KR101717955B1 - Polystyrenes with high refractive index and a manufacturing method using Reactive styrene derivatives - Google Patents

Abstract

The present invention can dramatically improve the refractive index through the synthesis of a curable polymer including cyanoepoxy styrene and thus can be applied to a flat layer for OLED light extraction having high light transmittance and transparency. Pattern formation is easy, yellowing is low and transmittance can be increased, and the OLED lighting or display field is highly applicable.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing high-refractive-index reactive styrenic compounds,

The present invention relates to a method for preparing the same using a high-refractive-index reactive polystyrene polymer and a reactive styrene derivative compound.

Next-generation organic light emitting diodes (OLED, organic EL (especially, AMOLED)) are useful as high-refraction thin film materials used to increase efficiency of display or illumination, and many studies are being conducted in the electronic materials market .

The external quantum efficiency of an organic light emitting diode (OLED) is determined by internal quantum efficiency and light extraction efficiency. At present, the internal quantum efficiency is close to 100% due to the development of phosphorescent organic materials, but the efficiency of external light is still low due to low light extraction efficiency.

That is, even if the internal quantum efficiency of the OLED shows a value close to 100%, only about 20% is emitted to the outside, and the remaining 80% of the light causes the wave guiding effect due to the difference in refractive index between the organic substrate, And the refractive index difference of the air.

In the high refractive index thin film manufacturing technology, the efficiency of the OLED panel can be improved by allowing the transparent thin film layer having the refractive index similar to that of the ITO layer to be consumed by the refractive index difference between the ITO layer and the glass layer to extract the isolated light to the outside will be.

Recently, as the performance of OLED materials has rapidly developed, the improvement of OLED power efficiency due to the development of organic light emitting materials has reached a critical point, and it is necessary to research and develop the refractive index or smoothness of interfaces of each structure, especially high refractive index flat layer.

In order for the optical film to have a light extraction efficiency, it should have a high refractive index of 1.8 to 2.0, which is similar to the refractive index of ITO, and should have stable heat resistance at a high temperature depending on the process used for manufacturing the device.

Examples of the material having a refractive index of 2.0 or higher include inorganic materials such as TiO ₂ and ZrO ₂ . However, the fabrication process using these devices is very difficult and complicated. In the case of a polymer material exhibiting a high refractive index, it is difficult to obtain a refractive index of 1.60 or more due to the electronic characteristics of internal constituent molecules.

Accordingly, it is an object of the present invention to overcome the limitations of the refractive index due to the intrinsic properties of polymers and to solve the difficulties of film forming, process temperature and pattern formation of metal nano-particles having a high refractive index, It is inevitable to develop hybrid materials with high refractive index.

Japanese Patent Application Laid-Open No. 2009-279923 (2009.12.03)

It is an object of the present invention to provide a high refractive index reactive polystyrene polymer which is a matrix compound for developing a high refractive index organic hybrid resin applicable to an OLED light extraction flat layer.

The present invention also provides a high refractive index reactive polystyrene polymer which can improve the refractive index remarkably as compared with an acrylate-based polymer and is easy to realize a high refractive index, realizes high light transmittance and transparency, and is excellent in thermal stability through crosslinking The purpose.

In order to achieve the above object,

The present invention provides a polymer compound represented by the following formula (1).

[Chemical Formula 1]

(Wherein R ₁ and R ₂ are hydrogen or (C ₁ -C 30) alkyl;

X is a single bond, (C1-C20) alkylene or (C2-C20) alkenylene;

Y is S, NH or O;

Z is (C6-C30) aryl or (C3-C30) heteroaryl,

A, b and c each independently represents an integer of 0 to 100.)

In the polymer compound according to an embodiment of the present invention, R ₁ and R ₂ in Formula 1 may be hydrogen or (C 1 -C 10) alkyl, and X may be a single bond or (C 1 -C 10) alkylene.

및

중에서 선택되는 것일 수 있다.In the polymer compound according to an embodiment of the present invention, Y in the formula (1) is S or O, and Z is

And

. ≪ / RTI >

The polymer compound according to one embodiment of the present invention may be selected from the following formulas (2) and (3).

(2)

(3)

(Wherein, a, b and c are each independently an integer of 0 to 100)

The weight average molecular weight of the polymer compound according to an embodiment of the present invention may be 500 to 20,000 g / mol.

The polymer compound according to an embodiment of the present invention may have a refractive index of 1.6 to 1.8.

The present invention relates to a process for preparing a polymerizable composition comprising a monomer mixture comprising a cyanoepoxystyrene compound, an acrylate-based compound represented by the following formula (5) and an acrylate-based compound represented by the following formula (6) And a method for producing the polymer compound.

[Chemical Formula 5]

[Chemical Formula 6]

(Wherein, in the above formulas (5) and (6), R ₁ and R ₂ are hydrogen or (C ₁ -C 30) alkyl;

X is a single bond, (C1-C20) alkylene or (C2-C20) alkenylene;

Y is S, NH or O; Wherein Z is (C6-C30) aryl or (C3-C30) heteroaryl.

In the polymer compound according to an embodiment of the present invention, the cyano epoxystyrene compound may be contained in an amount of 5 to 99 mol% in the monomer mixture.

In the method for preparing a polymer compound according to an embodiment of the present invention, the cyano epoxystyrene compound is a compound represented by the following formula (4), and may be contained in an amount of 5 to 30 mol% of the total monomers.

[Chemical Formula 4]

The present invention can provide a novel polystyrene polymer which has a high refractive index of 1.60 or more and is excellent in transparency, thermal stability, and chemical resistance and can be crosslinked by reaction with an inorganic substance or by self-reaction, and a process for producing the same.

In addition, the high-refractive index reactive polystyrene polymer according to the present invention can maximize the refractive index more than an acrylate compound, and when it is used as a matrix compound of an organic hybrid composition, a high refractive index of 1.6 to 2.0, It has an advantage that it can be applied to a buffer layer such as a light extracting flat layer used for extracting light attenuated by a difference in refractive index to the outside, exhibiting high light transmittance and transparency.

In addition, since the high refractive index reactive polystyrene polymer is easy to mold a thin film by using a thermosetting reaction and its refractive index is high, the content thereof can be drastically reduced even when an inorganic sol or the like is further added, It is possible to realize excellent optical characteristics in the field of illumination or display.

Hereinafter, a method for producing the high-refractive-index reactive polystyrene polymer and the reactive styrene derivative according to the present invention will be described in detail. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. In addition, unless otherwise defined in the technical terms and scientific terms used, those having ordinary skill in the art to which the present invention belongs have the same meaning as commonly understood.

The present invention provides a polymer compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ and R ₂ are hydrogen or (C ₁ -C 30) alkyl;

X is a single bond, (C1-C20) alkylene or (C2-C20) alkenylene;

Y is S, NH or O;

Z is (C6-C30) aryl or (C3-C30) heteroaryl,

A, b, and c each independently represent an integer of 0 to 100;

Herein, R ₁ and R ₂ are each preferably hydrogen or (C 1 -C 10) alkyl, and X is a single bond or (C 1 -C 10) alkylene, thereby improving the light transmittance and transparency of the polymer compound represented by the formula .

및

중에서 선택되는 것이 우수한 내열성을 구현하기에 더욱 좋다. Further, Y is preferably S or O, and Z is

And

Is more preferable for realizing excellent heat resistance.

The high-refractive-index reactive polystyrene polymer according to the present invention can use a cyano epoxystyrene as a monomer. The cyano epoxystyrene may be prepared through a synthesis route as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

An object of the present invention is to synthesize the polymer represented by the above formula (1) including the above-mentioned epoxide-styrene monomer.

The polymer compound represented by Formula 1 according to the present invention may be any one selected from the following Formulas 2 and 3 in view of high refractive index.

(2)

(3)

(Wherein, a, b and c are each independently an integer of 0 to 100)

Here, a, b, and c mean the composition ratio of the polymer compound.

The preferable range of a, b, and c may be a ratio of a to 90, b to 5 to 99, and c to 0 to 20, preferably a to 60 to 90, b to 5 to 30, and c to 1 Lt; / RTI >

The polymer compound according to the present invention is a polymer compound capable of being thermally cured and includes a cyano epoxystyrene and has a carboxylic acid functional group and is capable of a chemical reaction with metal nanosol and the like and is advantageous in forming a thin film and forming a pattern .

In one embodiment of the present invention, the polymer compound represented by Formula 1 may have a weight average molecular weight of 500 to 20,000 g / mol. Within the above range, the polymer compound is excellent in compatibility with the reaction solvent and is excellent in developing property in the patterning process at the time of coating. The weight average molecular weight is more preferably 1,000 to 10,000 g / mol. The weight average molecular weight may be measured by a conventional method. For example, the powder sample may be dissolved in tetrahydrofuran (THF) and then analyzed by Gel Permeation Chromatography (GPC; FUTECS, Shodex: RI detector) (Columns: Shodex KF-801, 802, 802.5, 803 (8.0 D x 300 mm) and standard samples using polystyrene (Shodex: SM-105).

The polymer compound represented by Formula 1 according to the present invention has a refractive index of 1.6 to 1.8.

The polymer compound having a high refractive index according to the present invention is prepared by radical polymerization of an acrylic monomer or a methacrylic monomer containing a high refractive index aromatic structure and a monomer mixture obtained by mixing a cy epoxystyrene compound. At this time, the high-refractive index aromatic structure is preferably naphthyl, benzene, or a heterocyclic structure.

More specifically, as shown in the following Reaction Schemes 1 and 2, the method of preparing the polymer compound represented by Formula 1 according to the present invention is characterized in that an acrylate-based compound represented by Formula 5 and an acrylate- The method comprising the steps of: preparing a polymerizable composition comprising a mixture of monomers and a radical initiator; and subjecting the polymerizable composition to radical polymerization.

[Reaction Scheme 1]

[Reaction Scheme 2]

In this case, the constitutional molar ratio of the monomers of the formulas (5) and (6) may be 1 to 90 mol% and 0 to 20 mol%, preferably 60 to 90 mol% and 1 to 20 mol% Lt; / RTI > Further, the amount of the cyanoepoxy styrene compound may be 5 to 99 mol%, preferably 5 to 30 mol%.

The polymer compound represented by formula (1) according to an embodiment of the present invention may be prepared by polymerizing a monomer mixture prepared by mixing a monomer mixture with an initiator by introducing a solvent, preferably, PGMEA (propylene glycol monomethyl ether acetate) into a reactor, Adding the composition dropwise to the solvent in the reactor and reacting.

At this time, the initiator may use a radical initiator for a conventional free radical polymerization reaction, and a redox initiator may be used, preferably, a radical initiator is used. The radical initiator may be a thermal initiator that can be activated at temperatures above ambient temperature. The initiator may be 0.05 to 10% by weight, preferably 0.05 to 2% by weight in the polymerizable composition in which the monomer mixture and the initiator are mixed. The polymerization rate can be controlled depending on the type and amount of the initiator.

In the present invention, the thermal initiator is not particularly limited, but examples thereof include 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis (2,4-dimethylpentanenitrile), V -601 (dimethyl 2,2'-azobis (2-methyl propionate)), V-65 (2,2'-azobis (2,4-dimethylvaleronitrile) 59 (2,2'-azobis (2-methylbutyronitrile)) can be used.

The polymerization reaction is not particularly limited, but may be carried out at a temperature ranging from 30 ° C to 160 ° C and 40 ° C to 150 ° C.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples and experimental examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the following examples.

(Example 1)

The synthesis of the P1 polymer is as follows.

20 ml of PGMEA was added to a 250 ml three-necked glass reactor and the temperature was heated to 65 占 폚 while replacing the internal air with nitrogen. The reactor was charged with 19 g of 2-naphthalene thio ethyl acrylate (NTEA, 70 mol%), 1.2 g of methacrylic acid (10 mol%), 1.60 g of initiator V-65, TS, 20 mol%) in 40 ml of PGMEA was slowly added dropwise for 1 hour while maintaining the temperature at 65 ° C. After the addition was complete, the reaction was stirred at 65 ° C for 24 hours. After the reaction is completed, the reaction product is slowly added dropwise to an excess amount of methanol solution to produce a white solid polymer. The resulting polymer is filtered and then vacuum dried in a vacuum oven for 24 hours.

The obtained polymer was confirmed to have a weight average molecular weight of 7,500 g / mol by GPC (solvent: 1% THF, 10 μl injection) and the refractive index was confirmed through a prism coupler (thin film thickness 7.65 μm) @ 830 nm.

(Example 2)

The synthesis of P2 polymers is as follows.

20 ml of PGMEA was added to a 250 ml three-necked glass reactor and the temperature was heated to 65 占 폚 while replacing the internal air with nitrogen. The reactor was charged with 18.76 g of phenylphenoxy ethyl acrylate (OPPEA, 70 mol%), 1.2 g of methacrylic acid (10 mol%), 1.60 g of initiator V-65, TS, 20 mol%) in 40 ml of PGMEA was slowly added dropwise for 1 hour while maintaining the temperature at 65 ° C. After the addition was complete, the reaction was stirred at 65 ° C for 24 hours. After the reaction is completed, the reaction product is slowly added dropwise to an excess amount of methanol solution to produce a white solid polymer. The resulting polymer is filtered and then vacuum dried in a vacuum oven for 24 hours.

The obtained polymer was confirmed to have a weight average molecular weight of 7,500 g / mol by GPC (solvent: 1% THF, 10 μl injection) and the refractive index was confirmed through a prism coupler (thin film thickness 7.6 μm) @ 830 nm.

The refractive index of the polymer resin according to the present invention prepared in Examples 1 and 2 was 1.655@550 nm and 1.640@550 nm respectively in the visible light region and 91% and 92% of the transmittance was measured by a UV spectrometer, , And it was confirmed that a high refractive index and excellent permeability were exhibited. This is applicable to a flat layer for light extraction and has an advantage that it can be applied to a lighting or display field.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Those skilled in the art will recognize that many modifications and variations are possible in light of the above teachings.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (10)

A polymer compound represented by the following formula (1) and having a refractive index of 1.6 to 1.8.
[Chemical Formula 1]

(Wherein R ₁ and R ₂ are hydrogen or (C ₁ -C 30) alkyl;
X is a single bond, (C1-C20) alkylene or (C2-C20) alkenylene;
Y is S, NH or O;
Z is (C6-C30) aryl or (C3-C30) heteroaryl,
A, b, and c each independently represent an integer of 0 to 100, and abc ≠ 0.
The method according to claim 1,
Wherein R ₁ and R ₂ are hydrogen or (C 1 -C 10) alkyl, and X is a single bond or (C 1 -C 10) alkylene.
The method according to claim 1,
Y in Formula 1 is S or O, and Z is

And

≪ / RTI >
The method according to claim 1,
Wherein the polymer compound is any one selected from the following formulas (2) and (3).
(2)

(3)

(Wherein a, b, and c are each independently an integer of 0 to 100, abc ≠ 0).
The method according to claim 1,
Wherein the polymer compound has a weight average molecular weight of 500 to 20,000 g / mol.
delete Preparing a polymerizable composition comprising a monomer mixture comprising a cyano epoxystyrene compound of the following formula (4), an acrylate-based compound of the following formula (5) and an acrylate-based compound of the following formula (6)
Adding the polymerizable composition to the solvent in the reactor and polymerizing
(1). ≪ / RTI >
[Chemical Formula 1]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(Wherein R ₁ and R ₂ are hydrogen or (C ₁ -C 30) alkyl;
X is a single bond, (C1-C20) alkylene or (C2-C20) alkenylene;
Y is S, NH or O; Z is (C6-C30) aryl or (C3-C30) heteroaryl, and a, b and c are each independently an integer of 0 to 100, abc ≠ 0.
delete 8. The method of claim 7,
Wherein the cyano epoxystyrene compound is contained in an amount of 5 to 99 mol% in the monomer mixture.
8. The method of claim 7,
Wherein the cyano epoxystyrene compound is contained in an amount of 5 to 30 mol% in the monomer mixture.