KR101768309B1 - Composition for encapsulating display member, sealing layer comprising the same, and display apparatus comprising the same - Google Patents

Abstract

There is provided a sealing material composition for a display member comprising ladder-type polysilsesquioxane and a radical initiator, and a display device manufactured using the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a sealing material composition for a display member, a sealing layer containing the sealing material, and a display device including the sealing material.

The present invention relates to a sealing material composition for a display member, a sealing layer comprising the same, and a display device comprising the same.

An organic electroluminescent device used in an optical display device is likely to suffer deterioration or deterioration of characteristics due to the influence of environment such as moisture or gas. Specifically, the interface between the metal electric field and the organic luminescent layer may be peeled off due to moisture, the metal may be highly resisted by oxidation of the metal, the organic material itself may be denatured by moisture or oxygen, The organic material and the electrode material may be oxidized to lower the light emitting property of the organic electroluminescent device. Therefore, the organic electroluminescent device should be sealed by a sealing composition which protects it from moisture or oxygen.

A method of forming an organic electroluminescent device on a lower substrate and an upper substrate facing the lower substrate so as to face the organic electroluminescent device and sealing the upper substrate and the lower substrate is used for such encapsulation.

The background art of the present invention is disclosed in Korean Patent Laid-Open Publication No. 2008-0065582.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a composition of a display seal material capable of reducing the generation of outgas and occurrence of dark spots.

Another problem to be solved by the present invention is to provide a composition for a display sealing material which has a high curing density and low outgassing amount and can reduce occurrence of dark spots.

Another object to be solved by the present invention is to provide a composition for a display sealing material having a significantly low moisture permeability and oxygen permeability.

Another object of the present invention is to provide a composition of a display seal material which can protect the device from the influence of environment including moisture and gas so as to impart storage stability to the device.

Another problem to be solved by the present invention is to provide a composition of a display seal material capable of reducing an outgassing occurring early due to a rapid reaction rate.

Another object of the present invention is to provide a composition for a display sealing material having excellent stability at room temperature and excellent storage stability without containing a reaction inhibitor.

Another object of the present invention is to provide a display device including a cured product of a composition of a display sealing material of the present invention.

The sealing material composition of the display member of the present invention comprises a ladder-type polysilsesquioxane and a radical initiator, and can be one-pack type.

The display device of the present invention includes a display member and a sealing layer formed on the display member, and the sealing layer may be formed of a sealing material composition of the display member.

The composition of the present invention can realize a display sealing material capable of reducing the occurrence of outgas and occurrence of dark spots in a display device.

The composition of the present invention can realize a display sealing material having a high curing density and a low outgassing amount and capable of reducing occurrence of dark spots.

The composition of the present invention can realize a display sealing material capable of remarkably reducing moisture permeability and oxygen permeability.

The composition of the present invention can protect the display from the effects of the environment including moisture and gas, thereby giving the display stability over time.

The composition of the present invention is capable of reducing the outgassing occurring early due to the fast reaction rate.

The composition of the present invention is excellent in stability at room temperature and can be excellent in storage stability without containing a reaction inhibitor.

1 is a cross-sectional view of a display device according to an embodiment of the present invention.
2 is a cross-sectional view of a display device according to another embodiment of the present invention.
3 (a) and 3 (b) are photographs showing cracks due to shrinkage of the sealing layer formed of the composition of Comparative Example 3.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings. However, the techniques disclosed in this application are not limited to the embodiments described herein but may be embodied in other forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the widths and thicknesses of components are slightly enlarged in order to clearly illustrate each component. In addition, although only a part of the components is shown for convenience of explanation, those skilled in the art can easily grasp the rest of the components. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention.

The terms "upper" and "lower" in this specification are defined with reference to the drawings, wherein "upper" may be changed to "lower", "lower" What is referred to as "on" may include not only superposition, but also intervening other structures in the middle. On the other hand, what is referred to as "directly on" or "directly above"

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

As used herein, unless otherwise defined, at least one hydrogen atom of the functional group is replaced by a halogen (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, an imino group is an alkyl group of C1 to C10), an amino group _{(-NH 2, -NH (R '} ), - N (R ") (R"'), R ', R ", R"' is C1 to carbon atoms are each independently A C1 to C20 alkyl group, a C6 to C30 aryl group, a C3 to C30 cycloalkyl group, a C3 to C30 heteroaryl group, or a C2 to C30 alkyl group), an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group, ≪ / RTI > of a heterocycloalkyl group.

As used herein, "hetero" means that a carbon atom is substituted with any one atom selected from the group consisting of N, O, S and P.

In the present specification, "Shore A hardness" for the sealing material composition is defined as the ratio of the thickness of the sealing material composition to the thickness of the sealing material composition of 7 mm to 10 mm thickness on the release film, thermosetting at 100 ° C for 1 hour, Shore A Measured at 25 ° C using a hardness tester.

In this specification, the term "display member" may mean an organic light emitting diode (OLED), a flexible organic light emitting diode, a light emitting diode (LED), a light instrument,

Hereinafter, a sealing material composition for a display member according to an embodiment of the present invention will be described.

The sealing material composition of the display member of one embodiment of the present invention may include a ladder type polysilsesquioxane and a radical initiator.

The ladder-type polysilsesquioxane does not shrink during curing and can stably seal the display member, thereby protecting the display member from the influence of the environment including gas such as moisture and / or oxygen. The radical initiator can cure the ladder-type polysilsesquioxane. The sealing material composition of the display member of the embodiment of the present invention includes the ladder-type polysilsesquioxane and the radical initiator to reduce the generation of outgas and occurrence of dark spots, and is excellent in stability at room temperature, It can be used in liquid form.

The ladder-type polysilsesquioxane and the radical initiator are different from each other.

Hereinafter, the ladder-type polysilsesquioxane and the radical initiator will be described in detail.

The ladder-type polysilsesquioxane can be cured to form the sealing layer of the display member. The ladder-type polysilsesquioxane may have at least one curable functional group. The curable functional group may be directly connected to silicon (Si) in the ladder-type polysilsesquioxane, or may be connected to silicon (Si) in the ladder-type polysilsesquioxane through an arbitrary connecting group. The curable functional group may include at least one of a vinyl group and a (meth) acrylate group.

The ladder-type polysilsesquioxane may contain 5 to 35 mol%, in particular 15 to 25 mol%, of a curable functional group. Within the above range, the sealing material composition of the display member is excellent in reactivity and curing rate, so that a sealing layer having a high hardening density can be formed, and a desired hardness can be secured to form a sealing layer free from cracks.

Ladder type polysilsesquioxane is to to units of formula (1) formula (2) and below, and include the general formula ^{3 R 1, R 2, R} 3, R 4, R 5, R 6, R 7, R 8, R ⁹ , and R ¹⁰ may be a vinyl group, a (meth) acrylate group, or * -OZY (*, Z and Y are as defined below)

≪ Formula 1 >

(In the formula 1,

* Is the connecting site of the element,

R ¹ , R ² , R ³ and R ⁴ each independently represent an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms An alkyl group having 1 to 10 carbon atoms having an alicyclic epoxy group having 5 to 10 carbon atoms, a vinyl group, a (meth) acrylate group, or * -OZY (wherein * denotes a connecting site of an element, Z denotes a substituted or unsubstituted An alkylene group having 1 to 10 carbon atoms, and Y is a vinyl group or a (meth) acrylate group)

n and m are each independently an integer of 1 to 10,

R ^a , R ^b , R ^c and R ^d each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, 20 < / RTI >

p1 and p2 are each independently an integer of 0 to 5)

(2)

(3)

(In the above formulas 2 and 3,

* Is the connecting site of the element,

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, A substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a vinyl group, a (meth) acrylate group or * -OZY Y is a vinyl group or a (meth) acrylate group).

Specifically, R ¹ , R ² , R ³ , and R ⁴ in Formula 1 may be an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. More specifically, R ¹ , R ² , R ³ , and R ⁴ in Formula 1 may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a phenyl group, or a naphthyl group.

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, -OZY, and at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may be * -OZY.

The ladder-type polysilsesquioxane may have a number average molecular weight (Mn) of 1,000 to 100,000, specifically 1,000 to 5,000. Within the above range, the viscosity of the display sealing material composition may be suitable for use as a sealing material.

The ladder-type polysilsesquioxane may be contained in an amount of 20% by weight to 99.9% by weight, for example, 30% by weight to 99.9% by weight, for example, 55% by weight to 99.9% by weight in the solid content based display sealant composition. In the above range, the display sealant composition is excellent in reactivity and curing rate, cracks may not be generated in the sealing layer, occurrence of outgas and occurrence of dark spots in the display device may be reduced, and water permeability and oxygen permeability may be remarkably low A sealing layer can be formed.

Hereinafter, a method for producing ladder-type polysilsesquioxane will be described.

In one embodiment, the ladder-type polysilsesquioxane is obtained by hydrolysis and condensation of a silicone monomer mixture comprising a silicone monomer represented by the following formula (4) and a silicone monomer represented by the following formula (5), and subjecting the resultant hydrolysis and condensation reaction product to a curing functional group Lt; / RTI > with a donating compound:

≪ Formula 4 >

(Wherein R ¹¹ represents an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 10 carbon atoms Of an alkyl group having 1 to 10 carbon atoms and having an alicyclic epoxy group,

R ¹² , R ¹³ and R ¹⁴ are each independently a substituted or unsubstituted C 1 -C 5 alkoxy group or hydroxyl group),

≪ Formula 5 >

(Wherein R ¹⁵ and R ¹⁶ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted group having 6 to 20 carbon atoms Lt; / RTI >

R ¹⁷ and R ¹⁸ are each independently a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms or a hydroxyl group).

The mixture of silicone monomers may comprise at least one silicone monomer of formula (4) and at least one silicone monomer of formula (5).

The silicone monomer represented by the formula (4) is a trialkoxysilane, and specifically includes at least one of methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane . The silicone monomer of formula (5) may specifically include diphenylsilanediol and the like.

The hydrolysis and condensation reaction of the silicone monomer mixture can be carried out in a conventional manner. Hydrolysis can comprise reacting the silicone monomer mixture in a desired solvent and at least one of the desired acid and base. Specifically, the solvent may include water and an organic solvent such as propylene glycol monomethyl acetate (PGMEA). Specifically, the acid is strong acid such as HCl, HNO ₃ , and the base may be NaOH, KOH, or the like as a strong base. The hydrolysis can be carried out at 20 ° C to 100 ° C for 10 minutes to 7 hours. Within this range, the hydrolysis efficiency of the silicon monomers of the formula (4) and the silicon monomers of the formula (5) can be increased. The condensation reaction can be carried out at 20 캜 to 100 캜 under the same conditions as hydrolysis for 10 minutes to 7 hours. Within the above range, the condensation reaction efficiency of the hydrolyzate of the silicone monomer represented by the formula (4) and the silicone monomer represented by the formula (5) can be enhanced.

The hydrolysis and condensation reaction product of the silicone monomer mixture may react with the curable functional group-providing compound to form a ladder-type polysilsesquioxane having at least one curable functional group. The curable functional group-providing compound may include a compound having a functional group capable of reacting with the hydroxyl group formed by the hydrolysis and condensation reaction of the silicone monomer in the product, such as an epoxy group or a glycidyl group and a curable functional group. Specifically, the curable functional group-providing compound may comprise at least one of glycidyl (meth) acrylate, allyl glycidylether. The reaction may be carried out at 30 ° C to 100 ° C for 1 hour to 10 hours. Within this range, ladder-type polysilsesquioxane having a curable functional group can be produced with high yield. A catalyst such as triphenylphosphine may be further added to increase the reaction yield or increase the reaction rate.

Hereinafter, the radical initiator will be described.

The radical initiator can cure the ladder-type polysilsesquioxane to facilitate the formation of the sealing layer. Radical initiators can catalyze curing by generating radicals by heat. The radical initiator may comprise conventional radical initiators. Specifically, the radical initiator may be at least one selected from the group consisting of azo, peroxy, phosphorus, triazine, acetophenone, benzophenone, thioxanthone, , Benzoin-based, oxime-based, and the like. When the azo-based radical initiator is used, the curing rate may be higher in the curing condition described below.

The radical initiator may be included in an amount of 0.01 to 7 parts by weight, specifically 0.1 to 3 parts by weight based on 100 parts by weight of the ladder-type polysilsesquioxane. The polymerization can sufficiently take place within the above range and the permeability of the sealing layer can be prevented from being lowered due to the remaining unreacted initiator.

The sealing material composition of the display member may form a sealing layer having a Shore A hardness of 25 to 40, specifically 30 to 35. [ In the above range, cracks are less likely to occur, the shock to the external pressure can be absorbed, and the dark spot can be small.

The sealing material composition of the display member may have a viscosity change rate of less than 10%, specifically 0.01% to 9.5%, in the following formula (1). Within the above range, the stability at room temperature is good and the storage time may be long. Even if used as a single-component composition, the processability and storage stability may be high

<Formula 1>

Viscosity change rate = (B - A) / A x 100

(Unit: cps) of 1 g of the display sealing material composition at 25 ° C, B is the viscosity (unit: cps) of the display sealing material composition at 25 ° C after storing 1 g of the display sealing composition at 25 ° C for 7 days, to be).

Hereinafter, the sealing material composition of the display member according to another embodiment of the present invention will be described.

The sealing material composition of the display member of another embodiment of the present invention may contain a ladder-type polysilsesquioxane, a radical initiator, and a siloxane resin (hereinafter may be referred to as a siloxane resin) in D units having at least one curable functional group . Is substantially the same as the display sealing material composition according to one embodiment of the present invention except that it further comprises a siloxane resin. The siloxane resin will be described below.

The ladder-type polysilsesquioxane, the radical initiator, and the siloxane resin are different from each other.

The sealing material composition of the display member of this embodiment may further include a siloxane resin. As a result, the sealing material composition of the display member may have a high reaction rate and may reduce the initial outgassing amount.

The siloxane resin may comprise a linear siloxane resin in D units. The siloxane resin may contain one or more D units.

The siloxane resin may have at least one curable functional group. The curable functional group may be directly connected to silicon (Si) in the siloxane resin, or may be connected to silicon (Si) in the siloxane resin via an arbitrary connecting group. The curable functional group may include at least one of a vinyl group and a (meth) acrylate group.

The siloxane resin may contain 20 to 60 mol%, specifically 30 to 40 mol% of a curable functional group. Within this range, it is possible to form a sealing layer having excellent reactivity and curing rate, having a desired hardness and having a low crack occurrence, and the initial outgassing amount can be remarkably reduced.

In one embodiment, the siloxane resin may be represented by the following formula:

(6)

(6)

R ¹⁹ , R ²⁰ , R ²¹ , R ²³ , R ²⁴ and R ²⁶ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, (Meth) acrylate group, and at least one of R ¹⁹ , R ²⁰ , R ²¹ , R ²³ , R ²⁴ and R ²⁶ is a vinyl group or a (meth) acrylate group Lt; / RTI &gt;

R ²² and R ²⁵ are each independently an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group,

and j is an integer of 1 to 10).

Specifically, R ¹⁹ and R ²⁰ each independently represent an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group. R ^21, R ^23, R ^24, and R ²⁶ is an aryl group, or a vinyl group of the alkenyl group of the alkyl group having 1 to 10 carbon atoms, having 3 to 10 carbon atoms, having a carbon number of 6 to 20, R ^21, R ^23, R ^24, And R &lt; ²⁶ &gt; may be a vinyl group. At this time, it is possible to form a sealing layer having excellent reactivity and curing rate, having a desired hardness and having a low crack occurrence, and the initial outgassing amount can be remarkably reduced.

Specifically, the siloxane resin may include a polydimethylsiloxane having at least one of a vinyl group and a (meth) acrylate group (when all of R ¹⁹ and R ²⁰ in the formula (6) are methyl groups) resin.

The siloxane resin may have a number average molecular weight (Mn) of 1,000 to 100,000. Within this range, the viscosity of the composition may be suitable for use as a sealant.

The siloxane resin may be included in an amount of 5 to 80 parts by weight, specifically 20 to 70 parts by weight, more specifically 30 to 70 parts by weight, based on 100 parts by weight of the ladder-type polysilsesquioxane. Within the above range, the sealing layer having excellent reactivity and curing rate and securing a desired hardness and having a low crack occurrence can be formed.

The sealing material composition for a display member may include 50 to 100 parts by weight of ladder-type polysilsesquioxane and 0 to 50 parts by weight of siloxane resin in 100 parts by weight of the total of ladder-type polysilsesquioxane and siloxane resin have. Within the above range, a desired hardness can be secured and a sealing layer free from cracks can be obtained.

The radical initiator is added in an amount of 0.01 to 7 parts by weight, specifically 0.01 to 4 parts by weight, more specifically 0.1 to 3 parts by weight, relative to 100 parts by weight of the total of the ladder-type polysilsesquioxane and siloxane resin . The polymerization can sufficiently take place within the above range and the permeability of the sealing layer can be prevented from being lowered due to the remaining unreacted initiator. In addition, specific details of the radical initiator are the same as those described for the display sealant composition of the present invention.

Hereinafter, a sealing material composition for a display member according to another embodiment of the present invention will be described.

The display sealant composition according to another embodiment of the present invention may include ladder-type polysilsesquioxane, a radical initiator, and an antioxidant. By further including an antioxidant, the thermal stability of the sealing material composition and the sealing layer of the display member can be improved.

The antioxidant may include, but is not limited to, at least one selected from the group consisting of phenol-based, quinone-based, amine-based, and phosphite-based antioxidants. For example, the antioxidant may be tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, tris (2,4-di- .

The antioxidant may be contained in an amount of 0.01 to 3 parts by weight, specifically 0.01 to 1 part by weight based on 100 parts by weight of the sum of the ladder-type polysilsesquioxane and the radical initiator. In the above range, it may exhibit excellent thermal stability and may not affect the sealing layer.

The sealing material composition of the display member according to another embodiment of the present invention may further include an antioxidant. At this time, the antioxidant may be included in an amount of 0.01 to 3 parts by weight, specifically 0.01 to 1 part by weight, based on 100 parts by weight of the sum of the ladder-type polysilsesquioxane, the siloxane resin and the radical initiator. In the above range, it may exhibit excellent thermal stability and may not affect the sealing layer.

The sealing material composition of the display member according to embodiments of the present invention can be used to form the sealing layer of the member of the display. Specifically, the display is prevented from being damaged by the surrounding environment, such as liquid or gas, specifically moisture or oxygen, or being damaged or deteriorated in properties by the chemicals used in the manufacturing process of the device including the display The display can be used as a sealing material to shield the display from the surrounding environment.

A display device according to embodiments of the present invention includes a display member, and a sealing layer formed on the display member, wherein the sealing layer may be formed of a sealing material composition of a display member according to embodiments of the present invention.

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

The display device 100 of the present embodiment includes a substrate 110, a display member 120 formed on the substrate 110, and a sealing layer 130 formed on the display member 120, May be formed of the sealing material composition of the display member of the embodiments of the present invention.

The display member 120 refers to an organic light emitting diode (OLED), a flexible organic light emitting diode, a light emitting diode (LED), and a light instrument, But includes all other display devices commonly used in the art.

The substrate 110 is not particularly limited, and for example, transparent glass, a plastic film, a silicon or metal substrate, and the like can be used.

The sealing layer 130 may be formed by deposition of the sealing material composition of the display member of the present invention, inkjet, screen printing, spin coating, blade coating, curing alone, or a combination thereof. For example, the sealing material composition of the display member may be coated to a thickness of 1 탆 to 50 탆 and heat-cured at 50 캜 to 200 캜 for 30 minutes to 2 hours

The display device 100 may have an outgassing amount of 2,000 ng / cm 2 or less. Within this range, the lifetime of the display member may be prolonged and reliability may be enhanced. Specifically, the outgassing amount may be 10 ng / cm 2 to 500 ng / cm 2.

Hereinafter, a display device according to another embodiment of the present invention will be described with reference to FIG. 2 is a cross-sectional view of a display device according to another embodiment of the present invention.

The display device 200 of the present embodiment includes a first substrate 210, an organic electroluminescent device D formed on a top surface of the first substrate 210, a second substrate 210 spaced apart from the first substrate 210 And a sealing layer 230 disposed between the first substrate 210 and the second substrate 220 and sealing the organic electroluminescent device D, (230) may be formed of a composition for a sealant according to embodiments of the present invention.

The first substrate 210 may be made of a material such as a transparent glass, a plastic sheet, a silicon or a metal substrate, but is not limited thereto, and may have a flexible or non-flexible characteristic and a transparent or non-transparent characteristic. At least one organic electroluminescent device D is formed on one surface of the first substrate 210. The organic light emitting device D may include a transparent electrode, a hole transport layer, an organic EL layer, and a back electrode.

The second substrate 220 may be disposed on the organic electroluminescent device D and may be spaced apart from the first substrate 210 and may be bonded to the first substrate 210 by the sealing material 230. [ have. The second substrate 220 may be a substrate having excellent barrier properties such as a transparent glass, a plastic sheet having metal laminated thereon, but is not limited thereto.

The display device 200 can be manufactured by coating the display sealing material composition of the present invention with a predetermined thickness on the second substrate 220 and laminating and thermally curing the first substrate 210 on which the organic light emitting device D is formed . Thermal curing includes but is not limited to curing at 50 占 폚 to 200 占 폚 for 30 minutes to 2 hours.

A getter 240 may be formed between the first substrate 210 and the second substrate 220 and on the side of the organic electroluminescent device D to bond the first substrate and the second substrate.

The getter 240 is formed on the side of the first substrate 210 on which the organic light emitting diode D is formed and the display device 200 is provided with the getter 240 in a space surrounded by the first substrate 210 and the getter 240, The display sealing material composition of the examples may be added, cured, and the second substrate 220 may be prepared by laminating the sealing material composition on top of the sealing material composition. The curing may include thermal curing at 50 ° C to 200 ° C for 30 minutes to 2 hours. The sealing material composition may be injected and subjected to primary thermosetting, followed by laminating the second substrate 220, followed by secondary thermosetting.

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.

The ingredients used in the following examples and comparative examples are as follows.

(A) Polysilsesquioxane

(A1) The ladder-type polysilsesquioxane

(A2) T8 type polysilsesquioxane of the following Production Example 2

(B) Radical initiator: AIBN (azobisisobutyronitrile) (azo system)

(C) Polydimethylsiloxane containing vinyl group (VDT-131, Gelest)

(D) polyhydroxysiloxane (HMS-064, Gelest)

(E) Platinum catalyst (SIP6829.2, Gelest)

(F) Reaction inhibitor (B22291, 3-Methyl-1-dodecyn-3-ol, Alfa Aesar)

Production Example 1: Preparation of ladder-type polysilsesquioxane

To a monomer mixture comprising 20.43 g of methyltrimethoxysilane (Gelest), 6.16 g of phenyltrimethoxysilane (Gelest), and 62.09 g of diphenylsilanediol (Gelest), propylene And 92.30 g of glycol monomethyl ether acetate (PGMEA) (Dicel) was added. 27.27 g of water and 0.25 g of nitric acid were added to the obtained reaction product, and the mixture was stirred at room temperature for 2 hours and then at 100 ° C for 2 hours. Then, 14.2 g of glycidyl methacrylate and 2.6 g of triphenylphospine were added in this order, and the mixture was reacted for 4 hours while maintaining the temperature at 60 캜.

After the reaction, the reaction mixture was cooled to room temperature, transferred to a separatory funnel, washed with distilled water for 2 to 3 times to remove remaining nitric acid, and the solvent was removed by a vacuum distillation apparatus to prepare ladder-type polysilsesquioxane having a number average molecular weight of 3200 Respectively. It was confirmed by ¹ H-NMR that the ladder-type polysilsesquioxane contained 24 mol% of methacrylate groups.

Production Example 2: Preparation of T8 type polysilsesquioxane

27.28 g of methyltrimethoxysilane (Gelest), and 49.56 g of phenyltrimethoxysilane (Gelest) were added 77.52 g of PGMEA (Dicel). 27.27 g of water and 0.25 g of nitric acid were added to the reaction product, and the mixture was stirred at room temperature for 2 hours and then at 100 ° C for 3 hours. Then, 14.2 g of glycidyl methacrylate and 2.6 g of triphenylphosphine were added, and the mixture was reacted for 4 hours while being heated to 60 캜.

After the reaction, the reaction mixture was cooled to room temperature, transferred to a separatory funnel, washed with distilled water several times with distilled water to remove the remaining nitric acid, and the solvent was removed by a vacuum distillation apparatus to obtain a cage-type T8 type polysilsesquioxane Polystyrene reduced, weight average molecular weight: 5,730).

Example 1

(A1) 100 parts by weight of ladder-type polysilsesquioxane, and (B) 0.5 part by weight of a radical initiator were mixed and defoamed to prepare a composition.

Example 2

(A1) 60 parts by weight of ladder-type polysilsesquioxane, (C) 40 parts by weight of polydimethylsiloxane containing a vinyl group, and (B) 0.5 parts by weight of a radical initiator were mixed and defoamed to prepare a composition.

Comparative Example 1

(D) 10 parts by weight of polyhydroxylsiloxane, (C) 90 parts by weight of polydimethylsiloxane containing vinyl groups, (E) 10 ppm of platinum catalyst, and (F) 5,000 ppm of reaction inhibitor were prepared and defoamed to prepare a composition.

Comparative Example 2

(D) 10 parts by weight of polyhydroxylsiloxane, (C) 90 parts by weight of polydimethylsiloxane containing vinyl groups, and (E) 10 ppm of a platinum catalyst were mixed and defoamed to prepare a composition.

Comparative Example 3

(A2) 60 parts by weight of T8 type polysilsesquioxane, (C) 40 parts by weight of a polydimethylsiloxane containing vinyl groups, and (B) 0.5 parts by weight of a radical initiator were mixed and defoamed to prepare a composition.

The properties of the compositions prepared in Examples and Comparative Examples were evaluated in the following Table 1, and the results are shown in Table 1 and FIG.

(1) Outgassing amount: The compositions of Examples and Comparative Examples were coated on a glass substrate and thermally cured at 100 占 폚 for 1 hour to prepare specimens of 12 cm 占 12 cm 占 20 占 퐉 (width 占 length 占 thickness). The amount of outgassing was measured using a gas chromatograph / mass spectrometer (Clarus 600, Perkin Elmer). Specifically, a helium gas (flow rate: 1.0 mL / min, average velocity = 32 cm / s) was used as a mobile phase using a DB-5 MS column (length: 30 m, diameter: 0.25 mm, , The split ratio is 20: 1, the temperature condition is kept at 40 ° C for 3 minutes, then the temperature is raised at a rate of 10 ° C / min, and the temperature is held at 320 ° C for 6 minutes. The adsorbent was Tenax GR (5% phenylmethylpolysiloxane, manufactured by Tosoh Corporation), a glass size 20 cm x 20 cm in outgas, a Tedlar bag, a collection temperature of 90 ° C, a collection time of 30 minutes, an N ₂ purge flow rate of 300 ml / ). As a standard solution, a calibration curve is prepared at 150 ppm, 400 ppm, and 800 ppm of a toluene solution in n-hexane, and R2 value is obtained as 0.9987.

(2) Dark spot: An organic electroluminescent layer was formed on a glass substrate, and an electrode was formed on the organic electroluminescent layer to form an organic light emitting device on the glass substrate. The compositions of Examples and Comparative Examples were coated on a release film to form a sealing film having a thickness of 20 mu m and the sealing film was transferred onto the glass substrate using a roll laminator so as to cover the organic light emitting device. A non-water-permeable glass substrate was superimposed on the transferred glass substrate and heat-pressed with a vacuum laminator to prepare a specimen. The prepared specimen was heat-treated at 100 ° C for 1 hour to thermally cure the sealing film. Immediately after creating the panel in this manner, the occurrence of dark spots was evaluated (initial dark spots). Growth of dark spots was then evaluated (dark spot after reliability evaluation) when each sample was allowed to stand at a reliability condition of 1000 hours at 95 캜 and 85% relative humidity. The evaluation method was based on an optical microscope by naked eye, and evaluation criteria were as follows.

○: Dark spot having a diameter of 100 μm or more is less than 5% of the total area of the specimen

△: Dark spot having a diameter of 100 탆 or more is 5% or more and less than 20% of the total area of the specimen

△△: 20% or more and less than 35% of the total area of the sample in a dark spot having a diameter of 100 μm or more

△ ΔΔ: 35% or more and less than 50% of the total area of the specimen as a dark spot having a diameter of 100 μm or more

X: A dark spot having a diameter of 100 占 퐉 or more occupies 50% or more of the entire area of the specimen

(3) Thermosetting rate: The calorific value (A) was measured using a differential scanning calorimeter DSC (Q20, TA) for 2 mg to 5 mg of the compositions of Examples and Comparative Examples, and 2 mg to 5 mg of the composition was heat- (B) was measured and calculated according to the following formula (2).

<Formula 2>

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

(4) Shore A hardness: Shore A hardness: Shore A hardness of each sample was measured by coating a sealant composition of Examples and Comparative Examples on a release film with a thickness of 7 mm to 10 mm, thermally curing at 100 ° C for 1 hour, releasing from the release film, A measuring hardness meter at 25 캜.

(5) Room temperature stability: The viscosity of 1 g of the composition of Examples and Comparative Examples at 25 캜 was measured using a Brookfield viscometer. 1 g of the composition was stored at 25 캜 for 7 days, and then the viscosity at 25 캜 was measured using a Brookfield viscometer. The viscosity change rate was calculated by the formula 1, and it was evaluated as "stable" when the viscosity change rate was less than 10%, "good" when it was 10% or more and less than 20%, and "poor" when it was 20% or more.

(6) Occurrence of shrinkage: The compositions of Examples and Comparative Examples were coated to a thickness of 20 탆 and thermally cured at 100 占 폚 for 1 hour, and then the appearance of shrinkage caused by wrinkles or the like was visually evaluated. X if shrinkage did not occur, and 0 if shrinkage occurred.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A)
(Parts by weight) (A1) 100 60 - - - (A2) - - - - 60 (B) (parts by weight) 0.5 0.5 - - 0.5 (C) (parts by weight) - 40 90 90 40 (D) (parts by weight) - - 10 10 - (E) (ppm) - - 10 10 - (F) (ppm) - - 5000 - - Outgas generation (ng / cm2) 315 325 675 730 1055 Early Dark Spot ○ ○ △△ △△△ X Dark spot after reliability evaluation △ △ △△△ X X Thermal curing rate (%) 100 100 98 97 100 Shore A hardness 35 32 16 17 55 Room temperature stability stability stability Good Bad stability Whether shrinkage occurred X X X X O

From the results of Table 1, it was found that when the sealing material was formed from the composition of Example 1, the outgassing amount was low, the initial dark spots and the dark spots after reliability evaluation were all small, the thermal hardening rate was high, Stability in reliability conditions is also excellent. Also, it can be confirmed that the composition of the Examples does not contain a platinum catalyst and thus has excellent stability at room temperature without the addition of an additional reaction inhibitor.

On the other hand, in the case of Comparative Example 1 using the hydrogen silylation reaction, the amount of outgassing was higher than those of the Examples, and the dark spots at the initial stage and 95 ° C after 1,000 hours were higher. Further, in the case of using the polyhydroxylsiloxane, since the platinum catalyst is included, the stability at room temperature is remarkably lowered in the case of Comparative Example 2, which does not contain a separate reaction inhibitor. In the case of Comparative Example 3 using T8 type polysilsesquioxane instead of the ladder type, cracks occurred in the sealing layer as shown in Fig. 3 (see Fig. 3 (b)), (See Fig. 3 (a)). As a result, in Comparative Example 3, shrinkage occurred after curing, and as a result, the organic EL device could be damaged, cracks were generated in the sealing layer, and the amount of generated outgas was remarkably increased.

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.

Claims (15)

Ladder-type polysilsesquioxane and a radical initiator,
One-pack type,
A sealing member composition for a display member,
Wherein the ladder-type polysilsesquioxane comprises at least one of a vinyl group and a (meth) acrylate group. delete The sealing material composition for a display member according to claim 1, wherein the ladder-type polysilsesquioxane comprises at least 5 mol% to 35 mol% of at least one of a (meth) acrylate group and a vinyl group. [2] The method according to claim 1, wherein the ladder-type polysilsesquioxane comprises a unit represented by the following formula (1), the following formula (2)
&Lt; Formula 1 >

(In the formula 1,
* Is the connecting site of the element,
R ¹ , R ² , R ³ and R ⁴ each independently represent an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, a substituted or unsubstituted group having 6 to 20 carbon atoms An alkyl group having 1 to 10 carbon atoms having an alicyclic epoxy group having 5 to 10 carbon atoms, a vinyl group, a (meth) acrylate group, or * -OZY (wherein * is a connecting site of an element, An alkylene group having 1 to 10 carbon atoms, and Y is a vinyl group or a (meth) acrylate group)
n and m are each independently an integer of 1 to 10,
R ^a , R ^b , R ^c and R ^d each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, 20 < / RTI >
p1 and p2 are each independently an integer of 0 to 5)
(2)

(3)

(In the above formulas 2 and 3,
* Is the connecting site of the element,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, A substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a vinyl group, a (meth) acrylate group, Y is a vinyl group or a (meth) acrylate group)),
At least ^{one of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a vinyl group, a (meth) acrylate group, &Lt; / RTI > The sealing material composition for a display member according to claim 1, wherein the ladder-type polysilsesquioxane has a number average molecular weight (Mn) of 1,000 to 100,000. The display according to claim 1, wherein the radical initiator comprises at least one of an azo system, a peroxide clock, a phosphorus system, a triazine system, an acetophenone system, a benzophenone system, a thioxanthone system, a benzoin system, Member. The sealing material composition for a display member according to claim 1, wherein the sealing material composition of the display member comprises 100 parts by weight of the ladder-type polysilsesquioxane and 0.01 to 7 parts by weight of the radical initiator. The sealing member composition according to claim 1, wherein the sealing material composition of the display member further comprises a siloxane resin containing at least one of a vinyl group and a (meth) acrylate group. The sealing material composition for a display member according to claim 8, wherein the siloxane resin comprises 20 to 60 mol% of at least one of a vinyl group and a (meth) acrylate group. The sealing material composition for a display member according to claim 8, wherein the siloxane resin is represented by the following formula (6)
(6)

(6)
R ¹⁹ , R ²⁰ , R ²¹ , R ²³ , R ²⁴ and R ²⁶ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, (Meth) acrylate group, and at least one of R ¹⁹ , R ²⁰ , R ²¹ , R ²³ , R ²⁴ and R ²⁶ is a vinyl group or a (meth) acrylate group Lt; / RTI &gt;
R ²² and R ²⁵ are each independently an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group,
and j is an integer of 1 to 10). The sealing material composition according to claim 8, wherein the siloxane resin comprises a polydimethylsiloxane resin having at least one of a vinyl group and a (meth) acrylate group. The sealing material composition according to claim 1, wherein the sealing material composition of the display member comprises 50 parts by weight to 100 parts by weight of the ladder-type polysilsesquioxane among 100 parts by weight of the total of the ladder-type polysilsesquioxane and the siloxane resin, 0 to 50 parts by weight of the radical initiator, 0.01 to 7 parts by weight of the radical initiator based on 100 parts by weight of the total of the ladder-type polysilsesquioxane and the siloxane resin. The sealing material composition for a display member according to claim 1, wherein the sealing material composition of the display member has a Shore A hardness of 25 to 40 after curing. A display member, and a sealing layer formed on the display member, wherein the sealing layer is formed of the sealing material composition of the display member of any one of claims 1 to 13. 15. The display device of claim 14, wherein the display member is an organic light emitting device or a light instrument.

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