KR101549722B1 - Photocurable composition, protective layer prepared from the same and optical member comprising the same - Google Patents

Abstract

The present invention relates to a photo-curable composition, a protective layer formed from the composition, and an optical member including the protective layer. More particularly, the present invention relates to a photocurable composition comprising a silicone compound containing a halogen and a (meth) acrylate group and a photopolymerization initiator, a protective layer formed from the composition, and an optical member including the protective layer.

Description

[0001] The present invention relates to a photocurable composition, a protective layer formed from the composition, and an optical member comprising the protective layer,

The present invention relates to a photocurable composition, a protective layer formed from the composition, and an optical member comprising the same. More particularly, the present invention relates to a protective layer which can impart hydrophobicity to shut off contact with moisture, reduce moisture permeability and / or oxygen permeability, and ultimately improve the long-term reliability of optical members including devices and the like. A protective layer formed from the composition, and an optical member comprising the same.

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.

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 capable of blocking the contact with moisture by imparting hydrophobicity.

Another object of the present invention is to provide a photocurable composition capable of realizing an organic protective layer having a significantly low moisture permeability and / or oxygen permeability.

Another object of the present invention is 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 a photocurable composition capable of realizing an organic protective layer having hydrophobicity.

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

The photocurable composition which is one aspect of the present invention may comprise a silicone compound containing a halogen and a (meth) acrylate group and a photopolymerization initiator.

In one embodiment, the silicone compound comprising a halogen and a (meth) acrylate group may have the structure of Formula 1:

≪ Formula 1 >

In one embodiment, the photocurable composition can further comprise a photocurable monomer selected from i) a non-silicon based monomer having a photocurable functional group, ii) a non-halogenated siloxane monomer having a photocurable functional group, or a mixture thereof .

The organic protective layer, which is another aspect of the present invention, may have a moisture permeability of 8 g / m ² .24 hr or less in the thickness direction measured for 24 hours under conditions of 50 캜 and 100% relative humidity for a film thickness of 5 탆.

The organic protective layer, which is another aspect of the present invention, may have an oxygen permeability of 300 cc / m ² .24 hr or less in the thickness direction measured at 25 캜 for 24 hours against a coating film thickness of 5 탆.

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

The optical member, which is another aspect of the present invention, may comprise the organic protective layer.

The present invention provides a method for producing an organic protective layer capable of realizing an organic protective layer capable of minimizing moisture permeability and / or oxygen permeability, minimizing the influence of elements on moisture due to hydrophobicity, It has an effect of providing a chemical composition. In addition, the present invention has an effect of providing a photocurable composition capable of realizing a layer in which a shift is not generated due to a high photo-curing rate and a low hardening shrinkage stress after curing.

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

One embodiment of the photocurable composition according to one aspect of the present invention may include a silicone compound containing a halogen and 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) halogen and ( Meta ) Acrylate group  Containing silicon compounds

In a silicone compound containing a halogen and a (meth) acrylate group, the halogen can impart hydrophobicity to the layer (for example, the organic electroluminescence portion protective layer) formed after curing, and can lower the permeability of oxygen and / or moisture , Silicon can impart resistance to plasma in the process of depositing the protective layer of the OLED, and the (meth) acrylate group enables the curing reaction to be performed by the initiator as a photo-curing functional group.

"Halogen" may be fluorine, chlorine, iodine or bromine, preferably fluorine.

The silicone compound containing a halogen and a (meth) acrylate group may be a halogenated aryl group (e.g., 6-30 carbon atoms), a halogenated aralkyl group (e.g., 7-30 carbon atoms), a halogenated arylalkyl group ), A halogenated alkyl group (e.g., 1-30 carbon atoms), and a (meth) acrylate group.

The halogen in the compound may be contained in an amount of 0.1-90 wt%, preferably 5-30 wt%. Within this range, sufficient hydrophobicity can be imparted, and water permeability and oxygen permeability reduction effect can be obtained.

The above compound may contain at least one, preferably 2 to 6, (meth) acrylate groups.

In one embodiment, the compound may have the structure:

≪ Formula 1 >

(Wherein R < ^{1 >} is an aryl group having 6 to 30 carbon atoms, a halogenated alkyl group having 7 to 30 carbon atoms, or a halogenated alkyl group having 1 to 30 carbon atoms,

R ² , R ³ and R ^{4 each} 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 to 10 carbon atoms or a substituted or unsubstituted silyl group having 1 to 10 carbon atoms,

At least one of R ² , R ³ and R ⁴ includes the following formula (2)

(2)

(Wherein R < ⁵ > is hydrogen, a substituted or unsubstituted alkyl group having 1-30 carbon atoms)

b is an integer of 0 or more and 4 or less, and a + b + c + d is an integer of 2 or more and 4 or less.

The arylalkyl group, alkyl group, alkenyl group, alkoxy group and silyl group for R ¹ to R ⁵ may be linear or branched.

Preferably, R ¹ is a - (CR ⁶ R ⁷ ) _n - group, wherein R ⁶ and R ⁷ are each independently selected from the group consisting of halogenated alkyl groups having from ¹ to ²¹ carbon atoms or halogenated aryl groups having from ⁶ to 20 carbon atoms, And n is an integer of 0 to 20).

Preferably, n is an integer of 0-10.

More preferably, R ¹ is C ₆ X ₅ (CX ₂ ) _x (CH ₂ ) _y - or CX ₃ (CX ₂ ) _x (CH ₂ ) _y - where X is fluorine, chlorine, iodine or bromine and x Is an integer from 0 to 10, and y is an integer from 0 to 10).

The weight average molecular weight of the compound may be 100-5,000 g / mol, preferably 200-2,000 g / mol, and more preferably 300-1,000 g / mol. Within the above range, it is possible to have an excellent effect of not only the degree of photo-curing but also the water permeability and oxygen permeability. These compounds can be synthesized by a conventional method or purchased as a commercial product.

The silicone compound comprising a halogen and a (meth) acrylate group is present in the photocurable composition in an amount of 0.1-99.9 wt%, preferably 0.1-99 wt%, 1-90 wt%, 40-99 wt%, or 20-70 wt% . Within the above range, hydrophobicity can be imparted to the protective layer formed at the time of curing, permeability of oxygen and moisture can be lowered, and ultimately reliability can be improved.

(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, but is not limited to, benzoyldiphenylphosphine oxide, bisbenzoylphenylphosphine oxide, and the like. 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 included in the photocurable composition in an amount of 0.1-99.9 wt%, preferably 0.1-60 wt%, 1-60 wt%, or 1-10 wt%. 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-halogenated 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 photo-cured by the photopolymerization initiator with a silicone compound containing the halogen and the (meth) acrylate group.

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. Preferably, the photocurable monomer may be a non-halogen-based monomer containing no halogen such as fluorine.

The photocurable monomer is a non-silicon-based, monofunctional or multifunctional monomer having 1-30, preferably 1-20, and more preferably 1-5, vinyl groups or (meth) acrylate groups as photocurable functional groups . In addition, the photocurable monomer may be a mixture of a monofunctional monomer and a polyfunctional monomer.

For example, the photo-curable monomer may be a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 carbon atoms, a substituted or unsubstituted aryl group having 6-20 carbon atoms, An aralkyl group having 7 to 20 carbon atoms, or an unsaturated carboxylic acid ester having a hydroxy group and an alkyl group having 1 to 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; A mono-alcohol or a polyfunctional (meth) acrylate of a polyhydric alcohol, and the like. 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, octyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decanyl Unsaturated carboxylic acid esters such as (meth) acrylate, cyclohexyl (meth) acrylate, 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 (Meth) acrylate, propyleneglycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, octyldiol di Monofunctional or polyfunctional (meth) acrylates having 5 to 30 carbon atoms in a monoalcohol or polyhydric alcohol including di (meth) acrylate, dodecyl diol di (meth) acrylate and the like, It is not.

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

For example, the photocurable monomer may be an alkyl of 2 to 30 carbon atoms, an aryl of 6 to 30 carbon atoms having at least one chain terminating group selected from a (meth) acrylate group or a (meth) acryloxyalkyl group , Or a non-halogen siloxane monomer having an arylalkyl group having 7 to 20 carbon atoms.

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 monohydric alcohol or a monohydric siloxane monomer having a polyfunctional (meth) acrylate, a di (meth) acrylate end group, or a mixture thereof .

The weight average molecular weight of the photocurable monomer may be 100-5,000 g / mol, preferably 200-2,000 g / mol, and more preferably 300-1,000 g / mol. Within this range, there can be obtained an effect of obtaining a composition excellent in the degree of photo-curing.

The photocurable monomer may be included in the photocurable composition in an amount of 1-90 wt%, preferably 10-70 wt%, 20-70 wt%, more preferably 30-70 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 photo-curable composition may further contain conventional additives in addition to the above-mentioned components. For example, the additive may be a curing accelerator, a curing inhibitor, a dispersing agent, or the like, but is not limited thereto.

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 96-98%.

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 < ² >. 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 cured specimen having a coating film thickness of 5 mu m is formed in the same manner as in the measurement of the photo-curability. Using a moisture permeability meter (PERMATRAN-W 3/33, MOCON), the moisture permeability was measured in the thickness direction for 5 hours at a temperature of 50 ° C and 100% relative humidity for 24 hours.

The organic protective layer has low oxygen permeability and can minimize the effect of oxygen on the device. Oxygen permeability was measured by using an oxygen permeability meter (OX-TRAN Model 2/21, MOCON Co.) in a thickness direction of 25 占 폚 for a film thickness of 5 占 퐉 for 24 hours. 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, 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 2,000 ppm, from 0 to 2,000 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 lower the moisture permeability, oxygen permeability, and outgassing amount of the organic protective layer, the smaller the effect on application to the device and the longer the life of the device.

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 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.

In the optical member of the present invention, the device is sealed by the inorganic protective layer, which is a protective layer having different properties, and the 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 100-2,000A.

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 of the present invention, 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.

Specific specifications of the components used in the following examples and comparative examples are as follows.

(A) a silicone compound containing a halogen and a (meth) acrylate group: C6F5 (CH2) 3Si (OSi (CH3) 2 (CH2) 3OCOCH = CH2)) 3

(B) Photopolymerization initiator: Darocur TPO (BASF)

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

Synthetic example : C ₆ F ₅ ( CH ₂ ) ₃ Si ( OSi ( CH ₃ ) ₂ (CH ₂ ) ₃ OCOCH = CH ₂ )) ₃  Produce

188.9 g of 3-acryloxypropyldimethylmethoxysilane (H ₃ COSi (CH ₃ ) ₂ (CH ₂ ) ₃ OCOCH═CH ₂ , Gelest), 31.5 g of H ₂ O and 300 g of toluene were charged into a jacketed reactor And the mixture was stirred at room temperature for 30 minutes. Thereafter, 100.0 g of pentafluorophenylpropyltrichlorosilane (C ₆ F ₅ (CH ₂ ) ₃ SiCl ₃ , Gelest) was slowly added dropwise to the reactor over a period of 1 hour while the reactor was cooled to 0 ° C. After the addition, the reactor was stirred at room temperature for 6 hours, and the reaction was terminated. The organic solution in the reactor was neutralized with water until the pH became neutral and then dried under reduced pressure to obtain the final product. The obtained product was identified by analyzing the final structure by NMR and GC.

Examples Comparative Example

(A) a silicone compound containing a halogen and a (meth) acrylate group, (B) a photopolymerization initiator, and (C) a photocurable monomer were blended in the contents (unit: parts by weight) .

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 < ² > 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. Water Permeability: Use a moisture permeability meter (PERMATRAN-W 3/33, MOCON). The photocurable composition is applied by spraying on an Al sample holder and irradiated at 100 J / cm ² for 10 seconds to UV cure to form a cured specimen of 5 μm thick. The moisture permeability is measured for 24 hours at 50 占 폚 and 100% relative humidity using a moisture permeability meter (PERMATRAN-W 3/33, MOCON) for a film thickness of 5 占 퐉.

3. Oxygen Permeability: A sample was prepared in the same manner as the above moisture permeability, and the oxygen permeability was measured for 24 hours at 25 ° C using an oxygen permeability meter (OX-TRAN Model 2/21, MOCON) .

4. 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.

5. Outgassing of Organic Protective Layer: A photocurable composition was applied on a glass substrate by spraying and irradiated at 100 mW / cm ² for 10 seconds to be UV-cured to form a 20 cm x 20 cm x 3 탆 (width x length x thickness) organic A protective layer specimen is obtained. For the specimen, use a GC / MS instrument (Perkin Elmer Clarus 600). As GC / MS, a helium gas (flow rate: 1.0 mL / min, average velocity = 32 cm / s) was used as a mobile phase using a DB-5MS column (length: 30 m, diameter: 0.25 mm, ), The split ratio is 20: 1, the temperature condition is kept at 40 占 폚 for 3 minutes, then the temperature is raised at a rate of 10 占 폚 / min, and the temperature is maintained at 320 占 폚 for 6 minutes. The outgas was 20 cm x 20 cm in glass size, the Tedlar bag was collected, the collection temperature was 90 ° C, the collection time was 30 minutes, the N ₂ purge flow was 300 mL / min and the adsorbent was Tenax GR (5% phenylmethylpolysiloxane ). 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. The above conditions are summarized in Table 1 below.

division
Detail Collection conditions





Glass size: 20cm * 20cm Collecting container: Tedlar bag Collecting temperature: 90 ℃ Collection time: 30 min N2 purge flow rate: 300 mL / min Adsorbent: Tenax GR (5% phenylmethylpolysiloxane) Calibration Curve Condition


Standard solution: Toluene in n-Hexane Concentration range: 150 ppm, 400 ppm, 800 ppm R2: 0.9987 GC / MS conditions



Column DB-5MS? 30 m 0.25 mm 0.25 占 퐉
(5% phenylmethylpolysiloxane) Mobile phase He Flow 1.0 mL / min (Average velocity = 32 cm / s) Split Split ratio = 20: 1 method 40 캜 (3 min) -10 캜 / min? 320 캜 (6 min)

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 Comparative Example 1 Comparative Example 2 (A) 98 88 49 49 - - (B) 2 2 2 2 2 2 (C) (C1) - 2 - 49 49 98 (C2) - 8 49 - 49 - Photocuring condition 100 J / cm ² , 10 sec UV irradiation Light curing rate (%) 98 97 97 96 93 94 Moisture permeability (g / m ² day) 3 4 5 6 9 10 Oxygen permeability (cc / m ² day) 256 261 282 283 384 420 responsibility 10 points 10 points 8 points 7 points 4 points 3 points Outgassing Amount (ppm) 39 37 42 41 45 43

As shown in Table 3, the photocurable composition of the present invention has a high photo-curability and the organic protective layer produced therefrom can reduce the moisture permeability and oxygen permeability, and consequently the long-term reliability of devices such as OLEDs or organic solar cells Can be improved.

On the other hand, the photocurable composition of Comparative Example 1-2, which did not contain a silicone compound containing a halogen and a (meth) acrylate group, had a relatively low photo-curing rate, and the organic protective layer prepared therefrom was also excellent in moisture permeability and oxygen permeability The reliability of the device is deteriorated and the effect of the present invention is not 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 (16)

A silicone compound containing a halogen and a (meth) acrylate group, and a photopolymerization initiator,
The silicone compound is a photocurable composition having a structure represented by the following formula (1)
Wherein the cured product of the photocurable composition has a moisture permeability of 8 g / m < ² > .24 hr or less in the thickness direction measured for 24 hours at 50 DEG C and 100%
&Lt; Formula 1 >

R ¹ is a halogenated aryl group having 6 to 30 carbon atoms, a halogenated arylalkyl group having 7 to 30 carbon atoms, or a halogenated alkyl group having 1 to 30 carbon atoms,
R ² , R ³ and R ^{4 each} 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 to 10 carbon atoms or a substituted or unsubstituted silyl group having 1 to 10 carbon atoms,
At least one of R ² , R ³ and R ⁴ contains the following formula
(2)

Wherein R ⁵ is hydrogen or a substituted or unsubstituted alkyl group having 1-30 carbon atoms,
a is an integer of 1 or more and 3 or less,
b, c and d each represent an integer of 0 to 4, provided that all of b, c and d are not 0,
a + b + c + d is an integer of 2 or more and 4 or less. The photocurable composition according to claim 1, wherein the silicone compound contains 0.1-90 wt% of a halogen. The photocurable composition according to claim 1, wherein the silicone compound contains halogen in a proportion of 5-30 wt%. delete The method of claim 1, wherein R ¹ is C ₆ X ₅ (CX ₂ ) _x (CH ₂ ) _y - or CX ₃ (CX ₂ ) _x (CH ₂ ) _y - wherein X is fluorine, chlorine, iodine, , x is an integer from 0 to 10, and y is an integer from 0 to 10). The photocurable composition according to claim 1, wherein the silicone compound has a weight average molecular weight of 100-5,000. 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-halogenated siloxane monomer having a photocurable functional group, or a mixture thereof . The photocurable monomer according to claim 8, 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 halogen-free siloxane monomer having at least one terminal group, or a mixture thereof. The photocurable composition of claim 8, 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. Characterized in that the moisture content in the thickness direction measured with the photocurable composition of any one of claims 1 to 3 and 5 to 10 measured for 24 hours at 50 DEG C and 100% relative humidity conditions for a film thickness of 5 mu m An organic electroluminescent portion or an organic solar cell element having a moisture permeability of 8 g / m ² .24 hr or less. 12. The method of claim 11, in 25 ℃ for the film thickness 5㎛ oxygen permeability of 24 hours the measured thickness while 300cc / m ² .24hr or less, the organic protective layer to seal the portion around the development of organic or organic solar cell device. 12. The organic protective layer according to claim 11, wherein the organic protective layer has an outgassing amount of 2,000 ppm or less. delete An optical member comprising the organic protective layer of claim 11. 16. The organic electroluminescent device according to claim 15, wherein the optical member comprises a substrate, an organic electroluminescent portion formed on the substrate, an inorganic protective layer sealing the organic electroluminescent portion, and an organic protective layer stacked on the inorganic protective layer absence.

Images