KR101518498B1 - Photocurable composition and optical member comprising protective layer prepared from the same - Google Patents

Abstract

The present invention relates to a photocurable composition, an organic protective layer formed from the composition, and an optical member comprising the same. More specifically, the present invention relates to a photocurable composition comprising a dipodal silicone compound having a (meth) acrylate group and a photopolymerization initiator and having a viscosity at 25 DEG C of 10 to 500 cps and an organic protective layer formed of the composition .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an optical member comprising a photocurable composition and a protective layer formed from the composition,

The present invention relates to an optical member comprising a photo-curing composition and a protective layer formed from the composition. More particularly, the present invention relates to a photocurable composition which is capable of realizing a protective layer capable of reducing the modulus and increasing the hardness, ultimately improving the long-term reliability of the device, And an optical member.

An organic light emitting diode (OLED) is a structure in which a functional organic layer is interposed between an anode and a cathode, and excitons having a high energy are recombined by holes injected into the anode and electrons injected into the cathode. Respectively. The exciton formed moves to the ground state and generates light of a specific wavelength. The organic electroluminescent part has advantages of self-emission, fast response, wide viewing angle, ultra-thin, high image quality and durability.

However, even when the organic electroluminescent unit is sealed, there is a problem that the organic material and / or the electrode material are oxidized due to moisture or oxygen introduced from the outside, or outgas generated from the outside or the inside, thereby deteriorating the performance and lifetime. In order to overcome such a problem, a method of applying a photocurable sealing agent to a substrate on which an organic electroluminescent unit is formed, attaching a transparent or opaque moisture absorber, or forming a frit has been proposed.

In particular, it is necessary for the OLED to be sealed with a protective layer capable of mitigating impact against an external impact due to its weak structure, and for this, the modulus is low but the hardness is high.

For example, Korean Patent Laid-Open Publication No. 2006-0084978 proposes an encapsulation structure of an organic light-emitting diode device using a sealing film formed of a moisture-permeation inhibiting material, either a silicone compound or a polymer resin.

An object of the present invention is to provide a photocurable composition capable of realizing an organic protective layer having a low modulus and a high hardness.

Another object of the present invention is to provide a photocurable composition capable of maintaining an appropriate viscosity to deposit an OLED organic protective layer.

It is still another object of the present invention to provide a photocurable composition having a high photo-curability.

It is still another object of the present invention to provide a photocurable composition capable of realizing an organic protective layer capable of improving the long-term reliability of a device including an OLED or an organic solar cell or the like.

It is still another object of the present invention to provide an optical member comprising an organic protective layer formed from the photocurable composition.

One aspect of the present invention is a photocurable composition comprising a dipodal silicone compound having a (meth) acrylate group and a photopolymerization initiator and having a viscosity of 10 to 500 cps at 25 ° C.

In one embodiment, the silicone compound may have the structure of Formula 1 below.

≪ Formula 1 >

In one embodiment, the composition may further comprise a photocurable monomer selected from i) non-silicon based monomers having photo-curable functional groups, ii) non-dipodal siloxane monomers having photo-curable functional groups, or mixtures thereof.

In another aspect of the present invention, an optical member includes a substrate, an organic electroluminescent portion formed on the substrate, and an organic protective layer sealing the organic electroluminescent portion, wherein the organic protective layer has a modulus of 100 to 1500 MPa and a hardness of 600 To 1000 MPa.

In one embodiment, an organic protective layer can be formed from the photocurable composition.

In one embodiment, it may further comprise an inorganic protective layer.

The present invention has the effect of providing a photocurable composition capable of reducing the modulus and increasing the hardness, thereby realizing an organic protective layer capable of improving the long-term reliability of the device and having an appropriate viscosity and being able to deposit as an organic protective layer . In addition, the present invention has the effect of providing a photocurable composition capable of realizing a layer in which the photo-curing rate is high and the hardening shrinkage stress is low after the curing, so that no shift occurs.

1 is a cross-sectional view schematically showing an optical member of an embodiment of the present invention.
2 is a cross-sectional view schematically showing an optical member of another embodiment of the present invention.

One aspect of the present invention is a photocurable composition comprising a dipodal silicone compound having a (meth) acrylate group and a photopolymerization initiator.

As used herein, unless otherwise defined, at least one hydrogen atom of the functional groups of the present invention is optionally substituted with at least one substituent selected from the group consisting of halogen (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, (R "), R ', R" and R "' each independently represent an alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group having 1-20 carbon atoms, a substituted or unsubstituted aryl group having 1-20 carbon atoms, an amidino group, a hydrazine or hydrazone group, Substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms.

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

(A) ( Meta ) Acrylate group  Have dipodal  Silicon compound

In the dipodal silicone compound having a (meth) acrylate group, the dipodal silicone structure causes a low modulus due to the rotation and flexibility of the bridge chain, and the (meth) acrylate group is a photocurable functional group that performs a curing reaction with a photopolymerization initiator .

The silicone compound may include a unit represented by the following formula (1A) and a unit represented by the following formula (1B)

≪

≪ Formula 1B >

(Wherein R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms A substituted or unsubstituted alkoxy group having 1-10 carbon atoms, an epoxy-containing organic group (e.g., an epoxy group, a glycidoxypropyl group, an epoxycyclohexyl group, etc.) )ego,

At least one of R ¹ and R ² comprises a formula (2),

(2)

(Wherein R < ³ > is hydrogen, a substituted or unsubstituted alkyl group having 1-30 carbon atoms)

Y is a substituted or unsubstituted alkylene group having 1-20 carbon atoms, a cycloalkylene group having 3-30 carbon atoms, a polycycloalkylene group having 5-30 carbon atoms, a substituted or unsubstituted arylene group having 6-20 carbon atoms, A substituted or unsubstituted C6-C20 arylalkylene group, a substituted or unsubstituted C2-C20 heteroarylene group, a substituted or unsubstituted C2-C20 unsaturated carbon-containing alkylene group,

Y may contain an element other than carbon and hydrogen (for example, oxygen, sulfur, halogen)

1.0? A < 4.0, and a is an integer.

In one embodiment, the silicone compound may have the structure of Formula 1:

&Lt; Formula 1 >

(Wherein R ¹ , R ² , and Y are as defined above,

1.0? A <4.0, a is an integer, b + c = 1, 0 <b <1, 0 <c <1).

In a dipodal silicone compound having a (meth) acrylate group, -Y- can be represented by the following formulas (3a) to (3f):

&Lt; EMI ID =

&Lt; EMI ID =

&Lt; Formula 3c >

<Formula 3d>

<Formula 3e>

(3f)

(Wherein L ¹ to L ¹² each independently represent a single bond, a substituted or unsubstituted alkylene group having 1-30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3-30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted arylalkylene group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 30 carbon atoms, A substituted or unsubstituted alkenylene group having 2-30 carbon atoms,

D is a single bond, an oxygen atom, an oxygen-containing group, a sulfonyl group, an alkylene group having 1-10 carbon atoms, a fluoroalkylene group having 1-10 carbon atoms,
L ¹¹ , L ¹² and D are both a single bond).

The silicone compound may include one or more, preferably 2 to 4, (meth) acrylate groups.

The weight average molecular weight of the silicone compound may be 100-5,000 g / mol, preferably 200-2,000 g / mol, and more preferably 300-1,000 g / mol. In the above range, there is an effect that the deposition is good and the photo-curing rate can be increased.

The silicone compound can be synthesized by a conventional method. For example, it can be synthesized by the same method as the following synthesis example.

The silicone compound may be included in the photocurable composition in an amount of 0.1-99.9 wt%, preferably 0.1-99 wt%, 1-90 wt%, 40-55 wt%, or 90-99 wt%. Within this range, it is possible to maximize the modulus reduction while the photo-curing rate is high.

(B) Light curing Initiator

The photopolymerization initiator includes, without limitation, conventional photopolymerization initiators capable of carrying out a photo-curable reaction. For example, the photopolymerization initiator may be a phosphorus-based, triazine-based, acetophenone-based, benzophenone-based, thioxanthone-based, benzoin-based, oxime based or mixtures thereof, and preferably a phosphorus-based photopolymerization initiator.

Phosphorous can be benzoyldiphenylphosphine oxide, bisbenzoylphenylphosphine oxide or mixtures thereof. The triazine system may be 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and the like, but is not limited thereto. The acetophenone type can be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, and the like, but is not limited thereto. The benzophenone-based compounds may be benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, and the like, but are not limited thereto. The thioxanthone system may be thioxanthone, 2-methylthioxanthone, or the like, but is not limited thereto. The benzoin group may be benzoin, benzoin methyl ether or the like, but is not limited thereto. Oxime-based compounds such as 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (o- 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, and the like.

The photopolymerization initiator may be contained in the photocurable composition in an amount of 0.1 to 99.9% by weight, preferably 0.1 to 99% by weight or 1 to 10% by weight. Within the above range, photopolymerization can sufficiently take place at the time of exposure, and the unreacted initiator can be prevented from remaining after the photopolymerization.

In addition to the above-mentioned components, the photocurable composition may further comprise a photocurable monomer.

(C) Photocurable Monomer

The photocurable monomer may be i) a non-silicon based monomer having a photocurable functional group, ii) a non-dipodal siloxane monomer having a photocurable functional group, or a mixture thereof. The photocurable functional group may be (meth) acrylate group, vinyl group, (meth) acrylate-containing group, and the like, but is not limited thereto. The photocurable monomer can be photocured by a photopolymerization initiator.

In one embodiment, the photocurable monomer is a non-silicon based monomer having a photocurable functional group, which may be a monofunctional monomer, a multifunctional monomer, or a mixture thereof.

The photocurable monomer may be a non-silicon-based monomer having a photocurable functional group having 1-30, preferably 1-20, and more preferably 1-5 (meth) acrylate groups.

The photocurable monomer may be an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 3-20 carbon atoms, an aryl group having 6-20 carbon atoms, an aralkyl group having 7-20 carbon atoms, or an unsaturated carboxylic acid ester having a hydroxy group and an alkyl group having 1-20 carbon atoms ; An aromatic compound having 6 to 20 carbon atoms and having a substituted or unsubstituted vinyl group; An unsaturated carboxylic acid ester having an aminoalkyl group having from 1 to 20 carbon atoms; Vinyl esters of saturated or unsaturated carboxylic acids having from 1 to 20 carbon atoms; Unsaturated carboxylic acid glycidyl esters having 1 to 20 carbon atoms; Vinyl cyanide compounds; Unsaturated amide compounds; Mono- or polyhydric (meth) acrylates of polyhydric alcohols. The 'polyhydric alcohol' may be an alcohol having two or more hydroxyl groups and having 2 to 20, preferably 2 to 10, more preferably 2 to 6 alcohols.

In embodiments, the photocurable monomer is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- hydroxyethyl (meth) (Meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, octyldiol di (meth) acrylate, nonyl Acrylate, dodecyl (meth) acrylate, undecyl (meth) acrylate, undecanyl diol di (meth) acrylate, dodecyl Unsaturated carboxylic acid esters such as benzyl (meth) acrylate and phenyl (meth) acrylate; An aromatic compound having 6 to 20 carbon atoms and having an alkenyl group including a vinyl group such as styrene,? -Methylstyrene, vinyltoluene, vinylbenzyl ether and vinylbenzyl methyl ether; Unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Saturated or unsaturated carboxylic acid vinyl esters such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl esters having 1 to 20 carbon atoms such as glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Unsaturated amide compounds such as acrylamide and methacrylamide; Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, triethylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri Acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, novolac epoxy (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Monoalcohols or polyhydric alcohols containing 5 to 30 carbon atoms such as acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) ) Acrylate, and the like, but is not limited thereto.

In other embodiments, the photocurable monomer can be a non-dipodal siloxane monomer having a photocurable functional group.

The photocurable monomer may be an alkyl of 2 to 30 carbon atoms, an aryl of 6 to 30 carbon atoms, or an aryl of 7 to 7 carbon atoms having at least one chain terminating group selected from a (meth) acrylate group or a (meth) acryloxyalkyl group. Lt; RTI ID = 0.0 &gt; arylalkyl &lt; / RTI &gt;

Specifically, the photo-curable monomer may be 1,3-bis (3- (meth) acryloxypropyl) tetramethyldisiloxane, 1,3-bis [(p- (meth) acryloxymethyl) phenethyl] tetramethyldisiloxane , 1,3-bis (3- (meth) acryloxypropyl) tetrakis (trimethylsiloxy) disiloxane, or mixtures thereof.

Preferably, the photocurable monomer is a siloxane monomer having a terminal group selected from monoalcohols or monohydric alcohols selected from monofunctional or polyfunctional (meth) acrylates, diacrylates or dimethacrylates having 5 to 30 carbon atoms, &Lt; / RTI &gt;

The photocurable monomer may be included in the photocurable composition in an amount of 0.1-99.9 wt%, preferably 1-90 wt% or 40-55 wt%. Within the above range, the photo-curing composition is resistant to plasma, and it is possible to lower or prevent deterioration of the out gas and the moisture permeability that may be generated from the plasma generated in the manufacture of the thin film encapsulation layer.

The photocurable composition may have a viscosity of 10 to 500 cps, preferably 10 to 200 cps, more preferably 10 to 20 cps at 25 degrees. In the above range, the organic protective layer can be deposited, and the photo-curing rate after deposition can be excellent.

The photo-curable composition may have a photo-curing rate of 95% or more. Within this range, it is possible to realize a layer in which the hardening shrinkage stress is low after curing and no shift occurs, and thus the layer can be used for sealing the device. Preferably 95-99%, more preferably 97-99%.

The photo-curing rate can be measured by a usual method. For example, the photocurable composition is applied onto a glass substrate and UV-cured by ultraviolet irradiation for 10 seconds at 100 J / cm &lt; ² &gt;. The cured film (film thickness: 5 mu m) was sampled and the photo-curability was measured using FT-IR. The photo-curing rate is obtained under the conditions described in the following experimental examples.

The photocurable composition of the present invention can seal an element including an organic electroluminescent portion, an organic solar cell, and the like.

The optical member, which is another aspect of the present invention, may include an organic protective layer formed from the composition. The organic protective layer may mean a sealing layer for protecting an organic electroluminescent unit, an organic solar cell, and the like.

The organic protective layer is prevented from being decomposed or oxidized due to the external environment due to moisture, oxygen or the like by sealing the device, and it is possible to prevent damage of the device due to outgas due to a small amount of outgas.

The organic protective layer has a low moisture permeability and can minimize the influence of moisture on the device. The moisture permeability may be 8 g / m ² .24 hr or less with respect to the thickness direction of the organic protective layer. Within this range, it can be used for sealing of devices. Preferably, there can be a 0-8g / m ² .24hr, 0 greater than 8g / m ² .24hr below, 1-8g / m ² .24hr, more preferably 3-6g / m ² .24hr.

The moisture permeability can be measured by a conventional method. For example, a photocurable composition is applied on an Al sample holder of a moisture permeability meter (PERMATRAN-W 3/33, MOCON) and irradiated at 100 mW / cm ² for 10 seconds to be UV-cured to form a cured specimen . The moisture permeability is measured for 24 hours at 50 占 폚 and 100% relative humidity for a coating thickness of 5 占 퐉.

The organic protective layer has low oxygen permeability and can minimize the effect of oxygen on the device. The oxygen permeability may be 300 cc / m ² .24 hr or less with respect to the thickness direction of the organic protective layer. Within this range, it can be used for sealing of devices. Preferably, there can be a 0-300cc / m ² .24hr, 0 greater than 300cc / m ² .24hr below, 100-300cc / m ² .24hr, more preferably 250-300cc / m ² .24hr.

The organic protective layer can prevent the outgassing of the device from degrading or degrading performance by minimizing the outgassing effect on the device. Specifically, the organic protective layer may have an outgassing amount of 2,000 ppm or less. Within the above range, there is little effect when applied to the device, and the life of the device can be prolonged. Preferably from 0 to 2000 ppm, from 0 to 2000 ppm, from 0 to 500 ppm, from 0 to 500 ppm, from 0 to 100 ppm, from 0 to 100 ppm, and from 1 to 2000 ppm.

The amount of generated outgas can be measured by a conventional method. For example, a photocurable composition is applied onto a glass substrate and irradiated with 100 mW / cm ² for 10 seconds to be UV cured to obtain an organic protective layer of 20 cm x 20 cm x 3 m (width x length x thickness). The specimen is obtained under the conditions described in the following experimental examples.

The lower the moisture permeability, the oxygen permeability, and the outgassing amount of the organic protective layer, the smaller the influence on application to the device and the longer the life of the device.

The organic protective layer may have a modulus of 100-1500 MPa, preferably 400-1100 MPa. Within the above range, the reliability of the organic protective layer may be good.

The organic protective layer may have a hardness of 600-1000 MPa, preferably 650-950 MPa. Within the above range, the reliability of the organic protective layer may be good.

The modulus and hardness of the organic protective layer are values measured for a film thickness of 5 mu m, but are not limited thereto.

The thickness of the organic protective layer is not particularly limited, but may be 0.1 占 퐉 to 10 占 퐉.

The organic protective layer can be prepared by curing the above-mentioned photocurable composition, and the curing method is not particularly limited. For example, 10-500 J / cm ² for 1 second-50 seconds to cure.

The optical member may include a substrate, an element formed on the substrate, an inorganic protective layer sealing the element, and an organic protective layer formed on the inorganic protective layer and formed of the composition.

The optical member may be an organic electroluminescent display device, a solar cell, or a liquid crystal display device including an organic electroluminescent portion, but is not limited thereto.

The substrate is not particularly limited as long as it is a substrate on which elements can be stacked. For example, a transparent glass, a plastic sheet, a silicon or metal substrate, or the like.

The device may be decomposed or oxidized or deteriorated in performance when exposed to an external environment such as moisture and oxygen, and examples thereof include an organic electroluminescent portion and an organic solar cell.

The optical member is sealed by an inorganic protective layer, which is a protective layer having different properties, and an organic protective layer. At least one of the inorganic protective layer and the organic protective layer may be combined with the substrate for sealing of the device.

The inorganic protective layer may mean a sealing layer for protecting an element including an organic electroluminescent portion, an organic solar cell, and the like. The inorganic protective layer may seal the element by contact with the element or may seal the internal space in which the element is accommodated without contacting the element. The inorganic protective layer can prevent the element from being decomposed or damaged by blocking external oxygen or moisture from contacting the element.

The inorganic protective layer may be a metal, an intermetallic compound or an alloy, an oxide of a metal and a mixed metal, a fluoride of a metal and a mixed metal, a nitride of a metal and a mixed metal, an oxynitride of a metal and a mixed metal, And oxides of mixed metals, silicides of metals and mixed metals, or combinations thereof. The metal may include a transition metal, a lanthanide metal, aluminum, indium, germanium, tin, antimony, bismuth, or a combination thereof.

The inorganic protective layer may be deposited using a vacuum process such as sputtering, chemical vapor deposition, metal organic chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma enhanced chemical vapor deposition, and combinations thereof.

The thickness of the inorganic protective layer is not particularly limited, but may be 100 to 2000 ANGSTROM.

The organic protective layer is laminated on the inorganic protective layer and is made of a material different from the inorganic protective layer, so that the inorganic protective layer can enhance the function of blocking external oxygen or moisture from contact with the element or compensate for the defect.

In the optical member, the inorganic protective layer and the organic protective layer may be included two or more times. In one embodiment, the inorganic protective layer and the organic protective layer may be alternately deposited, such as an inorganic protective layer / an organic protective layer / an inorganic protective layer / an organic protective layer. Preferably, the inorganic protective layer and the organic protective layer may be contained 10 times or less, more preferably 7 times or less.

 1 is a sectional view of an optical member according to an embodiment of the present invention. 1, an optical member 100 includes a substrate 10, an element 20 formed on the substrate, an inorganic protective layer 31 sealing the element, and a composite protective layer 30 including an organic protective layer 32 ), And the inorganic protective layer is in contact with the element.

 2 is a sectional view of an optical member according to another embodiment of the present invention. 3, the optical member 200 includes a substrate 10, an element 20 formed on the substrate, an inorganic protective layer 31 sealing the element, and a composite protective layer 30 including an organic protective layer 32 ), And the inorganic protective layer can seal the internal space in which the element is accommodated.

 1 and 2 show a structure in which the inorganic protective layer and the organic protective layer are formed as a single layer, respectively. However, the inorganic protective layer and the organic protective layer may be formed a plurality of times. Further, a sealant and / or a substrate may be further formed on the side and / or the upper side of the complex protective layer composed of the inorganic protective layer and the organic protective layer (not shown in FIGS. 1 and 2).

The optical member can be manufactured by a conventional method. A device is deposited over the substrate and an inorganic protective layer is formed. The photocurable composition can be coated with a thickness of 1 占 퐉 to 5 占 퐉 by spin coating, slit coating, or the like, and light can be irradiated to form an organic protective layer. The formation process of the inorganic protective layer and the organic protective layer may be repeated (preferably, 10 times or less).

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 contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Synthetic example  One:( Meta ) Acrylate group  Have dipodal  Compound manufacturing

A jacketed reactor capable of temperature control was charged with 100 g of 2-hydroxyethyl methacrylate (Aldrich), the same equivalent amount of triethylamine (triethylamine, Aldrich), and 70 wt% 1,2-dichloroethane (Aldrich) were added to the flask, and the mixture was stirred for 1 hour while purging with nitrogen at room temperature. (Chlorodimethylsilyl) ethyl benzene (bis (2- (chlorodimethylsilyl) ethyl) benzene in an amount of 0.5 equivalent to 2-hydroxyethyl methacrylate while keeping the reactor temperature at 0 degree and maintaining the nitrogen atmosphere, Gelest) was slowly added dropwise to the reactor for 2 hours. After the addition, the reactor temperature was adjusted to room temperature, and the reaction was terminated after stirring for 6 hours. The reaction solution was neutralized with distilled water until the pH of the reaction solution became neutral, and the solvent and byproducts were removed by distillation under reduced pressure, followed by drying to obtain the final product as shown in Chemical Formula 4 by NMR and GC.

&Lt; Formula 4 >

Synthetic example  2:( Meta ) Acrylate group  Have dipodal  Silicon compound manufacturing

(Chlorodimethylsilyl) ethyl) bicycloheptane was obtained in the same manner as in Synthesis Example 1, except that (chlorodimethylsilyl) -6- (2-chlorodimethylsilyl) (2- (chlorodimethylsilyl) ethyl) bicycloheptane, Gelest) was used as a silicone compound to prepare the following formula (5).

&Lt; Formula 5 >

Synthetic example  3 :( Meta ) Acrylate group  Have dipodal  Silicon compound manufacturing

1,2-bis (chlorodimethylsilyl) ethane (Gelest) was used instead of bis (2- (chlorodimethylsilyl) ethyl) benzene in the same manner as Synthesis Example 1, To prepare a compound represented by the following formula (6).

(6)

Specific specifications of the components used in Examples 1-5 and Comparative Examples 1-2 are as follows.

(A) a dipodal silicone compound having a (meth) acrylate group: (A1) a silicone compound represented by the formula (4), (A2) a silicone compound represented by the formula (5)

(B) Photopolymerization initiator: Darocur TPO (BASF)

(C) photocurable monomer: (C1) hexanediol diacrylate, (C2) 1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane

Examples Comparative Example

(A) a dipodal silicone compound having a (meth) acrylate group, (B) a photopolymerization initiator and (C) a photocurable monomer were blended in the contents (unit: parts by weight) shown in the following Table 1 to prepare a liquid composition.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 (A) (A1) 98 - - 49 49 - - (A2) - 98 - - - - - (A3) - - 98 - - - - (B) 2 2 2 2 2 2 2 (C) (C1) - - - - 49 49 98 (C2) - - - 49 - 49 -

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. sight rate: About photocurable composition FT-IR (NICOLET 4700, Thermo Co.) for use in the vicinity of 1635cm ^-1 (C = C), 1720cm ^-1 measured intensity of the absorption peak in the vicinity of the (C = O) do. The photocurable composition is applied on a glass substrate by spraying and irradiated at 100 J / cm &lt; ² &gt; for 10 seconds to be UV cured to obtain a cured specimen of 20 cm x 20 cm x 5 mu m (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 photo-curing rate is calculated according to the following formula (1).

<Formula 1>

(Wherein, A is the ratio of the intensity of the absorption peak of 1635cm ^-1 in the vicinity of the intensity of the absorption peak in the vicinity of 1720cm ^-1 for the cured film, B is in the vicinity of 1720cm ^-1 for the photocurable composition The ratio of the intensity of the absorption peak at around 1635 cm &lt; ^-1 &gt; to the intensity of the absorption peak)

2. Modulus and Hardness: Cured film specimens are obtained as in the photocuring rate measurement. The surface was scanned with a Nanoindentor (Hysitron TI750 Ubi) instrument to determine the modulus and hardness. The specimens were placed on a Nanoindentor bench and focused for 5 seconds to a maximum force. The specimen was held for 2 seconds and unloaded for 5 seconds. The surface of the specimen was scanned to automatically measure the modulus and hardness from the diplacement-force plot. Respectively.

3. Reliability: Deposition the device on the substrate and deposit an inorganic protective layer. And a photocurable composition is applied thereon and UV-cured to form an organic protective layer having a film thickness of 5 占 퐉 to prepare an OLED device package for reliability evaluation. It is distinguished by observing the time during which the discoloration occurs inside the package under a microscope while being left at 85 캜 and 85% relative humidity. The reliability score was given based on the time point of discoloration as shown in Table 2 below.

When discoloration occurred Reliability score Less than 1 week 0 point More than 1 week ~ 2 weeks 1 point More than 2 weeks ~ less than 3 weeks 2 points Less than 3 weeks to less than 4 weeks 3 points Less than 4 weeks to less than 5 weeks 4 points More than 5 weeks ~ less than 6 weeks 5 points More than 6 weeks ~ less than 7 weeks 6 points More than 7 weeks ~ less than 8 weeks 7 points More than 8 weeks ~ less than 9 weeks 8 points Less than 9 weeks to less than 10 weeks 9 points More than 10 weeks 10 points

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Curing condition 100 J / cm ² , 10 sec, UV curing The viscosity of the composition (25 degrees cps) 19 18 11 12 13 6 7 Light curing rate (%) 99 99 99 98 97 93 94 Modulus (MPa) 480 430 425 967 1,045 2,624 3,890 Hardness (MPa) 938 910 909 782 658 425 239 responsibility 10 points 10 points 10 points 8 points 8 points 4 points 3 points

As shown in Table 3, the photocurable composition of the present invention has a high photo-curability, and the organic protective layer prepared by photocuring it has a low modulus and a high hardness, and ultimately has a long-term reliability of devices such as OLEDs or organic solar cells Of the present invention.

On the other hand, the composition of Comparative Example 1-2, which does not contain a dipodal silicone compound having a (meth) acrylate group, has a low photo-curability and an organic protective layer prepared therefrom has a low hardness and a high modulus, , The effect of the present invention can not be realized.

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

Claims (11)

A photocurable composition comprising a silicone compound having a structure represented by the following formula (1) and a photopolymerization initiator and having a viscosity of 10 to 500 cps at 25 DEG C:
&Lt; Formula 1 >

(Wherein R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms A substituted or unsubstituted silanol group having 1-10 carbon atoms, a substituted or unsubstituted alkoxy group having 1-10 carbon atoms, or an epoxy-containing organic group,
However, at least one of R ¹ and R ² comprises a formula (2),
(2)

(Wherein R < ³ > is hydrogen or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms)
Y is a substituted or unsubstituted alkylene group having 1-20 carbon atoms, a cycloalkylene group having 3-30 carbon atoms, a polycycloalkylene group having 5-30 carbon atoms, a substituted or unsubstituted arylene group having 6-20 carbon atoms, A substituted or unsubstituted arylalkylene group having 2 to 20 carbon atoms or a substituted or unsubstituted alkylene group containing an unsaturated carbon-carbon bond having 2 to 20 carbon atoms,
1.0? A <4.0, a is an integer, b + c = 1, 0 <b <1, 0 <c <1). delete The photocurable composition according to claim 1, wherein Y of the silicon compound comprises any one of the structures represented by the following formulas (3a) to (3f):
&Lt; EMI ID =

&Lt; EMI ID =

&Lt; Formula 3c >

<Formula 3d>

<Formula 3e>

(3f)

(Wherein L ¹ to L ¹² each independently represent a single bond, a substituted or unsubstituted alkylene group having 1-30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3-30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted arylalkylene group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 30 carbon atoms, Or a substituted or unsubstituted alkenylene group having 2-30 carbon atoms,
D is a single bond, an oxygen atom, an oxygen-containing group, a sulfonyl group, an alkylene group having 1-10 carbon atoms, or a fluoroalkylene group having 1-10 carbon atoms,
L ¹¹ , L ¹² and D are both a single bond). The photocurable composition of claim 1, wherein the silicone compound has a weight average molecular weight of 100-5,000 g / mol. The photocurable composition of claim 1, wherein the composition comprises 0.1-99.9 wt% of the silicone compound and 0.1-99.9 wt% of the photopolymerization initiator. The photocurable composition of claim 1, wherein the composition further comprises a photocurable monomer selected from i) a non-silicon based monomer having a photocurable functional group, ii) a non-dipodal siloxane monomer having a photocurable functional group, or a mixture thereof. The photocurable monomer according to claim 6, wherein the photocurable monomer is selected from the group consisting of i) a non-silicon-based (meth) acrylate of 5-30 carbon atoms of a monoalcohol or a polyhydric alcohol, ii) a (meth) acrylate group or A non-dipodal siloxane monomer having at least one terminal group, or a mixture thereof. The photocurable composition of claim 6, wherein the composition comprises 1-90 wt% of the silicone compound, 1-10 wt% of the photopolymerization initiator, and 1-90 wt% of the photocurable monomer. A substrate, an organic electroluminescent portion formed on the substrate, and an organic protective layer sealing the organic electroluminescent portion,
Wherein the organic protective layer is formed of the photocurable composition of any one of claims 1 to 8, having a modulus of 100 to 1500 MPa and a hardness of 600 to 1000 MPa. delete The optical member according to claim 9, further comprising an inorganic protective layer.

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