiloxane can be represented by the following formula (1):

≪ Formula 1 >

^{_{(R 21 SiO 3/2)}} a (R 22 SiO 3/2) b (R 23 R 24 SiO 2/2) c

(Wherein R ²¹ represents an alkenyl group having 2 to 10 carbon atoms, R ²² represents an aryl group having 6 to 10 carbon atoms, R ²³ and R ²⁴ each independently represent an aryl group having 6 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms Wherein 0 <a <1, 0 <b <1, 0 <c <1 and a + b + b is an organic group containing an alkyl group, an epoxy group or an epoxy group, at least one of R ²³ and R ²⁴ is an epoxy group or an epoxy group- c = 1)

The "epoxy group-containing organic group" may be a glycidoxin group, an alkyl group having 1 to 5 carbon atoms having an epoxy group, or an alkyl group having 1 to 5 carbon atoms having a glycosidic group.

(B) organopolysiloxane may further comprise a SiO _4/2 units and _{^{R 4 R 5 R 6 SiO 1}} /2 units. Each of R ⁴ , R ⁵ and R ⁶ may independently be an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an epoxy group, or an epoxy group-containing organic group.

The organopolysiloxane (B) may have a weight average molecular weight in terms of polystyrene calculated by gel permeation chromatography (GPC) of 1,000 to 10,000 g / mol, specifically 1,500 to 5,000 g / mol, and the storage stability of the composition And the sealed organic light emitting device can have long term reliability.

(B) the organopolysiloxane is used in an amount of 1 to 30% by weight, specifically 2 to 15% by weight, specifically 5 to 10% by weight, more specifically 5, 6, 7, 8, 9, or 10% by weight, the storage stability of the composition can be increased within the above range, and the sealed organic light emitting device can have long-term reliability.

(A) organopolysiloxane is one group one or more unsaturated organopolysiloxane having in a ^{molecule, (A1) R 7 R 8} R 9 SiO 1/2 3 -D (mesh) with the units and R ¹⁰ SiO _3/2 units the structure of the ^{organopolysiloxane, (A2) R 11 R 12} R 13 SiO 1/2 units and R ¹⁴ R ¹⁵ SiO _2/2 organopolysiloxane of straight-chain having a unit, (A3) one or more of the cyclic siloxane compound or Mixtures of these may be used. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ is one or more of the groups may be alkenyl of 2 to 10 carbon atoms. More specifically, at least one of R ⁷ , R ⁸ and R ⁹ may be a vinyl group, and R ¹⁰ may be an aryl group having 6 to 10 carbon atoms. In the ^{above, R 11, R 12, R} 13, R 14, R 15 can be an aryl group having 1 to 10 carbon alkyl group, a C2 to 10 alkenyl group, or a 6 to 10 carbon atoms of, R ^11, R ¹² , ^At least one of R ¹³ , R ¹⁴ and R ¹⁵ may be an alkenyl group having 2 to 10 carbon atoms. More specifically, at least one of R ¹¹ , R ¹² and R ¹³ may be a vinyl group, and R ¹⁴ and R ¹⁵ may be an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

In (A) the organopolysiloxane having a three-dimensional ^{structure, R 7 R 8 R 9 SiO} 1/2 units: R ¹⁰ the number of moles of SiO _3/2 units is from 1: 1 to 1: 100, particularly 1: 5 to 1: 20, more specifically from 1: 6 to 1:10, and the organic sealing layer for sealing an organic light emitting element can be formed within the above range. In a straight-chain (A) ^{organopolysiloxane, R 11 R 12 R 13 SiO} 1/2 units: R ¹⁴ R ¹⁵ the number of moles of SiO _2/2 units is from 1: 1 to 1: 100, particularly 1: 5 to 1: 20, more specifically from 1: 6 to 1:10, and the organic sealing layer for sealing an organic light emitting element can be formed within the above range.

In one embodiment, the organopolysiloxane of the (A1) three-dimensional structure can be represented by the formula (2)

(2)

^{(R 25 R 26 R 27 SiO} 1/2) d (R 28 SiO 3/2) e

(Wherein R ²⁵ , R ²⁶ and R ²⁷ are an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one of R ²⁵ , R ²⁶ and R ²⁷ is an alkenyl group having 2 to 10 carbon atoms 0 <d <1, 0 <e <1, and d + e = 1), and R ²⁸ is an aryl group having 6 to 10 carbon atoms.

In one embodiment, the straight chain organopolysiloxane (A2) can be represented by the formula (3)

(3)

^{(R 29 R 30 R 31 SiO} 1/2) f (R 32 R 33 SiO 2/2) g

(Wherein R ²⁹ , R ³⁰ and R ³¹ are an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one of R ²⁹ , R ³⁰ and R ³¹ is an alkenyl group having 2 to 10 carbon atoms 0 &lt; g &lt; 1 and f + g = 1), wherein R &lt; ³² &gt; and R &lt; ³³ &gt; are an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

In one embodiment, the cyclic siloxane compound is a structure in which siloxane units are linked in the form of a ring, and it is possible to achieve the effect of adjusting the viscosity of the composition liquid to the target value or other property changes with respect to the encapsulation layer. Specifically, the cyclic organosilicon compound may contain at least one unsaturated group.

In embodiments, the cyclic siloxane compound is a cyclic siloxane compound having from 3 to 10 identical or different siloxane units linked together, such as cyclotrisiloxane, cyclotetrasiloxane, cyclopentasiloxane, A cyclohexasiloxane, a cycloheptasiloxane, or a cyclooctasiloxane may be combined with a vinyl group, an allyl group, or the like. For example, cyclic siloxane compounds can include tetravinyltetramethylcyclotetrasiloxane, derivatives prepared from tetravinyltetramethylcyclotetrasiloxane, derivatives prepared from tetramethylcyclotetrasiloxane, and the like .

In one embodiment, the (A3) cyclic siloxane compound may be represented by the formula (4): &lt; EMI ID =

&Lt; Formula 4 >

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _{6 ,} R _{7 and} R ₈ each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, , An allyl group, an allyloxy group, a vinyloxy group, or a group represented by the following formula (5)

&Lt; Formula 5 >

(Wherein, * is a connecting site to Si in the above formula (4)

R ₉ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms and R ₁₀ , R ₁₁ and R ₁₂ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, , An allyl group, an allyloxy group, or a vinyloxy group, X ₁ and X ₂ each independently represent a single bond, O, S, or NR (R is hydrogen or an alkyl group having 1 to 10 carbon atoms)

_{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R one or more of the ₈ is a vinyl group, an allyl group, an allyloxy group, a vinyloxy group, R _10, R _11, R ₁₂ of the one or more vinyl group formula 5, R _10, R _11, R ₁₂ is one or more of allyl group of the formula (V), R _10, R _11, R one or more of ₁₂ the allyloxy group formula (5), or R _10, R _11, R &lt; ₁₂ &gt; is a vinyloxy group.

The derivative can be prepared by a conventional method. For example, it can be prepared by converting an alkyl group in a tetravinyl tetraalkylcyclotetrasiloxane to a halogenated alkyl group and reacting a vinyl group or an allyl group-containing compound such as allyl alcohol, vinyl alcohol, etc. under a Karstedt platinum catalyst.

(A1) of the sum of (A) + (B) + (C) is 1 to 60% by weight, specifically 50 to 60% by weight, more specifically 50, 51, 52, 53, 54, 55, 56, , 59 or 60 wt%, (A2) 1 to 25 wt%, specifically 8 to 25 wt%, more specifically 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 1, 2, 3, 4, 5, 6, 7 weight%, more specifically 0 to 7 weight% %, And the organic sealing layer for encapsulating an organic light emitting element can be formed within the above range.

(A) the organopolysiloxane is present in an amount of from 20 to 80% by weight, specifically from 30 to 75% by weight, more specifically from 60 to 75% by weight, more particularly from 60 to 61% by weight, based on solids in (A) + , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75 weight%, and the organic sealing layer .

The organosilicon compound (C) is an organosilicon compound having at least one Si-H group in one molecule. The Si-H group is not particularly limited, but may be present at the terminal of the molecule or at the non-terminal end of the molecule. The Si-H group-containing organosilicon compound may be at least one of linear, cyclic, and three-dimensional structures.

Specifically, the organosilicon compound (C) may comprise the following structural formulas (6), (7) and (8)

(6)

&Lt; Formula 7 >

(8)

Wherein R _a , R _b , R _c , R _d , R _e , R _f , R _g and R _h are each independently selected from the group consisting of hydrogen, alkyl group, an aryl group, or a silyl oxy group having 6 to 20, R _a, R _b, R _c, R _d, R _e, R _f, R _g, R _h Lt; / RTI &gt; is hydrogen). The "silyloxy group" means an -Si-O- group having an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. That is, the Si-H group-containing organosilicon compound may contain the repeating unit represented by the formula (6), while the terminals may include the formulas (7) and (8).

Specifically, the Si-H group-containing organosilicon compound may be selected from the group consisting of compounds represented by any one of the following formulas (9) to (13) and oligomers of the following formula (14)

&Lt; Formula 9 >

&Lt; Formula 10 >

&Lt; Formula 11 >

&Lt; Formula 12 >

&Lt; Formula 13 >

&Lt; Formula 14 >

(In the formula (14), 0? X? 30, 0? Y? 40, 0? Z? 40, and Me is a methyl group).

(C) the organosilicon compound is contained in an amount of 10 to 50% by weight, specifically 15 to 30% by weight, more specifically 15, 16, 17, 18, 19, 20 , 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 weight percent.

In an embodiment, the composition comprises 20 to 80 parts by weight of the organopolysiloxane (A) containing unsaturated groups, 1 to 30 parts by weight of the unsaturated group and the epoxy group-containing organopolysiloxane (B) And 10 to 50 parts by weight of a silicon-silicon compound, and may contain a mixture of silicone compounds employing a hydrosilylation reaction in the above-mentioned range, and the rate of change in viscosity and the rate of change in permeability may be low even after storage for a long period of time.

The platinum catalyst may be represented by the following formula (15)

&Lt; Formula 15 >

Wherein X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms And Y ₁ , Y ₂ and Y ₃ are each independently an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms)

Specifically, the platinum catalyst may be trimethyl (methylcyclopentadienyl) platinum or the like, but is not limited thereto.

The platinum catalyst contained platinum in an amount of 100 parts by weight based on 100 parts by weight of the total solid content of the (A) unsaturated group-containing organopolysiloxane, (B) the unsaturated group and the epoxy-containing organopolysiloxane, and (C) 2 to 200 ppm is preferable, and it may be added to the composition to be 10 to 50 ppm. In this range, the rate of crosslinking and / or curing reaction can be sufficiently increased and the use of unnecessary catalysts can be avoided.

The composition for encapsulating an organic light emitting device may have a viscosity of from 100 to 10,000 cP, specifically from 600 to 3000 cP at 25 DEG C, and the ease of coating when sealing the organic light emitting device within the above range can be ensured.

As described above, the composition for encapsulating an organic luminescent element is a one-component composition in which an organopolysiloxane containing an unsaturated group and an organosilicon compound containing an Si-H group coexist, and can be thermally cured. Specifically, Can be thermally cured for 300 minutes.

The composition for encapsulating an organic light emitting diode according to an embodiment of the present invention contains an organopolysiloxane containing an unsaturated group and an epoxy group as described above, thereby lowering the rate of change in viscosity and the rate of change in transparency after storage for a predetermined period, . Specifically, the composition for encapsulating an organic luminescent element according to an embodiment of the present invention may have a viscosity change rate of 1 to 10%, specifically 2 to 6% in the following formula 1, and a transmittance change rate of -0.3 To -0.8%, and the storage stability of the composition for encapsulating an organic light emitting element and the long-term reliability of the organic light emitting device can be secured within the above range:

<Formula 1> Viscosity Change Rate = | (B-A) / A) | x 100

(Where A is the viscosity of the initial composition at 25 캜 and B is the viscosity of the composition measured after storage at 23 캜 and 43% relative humidity for 7 days at 25 캜)

(2) Transmittance change rate = (D-C) / C x 100

C is the transmittance at a wavelength of 589 nm for a specimen of 1 mm thickness prepared by thermosetting the composition at 150 캜 for 1 hour and D is a thickness of 1 mm prepared by thermally curing the composition at 150 캜 for 1 hour Of the specimen was allowed to stand at 85 DEG C and 85% relative humidity for 1000 hours, which was the transmittance at a wavelength of 589 nm)

Hereinafter, an OLED display device according to an embodiment of the present invention will be described with reference to FIG. 1 is a cross-sectional view of an OLED display device according to an embodiment of the present invention. 1, an organic light emitting diode display 100 includes a substrate 10, an organic light emitting diode 20 formed on the substrate 10, an organic light emitting diode 20, an inorganic encapsulation layer 31 And the organic encapsulation layer 32. The inorganic encapsulation layer 31 is in contact with the organic light emitting element 20. [

The substrate 10 may be formed of a transparent glass, a plastic sheet, a silicon or a metal substrate.

Although not shown in FIG. 1, the organic light emitting diode 20 includes a first electrode, a second electrode, and an organic light emitting layer formed between the first electrode and the second electrode , And the organic light emitting layer may be a layer in which a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are sequentially laminated.

The inorganic encapsulation layer 31 is made of metal; nonmetal; Oxides of metals, gold or mixtures thereof; Fluorides of metals, nonmetals, or mixtures thereof; Nitrides of metals, nonmetals or mixtures thereof; Carbides of metals, non-metals or mixtures thereof; Oxygen nitrides of metals, nonmetals or mixtures thereof; Borides of metals, non-metals or mixtures thereof; Silicides of metals, nonmetals or mixtures thereof; An alloy of two or more metals; The metal may include at least one of a metal and an alloy of a nonmetal, and the metal may be, but is not limited to, a metal, a metalloid, a transition metal, a lanthanide metal, or the like after the transition. For example, the metal may be silicon, aluminum, iron, nickel, or the like, the inorganic barrier layer is silicon oxide, silicon nitride, silicon oxygen nitride, ZnSe, ZnO, Sb ₂ O _3, Al ₂ O _3, In ₂ O ₃ , and SnO ₂ .

The organic encapsulation layer 32 is formed of a composition for encapsulating an organic light emitting diode according to the embodiments of the present invention. Specifically, the organic encapsulation layer 32 may be formed by a vacuum process such as sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance- Plasma vapor deposition, and combinations thereof, and thermoset at 100 to 200 占 폚 for 1 to 300 minutes.

In the barrier stack, the thickness of one of the organic sealing layers may be 0.1 占 퐉 to 20 占 퐉, for example 1 占 퐉 to 10 占 퐉, and the thickness of one inorganic encapsulating layer may be 5 nm to 500 nm, for example, 5 nm to 50 nm. The barrier stack may be a thin film encapsulant and have a thickness of 5 탆 or less, for example, 1.5 탆 to 5 탆. Within the above range, the long-term reliability of the organic light emitting device can be improved while sealing the organic light emitting device.

Although not shown in Fig. 1, the inorganic encapsulating layer and the organic encapsulating layer may be formed in a plurality of circuits, respectively. Specifically, the inorganic encapsulation layer and the organic encapsulation layer can be alternately deposited, such as an inorganic encapsulation layer / an organic encapsulation layer / an inorganic encapsulation layer / an organic encapsulation layer. Preferably, the inorganic encapsulating layer and the organic encapsulating layer may be contained in a total of 10 or less (e.g., 2-10 layers), more preferably 7 or less (e.g., 2-7 layers).

2 is a cross-sectional view of an OLED display device according to another embodiment of the present invention. 2, the organic light emitting diode display 200 includes a substrate 10, an organic light emitting diode 20 formed on the substrate 10, an organic light emitting diode 20, an inorganic encapsulation layer 31, And an organic encapsulation layer 32. The inorganic encapsulation layer 31 can seal the internal space 40 in which the organic light emitting element 20 is accommodated. Except that the inorganic sealing layer 31 is spaced apart from the organic light emitting diode 20 at a predetermined distance to seal the internal space 40 in which the organic light emitting diode 20 is accommodated. It is the same as the display device.

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

Manufacturing example  One: Unsaturated group  contain Organopolysiloxane  Produce

219.3 g (1.1 mol) of toluene, 5.0 g (0.06 mol) of tetramethylammonium hydroxide and 31.9 g (1.8 mol) of distilled water were added to a 1 L three-necked flask under nitrogen atmosphere. Then, 219.3 g (1.1 mol) of phenyltrimethoxysilane was added dropwise over 2 hours while maintaining the temperature at 25 ° C. After the dropwise addition was completed, the mixture was stirred for 1 hour. Subsequently, methanol as a by-product was removed by using Deanstock at 75 DEG C, the water was removed to an internal temperature of 110 DEG C, 40.0 g (0.3 mol) of chlorodimethylvinylsilane was added, and the reaction was carried out for 10 hours . Subsequently, 200 g of distilled water was added thereto and washed 10 times. Subsequently, toluene and volatile components were removed under a reduced pressure of 120 ° C to obtain a compound represented by the formula (2a).

(2a)

_{(Me 2 ViSiO 1/2)} 0.1 (PhSiO 3/2) 0.9

(In Formula 2a, Me is a methyl group, Vi is a vinyl group, and Ph is a phenyl group).

Manufacturing example  2: Unsaturated group  contain Organopolysiloxane  Produce

266.9 g (1.5 mol) of dimethoxymethylphenylsilane, 4.1 g (0.07 mol) of KOH and 29.0 g (1.6 mol) of distilled water were added to a 1 L three-necked flask under nitrogen atmosphere. Subsequently, the mixture was stirred at 75 ° C for 2 hours, methanol was removed using Deanstock, 200 g of toluene and 200 g of distilled water were added thereto, and the mixture was washed 10 times. Then, water was removed therefrom until the internal temperature reached 110 ° C. Subsequently, 8.8 g (0.07 mol) of chlorodimethylvinylsilane was added thereto, stirred at 50 ° C for 2 hours, and then 200 g of distilled water was added thereto, followed by washing 10 times. Subsequently, toluene and volatile components were removed under a reduced pressure at 90 ° C to obtain a compound represented by the formula (3a).

[Chemical Formula 3]

_{(Me 2 ViSiO 1/2)} 0.1 (PhMeSiO 2/2) 0.9

(In the above formula (3a), Me is a methyl group, Vi is a vinyl group, and Ph is a phenyl group).

Manufacturing example  3: Unsaturated group  And an epoxy group-containing Organopolysiloxane  Produce

A 1 L three-necked flask was charged with 198.3 g (1.0 mol) of phenyltrimethoxysilane, 59.3 g (0.4 mol) of vinyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, (0.1 mol) of KOH and 36.0 g (2.0 mol) of distilled water under nitrogen atmosphere. Methanol as a by-product was removed by using Dean Stark at 75 캜, and the water was removed by setting the internal temperature to 110 캜. After cooling to room temperature, 200 g of toluene and 200 g of distilled water were added and the mixture was washed 10 times. Then toluene and volatile components were removed under a reduced pressure of 120 ° C to obtain a compound represented by the formula (Ia).

[Formula 1a]

_{(ViSiO 3/2) 0.2 (} PhSiO 3/2) 0.5 (GpMeSiO 2/2) 0.3

(In the formula (1a), Me is a methyl group, Vi is a vinyl group, Ph is a phenyl group, and Gp is a 3-glycidoxypropyl group)

(A) an organopolysiloxane containing an unsaturated group: (A1) an organopolysiloxane of Production Example 1, (A2) an organopolysiloxane of Production Example 2, (A3) 1,3,5,7-tetravinyl- 5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (Gelest).

(B) Organopolysiloxane containing an unsaturated group and an epoxy group: The organopolysiloxane of Production Example 3

(C) Organosilicon compound containing Si-H group: phenyltris (dimethylsiloxy) silane (Gelest)

Platinum (IV) (trimethyl (methylcyclopentadienyl) platinum, Sigma-Aldrich), (D2) Pt-CS-1.8CS (Umicore)

Example  1 to 4 and Comparative Example  1 to 2

An organopolysiloxane containing an unsaturated group without an solvent, an organopolysiloxane containing an unsaturated group and an epoxy group, an organohydrogenpolysiloxane containing an Si-H group, and a platinum catalyst were mixed in the contents (unit: parts by weight) To prepare a sealing composition.

Example Comparative Example One 2 3 4 One 2  Unsaturated group-containing organopolysiloxane (A1) 50 60 50 50 50 50 (A2) 18 8 13 25 23 18 (A3) 7 7 7 - 7 7 Unsaturated group and epoxy group-containing organopolysiloxane 5 5 10 5 - 5 The Si-H group-containing organosilicon compound 20 20 20 20 20 20 Platinum catalyst (D1) 20 ppm 20 ppm 20 ppm 20 ppm 20 ppm - (D2) - - - - - 3.5 ppm

The following properties of the compositions prepared in Examples and Comparative Examples were evaluated, and the results are shown in Table 3 below.

Property evaluation method

1. Curing rate: 7 g of the composition was put into a mold of 190 mm x 280 mm (width x length), and then cured at 150 ° C for 1 hour. The reaction heat was measured using a differential scanning calorimeter (model name Q1000, TA instruments) for the liquid composition before curing and the cured specimens. The measurement conditions were as follows: the temperature was raised to 250 ° C at a rate of 10 ° C / min under N ₂ gas Respectively. The curing rate was obtained from the following formula 3 using the heat of reaction before curing and after curing.

<Formula 3> Cure rate (%) = | 1 - (reaction heat after curing / reaction heat before curing) | x 100

2. TGA weight loss ratio: In the above 1 hardening rate measurement, the cured specimens were subjected to thermogravimetric analysis (TGA) through Q5000 of TA instruments under the isothermal condition of 150 ° C for 2 hours.

3. Viscosity and viscosity change rate: Measured with a Brookfield DV-III ultra rheometer (Model DV3TLV). The viscosity (A, unit: cP) of the initial composition was measured at 25 캜. The composition was stored for 7 days in a space maintained at 23 캜 and 43% relative humidity, and then the viscosity (B, unit: cP) was measured at 25 캜 in the same manner. The viscosity change rate was obtained from the following equation 1 using A and B:

<Formula 1> Viscosity Change Rate = | (B-A) / A) | x 100

(Where A is the viscosity of the initial composition at 25 캜 and B is the viscosity of the composition measured after storage at 23 캜 and 43% relative humidity for 7 days at 25 캜)

4. Adhesion force: The adhesive force was measured in the same manner as the method of measuring the die shear strength as a method for measuring the adhesion between the glass and the cured product. The force to peel the upper glass from the side was measured with an adhesive force measuring instrument Dage series 4000PXY at a force of 200 kgf at 25 ° C. The lower glass was coated with the silicone composition and the upper glass was covered and cured at 150 ° C for 1 hour. The size of the lower glass was 2 cm x 2 cm x 1 mm (width x length x thickness), and the size of the upper glass was 1.5 cm x 1.5 cm x 1 mm (width x length x thickness) Respectively.

5. Transmittance: The composition was injected into a mold using a syringe, and cured at 150 ° C for 1 hour to form a cured product having a thickness of 1 mm. The transmittance at a wavelength of 589 nm was measured using a UV spectrometer (Shimazu UV-3600) Respectively. Then, the cured specimens were allowed to stand at 85 ° C and 85% RH for 1000 hours, and the permeability was measured in the same manner.

6. Device Reliability: A green OLED device with a size of 2 mm x 2 mm (width x length) was coated on the sealing glass with the composition applied and cured on top of it, and the sealing glass was attached between the sealing glass and the lower substrate. Reliability was determined by observing the number of dark spots generated inside the device under a microscope while the prepared package was left at 85 ° C and 85% relative humidity for 1000 hours. The reliability score was evaluated based on the number of dark spots as shown in Table 2 below.

Dark spot count Reliability score none 5 points 1 to 2 4 points 3 to 5 3 points 6 to 7 2 points 8 to 10 1 point Greater than 10 0 point

Example Comparative Example One 2 3 4 One 2 Curing rate (%) 100 100 100 100 100 100 TGA weight loss (%) 0.01 0.01 0.01 0.01 0.01 0.01 Viscosity Initial viscosity (cP) 690 960 700 2800 700 690 After 7 days the viscosity (cP) 730 1020 740 2980 870 2260 Viscosity change rate (%) 6 6 6 6 24 228 Adhesion (kgf / mm ² ) 45 43 52 46 29 42 Permeability Initial permeability (%) 99.9 99.9 99.9 99.9 99.9 99.9 Transmittance (%) after 1000 hours 99.4 99.2 99.6 99.5 91.6 99.2 Device reliability 5 points 5 points 5 points 5 points 2 points 5 points

As shown in Table 3, even though the composition for encapsulating an organic luminescent element of the present invention has a high curing rate even after being stored for a predetermined period, even if it is a single-component type containing an organopolysiloxane containing an unsaturated group and an organosilicon compound containing an Si- Low change in transmittance, and high reliability of the device when the sealing material of the organic light emitting device is applied.

On the other hand, Comparative Example 1 which did not contain an unsaturated group and an epoxy group-containing organopolysiloxane showed a high rate of change in viscosity and a low device reliability compared to the present invention, and Comparative Example 2 containing a conventional platinum catalyst also had a high rate of change in viscosity .

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

100, 200: organic light emitting diode display device,
10: substrate, 20: organic light emitting device, 30: barrier stack, 40: inner space
31: inorganic encapsulating layer, 32: organic encapsulating layer

Claims (10)

(A) an organopolysiloxane containing an unsaturated group,
(B) an unsaturated group represented by the following formula (1) and an organopolysiloxane containing an epoxy group,
(C) an Si-H group-containing organosilicon compound, and
(D) a platinum catalyst of the following formula (15):
&Lt; Formula 1 >
(R ²¹ SiO _3/2 ) a (R ²² SiO _3/2 ) b (R ²³ R ²⁴ SiO _2/2 ) c
(Wherein R ²¹ represents an alkenyl group having 2 to 10 carbon atoms, R ²² represents an aryl group having 6 to 10 carbon atoms, R ²³ and R ²⁴ each independently represent an aryl group having 6 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms Wherein 0 <a <1, 0 <b <1, 0 <c <1 and a + b + b is an organic group containing an alkyl group, an epoxy group or an epoxy group, at least one of R ²³ and R ²⁴ is an epoxy group or an epoxy group- c = 1,
&Lt; Formula 15 &gt;

X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms , Y ₁ , Y ₂ , and Y ₃ are each independently an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The positive resist composition according to claim 1, wherein the organopolysiloxane (A) contains 20 to 80 parts by weight of the organopolysiloxane, the organopolysiloxane (B) contains 1 to 30 parts by weight of an unsaturated group and an epoxy group- Containing organosilicon compound is contained in an amount of 10 to 50 parts by weight. The organopolysiloxane composition according to claim 1, wherein the organopolysiloxane (A) contains at least one unsaturated group-containing organopolysiloxane having a three-dimensional structure, an unsaturated group-containing organopolysiloxane having a linear structure, and a cyclic unsaturated group- By weight based on the total weight of the composition. 4. The composition for encapsulating an organic electroluminescence device according to claim 3, wherein the organopolysiloxane containing an unsaturated group of the three-dimensional structure is represented by the following formula (2)
(2)
(R ²⁵ R ²⁶ R ²⁷ SiO _1/2 ) d (R ²⁸ SiO _3/2 ) e
(Wherein R ²⁵ , R ²⁶ and R ²⁷ are an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one of R ²⁵ , R ²⁶ and R ²⁷ is an alkenyl group having 2 to 10 carbon atoms 0 <d <1, 0 <e <1, and d + e = 1), and R ²⁸ is an aryl group having 6 to 10 carbon atoms. 4. The organic electroluminescent device encapsulating composition according to claim 3, wherein the organopolysiloxane having an unsaturated group in the linear structure is represented by the following formula (3)
(3)
(R ²⁹ R ³⁰ R ³¹ SiO _1/2 ) f (R ³² R ³³ SiO _2/2 ) g
(Wherein R ²⁹ , R ³⁰ and R ³¹ are an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one of R ²⁹ , R ³⁰ and R ³¹ is an alkyl group having 2 to 10 carbon atoms group and, R ^32, R ³³ is an alkyl group or an aryl group having 6 to 10 carbon atoms having 1 to 10 carbon atoms, and 0 <f <1, 0 < g <1, f + g = 1). The composition for encapsulating an organic light emitting device according to claim 3, wherein the cyclic unsaturated group-containing siloxane compound comprises tetravinyltetramethylcyclotetrasiloxane. The composition according to claim 1, wherein the number of moles of unsaturated groups in the organopolysiloxane (B) and the epoxy-containing organopolysiloxane and the unsaturated group-containing organopolysiloxane (C) in the organosilicon compound -H in a molar ratio of 2: 1 to 0.5: 1. The catalyst according to claim 1, wherein the platinum catalyst is a solid component 100 (A) of an organopolysiloxane containing an unsaturated group (A), an organopolysiloxane (B) containing an unsaturated group and an epoxy group, and an organosilicon compound And a platinum content of 2 to 200 ppm on a weight basis. The composition according to claim 1, wherein the composition for encapsulating an organic luminescent element is a thermosetting composition. A light emitting device comprising: a substrate; an organic light emitting device formed on the substrate; and a barrier stack formed on the organic light emitting device and including an inorganic encapsulation layer and an organic encapsulation layer,
Wherein the organic sealing layer is formed of the composition for encapsulating an organic light emitting diode according to any one of claims 1 to 9.

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