KR102321774B1 - A organic layer composition for sealing organic light emitting device - Google Patents

Abstract

The present invention relates to an organic film composition for encapsulation of an organic light emitting device, and more particularly, to a composition for encapsulation comprising a first photocurable monomer, a second photocurable monomer and a third photocurable monomer.
The present invention can provide an encapsulation composition having excellent plasma resistance, low curing shrinkage, and excellent durability and weather resistance.
In addition, the present invention can provide an encapsulation composition that can be stably used as a material for encapsulation of electronic devices due to excellent moisture and oxygen barrier properties.

Description

An organic layer composition for sealing organic light emitting device

The present invention relates to an organic film composition for encapsulation of an organic light emitting device, and more particularly, to a composition for encapsulation comprising a first photocurable monomer, a second photocurable monomer and a third photocurable monomer.

Currently, most of the flexible displays we use are OLED driven, which is a self-luminous display that can realize full color without a stacked structure like an LCD.

However, since organic materials and electrodes of OLED are very sensitive to oxygen and moisture, they lose their light emitting properties in an environment with moisture or oxygen.

Meanwhile, a process called encapsulation can be used to block external oxygen and moisture, and to preserve and improve the lifespan of the OLED panel.

The encapsulation technology refers to a technology that protects the OLED device from moisture permeation, oxygen permeation, and external impact.

In this regard, Korean Patent Application Laid-Open No. 10-2010-0124918 discloses a photocurable resin composition for encapsulating electrical devices comprising a molten mixture of two or more types of solid epoxy resins, a photosensitizer, a photoinitiator, an inorganic filler, and a coupling agent, and There is.

However, this technique presents problems in that the cure shrinkage rate is high and durability and weather resistance are poor.

Therefore, it is necessary to develop a technology for an encapsulation composition having excellent plasma resistance, low curing shrinkage, and excellent durability and weather resistance.

Korean Patent Publication No. 10-2010-0124918

An object of the present invention is to solve the problems of the prior art, and it is an object of the present invention to provide a composition for encapsulation having excellent plasma resistance, low curing shrinkage, and excellent durability and weather resistance.

Another object of the present invention is to provide an encapsulation composition that can be stably used as an organic film of an electronic device having excellent moisture and oxygen barrier properties.

In order to achieve the above object, the present invention provides a composition for encapsulation comprising a first photocurable monomer, a second photocurable monomer and a third photocurable monomer.

In one embodiment of the present invention, the first photocurable monomer is at least one of 2-phenoxyethyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate and phenoxybenzyl (meth)acrylate. characterized in that it is selected.

In one embodiment of the present invention, the second photocurable monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate , characterized in that at least one selected from nonyl (meth) acrylate, dodecyl (meth) acrylate and cetyl (meth) acrylate.

In one embodiment of the present invention, the third photocurable monomer is at least one selected from diethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate and tetraethylene glycol di (meth) acrylate characterized in that

In one embodiment of the present invention, the composition for encapsulation comprises 20 to 60 parts by weight of the second photocurable monomer and 10 to 40 parts by weight of the third photocurable monomer with respect to 100 parts by weight of the first photocurable monomer. do.

In one embodiment of the present invention, the composition for encapsulation further comprises 2 to 10 parts by weight of an acrylate group-containing silane coupling agent.

In one embodiment of the present invention, the composition for encapsulation further comprises 2 to 10 parts by weight of the silane coupling agent oligomer.

In one embodiment of the present invention, the encapsulation composition further comprises 2 to 10 parts by weight of a copolymer of an acrylate group-containing silane coupling agent and an acrylic acid monomer.

In addition, the present invention provides an organic film prepared by photocuring the composition for encapsulation.

The present invention can provide a composition for encapsulation having excellent plasma resistance, low curing shrinkage, and excellent durability and weather resistance.

In addition, the present invention can provide an encapsulation composition that can be stably used as a material for encapsulation of electronic devices due to excellent moisture and oxygen barrier properties.

The present invention will be described in detail with reference to the following examples. The terms, examples, etc. used in the present invention are merely exemplified to explain the present invention in more detail and help those of ordinary skill in the art to understand, and the scope of the present invention should not be construed as being limited thereto.

Technical terms and scientific terms used in the present invention represent meanings commonly understood by those of ordinary skill in the art to which this invention belongs, unless otherwise defined.

The present invention relates to a composition for encapsulation comprising a first photocurable monomer, a second photocurable monomer and a third photocurable monomer.

The encapsulation composition may include 20 to 60 parts by weight of the second photocurable monomer and 10 to 40 parts by weight of the third photocurable monomer based on 100 parts by weight of the first photocurable monomer.

The first photocurable monomer may improve the plasma resistance of the composition and lower the curing shrinkage.

The first photocurable monomer may be one or more selected from 2-phenoxyethyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, and phenoxybenzyl (meth)acrylate.

The viscosity at 25° C. of the first photocurable monomer is preferably 5-200 cPs from the viewpoints of processability, durability, and the like.

The second photocurable monomer serves to control the viscosity of the composition and lower the cure shrinkage.

The second photocurable monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dode At least one may be selected from syl (meth) acrylate and cetyl (meth) acrylate.

The second photocurable monomer is preferably used in an amount of 20 to 60 parts by weight based on 100 parts by weight of the first photocurable monomer, and when the content is less than 20 parts by weight, workability is reduced, and when it exceeds 60 parts by weight, the durability of the composition is reduced do.

The third photocurable monomer may improve durability of the composition and improve cure shrinkage.

The third photocurable monomer may be one or more selected from diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate.

The third photocurable monomer is preferably used in an amount of 10 to 40 parts by weight based on 100 parts by weight of the first photocurable monomer, and when the content is less than 10 parts by weight, workability is reduced, and when it exceeds 40 parts by weight, the durability of the composition is reduced do.

In addition, the composition may further include an acrylate group-containing silane coupling agent. The silane coupling agent may improve the durability of the organic layer by improving the bonding strength of the composition.

The acrylate group-containing silane coupling agent is 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri ethoxysilane, 3-acryloxypropyltrimethoxysilane, methacryloxymethyltriethoxysilane, and methacryloxymethyltrimethoxysilane.

The content of the silane coupling agent is preferably 2 to 10 parts by weight based on 100 parts by weight of the first photocurable monomer. When the content is less than 2 parts by weight, the effect of addition is insignificant, and when it exceeds 10 parts by weight, the cure shrinkage is reduced. .

The encapsulation composition may further include a silane coupling agent oligomer.

The silane coupling agent oligomer is used to improve the adhesion and durability of the organic layer, and may be prepared by pre-reacting the epoxy group-containing silane coupling agent with the acrylate group-containing silane coupling agent.

Epoxy group-containing silane coupling agents include 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-(3,4-epoxycyclohexyl)propylmethyldimethoxysilane, 3-(3 ,4-epoxycyclohexyl)propylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-( 3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, and the like.

The acrylate group-containing silane coupling agent is 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri ethoxysilane, 3-acryloxypropyltrimethoxysilane, methacryloxymethyltriethoxysilane, and methacryloxymethyltrimethoxysilane.

The weight average molecular weight of the silane coupling agent oligomer is preferably 1,000 to 10,000 g/mol.

The content of the silane coupling agent oligomer is preferably 2 to 10 parts by weight based on 100 parts by weight of the first photocurable monomer. When the content is less than 2 parts by weight, the effect of addition is insignificant, and when it exceeds 10 parts by weight, durability is reduced. .

The encapsulation composition may further include 2 to 10 parts by weight of a copolymer of an acrylate group-containing silane coupling agent and an acrylic acid monomer.

A plurality of carboxyl groups included in the copolymer may improve the binding force of the composition.

The acrylate group-containing silane coupling agent is 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri ethoxysilane, 3-acryloxypropyltrimethoxysilane, methacryloxymethyltriethoxysilane, and methacryloxymethyltrimethoxysilane.

The acrylic acid monomer is acrylic acid, methacrylic acid, methyl acrylic acid, ethyl acrylic acid, butyl acrylic acid, 2-ethyl hexyl acrylic acid, decyl acrylic acid, methyl methacrylic acid, ethyl methacrylic acid, butyl methacrylic acid, 2-ethyl hexyl methacrylic acid , and decyl methacrylic acid.

The weight ratio of the acrylate group-containing silane coupling agent and the acrylic acid monomer is preferably 10 to 30:70 to 90, and when the weight ratio is less than 10:90, the bonding strength is reduced, and when it exceeds 30:70, durability is reduced.

The content of the copolymer of the acrylate group-containing silane coupling agent and the acrylic acid monomer is preferably 2 to 10 parts by weight based on 100 parts by weight of the first photocurable monomer, and when the content is less than 2 parts by weight, the effect of addition is insignificant, When it exceeds 10 parts by weight, durability is reduced.

In addition, the composition may further include a copolymer of an unsaturated monomer containing a carboxyl group and an unsaturated monomer containing an epoxy group.

The unsaturated monomer containing a carboxyl group is a vinyl aromatic monomer containing a carboxyl group; an acrylate-based monomer containing a carboxyl group; a vinyl cyanide-based monomer containing a carboxyl group; A vinyl halogen-based monomer including a carboxyl group may be used.

The unsaturated monomer containing an epoxy group is a vinyl aromatic monomer containing an epoxy group; an acrylate-based monomer containing an epoxy group; a vinyl cyanide-based monomer containing an epoxy group; A vinyl halogen-based monomer including an epoxy group may be used.

It is preferable that the weight ratio of the unsaturated monomer containing a carboxyl group and the unsaturated monomer containing an epoxy group is 70-90:10-30.

The content of the copolymer of the unsaturated monomer containing the carboxyl group and the unsaturated monomer containing the epoxy group is preferably 1 to 5 parts by weight based on 100 parts by weight of the first photocurable monomer, and when the content is less than 1 part by weight, the effect of addition is It is insignificant, and when it exceeds 5 parts by weight, durability is reduced.

In addition, the composition may further comprise a polyester polyol. Polyester polyol contains a number of hydroxyl groups in the molecule, so it can improve the bonding strength of the composition. It may be prepared by polymerizing an acid component such as dipic acid, terephthalic acid, or isophthalic acid.

It is preferable that the weight average molecular weight of the polyester polyol is 1,000 to 10,000 g/mol.

The content of the polyester polyol is preferably 1 to 5 parts by weight based on 100 parts by weight of the first photocurable monomer. When the content is less than 1 part by weight, the effect of addition is insignificant, and when it exceeds 5 parts by weight, durability and workability are reduced. do.

The composition may further include initiators such as phosphorus-based, acetophenone-based, triazine-based, benzophenone-based, thioxanxanthone-based, benzoin-based, and oxime-based initiators.

The content of the initiator is preferably 1 to 10 parts by weight based on 100 parts by weight of the first photocurable monomer, and curing shrinkage and durability can be maximized in the above numerical range.

The composition may further include a thermal stabilizer such as a phenol-based, quinone-based, amine-based, or phosphite-based thermal stabilizer.

The content of the heat stabilizer is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the first photocurable monomer, and curing shrinkage and durability can be maximized in the above numerical range.

The present invention also relates to an organic film prepared by photocuring the composition for encapsulation.

The viscosity at 25° C. of the composition for encapsulation is preferably 5-200 cPs from the viewpoints of processability, durability, and the like.

After coating the composition for encapsulation in a thickness of 0.1 to 20 μm, it can be photocured by irradiation at ^{10 to 500 mW/cm 2 for 1 to 100 seconds.}

Since the organic film has excellent moisture and oxygen barrier properties, it can be stably used as a material for encapsulation of electronic devices (organic light emitting devices, lighting devices, displays, sensors, lasers, color change devices, solar cells, diodes, etc.).

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. The following examples are only exemplified for the practice of the present invention, and the content of the present invention is not limited by the following examples.

(Example 1)

2-phenylphenoxyethyl acrylate (OPPEA) 100 parts by weight, dodecyl methacrylate 40 parts by weight, diethylene glycol diacrylate 30 parts by weight, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide 2 An encapsulation composition was prepared by mixing parts by weight and 0.2 parts by weight of pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl))propionate.

(Example 2)

An encapsulation composition was prepared in the same manner as in Example 1, except that 15 parts by weight of dodecyl methacrylate was used.

(Example 3)

A composition for encapsulation was prepared in the same manner as in Example 1, except that 70 parts by weight of dodecyl methacrylate was used.

(Example 4)

A composition for encapsulation was prepared in the same manner as in Example 1, except that 5 parts by weight of 3-methacryloxypropyltrimethoxysilane was additionally used.

(Example 5)

Example 1 except that 5 parts by weight of a silane coupling agent oligomer prepared by reacting 70% by weight of 3-glycidoxypropyltrimethoxysilane and 30% by weight of 3-methacryloxypropyltrimethoxysilane in advance was additionally used A composition for encapsulation was prepared in the same manner as described above.

(Example 6)

A primer composition was prepared in the same manner as in Example 1, except that 5 parts by weight of a copolymer of 3-methacryloxypropyltrimethoxysilane and acrylic acid was additionally used.

(Comparative Example 1)

A composition for encapsulation was prepared in the same manner as in Example 1, except that dodecyl methacrylate was not used.

After the composition for encapsulation prepared in Examples and Comparative Examples was photocured to form an organic film, characteristics were evaluated, and the results are shown in Table 1 below.

The dimensional change rate was measured according to KS K ISO 3759.

Water resistance was measured according to KS M ISO 1514, and after drying for 72 hours, it was immersed in water and left for 24 hours. Then, it was taken out and dried at room temperature for 2 hours to observe the state of the coating film. At this time, the state of the coating film was expressed as excellent, excellent, average, and poor.

Curing shrinkage (%) was calculated by measuring the specific gravity of the liquid composition before photocuring and the specific gravity of the solid after photocuring with a digital solid hydrometer.

Adhesiveness was measured according to JIS K 5600-5-6 and marked as excellent, excellent, average, and poor.

division Example comparative example One 2 3 4 5 6 One dimensional change rate
(%) 2.4 3.1 3.2 1.6 1.4 1.3 4.5 water resistance Great commonly commonly eminence eminence eminence error cure shrinkage
(%) 4.8 5.4 5.5 4.1 3.9 3.6 7.9 adhesive Great commonly commonly eminence eminence eminence error

From the results of Table 1, it can be confirmed that the encapsulation compositions of Examples 1 to 6 are excellent in dimensional change rate, water resistance, curing shrinkage rate, and adhesiveness. In particular, in the case of Examples 4 to 6, it can be seen that the above characteristics are the best.

On the other hand, it can be seen that Comparative Example 1 is inferior in the above properties to that of Example.

Claims (6)

a first photocurable monomer; a second photocurable monomer; a third photocurable monomer; And in the encapsulation composition comprising a copolymer of an acrylate group-containing silane coupling agent and an acrylic acid monomer,
The first photocurable monomer is at least one selected from 2-phenoxyethyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate and phenoxybenzyl (meth)acrylate,
The second photocurable monomer is methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl At least one selected from (meth)acrylate and cetyl (meth)acrylate,
The third photocurable monomer is at least one selected from diethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate and tetraethylene glycol di (meth) acrylate,
The weight ratio of the acrylate group-containing silane coupling agent and the acrylic acid monomer is 10-30:70-90,
The composition for encapsulation comprises 20 to 60 parts by weight of the second photocurable monomer, 10 to 40 parts by weight of the third photocurable monomer, and 2 to 10 parts by weight of the copolymer with respect to 100 parts by weight of the first photocurable monomer. composition for encapsulation.
delete According to claim 1,
The encapsulation composition further comprises 2 to 10 parts by weight of an acrylate group-containing silane coupling agent.
4. The method of claim 3,
The encapsulation composition further comprises 2 to 10 parts by weight of the silane coupling agent oligomer.
delete An organic film prepared by photocuring the composition for encapsulation of claim 1.