KR20210082015A - Composition for encapsulation, encapsulation layer comprising the same and encapsulated apparatus comprising the same - Google Patents

Abstract

The present invention relates to an encapsulation composition comprising at least one photocurable monomer and an initiator, an encapsulation layer comprising the same, and an encapsulated device which can implement high reliability by including the encapsulation layer.

Description

Encapsulation composition, encapsulation layer comprising the same, and encapsulation device comprising the same

The present invention relates to a composition for encapsulation comprising a novel photocurable monomer and an initiator, an encapsulation layer comprising the same, and an encapsulated device comprising the same.

Organic optoelectronic devices such as organic light emitting diodes, devices including photovoltaic cells, and display devices such as organic thin film transistors must be encapsulated to protect their sensitive electronic components (eg devices) from atmospheric oxygen and/or moisture. If adequate protection is not provided, deterioration of quality such as occurrence of non-radiative dark spots may result. In particular, in the case of an organic light emitting diode, the quality may be deteriorated due to water vapor penetrating into the diode, and quality deterioration may occur at the cathode (or anode)/organic film interface.

An encapsulation layer including an organic film and an inorganic film is used as a means for sealing the components embedded in the above-described display device. The encapsulation layer has a multilayer thin film structure in which organic layers and inorganic layers are alternately stacked. Since the organic and inorganic layers alternately stacked in this way have a relatively low adhesion, there is a problem in that the moisture barrier effect is relatively low. In particular, when applied to a large screen such as an OLED mobile phone or OLED TV, higher adhesion between the inorganic layer and the organic layer constituting the encapsulation layer is required.

The present invention has been devised to solve the above-described problems, comprising: a composition for encapsulation capable of realizing high adhesion with an inorganic layer even when applied to a large screen, an encapsulation layer formed from the composition; And it is a technical task to provide an encapsulated device that exhibits high reliability by providing the encapsulation layer.

Other objects and advantages of the present invention may be more clearly explained by the following detailed description and claims.

In order to achieve the above object, the present invention provides at least one photocurable monomer; and a polymerization initiator, wherein the at least one photocurable monomer provides a composition for encapsulation comprising a first monomer (A1) represented by the following Chemical Formula 1 or an oligomer thereof.

In Formula 1,

Ar ₁ and Ar ₂ are the same or different, and are each independently an alicyclic, heteroalicyclic, aromatic or heteroaromatic hydrocarbon group having 5 to 20 carbon atoms,

X ₁ is a single bond or O, Si(R ₄ ) ₂ , NR ₄ , and a substituted or unsubstituted C 1 to C 5 alkylene group is selected from the group consisting of,

a and b are each 0 or 1, a+b ≥1,

Z ₁ is a moiety represented by the following formula 1a,

[Formula 1a]

In Formula 1a,

* means a portion in which a bond is formed with Chemical Formula 1,

Y ₁ is a single bond or is selected from the group consisting of _{O, Si(R 4} ) ₂ , and NR _{4 ,}

R ₁ and R ₂ are the same as or different from each other, and are each independently a substituted or unsubstituted C 1-10 alkylene group,

R ₃ and R ₄ are the same as or different from each other, and each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms.

In one embodiment of the present invention, the first monomer may have a weight average molecular weight (Mw) of greater than 0, 500 g/mol or less, and a viscosity of greater than 0, 10,000 cps or less (based on 25°C).

For one embodiment of the present invention, the first monomer may be included in an amount of 0.01 to 40 parts by weight based on the solid content.

In one embodiment of the present invention, the at least one photocurable monomer may include a second monomer (A2) represented by the following formula (2); and at least one of a third monomer (A3) represented by Formula 3 below.

[Formula 2]

[Formula 3]

In Formula 2 or 3,

Ar _{3 To} Ar ₄ are the same or different, and each independently represents an alicyclic having 5 to 20 carbon atoms, a heteroalicyclic having 5 to 20 nuclear atoms, an aromatic having 6 to 20 carbon atoms, or a heteroaromatic having 5 to 20 nuclear atoms. is a hydrocarbon group of

Ar _{5 To} Ar _{6 Are} the same or different, and each independently is a single bond or _{is selected from the group consisting of O, S, NR 4} , and a substituted or unsubstituted C 1 to C 5 alkylene group,

X ₂ and X ₃ are the same as or different from each other, and each independently a single bond or O, S, Si(R ₄ ) ₂ , NR ₄ , and a group consisting of a substituted or unsubstituted C 1 to C 5 alkylene group is selected from

a and b are each 0 or 1, a+b ≥1,

n1 and n2 are respectively 0 or 1, n1+n2 ≥ 1,

m is an integer from 1 to 12,

Z _{3 To} Z ₆ are each independently a moiety represented by the following formula (4),

[Formula 4]

* is _{a connecting portion of carbon of Ar 3} or Ar ₄ of Formula 2, or a connecting portion of carbon of Ar ₅ or Ar ₆ of Formula 3,

Y ₂ is a single bond or _{is selected from the group consisting of O, Si(R 4} ) ₂ , NR ₄ and a substituted or unsubstituted C 1 to C 5 alkylene group,

R ₅ are the same as or different from each other, and are each independently a substituted or unsubstituted C 1-10 alkylene group,

R ₄ and R ₆ are the same as or different from each other, and each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms.

In one embodiment of the present invention, the second monomer may have a weight average molecular weight (Mw) of more than 0 and 500 g/mol or less, and a viscosity of more than 0 and 500 cps or less (based on 25°C).

In one embodiment of the present invention, the second monomer may be included in an amount of 0 to 60 parts by weight based on the solid content.

In one embodiment of the present invention, each of the first monomer and the second monomer may include a biphenyl group.

For example, the third monomer may have a weight average molecular weight (Mw) of greater than 0, 500 g/mol or less, and a viscosity of greater than 0 and 500 cps or less (based on 25°C).

In one embodiment of the present invention, the third monomer may be included in an amount of 30 to 99.5 parts by weight based on the solid content.

For one embodiment of the present invention, the polymerization initiator may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the (A1)+(A2)+(A3) in the solid content.

For one embodiment of the present invention, the composition may further include 0.01 to 1 part by weight of an antioxidant based on 100 parts by weight of the (A1)+(A2)+(A3) in the solid content.

In one embodiment of the present invention, the composition may have a viscosity of 10 to 100 cps at 25° C., and may be solvent-free including a solvent.

In one embodiment of the present invention, the composition may have a cure shrinkage rate of greater than 0 and less than or equal to 10% according to Equation 1 after curing.

[Equation 1]

Curing shrinkage rate (%) = (specific gravity of solid after curing - specific gravity of liquid composition before curing) / specific gravity of liquid composition before curing × 100

For one embodiment of the present invention, the composition may have a plasma etch rate of 0 to 30% by Equation 2 below after curing.

[Equation 2]

Etching rate of organic layer by plasma (%) = (T1-T2)/T1×100

(In Equation 2, T1 is the initial height of the organic layer formed by photocuring the composition for encapsulation, and T2 is ICP (inductively coupled plasma) power: 2500W, RF (radio frequency) power by using ICP-CVD on the organic layer: 300W, DC bias: 200V, Ar flow: 50sccm, etching time: 1min, pressure: the height of the organic layer after plasma treatment at 10mtorr).

In addition, the present invention is a device member; and an encapsulation layer formed on the device member and including an inorganic layer and an organic layer, wherein the organic layer provides an encapsulated device including a cured product of the above-described encapsulation composition.

In one embodiment of the present invention, the organic layer may have an adhesive strength of 0.2 kg/inch ^{2 or} more to the inorganic layer.

In one embodiment of the present invention, the organic layer may have a storage modulus of 1 to 20 GPa, a chlorine ion content of 30 ppm or less, and a transmittance measured in a 550 nm wavelength region of 95% to 100%.

In one embodiment of the present invention, the encapsulation layer may be formed by alternately stacking at least one inorganic layer and at least one organic layer, and may include a total of 10 layers or less.

In one embodiment of the present invention, one organic layer may have a thickness of 0.1 to 20 μm, and one inorganic layer may have a thickness of 5 to 500 nm.

In one embodiment of the present invention, the inorganic layer includes a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxygen nitride, a metal oxyboride, or a mixture thereof, and the metal is silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), a transition metal, and at least one of a lanthanide metal may include

In one embodiment of the present invention, the device member includes a flexible organic light emitting device, an organic light emitting device, a lighting device, a metal sensor pad, a microdisc laser, an electrochromic device, a photochromic device, a microelectromechanical system, solar cells, integrated circuits, charge coupled devices, light emitting polymers or light emitting diodes.

According to an embodiment of the present invention, by including a novel photocurable monomer capable of imparting high adhesion with the inorganic layer, even when applied to a large area (large screen), moisture and oxygen penetration is effectively blocked to improve the quality of the final display device can be raised

In addition, in the present invention, it is possible to implement an encapsulation layer (barrier layer) having excellent plasma resistance, high storage modulus, and low chlorine ion generation due to a low etching rate of the organic layer by plasma after curing.

In addition, the composition for encapsulation according to the present invention not only has a low curing shrinkage rate, it can be manufactured in a solvent-free type and can reduce outgas. In addition, it is possible to easily form a barrier layer for encapsulation of a member for a display device sensitive to the environment.

The effect according to the present invention is not limited by the contents exemplified above, and more various effects are included in the present specification.

1 is a cross-sectional view of an encapsulated device in accordance with an embodiment of the present invention.
2 is a cross-sectional view of an encapsulated device according to another embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Examples of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art, and the following examples may be modified in various other forms, and the scope of the present invention is not limited to the following examples It is not limited to an example. In this case, like reference numerals refer to like structures throughout this specification.

Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with the meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly specifically defined.

In addition, since the size and thickness of each component shown in the drawings are arbitrarily indicated for convenience of description, the present invention is not necessarily limited to the illustrated bar. In order to clearly express various layers and regions in the drawings, the thicknesses are enlarged. And in the drawings, for convenience of description, the thickness of some layers and regions are exaggerated.

In addition, throughout the specification, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated. In addition, throughout the specification, "on" or "on" means that it includes not only the case where it is located above or below the target part, but also the case where there is another part in the middle, and the direction of gravity must be It does not mean that it is positioned above the reference. And, in the present specification, terms such as “first” and “second” do not indicate any order or importance, but are used to distinguish components from each other.

In addition, throughout the specification, when referred to as "planar", it means when the target part is viewed from above, and "in cross-section" means when viewed from the side when the cross-section of the target part is vertically cut.

In the present specification, "(meth)acrylate" refers to acrylate and methacrylate, "(meth)acryl" refers to acryl and methacryl, and "(meth)acryloyl" refers to acryloyl and methacrylate. It means krill.

In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in the present invention is distinguished from an oligomer, a polymer, and a resin, which are polymers polymerized with the monomer, and refers to a compound having a weight average molecular weight of 1,000 g/mol or less. In the present specification, "polymerizable functional group" refers to a group involved in a polymerization reaction, such as a (meth)acrylate group.

In the present specification, 'substituted' in 'substituted or unsubstituted' means that at least one hydrogen atom in the functional group of the present invention is halogen (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, an imino group (=NH, = NR and R are alkyl groups having 1-10 carbon atoms), amino groups (-NH ₂ , -NH(R'), -N(R")(R"'), R', R", R"' are each independently is an alkyl group having 1-10 carbon atoms), an alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, a cycloalkyl group having 3-10 carbon atoms, a heteroaryl group having 5-20 nuclear atoms, 2-30 nuclear atoms of a heterocycloalkyl group, and may mean being substituted with an arylalkyl group having 7-21 carbon atoms.

In the present specification, the solid content means a component other than the solvent in the composition for sealing. Therefore, even if it is a liquid component, it is a solid component unless it is a component used as a solvent. In addition, in the present specification, '*' may represent an inter-element bonding site.

<Composition for Encapsulation>

The composition for encapsulation according to the present invention is a composition for encapsulation that encapsulates a display device including a light emitting diode device, and is a photocurable composition comprising a photocurable monomer and an initiator.

In one embodiment, the composition comprises at least one photocurable monomer; and a polymerization initiator, wherein the at least one photocurable monomer includes a first monomer (A1) represented by the following Chemical Formula 1 or an oligomer thereof. If necessary, it may further include at least one or more conventional photocurable monomers, antioxidants, and additives known in the art.

Hereinafter, a detailed look at the composition of the composition for encapsulation is as follows.

photocurable monomer

The adhesive composition according to the present invention includes at least one conventional photocurable monomer known in the art as a compound that polymerizes by light of a specific wavelength, for example, ultraviolet (UV) light.

As a specific example, the at least one photocurable monomer includes the first monomer (A1) represented by the following Chemical Formula 1 or an oligomer thereof.

[Formula 1]

In Formula 1,

Ar ₁ and Ar ₂ are the same or different, and are each independently an alicyclic having 5 to 20 carbon atoms, a heteroalicyclic having 5 to 20 nuclear atoms, an aromatic having 6 to 20 carbon atoms, or a heteroaromatic having 5 to 20 nuclear atoms. is a hydrocarbon group of

X ₁ is a single bond or O, Si(R ₄ ) ₂ , NR ₄ , and a substituted or unsubstituted C 1 to C 5 alkylene group is selected from the group consisting of,

a and b are each 0 or 1, a+b ≥1,

Z ₁ is a moiety represented by the following formula 1a,

[Formula 1a]

In Formula 1a,

* means a portion in which a bond is formed with Chemical Formula 1,

Y ₁ is a single bond or is selected from the group consisting of _{O, Si(R 4} ) ₂ , and NR _{4 ,}

R ₁ and R ₂ are the same as or different from each other, and are each independently a substituted or unsubstituted C 1-10 alkylene group,

R ₃ and R ₄ are the same as or different from each other, and each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms.

The above-described first monomer (A1) or an oligomer thereof not only has a photopolymerizable functional group in the molecule, but also includes a predetermined cyclic ring and a hydroxyl group. Accordingly, it is possible to exhibit high adhesive properties with other substrates (eg, the inorganic layer of the encapsulation layer) compared to the conventional photocurable monomer forming the encapsulation layer. In addition, by improving the plasma resistance of the cured product formed from the encapsulation composition according to the present invention and lowering the curing shrinkage, it can be used as an encapsulation layer (eg, an organic layer) of a device member such as an organic light emitting device.

In Formula 1, Ar ₁ and Ar ₂ are a conventional alicyclic having 5 to 20 carbon atoms, a heteroalicyclic having 5 to 20 nuclear atoms, an aromatic having 6 to 20 carbon atoms, or 5 to 20 nuclear atoms known in the art. It may be a heteroaromatic monocyclic or polycyclic hydrocarbon group. Specifically, it may be an alicyclic group having 5 to 20 carbon atoms, or a heteroalicyclic hydrocarbon group having 5 to 20 nuclear atoms. In this case, a and b may be 0 or 1, respectively, and a+b ≥1. Here, when a+b _{≥1, the -Ar 1} -X ₁ -Ar ₂ - is tetrahydrofuran (oxolane), furan (furan), thiophene, pyrrole (pyrrole), pyrrolidine (pyrrolidine) , pyran, pyridine, piperidine, imidazole, thiazole, dioxane, morpholine, pyrimidine, phenyl, bi It may be phenyl (biphenyl), cyclopentane, cyclohexane, and the like.

In addition, in the moiety (Z ₁ ) represented by Formula 1a, R ₁ and R ₂ may be an alkylene group having 1 to 5 carbon atoms, and R ₃ may be hydrogen or a methyl group.

For example, the first monomer (A1) represented by Formula 1 has a weight average molecular weight (Mw) of greater than 0, 500 g/mol or less, and specifically 200 to 500 g/mol. . Also, the viscosity at 25° C. is greater than 0 and less than or equal to 10,000 cPs, and may specifically be 50 to 1,000 cPs. When it has the above-described molecular weight and viscosity, it is possible to exhibit the effect of increasing deposition efficiency.

The first monomer (A1) or its oligomer may be a mono(meth)acrylate monomer including one photopolymerizable functional group. These mono (meth) acrylate monomers can lower the amount of outgas generated during photocuring of the encapsulation composition compared to the conventionally known di (meth) acrylate monomers. The first monomer (A1) or its oligomer may be synthesized according to a conventional method known in the art, or a commercially available product may be used.

In the present invention, the content of the first monomer (A1) is not particularly limited, and may be appropriately adjusted within a content range known in the art. For example, the first monomer (A1) may be included in an amount of 0.01 to 40 parts by weight, specifically, 1 to 30 parts by weight based on the solid content of the composition. When the content of the first monomer falls within the above-described range, deposition efficiency may be increased, and adhesive properties of the cured encapsulation layer may be increased.

In the present invention, in addition to the first monomer described above, at least one type of photopolymerizable monomer is mixed. In one embodiment, the at least one photocurable monomer may include a second monomer (A2) represented by the following Chemical Formula 2; It may include a third monomer (A3) represented by the following Chemical Formula 3 or both.

[Formula 2]

[Formula 3]

In Formula 2 or 3,

Ar _{3 To} Ar ₄ are the same or different, and each independently represents an alicyclic having 5 to 20 carbon atoms, a heteroalicyclic having 5 to 20 nuclear atoms, an aromatic having 6 to 20 carbon atoms, or a heteroaromatic having 5 to 20 nuclear atoms. is a hydrocarbon group of

Ar _{5 To} Ar _{6 Are} the same or different, and each independently is a single bond or _{is selected from the group consisting of O, S, NR 4} , and a substituted or unsubstituted C 1 to C 5 alkylene group,

X ₂ and X ₃ are the same as or different from each other, and each independently a single bond or O, S, Si(R ₄ ) ₂ , NR ₄ , and a group consisting of a substituted or unsubstituted C 1 to C 5 alkylene group is selected from

a and b are each 0 or 1, a+b ≥1,

n1 and n2 are respectively 0 or 1, n1+n2 ≥ 1,

m is an integer from 1 to 12,

Z _{3 To} Z ₆ are each independently a moiety represented by the following formula (4),

[Formula 4]

* is _{a connecting portion of carbon of Ar 3} or Ar ₄ of Formula 2, or a connecting portion of carbon of Ar ₅ or Ar ₆ of Formula 3,

Y ₂ is a single bond or _{is selected from the group consisting of O, Si(R 4} ) ₂ , NR ₄ and a substituted or unsubstituted C 1 to C 5 alkylene group,

R ₅ are the same as or different from each other, and are each independently a substituted or unsubstituted C 1-10 alkylene group,

R ₄ and R ₆ are the same as or different from each other, and each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms.

The second monomer (A2) is used as an encapsulation layer (eg, an organic layer) of a device member such as an organic light emitting device by improving plasma resistance and lowering curing shrinkage of a cured product formed from the encapsulation composition according to the present invention. make it possible

In a preferred example of Chemical Formula 2, Ar ₃ is an aryl group having 6-20 carbon atoms, and specifically, may be a phenyl group. In addition, Ar ₄ is an arylene group having 6-20 carbon atoms, and specifically may be a phenylene group.

a and b are 0 or 1, respectively, but a+b ≥ 1, n1 and n2 are 0 or 1, respectively, and n1+n2 ≥ 1. In this case, when a+b ≥ 1, '-Ar ₃ -X ₂ -Ar ₄ -' in Formula 2 may be a biphenyl group.

In addition, in the photopolymerizable functional group (Z ₃ to Z ₄ ) connected to Chemical Formula 2, R ₅ may be an alkylene group having 1 to 5 carbon atoms, and R ₆ may be hydrogen or a methyl group.

For one embodiment of the present invention, the second monomer (A2) represented by Formula 2 has a weight average molecular weight (Mw) of greater than 0, 500 g/mol or less, and specifically 200 to 500 g/mol. . In addition, the second monomer (A2) may have a viscosity of greater than 0 and 500 cPs or less at 25° C., specifically 5 to 150 cPs. When it has the above-described molecular weight and viscosity, it is possible to exhibit the effect of increasing deposition efficiency.

The second monomer (A2) may be a mono (meth) acrylate monomer including one photopolymerizable functional group. These mono (meth) acrylate monomers can lower the amount of outgas generated during photocuring of the encapsulation composition compared to the conventionally known di (meth) acrylate monomers. The second monomer (A2) may be synthesized according to a conventional method known in the art, or a commercially available product may be used.

In the present invention, the content of the second monomer (A2) is not particularly limited, and may be appropriately adjusted within a content range known in the art. For example, the second monomer (A2) may be included in an amount of 0 to 60 parts by weight, specifically 0 to 50 parts by weight, based on the solid content of the composition. When the content of the second monomer falls within the above range, deposition efficiency may be increased, and plasma resistance during photocuring may be improved, and curing shrinkage may be lowered.

The third monomer (A3) represented by Formula 3 is a non-silicone-based photocurable monomer that does not contain silicone, and includes at least one conventional photopolymerizable functional group known in the art. Specifically, '-Ar ₃ -X ₂ -Ar ₄ -' of Formula 2 may not be included.

The third monomer (A3) is included in the encapsulation composition to lower the viscosity, thereby improving the physical properties of the composition such as coating easiness, increasing the storage modulus after curing, and reducing the curing shrinkage rate.

For example, the photopolymerizable functional group included in the third monomer (A3) may be a vinyl group, an acrylate group, and/or a methacrylate group. In addition, the number of the photopolymerizable functional groups may be 1 to 30, specifically 1 to 20, more specifically 1 to 6.

The third monomer (A3) may include a monofunctional monomer having a photopolymerizable functional group, a polyfunctional monomer, or a mixture thereof.

For example, the third monomer (A3) may be an aromatic hydrocarbon compound having 6-20 carbon atoms having a substituted or unsubstituted vinyl group; unsaturated carboxylic acid esters having an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a hydroxy group and an alkyl group having 1 to 20 carbon atoms; unsaturated carboxylic acid esters having an amino alkyl group having 1 to 20 carbon atoms; vinyl esters of saturated or unsaturated carboxylic acids having 1 to 20 carbon atoms; vinyl cyanide compounds; unsaturated amide compounds; It may be a monofunctional or polyfunctional (meth)acrylate of monoalcohol or polyhydric alcohol. The 'polyhydric alcohol' is an alcohol having two or more hydroxyl groups, and may mean an alcohol having 2-20, preferably 2-10, more preferably 2-6 hydroxyl groups.

Non-limiting examples of the usable third monomer (A3) include an alkenyl group containing a vinyl group such as styrene, alpha-methyl styrene, vinyl toluene, vinyl benzyl ether, vinyl benzyl methyl ether, and an aromatic having 6-20 carbon atoms. hydrocarbon compounds; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, hexyl (meth)acrylate, Octyl (meth) acrylate, nonyl (meth) acrylate, decanyl (meth) acrylate, undecanyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) unsaturated carboxylic acid esters including (meth)acrylic acid esters such as acrylate and phenyl (meth)acrylate; unsaturated carboxylic acid amino alkyl 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; Vinyl cyanide compounds, such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; Ethylene glycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) ) acrylate, octyldiol di(meth)acrylate, nonyldiol di(meth)acrylate, decanyldiol di(meth)acrylate, undecanyldiol di(meth)acrylate, dodecyldiol di(meth)acryl Rate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate Acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A di (meth)acrylate, novolac epoxy (meth)acrylate, diethylene glycol di(meth)acrylate, tri(propylene glycol) di(meth)acrylate, poly(propylene glycol) di(meth)acrylate, tetra It may be a monofunctional or polyfunctional (meth)acrylate of a monoalcohol or polyhydric alcohol, including ethylene glycol di(meth)acrylate, and the like, but is not limited thereto. The 'polyhydric alcohol' is an alcohol having two or more hydroxyl groups, and may mean an alcohol having 2-20, preferably 2-10, more preferably 2-6 hydroxyl groups.

Specifically, the third monomer (A3) may include polyalkylene glycol di(meth)acrylate. Such polyalkylene glycol di(meth)acrylate can supplement the physical properties of other photocurable monomers having relatively high viscosity by increasing the storage modulus after curing, lowering the curing shrinkage of the composition, and lowering the viscosity of the composition. More specifically, the polyalkylene glycol di(meth)acrylate may include di(meth)acrylate including a linear or branched alkylene glycol unit having 2-5 carbon atoms.

In one embodiment of the present invention, the third monomer (A3) represented by Formula 3 has a weight average molecular weight (Mw) of greater than 0, 500 g/mol or less, and specifically 200 to 500 g/mol. . In addition, the third monomer (A3) may have a viscosity of greater than 0 and 200 cPs or less at 25° C., specifically 5 to 150 cPs. When it has the above-described molecular weight and viscosity, the amount of outgas generated may be low, and there may be an effect of increasing deposition efficiency.

In the present invention, the content of the third monomer (A3) is not particularly limited, and may be appropriately adjusted within a content range known in the art. For example, the third monomer (A3) may be included in an amount of 30 to 99.5 parts by weight, specifically 45 to 99 parts by weight, based on the solid content of the composition. When the content of the third monomer (A3) falls within the above-described range, deposition efficiency may be increased, and plasma resistance during photocuring may be improved, and curing shrinkage may be reduced.

The composition for sealing according to the present invention, if necessary, (A4) a siloxane group-containing fourth monomer; and (A5) at least one of a fifth monomer containing silicone and a urethane group. These (A4), (A5) monomers are included in the composition to lower the viscosity to improve the physical properties of the composition, to further improve plasma resistance, to increase the adhesion to the inorganic layer, and to increase the deposition efficiency. can

For example, the siloxane group-containing fourth monomer (A4) may include a polysiloxane-containing di(meth)acrylate monomer. The fourth monomer (A4) may have a weight average molecular weight of greater than 0 and 500 g/mol or less, preferably 200-500 g/mol. Also, the viscosity at 25° C. may be greater than 0 and less than or equal to 500 cPs, preferably 150-500 cPs.

In another embodiment, the fifth monomer (A5) containing silicone and urethane groups may include (meth)acryl alkoxysilane or an oligomer thereof.

This fifth monomer (A5) or an oligomer thereof may be monofunctional or polyfunctional, preferably monofunctional. In the case of monofunctionality, it is possible to further increase the effect of improving adhesion to the inorganic layer, thereby further increasing reliability.

The fifth monomer (A5) or an oligomer thereof may have a weight average molecular weight of 50 to 1000 g/mol, specifically 150 to 600 g/mol. In addition, the viscosity at 25° C. is greater than 0 and 200 cPs or less, and may preferably be 5 to 150 cPs.

In the present invention, the content of the above-described fourth monomer and/or fifth monomer is not particularly limited, and may be appropriately adjusted within a content range known in the art.

polymerization initiator

In the composition for encapsulation according to the present invention, the polymerization initiator is a component that is excited by a light source having a predetermined wavelength region to perform a photocurable reaction, and a conventional photopolymerization photoinitiator known in the art may be used without limitation. .

Specifically, the polymerization initiator may include both an ultraviolet (UV) photoinitiator and a visible light photoinitiator, preferably a UV photoinitiator. In the present invention, the photoinitiator is mainly described, but using a thermal initiator known in the art also falls within the scope of the present invention.

The UV photoinitiator can generally use a compound having an absorption wavelength at a wavelength of 200 to 400 nm, and specifically absorbs a portion of the spectrum adjacent to invisible light and a portion of visible light slightly outside this spectrum, such as greater than 200 nm to about 390 nm. A compound having a wavelength is effective. As an example of the polymerization initiator that can be used, phosphorus compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, benzyldimethyl-ketal, hydroxyketone (α -hydroxyketone), aminoketone (α-aminoketone), phenylglyoxylate, mono acyl phosphine, bis acryl phosphine, or a mixture thereof may be used.

For one embodiment, it is preferable to use a phosphorus-based or acetophenone-based compound. Examples of such an acetophenone-based compound include 2-methyl-1-(4-(methylthio)phenyl)-2-morpholino propan-1-one, 2-benzyl-2-dimethyl amino-1-(4-mo polyno phenyl)-butan-1-one, or a mixture thereof. In addition, examples of the phosphorus compound include benzoyldiphenyl phosphine oxide, benzyl trimethylbenzoyl phosphine oxide, or a mixture thereof.

Non-limiting examples of usable photoinitiators, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, benzion alkyl ether (Benzionalkylether), benzophenone (Benzophenone), benzyl dimethyl catal (Benzyl dimethyl kata), hydride Hydroxycyclohexyl phenylacetone, Chloroacetophenone, 1,1-Dichloro acetophenone, Diethoxy acetophenone, Hydroxyacetophenone (diethoxyaceto) Phenone (Hydroxy Acetophenone), 2-Choro thioxanthone (2-Choro thioxanthone), 2-ETAQ (2-EthylAnthraquinone), 1-Hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxy-cyclohexyl-phenyl-ketone) , 2-hydroxy-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-hydroxy-1-[4- (2-hydroxyl) Roxyethoxy)phenyl]-2-methyl-1-propanone (2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone), methylbenzoylformate, etc. These can be used alone or two or more of them can be mixed In the present invention, a photoinitiator can be freely selected according to the UV or LED lamp to be used.

In the present invention, the content of the polymerization initiator is not particularly limited, and may be appropriately adjusted within a range known in the art. For example, the polymerization initiator may be included in an amount of 0.01 to 10 parts by weight, specifically 0.5 to 5 parts by weight, based on 100 parts by weight of (A1)+(A2)+(A3) in the solid content. When the content of the polymerization initiator falls within the above-described range, aging of the encapsulation layer after curing may be prevented, and excellent thermal stability may be exhibited.

For another example, the polymerization initiator may be included in an amount of 0.1 to 5 parts by weight, specifically 0.1 to 4 parts by weight, based on the solid content (eg, 100 parts by weight) of the composition. When the content of the polymerization initiator falls within the above-described range, photopolymerization may sufficiently occur, and a decrease in transmittance due to the remaining unreacted initiator may be prevented.

antioxidant

The composition for encapsulation according to the present invention may further include an antioxidant (thermal stabilizer).

These antioxidants serve to improve the thermal stability of the encapsulation layer after curing, and conventional antioxidants known in the art may be used without limitation. Non-limiting examples of antioxidants that can be used include phenolic, quinone, amine, phosphite, or mixtures thereof. Specific examples include tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, tris(2,4-di-tert-butylphenyl)phosphite, and the like. have.

In the present invention, the content of the antioxidant is not particularly limited, and may be appropriately adjusted within a range known in the art. For example, 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 (A1)+(A2)+(A3) in the solid content. When the content of the antioxidant falls within the above-described range, the aging of the film after curing may be prevented, and excellent thermal stability may be exhibited.

additive

In addition to the above-mentioned components, the adhesive composition of the present invention may use at least one additive known in the art without limitation within a range that does not impair the effects of the present invention.

As an example of usable additives, a light stabilizer, a heat stabilizer, a light initiation accelerator, a thermal initiation accelerator, a smoothing agent, a toughening agent, a thickener, a solvent, and the like may be contained. These may be used alone or in combination of two or more. In this case, the content of the additive may be appropriately adjusted within a range known in the art, and is not particularly limited. For example, the at least one additive may be included in an amount of 0.01 to 5 parts by weight, specifically 0.01 to 2 parts by weight, based on the total weight of the adhesive composition.

The composition for encapsulation according to the present invention comprises mixing and stirring at least one of the above-mentioned photopolymerizable monomers or oligomers, polymerization initiators, antioxidants to be blended as necessary, and other additives according to a conventional method known in the art. can be manufactured.

For a specific example, the composition for encapsulation may include 0.01 to 40 parts by weight of the first monomer (A1) based on the total weight of the composition; 0 to 60 parts by weight of the second monomer (A2); a polymerization initiator comprising 30 to 99 parts by weight of a third monomer (A3), and 0.01 to 10 parts by weight of the solid content based on 100 parts by weight of (A1)+(A2)+(A3); and 0.01 to 1 part by weight of an antioxidant.

The composition for encapsulation of the present invention described above may be a solvent-free type that does not contain a solvent. For example, the viscosity at 25° C. may be 10 to 100 cps, specifically 10 to 50 cps, and more specifically 10 to 30 cps. By adjusting the viscosity to an appropriate range, excellent workability and processability can be imparted, and deposition can be possible.

The composition for sealing of the present invention constituted as described above and a cured product formed therefrom include a first monomer having a predetermined cyclic ring and a hydroxyl group and having excellent adhesion properties, thereby forming another substrate (eg, an inorganic layer constituting an encapsulation layer). ) can exhibit high adhesive properties. In addition, it is possible to secure a low curing shrinkage rate after curing, and a low plasma etching rate, so that an encapsulation layer having excellent plasma resistance, a large storage modulus, and low chlorine ion generation can be realized.

For example, the cured product (eg, organic layer) cured from the composition for encapsulation may have an adhesion strength to the inorganic layer of 0.2 kg/inch ^{2 or} more, specifically 2 to 50 kg/inch ² . The inorganic layer may be applied if the inorganic component is in the encapsulation layer in the art is not particularly limited, and the inorganic layer components, which will be described later (for example, SiOx, SiNx, A _l2 O _3, etc.).

For example, the cured product cured from the composition for encapsulation may have a cure shrinkage rate of 10% or less according to the following [Equation 1]. For example, the curing shrinkage rate may be greater than 0, 10% or less, specifically 0.01 to 10%, more specifically 0.01 to 8%.

[Equation 1]

Curing shrinkage rate (%) = (specific gravity of solid after curing - specific gravity of liquid composition before curing) / specific gravity of liquid composition before curing × 100

In this case, when the curing shrinkage rate is more than 10%, the smoothing properties are deteriorated due to the shrinkage of the organic layer formed from the photocured composition for encapsulation, and thus defects may easily occur during deposition of the inorganic layer. Accordingly, the water vapor transmission rate (WVTR) of the encapsulation layer is poor, and the display device (eg, organic light emitting device) does not emit light due to the permeated oxygen and/or moisture, resulting in dark spots. the possibility may increase. In addition, in the structure of the encapsulation layer in which the organic layer and the inorganic layer are repeatedly stacked, a warpage phenomenon may occur at the edge portion due to the large shrinkage of the organic layer, and thus the role of the thin film encapsulation layer may not be faithfully performed. In addition, when forming the encapsulation layer having a multilayer structure, the effect of suppressing pin-hole generation by minimizing the stress on the deposited inorganic layer cannot be realized.

For another example, in the cured product cured from the composition for encapsulation, the etch rate of the organic layer with respect to plasma may be 0 to 30%, specifically 0 to 20%.

In general, in the process of forming the encapsulation layer (protective layer) of the organic light emitting device, after depositing the organic layer, an inorganic layer is deposited with argon oxide in the presence of argon plasma and oxygen. It can be etched to reduce the organic layer. On the other hand, since the composition for encapsulation of the present invention has excellent plasma resistance after curing, a reliable organic layer can be implemented. The plasma etch rate according to the present invention may be embodied in Equation 2 below. In addition, the above-described plasma etch rate parameter and its numerical range may be different depending on plasma processing conditions.

[Equation 2]

Etching rate of organic layer by plasma (%) = (T1-T2)/T1×100

In Equation 2, T1 is the initial height (μm) of the organic layer formed by depositing and photocuring the encapsulation composition to a predetermined thickness, and T2 is the height after plasma treatment of the organic layer, specifically using ICP-CVD. ICP (inductively coupled plasma) power: 2500W, RF (radio frequency) power: 300W, DC bias: 200V, Ar flow: 50sccm, etching time: 1min, pressure: Height of organic layer after plasma treatment at 10mtorr (μm).

In another embodiment, the cured product cured from the composition for encapsulation may have a storage modulus of 1 to 20 GPa, specifically 1 to 10 GPa. When the storage modulus is less than 1 GPa, the expansion force of the organic layer is relatively greater than that of the inorganic layer during evaluation of high temperature and high humidity, so that micro-cracks may easily occur in the inorganic layer and reliability may be poor. In addition, when the storage modulus exceeds 20 GPa, cracks may easily occur in the organic layer, resulting in poor reliability, when an external force above a certain level is applied in terms of bending characteristics, which are characteristics of flexible displays.

For another example, the cured product cured from the composition for encapsulation may have a transmittance of 95% to 100%, specifically 96 to 100%, measured in a 550nm wavelength region. When the light transmittance falls within the above-described range, the visibility of the display device may be increased when the display device is encapsulated.

For another example, the cured product cured from the composition for encapsulation may have a chlorine ion content of 0 to 30 ppm, specifically 0 to 10 ppm. When the chlorine ion content falls within the above-described range, it is possible to prevent adverse effects on the device when the display device is encapsulated.

The composition for encapsulation according to the present invention satisfies at least one of the above-described physical properties, for example, high adhesion to an inorganic layer, and curing shrinkage after curing, plasma etching rate, storage modulus, and transmittance through photocuring known in the art. can Accordingly, it may be applied to a sealing or encapsulation use for sealing a display device, particularly a flexible display device. In order to maximize the above-described sealing effect, it may be used in combination with an inorganic layer to be described later.

Non-limiting examples of a member for a display device to which the composition for encapsulation is applicable, an organic light emitting device (OLED), a lighting device, a flexible organic light emitting device display, a metal sensor pad, a microdisc laser, an electrochromic device, photochromic devices, microelectromechanical systems, solar cells, integrated circuits, charge coupled devices, light emitting polymers, light emitting diodes, and the like. However, it is not particularly limited thereto.

<Encapsulated device>

An embodiment according to the present invention provides a device encapsulated using the above-described composition for encapsulation.

In one embodiment, the encapsulated device includes a device member, and an encapsulation layer formed on the device member and including an inorganic layer and an organic layer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of an encapsulated device according to the present invention will be described with reference to the accompanying drawings. However, the embodiment of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

1 is a cross-sectional view schematically showing the structure of an encapsulated device 100 according to an embodiment of the present invention.

Referring to FIG. 1 , an encapsulated device 100 according to an embodiment of the present invention includes a substrate 10 ; and a device member (20) disposed on the substrate (10); and an encapsulation layer 30 covering the device member 20 , wherein the encapsulation layer 30 includes an inorganic layer 31 and an organic layer 32 .

The substrate 10 is not particularly limited as long as it is a substrate on which the device member 20 can be laminated. For example, it may be made of a material such as a transparent glass, a plastic sheet, a flexible substrate such as silicon, or a metal substrate. Also, depending on the member 20 for the device, the substrate 10 may not be necessary.

The device member 20 attached to the substrate 10 is not particularly limited, and for example, an organic light emitting device (OLED), a lighting device, a flexible organic light emitting device display, a metal sensor pad, a microdisc laser, electrochromic devices, photochromic devices, microelectromechanical systems, solar cells, integrated circuits, charge coupled devices, light emitting polymers, light emitting diodes, and the like.

The aforementioned device member 20 , in particular a display member (not shown), is permeable to gases or liquids in the surrounding environment, for example oxygen and/or moisture and/or water vapor in the atmosphere, and chemicals used in processing into electronic products. Since it is decomposed or defective, it is necessary to encapsulate or encapsulate the display member.

The encapsulation layer 30 is formed on the device member 20 to protect the device member 20 . The encapsulation layer 30 has a structure in which a plurality of thin film layers are stacked, and includes at least one inorganic layer 31 and at least one organic layer 32 .

Here, the inorganic layer 31 may seal the device member 20 to firmly block the penetration of oxygen or moisture. The inorganic layer 31 may include a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxygen nitride, a metal oxyboride, or a mixture thereof known in the art, and specifically includes a metal oxide or a metal nitride may be a single film or a laminate film. At this time, the metal is silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition It may include at least one of a metal and a lanthanide metal.

Specifically, the inorganic layer 31 is silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide, hafnium nitride, zirconium oxide , zirconium nitride, cerium oxide, cerium nitride, tin oxide, tin nitride, and may include at least one inorganic material selected from the group consisting of magnesium oxide. For a more specific example, SiOx, SizNx, SiOxNy, ZnSe, ZnO, Sb2O3, Al2O3, In2O3, SnO2 (in the above, x is 1-5, y is 1-5, z is 1-5), etc. have.

In addition, the organic layer 32 covers at least a part or all of the inorganic layer 31 , and relieves the internal stress of the inorganic layer 31 or fills microcracks and pinholes of the inorganic layer 31 to prevent moisture or oxygen from outside. It is possible to enhance the anti-permeation effect.

The organic layer 32 may have a single-layer or multi-layer structure, and includes a cured product of the above-described composition for encapsulation.

For example, the encapsulation layer 30 may have a structure in which at least one inorganic layer 31 and at least one organic layer 32 are alternately stacked, and more specifically, at least two inorganic layers 31 . and at least one organic layer 32 may be alternately stacked. In this way, when the organic layer 32 and the inorganic layer 31 are alternately formed, the smoothing characteristic of the inorganic layer 31 can be secured, and the inorganic layer 31 having different defects of the inorganic layer 31 . ) can be prevented from spreading.

In the present invention, as long as the cured product of the above-described composition for encapsulation is included as a component of the organic layer 32 constituting the encapsulation layer 30 , the inorganic layer 31 and the organic layer 32 are laminated (stacking order) , and/or the number of layers of the encapsulation layer 30 is not particularly limited. That is, the encapsulation layer 30 may further include a plurality of inorganic layers (not shown) and organic layers (not shown) arranged alternately, and the number of stacking of the inorganic layers 31 and the organic layers 32 is also particularly limited. doesn't happen It can be suitably changed according to the level of permeation resistance to oxygen and/or moisture and/or water vapor and/or chemicals.

For example, in the encapsulation layer 30 , the organic layer 32 and the inorganic layer 31 are respectively 2 or more layers and alternately 10 layers or less (eg, 2 to 10 layers), specifically 7 layers or less, more specifically It can be laminated in 2 to 7 layers. Preferably, it may be formed in a seven-layer structure of inorganic layer-organic layer-inorganic layer-organic layer-inorganic layer-organic layer-inorganic layer.

In the encapsulation layer 30 according to the present invention, the thickness of one organic layer 32 may be 0.1 to 20 μm, specifically, 1 to 10 μm. In addition, the thickness of one inorganic layer 31 may be 5 to 500 nm, specifically 5 to 200 nm. In addition, the total thickness of the encapsulation layer 30 may be 5 μm or less, preferably 1.5 to 5 μm.

The encapsulated device 100 according to an embodiment of the present invention may be manufactured according to a conventional method known in the art. In one embodiment, the device member 20 is disposed on the substrate 10 , and the inorganic layer 31 is formed to cover the device member 20 . Then, the organic layer 32 may be formed by applying the encapsulation composition according to a method known in the art, and then curing it through light irradiation.

The inorganic layer 31 may be formed by a vacuum process known in the art, for example, sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma vapor deposition, and combinations thereof.

When the organic layer 32 is formed, a method of applying the encapsulation composition is not particularly limited, and for example, a method such as vapor deposition, spin coating, or slit coating may be used. In addition, the photocuring conditions are not particularly limited, and for example, the encapsulation composition is applied to a thickness of 0.1 to 20 μm, specifically 1 to 10 μm, and then irradiated at 10 to 500 mW/cm ² for 1 to 50 seconds to cure. can In addition, a deposition method known in the art may be applied.

If necessary, the process of forming the inorganic layer 31 and the organic layer 32 may be repeated at least once, respectively, thereby completing the manufacture of the encapsulation layer 30 .

2 is a cross-sectional view schematically illustrating a cross-section of an encapsulated device 200 according to another embodiment of the present invention. In Fig. 2, the same reference numerals as in Fig. 1 denote the same members.

Hereinafter, in the description of FIG. 2 , content overlapping with FIG. 1 will not be described again, and only differences will be described. Referring to FIG. 2 , an encapsulated device 200 according to an embodiment of the present invention is used for the device of FIG. 2 , compared to FIG. 1 in direct contact with the device member 20 and the inorganic layer 31 . The member 20 does not come into contact with the inorganic layer 31 , and the inorganic layer 31 seals the internal space 40 in which the device member 20 is accommodated.

In addition, for the description of the material and structure of each component in the encapsulated device 200 according to the embodiment of FIG. 2 , the description of the encapsulated device 100 according to the embodiment of FIG. 1 may be applied as it is. have.

The above-described encapsulated device of the present invention includes an inorganic layer and an organic layer exhibiting high adhesion, so that even when applied to a large area (large screen), it is possible to effectively block moisture and oxygen penetration, thereby increasing the quality of the final display device. Such a display device is a flat panel display device (FPD), including a curved display device (Curved Display Device), a foldable display device (Foldable Display Device), a flexible display device (Flexible Display Device), etc. in the art. It can be usefully applied to all known display devices.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to help the understanding of the present invention, and the scope of the present invention is not limited thereto.

[Production Example]

In a 2L reactor, 601.2 g of dicyclopentadiol, 209.8 g of acrylic acid, and 0.02 g of a PTSA (para-toluene sulfonic acid) catalyst were added and stirred at 110° C. for 12 hours to synthesize monomers of the following formula 5 in Table 1. The chemical structure of the prepared monomer [2-([1,1'-biphenyl]-2-yloxy)ethyl acrylate, A1] is as follows.

[Formula 5]

[Preparation example]

Specifications of raw materials constituting the composition for encapsulation according to the present invention are shown in Table 1 below.

[Examples 1-6. Preparation of composition for encapsulation]

The composition for encapsulation of Examples 1 to 6 was mixed using a composition (unit: parts by weight, based on solid content) including the monomers, photopolymerization initiator, and antioxidant described in Table 2 below, and mixed for 3 hours using a shaker. each was prepared.

Example comparative example One 2 3 4 5 6 One 2 3 monomer
(A) (A1) One 10 10 5 One 25 - - - (A2) - 10 - 25 50 - 25 70 100 (A3) 99 80 90 70 49 75 75 30 - photopolymerization initiator
(B) (B1) 3 3 3 3 3 3 3 3 3 (B2) One One One One One One One One One Antioxidant (C) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

[Comparative Examples 1-3. Preparation of composition for encapsulation]

The composition for sealing of Comparative Examples 1 to 3 was carried out in the same manner as in Example 1, except that the composition (unit: parts by weight, based on solid content) including the monomer, photopolymerization initiator, and antioxidant described in Table 2 was used. was prepared.

[Experimental example. Physical property evaluation]

The following physical properties were evaluated for the encapsulation compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 3, and the results are shown in Table 3 below.

<Method for evaluating physical properties>

(1) Curing shrinkage (%)

A: (g / cm ³ units) by measuring the curing shrinkage: Digital solid hydrometer DME-220E (Shinko Co., Japan) as a photo-curing before the liquid compositions of the weight (in g / cm ³⁾ and a specific gravity of after photocuring solid Calculated. At this time, the encapsulation composition is coated to a thickness of about 10㎛±2㎛ and then UV cured (100mW/cm ² x 10 seconds) to make a film (thickness: 8-12㎛, width 1.5-2.5cm, length 1.5-2.5cm) was prepared and performed. At this time, the cure shrinkage was calculated according to the following [Equation 1].

[Equation 1]

Curing shrinkage (%) = (Solid specific gravity after curing - specific gravity of liquid composition before curing)/Specific gravity of liquid composition before curing × 100

(2) Etching rate of organic protective layer by plasma (%)

The encapsulation composition was deposited to a predetermined thickness and photocured to measure the deposition height (T1, unit: μm) of the organic layer. After ICP power: 2,500W, RF power: 300W, DC bias: 200V, Ar flow: 50sccm, Etching time: 1min, Pressure: 10 mtorr After plasma treatment on the organic layer, the height of the organic layer (T2 , unit: μm) was measured. The etching rate of the organic protective layer by plasma was calculated according to the following [Equation 2].

[Equation 2]

Etching rate of organic layer by plasma (%) = (T1-T2)/T1×100

In Equation 2, T1 is the initial height (unit: μm) of the organic layer formed by photocuring the encapsulation composition, T2: ICP (inductively coupled plasma) power: 2500W, RF (inductively coupled plasma) using ICP-CVD on the organic layer ( radio frequency) power: 300W, DC bias: 200V, Ar flow: 50sccm, etching time: 1min, pressure: the height of the organic layer after plasma treatment at 10mtorr.

(3) storage modulus (GPa)

After coating the composition for encapsulation on the cleaned glass substrate, the amount of light was irradiated at 2000 mJ/cm, and the film was cured to about 500 μm in thickness and 25 mm in diameter to prepare a film. Using an ARES-G2 rheometer (TAinstrument, Inc.), the frequency was measured at 1 rad/s, and the temperature at a tensile strain of 0.01% was increased from 25° C. to 100° C. at a rate of 10° C./min.

(4) Chloride ion content (ppm)

A predetermined amount (1-50 mg) of the composition for encapsulation was weighed and transferred to a boat, and then mounted on an autosampler. After checking the conditions in the automatic combustion device such as absorption solvent and rinse, analysis was performed. AQF-2100H (Mitsubishi Chemical) was used as a combustion device, and IC-5000S (DIONEX) was used for ion chromatography. In Table 2 below, N.D means not measured at the detection limit of 10 ppm.

(5) Adhesion

On a cleaned glass substrate having a size of 2 cm x 2 cm x 1 mm (width x length x thickness), a thickness of SiNx was continuously deposited to 10 μm±2 μm, and the composition was coated to a thickness of 10 μm±2 μm.

As a method for measuring the adhesion force between silicon nitride and organic material, the adhesion force was measured in the same way as the feel test method. The peeling force was measured by pulling 180 ° at a moving speed of 100 mm/min with a force of ⁸ kgf/inch 2 from the end where the composition was adhered at 25 ° C with JSV H1000 of ALGOL, which is an adhesive force measuring instrument.

(6) light transmittance (%)

A film (thickness: 9 μm±2 μm) was prepared by coating the composition on the cleaned glass substrate to about 10 μm±2 μm and then UV curing (100 mW/cm 2 X 10 sec). Visible light transmittance in a wavelength region of 550 nm was measured with a Lambda 950 (Perkin elmer) instrument for the prepared film.

Example comparative example One 2 3 4 5 6 One 2 3 in plasma
Etching rate of organic layer protective layer by (%) 2 4 5 15 10 10 11 10 12 Curing Shrinkage (%) 3.5 3.8 4.2 4.7 5.0 4.5 5.5 8.0 9.2 Storage Modulus (GPa) 7.2 7.0 6.3 6.9 6.0 6.5 5.5 3.0 0.9 Chloride ion content (ppm) N/D N/D N/D N/D N/D N/D N/D N/D N/D Adhesion (kg/inch ² ) 2 20 25 12 3 55 0.01 0.05 0.1

As shown in Table 3, the encapsulation compositions of Comparative Examples 1 to 3 that do not include the novel photocurable monomer or oligomer thereof according to the present invention are plasma resistance, curing shrinkage, modulus, chlorine ion content, and adhesion in terms of showed poor characteristics.

In contrast, it was confirmed that the composition for encapsulation according to the present invention has excellent plasma resistance, high storage modulus, low curing shrinkage, low chlorine ion generation, and adhesive strength of 2 kg/inch ^{2 or more.}

100, 200: encapsulated device
10: substrate
20: member for device
30: encapsulation layer
31: inorganic layer
32: organic layer
40: inner space

Claims (21)

at least one photocurable monomer; and a polymerization initiator,
The at least one photocurable monomer is a composition for encapsulation comprising a first monomer (A1) represented by the following Chemical Formula 1 or an oligomer thereof:
[Formula 1]

In Formula 1,
Ar ₁ and Ar ₂ are the same or different, and are each independently an alicyclic, heteroalicyclic, aromatic or heteroaromatic hydrocarbon group having 5 to 20 carbon atoms,
X ₁ is a single bond or O, Si(R ₄ ) ₂ , NR ₄ , and a substituted or unsubstituted C 1 to C 5 alkylene group is selected from the group consisting of,
a and b are each 0 or 1, a+b ≥1,
Z ₁ is a moiety represented by the following formula 1a,
[Formula 1a]

In Formula 1a,
* means a portion in which a bond is formed with Chemical Formula 1,
Y ₁ is a single bond or is selected from the group consisting of _{O, Si(R 4} ) ₂ , and NR _{4 ,}
R ₁ and R ₂ are the same as or different from each other, and are each independently a substituted or unsubstituted C 1-10 alkylene group,
R ₃ and R ₄ are the same as or different from each other, and each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms. According to claim 1,
The first monomer has a weight average molecular weight (Mw) of more than 0, 500 g/mol or less, and a viscosity of more than 0, 10,000 cps or less (based on 25°C). According to claim 1,
The first monomer is contained in an amount of 0.01 to 40 parts by weight based on the solid content of the composition for encapsulation. According to claim 1,
The at least one photocurable monomer,
a second monomer (A2) represented by the following formula (2); and
A composition for encapsulation comprising at least one of the third monomers (A3) represented by the following formula (3):
[Formula 2]

[Formula 3]

In Formula 2 or 3,
Ar _{3 To} Ar ₄ are the same or different, and each independently represents a hydrocarbon group of 5 to 20 carbon atoms, alicyclic, heteroalicyclic, aromatic or heteroaromatic,
Ar _{5 To} Ar _{6 Are} the same or different, and each independently is a single bond or _{is selected from the group consisting of O, S, NR 4} , and a substituted or unsubstituted C 1 to C 5 alkylene group,
X ₂ and X ₃ are the same as or different from each other, and each independently a single bond or O, S, Si(R ₄ ) ₂ , NR ₄ , and a group consisting of a substituted or unsubstituted C 1 to C 5 alkylene group is selected from
a and b are each 0 or 1, a+b ≥1,
n1 and n2 are respectively 0 or 1, n1+n2 ≥ 1,
m is an integer from 1 to 12,
Z _{3 To} Z ₆ are each independently a moiety represented by the following formula (4),
[Formula 4]

* is _{a connecting portion of carbon of Ar 3} or Ar ₄ of Formula 2, or a connecting portion of carbon of Ar ₅ or Ar ₆ of Formula 3,
Y ₂ is a single bond or _{is selected from the group consisting of O, Si(R 4} ) ₂ , NR ₄ and a substituted or unsubstituted C 1 to C 5 alkylene group,
R ₅ are the same as or different from each other, and are each independently a substituted or unsubstituted C 1-10 alkylene group,
R ₄ and R ₆ are the same as or different from each other, and each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms. 5. The method of claim 4,
The second monomer, the weight average molecular weight (Mw) is greater than 0, 500 g / mol or less, the viscosity is more than 0, 500 cps or less (based on 25 ℃) for sealing composition. 5. The method of claim 4,
The second monomer is contained in an amount of 0 to 60 parts by weight based on the solid content of the composition for encapsulation. 3. The method of claim 2,
The first monomer and the second monomer each include a biphenyl group. 5. The method of claim 4,
The third monomer is a non-silicone monomer having a weight average molecular weight (Mw) of greater than 0, 500 g/mol or less, and a viscosity of greater than 0, 500 cps or less (based on 25° C.), a composition for sealing. 5. The method of claim 4,
The third monomer is a composition for encapsulation contained in an amount of 30 to 99.5 parts by weight based on the solid content. 5. The method of claim 4,
The polymerization initiator, (A1) + (A2) + (A3) 100 parts by weight based on 0.01 to 10 parts by weight of the encapsulation composition. According to claim 1,
The composition is (A1) + (A2) + (A3) 100 parts by weight based on the antioxidant 0.01 to 1 part by weight of the composition for encapsulation further comprising. According to claim 1,
The composition has a viscosity at 25° C. of 10 to 100 cps, and a solvent-free type (solvent-free), encapsulating composition. According to claim 1,
The composition is, after curing, the curing shrinkage according to the following formula 1 is greater than 0, 10% or less of the encapsulation composition:
[Equation 1]
Curing shrinkage rate (%) = (specific gravity of solid after curing - specific gravity of liquid composition before curing) / specific gravity of liquid composition before curing × 100 According to claim 1,
The composition is, after curing, the plasma etching rate according to the following formula 2 is 0 to 30%, the composition for encapsulation:
[Equation 2]
Etching rate of organic layer by plasma (%) = (T1-T2)/T1×100
(In Equation 2, T1 is the initial height of the organic layer formed by photocuring the composition for encapsulation, and T2 is ICP (inductively coupled plasma) power: 2500W, RF (radio frequency) power by using ICP-CVD on the organic layer: 300W, DC bias: 200V, Ar flow: 50sccm, etching time: 1min, pressure: the height of the organic layer after plasma treatment at 10mtorr). member for device; and
It is formed on the member for the device and includes an encapsulation layer comprising an inorganic layer and an organic layer,
The organic layer is encapsulated device comprising a cured product of the composition for encapsulation according to any one of claims 1 to 14. 16. The method of claim 15,
The organic layer has an adhesion to the inorganic layer of 0.2 kg/inch ² or more, the encapsulated device. 16. The method of claim 15,
The organic layer is
a storage modulus of 1 to 20 GPa,
Chloride ion content not more than 30 ppm
The encapsulated device, wherein the transmittance measured in the 550 nm wavelength region is 95% to 100%. 16. The method of claim 15,
The encapsulation layer is an encapsulated device in which at least one inorganic layer and at least one organic layer are alternately stacked, and a total of 10 layers or less. 16. The method of claim 15,
The thickness of one of the organic layers is 0.1 to 20 μm,
The thickness of one inorganic layer is 5 to 500 nm, the encapsulated device. 16. The method of claim 15,
The inorganic layer includes a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxygen nitride, a metal oxyboride, or a mixture thereof,
The metal is silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition metal and at least one of a lanthanide metal. 16. The method of claim 15,
The device member includes a flexible organic light emitting device, an organic light emitting device, a lighting device, a metal sensor pad, a microdisc laser, an electrochromic device, a photochromic device, a microelectromechanical system, a solar cell, an integrated circuit, and a charge coupled device. , an encapsulated device comprising a light emitting polymer or a light emitting diode.

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