KR101472126B1 - Composition for forming organic insulating film and display device having organic insulating film made therefrom - Google Patents

Abstract

The present invention relates to a display device, and a display device of the present invention includes a protective film composed of an organic insulating film formed from polyamide or polythioether compound having a triazine group, so that the display device of the present invention can be formed through a simple process And reliability can be secured.

Polyamide, polythioether, triazine, organic insulating film

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for forming an organic insulating film, and a display device including the organic insulating film formed therefrom. BACKGROUND ART [0002]

And more particularly to a display device having a composition for forming an organic insulating film and an organic insulating film formed therefrom.

Today, the display device is a device that informs the user of the information through the image. Examples of recently widely used display devices include a liquid crystal display device, an organic light emitting diode display device, and the like.

Liquid crystal display devices (LCDs) are attracting attention as next-generation advanced display devices with low power consumption, good portability, and high value-added.

Such a liquid crystal display device includes a liquid crystal panel for displaying an image according to the transmittance of light and a backlight for providing the light to the liquid crystal panel.

The liquid crystal panel includes a lower substrate and an upper substrate facing each other, and a liquid crystal layer interposed between the lower substrate and the upper substrate.

The lower substrate includes a thin film transistor and a pixel electrode. And a protective film is interposed between the thin film transistor and the pixel electrode. Here, the protective layer may include a contact hole for electrically connecting the thin film transistor and the pixel electrode to each other. The protective film is generally formed of an inorganic film such as a silicon nitride film. Thus, in order to form a protective film having the contact holes, a deposition process and a photolithography process must be performed. As the deposition process is performed in a vacuum chamber, there is a limit to the applicable substrate size, and there is a problem that the process equipment is expensive. In addition, the photolithography process involves complicated processes, including a film forming process, an exposure process, a development process, and an etching process. Accordingly, when the protective film is formed of an inorganic film, the process for forming the display device is complicated and the process cost is increased.

When the protective film is formed of an organic film, the organic film can be formed through a coating process, so that the process of the display device can be simplified. However, the liquid crystal display device is easily exposed to harsh environmental conditions such as high temperatures during or after the process, and the organic film is deformed or damaged in a harsh environment. In addition, the organic film has a low adhesion to a substrate on which the thin film transistor is formed and thus has a low stability.

In addition, the thin film transistor can be applied not only to a liquid crystal display but also to an organic light emitting diode display. Thus, application of the protective film as an organic film is not limited to the liquid crystal display device alone. Particularly, the organic light emitting diode display device has a problem that the lifetime is reduced due to the outgassing generated from the organic layer. As a result, the thermal stability of the organic layer applied to the organic light emitting diode display device is essentially required.

That is, the display device attempts to form the protective film as an organic film in order to reduce the number of steps, but the organic film has a lower thermal, electrical, chemical, and physical characteristics than the inorganic film, which lowers the reliability of the display device.

One object of the present invention is to provide an organic insulating film forming composition for forming an organic insulating film having thermal, electrical, chemical and physical properties.

A further object of the present invention is to provide a display device having a protective film formed from the organic insulating film forming composition and capable of reducing the number of steps and ensuring reliability.

According to one aspect of the present invention, there is provided a composition for forming an organic insulating layer. The organic insulating film forming composition includes a compound represented by the following formula (1).

M + n = 1, O ≤ m ≤ 1 and O ≤ And R 1 are each independently selected from the group consisting of compounds (1) to (4) represented by the following formula (2).

In (1) of the above formula (2), X is any one of the compounds represented by the following formula (3).

In Formula 3, m and n are each 0 to 10.

In the formula (1) of formula (2), Y is any one selected from the group represented by the following formula (4).

In Formula 4, 1, 2, 3, 4, 5, 6, 7, and 8 are independently selected from the group consisting of compounds represented by Formula 5 below.

In Formula 5, m and n are each 0 to 10. In Formula 5, A and B are each independently selected from the group consisting of H, F, Cl, CN, CF _3, and CH ₃ .

In the formula (2), Y is any one selected from the group consisting of the following formula (6).

In Formula 6, n is 0 to 10. In Formula 6, 1 and 2 are any one selected from the group consisting of Formula (7).

In Formula 7, A is any one selected from the group consisting of H, F, CH ₃ , CF _3, and CN.

In the above formulas (3) and (4), n is 0 to 10. In the above formulas (3) and (4), 1, 2, 3, 4, and 5 are independently selected from the group consisting of the following formula (8).

For Formula 8, m and n are each 0 to 10, A and B each independently is any one selected from the group consisting of H, F, Cl, CN, CF 3 and CH _3.

In the above formula (1), R 2 and R 3 are independently selected from the group represented by the following formula (9).

In Formula 9, m and n are each 0 to 10. In Formula 9, A and 1, 2, 3, 4, 5, 6, 7 and 8 are each independently selected from the group consisting of H, F, CN, CF ₃ and CH ₃ .

In formula (1), R4 and R5 are independently selected from the group consisting of the following formula (10).

In Formula 10, m and n are each 0 to 10. In Formula 9, A and 1, 2, 3, 4, 5, 6, 7 and 8 are each independently selected from the group consisting of H, F, CN, CF ₃ and CH ₃ .

According to another aspect of the present invention, there is provided a display device. The display device includes a first substrate on which a thin film transistor is formed, a protective film formed on the first substrate including the thin film transistor and formed from the compound represented by Formula 1, and a pixel electrode disposed on the protective film.

A display device according to an embodiment of the present invention includes a protective film to which an organic insulating film formed from a polyamide-based compound or a polythioether-based compound having a triazine-based compound having a photoactive group is applied. Therefore, the protective film has heat resistance, chemical resistance, And the reliability of the display device can be ensured, and can be formed through a simple process.

In addition, since the organic insulating layer has a small dielectric constant, the organic insulating layer is used as the protective layer, so that the thin film transistor and the pixel electrode disposed over the protective layer can be overlapped with each other to improve the aperture ratio of the display device. .

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings of a liquid crystal display device. 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. Therefore, the present invention is not limited to the embodiments described below, but may be embodied in other forms. In the drawings, the size and thickness of an apparatus may be exaggerated for convenience. Like reference numerals designate like elements throughout the specification.

1 is a cross-sectional view illustrating a liquid crystal display device according to a first embodiment of the present invention.

1, a liquid crystal display includes a first substrate 100, a second substrate 200 facing the first substrate 100, and a second substrate 200 interposed between the first substrate 100 and the second substrate 200 And a liquid crystal layer (300).

Specifically, the first substrate 100 includes a plurality of pixels for displaying an image. Here, each of the pixels may be defined by a gate wiring and a data wiring (not shown in the drawings) which intersect with each other on the first substrate 100. A thin film transistor (Tr) electrically connected to the gate wiring and the data wiring is disposed in each of the pixels. The thin film transistor Tr includes a gate electrode 110 branched from the gate wiring, a gate insulating film 120 covering the gate electrode 110, and a gate electrode 110 disposed on the gate insulating film 120 in correspondence with the gate electrode 110 A semiconductor pattern 130, a source electrode 140a disposed on the semiconductor pattern 130, and a drain electrode 140b disposed on the semiconductor pattern 130 and spaced apart from the source electrode 140a.

A protective film 150 covering the thin film transistor Tr is disposed on the first substrate 100. The passivation layer 150 has a contact hole exposing a portion of the drain electrode 140b of the thin film transistor Tr.

The protective layer 150 may be formed from a composition containing a compound represented by Formula 1.

[Chemical Formula 1]

M + n = 1, O ≤ m ≤ 1 and O ≤ R1 may be independently selected from the group consisting of compounds (1) to (4) represented by the following general formula (2).

(2)

In the formula (1), X may be any of the compounds represented by the following formula (3).

(3)

In Formula 3, m and n are each 0 to 10.

In the formula (1) of formula (2), Y is any one selected from the group represented by the following formula (4).

[Chemical Formula 4]

In Formula 4, 1, 2, 3, 4, 5, 6, 7, and 8 may be independently selected from the group consisting of compounds represented by Formula 5 below.

[Chemical Formula 5]

In Formula 5, m and n are each 0 to 10. In Formula 5, A and B may be independently selected from the group consisting of H, F, Cl, CN, CF _3, and CH ₃ .

In the formula (2), Y may be any one selected from the group represented by the following formula (6).

[Chemical Formula 6]

In Formula 6, n is 0 to 10. In Formula 6, 1 and 2 may be any one selected from the group consisting of Formula (7).

(7)

In Formula 7, A may be any one selected from the group consisting of H, F, CH ₃ , CF _3, and CN.

In the above formulas (3) and (4), n is 0 to 10. In the above formulas (3) and (4), 1, 2, 3, 4, and 5 may be independently selected from the group consisting of the following formula (8).

[Chemical Formula 8]

In Formula 8, m and n are each 0 to 10, and A and B may be independently selected from the group consisting of H, F, Cl, CN, CF _3, and CH ₃ .

In Formula 1, R 2 and R 3 may be independently selected from the group consisting of the following Formula (9).

[Chemical Formula 9]

In Formula 9, m and n are each 0 to 10. In Formula 9, A and 1, 2, 3, 4, 5, 6, 7, and 8 may be independently selected from the group consisting of H, F, CN, CF _3, and CH ₃ .

In formula (1), R4 and R5 may be independently selected from the group consisting of the following formula (10).

[Chemical formula 10]

In Formula 10, m and n are each 0 to 10. In Formula 9, A and 1, 2, 3, 4, 5, 6, 7, and 8 may be independently selected from the group consisting of H, F, CN, CF _3, and CH ₃ .

The protective film 150 has a triazine ring having a photoactive group introduced into a main chain of any one of a polyamide-based polymer and a polythioether-based polymer. The triazine ring is an aromatic compound having a nitrogen atom and improves physical properties such as heat resistance and dielectric constant of the protective film 150. In addition, the photoactive group may be a compound represented by Chemical Formula 2, which may cause a crosslinking reaction by light to improve physical properties such as heat resistance, dimensional stability, mechanical properties, and adhesiveness of the protective layer 150 itself.

In addition, since the protective layer 150 is formed of an organic insulating layer, the protective layer 150 may have a flat upper surface.

A pixel electrode 180 electrically connected to the drain electrode 140b is disposed on the passivation layer 150 through the contact hole.

The pixel electrode 180 overlaps the thin film transistor Tr, the gate line, and the data line, and may be disposed on the passivation layer 150. Since the protective layer 150 is formed of an organic insulating layer having a smaller dielectric constant than the silicon based inorganic layer, a parasitic capacitance is formed between the pixel electrode 180 and the thin film transistor Tr, the gate wiring, and the data wiring It is possible to prevent such a problem. Thus, the aperture ratio of the liquid crystal display device can be improved.

On the other hand, a color filter pattern 220 for coloring is disposed on the inner surface of the second substrate 200. In detail, a black matrix 210 for preventing light leakage is disposed on the inner surface of the second substrate 200. The black matrix 210 has openings exposing pixels for displaying images. A color filter pattern 220 is disposed on the opening, that is, the pixel. The overcoat layer 230 may be disposed on the entire surface of the second substrate 200 including the black matrix 210 and the color filter pattern 220. The overcoat layer 230 has a flat upper surface to remove the step formed by the black matrix 210 and the color filter pattern 220.

A common electrode 240 is disposed on the overcoat layer 230. Here, the liquid crystal molecules of the liquid crystal layer 300 are driven by an electric field formed by the common electrode 240 and the pixel electrode 240.

In addition, the gate insulating layer 120 and the overcoat layer 250 may be formed from a composition including the compound represented by Formula 1, respectively.

Accordingly, a liquid crystal display device according to an embodiment of the present invention includes at least one of a gate insulating film, a protective film, and an overcoat layer formed from a composition including the compound represented by Chemical Formula 1, And the reliability of the liquid crystal display device can be ensured.

In the first embodiment of the present invention, the organic insulating layer represented by Formula 1 is applied to a liquid crystal display device, but the present invention is not limited thereto. That is, the organic insulating layer represented by Formula 1 may be applied to other display devices such as organic light emitting diode display devices.

2A to 2D are cross-sectional views illustrating a method of manufacturing a liquid crystal display device according to a second embodiment of the present invention.

Referring to FIG. 2A, in order to manufacture a liquid crystal display, a gate wiring and a data wiring intersecting each other on a first substrate 100 on which a plurality of pixels are defined, and a thin film transistor Tr). The thin film transistor Tr includes a gate electrode 110 branched from the gate wiring, a gate insulating film 120 covering the gate electrode 110, a semiconductor insulating film 120 disposed on the gate insulating film 120 corresponding to the gate electrode 110, A source electrode 140a disposed on the semiconductor pattern 130 and a drain electrode 140b disposed on the semiconductor pattern 130 and spaced apart from the source electrode 140a.

The passivation layer 150 is formed on the first substrate 110 by the thin film transistor Tr. In order to form the passivation layer 150, the thin film transistor Tr is first applied on the first substrate 110 to form an organic insulating layer forming composition. The composition for forming an organic insulating film may include a binder resin, a curing agent, an initiator, and a solvent.

The binder resin may include the compound represented by Formula 1 to improve physical properties such as heat resistance, chemical resistance and dimensional stability of the protective layer 150.

The curing agent may function to cross-link the compound represented by Formula 1 by light or heat. Examples of the material used as the hardener include epoxy compounds, phenol compounds, amine compounds, maleic anhydride, tetrahydrophthalic anhydride, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, trimethylolpropane triacrylate, Erythritol trimethacrylate, erythritol trimethacrylate, petaerythritol tetramethacrylate, phenoxy ethyl acrylate, dipentaerythritol penta methacrylate and dipentaerythritol hexamethacrylate.

The initiator serves to activate the crosslinking reaction of the curing agent. Examples of the material used as the initiator include a sulfotitic salt-based compound, an iodonium salt-based compound, a phosphine-based compound, a benzoin-based compound, a benzophenone-based compound, and an acetophenone-based compound.

The solvent may be a material having excellent volatility. Examples of materials usable as the solvent may include diethylene glycol, methyl ethyl ether, diethylene glycol dimethyl ether, triethylene glycol motomonyl ether, propylene glycol, methyl ethyl ketone, cyclohexane, toluene and xylene.

The organic insulating film composition may further include at least one of a filler, a surfactant, an antioxidant, and an antiflocculating agent.

Examples of the method of applying the organic insulating film composition include a spin coating method, a spray coating method, a slit coating method, and an inkjet printing method.

Referring to FIG. 2C, the protective film 150 is exposed and developed using a mask to form a contact hole exposing a part of the drain electrode 140b.

A pixel electrode 180 electrically connected to the drain electrode 140b is formed on the passivation layer 150. Referring to FIG. A transparent conductive layer is formed on the passivation layer 150 to form the pixel electrode 180. The transparent conductive film may be formed by vapor deposition. An example of the material of the transparent conductive film may be ITO or IZO. The pixel electrode 180 can be formed by etching the transparent conductive film.

At this time, the pixel electrode 180 is formed to overlap with the thin film transistor Tr, the gate wiring, and the data wiring with the protective film 150 interposed therebetween, thereby improving the aperture ratio of the liquid crystal display device.

Referring to FIG. 2C, the second substrate 200 is provided separately from forming the thin film transistor Tr on the first substrate 100.

A black matrix 210 having a plurality of openings is formed on the second substrate 200. That is, the black matrix 210 is disposed on the second substrate 200 in correspondence with the gate wiring, the data wiring, and the thin film transistor of the first substrate 100.

The black matrix 210 may be formed by forming a black resin film on the second substrate 200, and then exposing and developing the black resin film. Alternatively, when the black matrix 210 is formed of an inorganic material such as chromium, the black matrix 210 may be formed by an etching process using a photoresist.

A color filter pattern 220 is formed on the opening. A color filter resin film is formed on the second substrate 200 including the black matrix 210 to form the color filter pattern 220 and then exposure and development are performed to form the color filter pattern 220 ).

An overcoat layer 230 is formed on the second substrate 200 including the black matrix 210 and the color filter pattern 220.

A common electrode 240 is formed on the overcoat layer 230. The common electrode 240 may be formed of a transparent conductive film such as ITO or IZO.

Referring to FIG. 2D, a sealing member (not shown in the drawing) is formed along the edges of the first and second substrates. Thereafter, liquid crystal is dropped onto the first and second substrates, and then the first and second substrates are bonded together using the sealing member. In the embodiments of the present invention, the method of forming the liquid crystal layer has been described by the liquid crystal dropping method, but the present invention is not limited thereto. That is, the liquid crystal layer may be formed by a liquid crystal injection method.

In the embodiment of the present invention, by providing a protective film to which an organic insulating film formed from a polyamide-based compound or a polythioether-based compound having a triazine-based compound having a photoactive group is applied, the heat resistance, chemical resistance, Can be improved, and the aperture ratio and the reliability of the liquid crystal display device can be ensured and can be formed through a simple process.

Hereinafter, the method of synthesizing the compounds represented by Formula 1 contained in the composition for forming an organic insulating layer according to an embodiment of the present invention will be described in more detail with reference to the following experimental examples.

Experimental Example  One

Experimental Example 1 of the present invention relates to the synthesis of a polyamide-based photosensitive polymer having a cinnamate photosensitive functional group and a method of forming an organic insulating film using the same.

(1) Formation of a cinnamate precursor

    14.8 g of cinnamic acid was placed in a round bottom flask filled with nitrogen. Then, 17.8 g of thionyl chloride (SOCl2) was added to the flask containing the cinnamic acid, and the mixture was stirred. Then, 0.5 ml of dimethylformamide (DMF) was further added to the flask, and the reaction was allowed to proceed at room temperature for 24 hours. After completion of the reaction, distillation under reduced pressure yielded 16 g of cinnamoyl chloride as a cinnamate precursor.

(2) introducing a hydroxy functional group into the triazine ring

   18.4 g of cyanuric chloride was added to a round bottom flask filled with nitrogen, and 200 ml of tetrahydrofuran in which moisture was removed was dissolved therein. To this solution, 15.2 g of triethylamine is added and the temperature is lowered to -5 ° C. Thereafter, 20 ml of tetrahydrofuran, from which moisture was removed, was added to the cinnamoyl chloride obtained in (1) of Experimental Example 1 to dilute it. Thereafter, the diluted cinnamic chloride solution was slowly added dropwise to the flask and stirred vigorously for 12 hours. After completion of the reaction, the reaction solution is distilled under reduced pressure to remove tetrahydrofuran and then dissolved in methylene chloride. Thereafter, the solution was passed through a filter packed with silica gel, and then distilled under reduced pressure to remove the solvent. Finally, recrystallization was performed in a 1: 1 mixed solvent of methylene chloride and n-hexane, followed by filtration under reduced pressure. The obtained solid substance was vacuum dried to obtain 2-cinnamoyl-4,6-dichloro-1,3,5-triazine.

(3) Synthesis of triazine monomers having two amine functional groups

   In a round bottom flask, 29.6 g of 2-cinnamoyl-4,6-dichloro-1,3,5-triazine obtained in (2) of Experimental Example 1 was dissolved in 300 ml of chloroform to form a first solution. 32.8 g of 4-aminophenol and 12 g of sodium hydroxide were dissolved in 300 ml of distilled water containing 3 g of cetyltrimethylammonium bromide, followed by vigorous reaction for 24 hours with the first solution. After the reaction was terminated, the organic phase was separated, transferred to a separating funnel, washed three times with distilled water to remove impurities, and water was removed with calcium chloride. The water-free solution was distilled under reduced pressure to remove chloroform, which was an organic solvent, and recrystallized in a mixed solvent of methylene chloride and n-hexane. The precipitated crystals were filtered under reduced pressure and vacuum dried to obtain a triazine monomer having two amine functional groups.

(4) Polymerization of polyamide polymers having cinnamate photosensitive functional groups

   44.144 g of the triazine monomer having two amine functional groups obtained in (3) of Experimental Example 1 was placed in a round bottom flask filled with nitrogen and dissolved in 400 ml of water-free tetrahydrofuran. To this solution, 20.238 g of triethylamine was added to form a second solution. 20.3 g of terephthaloyl chloride was dissolved in 100 ml of tetrahydrofuran from which water had been removed, and the solution was slowly added dropwise to the second solution, followed by vigorous stirring for 12 hours. After completion of the reaction, the reaction solution was slowly poured into methanol, precipitated, filtered and the precipitate was vacuum dried. The precipitate thus obtained was dissolved again in tetrahydrofuran and precipitated in methanol. This procedure was repeated twice, followed by vacuum drying. Finally, a polyamide-based polymer having a cinnamate photosensitive functional group represented by the following formula 11 was obtained using a triazine ring .

(5) Formation of organic insulating film

8 g of the polyamide-based polymer obtained in (4) of Experimental Example 1, which is a binder resin, was mixed with 100 g of a composition containing a curing agent, an initiator and a solvent to form a composition for forming an organic insulating film. The composition for forming an organic insulating film was coated on a substrate on which ITO was formed, baked at 80 to 90 ° C for 3 minutes, and then subjected to UV irradiation. The UV irradiation wavelength was 365 nm and the UV irradiation energy amount was 50 mJ / cm 2. After completion of the UV irradiation, the resultant was further baked at 220 ° C for 1 hour to complete an organic insulating film.

Experimental Example  2

Experimental Example 2 of the present invention relates to the synthesis of a thermosetting triazine-based polyamide photosensitive polymer and a method of forming an organic insulating film using the same.

(1) Synthesis of N-hydroxymaleimide

42.26 g of N- (phenyloxycarbonyloxy) maleimide (II) was dissolved in 500 ml of methanol and refluxed for 3 hours. After the reaction, the methanol is removed by evaporation, and the residue liquid is poured into benzene to obtain a solid. This solid was recrystallized using a mixed solvent of tetrahydrofuran (THF) and hexane to obtain 12.60 g of N-hydroxymaleimide in a yield of 62%. The crystalline melting point was measured at 125 캜 and agreed with the reported value (125-126 캜) in the literature (Akiyama, M., et al., J. Chem. Soc., Perkin 1 1980,2122).

(2) Synthesis of maleimide-substituted triazine compound

11.3 g of the N-hydroxymaleimide obtained in (1) of Experimental Example 2 was dissolved in 100 ml of THF to form a first solution. 3 g of NaH was added to the first solution, and the reaction solution was allowed to react for 2 hours. The reaction solution was slowly added dropwise to a solution of 18.4 g of triazine dissolved in THF at -20 ° C. After completion of the dropwise addition of the reaction solution, the reaction was further continued for about 1 hour. The THF was removed from the solution after the reaction was terminated, and the salt component was removed from the solid phase reaction product. The salt was recrystallized in a mixed solvent of methylene chloride and normal hexane to prepare maleimide-substituted triazine compound. The yield was 60% .

(3) Synthesis of triazine monomers

26.1 g of the maleimide-substituted triazine compound obtained in (2) of Experimental Example 2 was dissolved in 200 ml of chloroform to form a second solution. 32.8 g of 4-aminophenol and 12 g of sodium hydroxide were dissolved in 300 ml of distilled water containing 3 g of cetyltrimethylammonium bromide, and the mixture was reacted vigorously for 24 hours with the second solution. After the reaction was terminated, the organic phase was separated, transferred to a separating funnel, washed three times with distilled water to remove impurities, and water was removed with calcium chloride. The water-free solution was distilled under reduced pressure to remove chloroform, which was an organic solvent, and recrystallized in a mixed solvent of methylene chloride and n-hexane. The precipitated crystals were filtered under reduced pressure and vacuum dried to obtain a triazine monomer.

(4) Synthesis of polyamide polymer having maleimide group

40.24 g of the triazine monomer obtained in (3) of Example 2 is placed in a round bottom flask filled with nitrogen and dissolved in 400 ml of toluene in which moisture is removed. To this solution, 20.238 g of triethylamine is added. 20.3 g of terephthaloyl chloride was dissolved in 100 ml of toluene, and the solution was stirred vigorously with slow dropwise addition to the above solution of the triazine monomer and triethylamine dissolved therein, followed by reaction for 12 hours. After the completion of the reaction, the reaction solution was slowly poured into methanol, precipitated in water, filtered and the precipitate was vacuum dried. The obtained precipitate was dissolved again in tetrahydrofuran and precipitated in methanol. This procedure was repeated twice, followed by vacuum drying. Finally, a compound represented by the following formula (12), i.e., a polyamide-based polymer having a maleimide functional group .

(5) Formation of organic insulating film

An organic insulating film was formed in the same manner as in (5) of Experimental Example 1, except that the binder resin was used as the polyamide-based polymer having a maleimide functional group obtained in (4) of Experimental Example 2.

Experimental Example  3

Experimental Example 3 of the present invention relates to the synthesis of a polythioether-based polymer having a chalcone functional group and a method for forming an organic insulating film using the same.

(1) Synthesis of chalcone photosensitive functional group

10 g of 4-methoxycalcone and 2.05 g of sodium cyanide were dissolved in 100 ml of dimethyl sulfoxide and reacted for 24 hours. After completion of the reaction, the reaction solution was mixed with chloroform and stirred with distilled water to extract impurities. After the aqueous phase was removed, the chloroform was removed under reduced pressure at room temperature. The remaining solid phase was recrystallized from methanol and vacuum dried at 40 < 0 > C to obtain the side chain 4-hydroxycalcone for the photoreaction.

(2) introduction of a chalcone photosensitive functional group into a triazine ring

23.8 g of 4-hydroxycalcone obtained in (1) of Experimental Example 3 was placed in a round bottom flask filled with nitrogen and dissolved in 240 ml of tetrahydrofuran in which water was removed. 2.4 g of sodium hydride (NaH) was added thereto and reacted at room temperature for 6 hours to form a first solution. 18.4 g of triazine was placed in a round bottom flask and dissolved in 200 ml of tetrahydrofuran in which water was removed. The first solution was slowly dropped at -5 ° C while stirring vigorously and reacted for 24 hours. After the reaction was terminated, the tetrahydrofuran was removed by distillation under reduced pressure, and the obtained solid was dissolved again in chloroform. The solution was washed three times with distilled water in a separating funnel to remove impurities, and water was removed with calcium chloride. This solution was again distilled under reduced pressure to remove chloroform, and recrystallized from a mixed solvent of methylene chloride and normal nucleic acid. The resulting material was filtered under reduced pressure and vacuum dried to obtain triazine having a chalcone photosensitive functional group.

(3) Synthesis of triazine monomer having two halide functional groups

38.6 g of triazine having a chalcone photosensitive functional group obtained in (2) of Experimental Example 3 was dissolved in 400 ml of chloroform. 25.6 g of 4-chlorophenol and 8 g of sodium hydroxide were dissolved in 300 ml of distilled water containing 3 g of cetyltrimethylammonium bromide, mixed with the above triazine solution, and vigorously reacted for 24 hours. After the reaction was terminated, the organic phase was separated, transferred to a separating funnel, washed three times with distilled water to remove impurities, and water was removed with calcium chloride. The water-free solution was distilled under reduced pressure to remove chloroform, which was an organic solvent, and recrystallized in a mixed solvent of methylene chloride and n-hexane. The precipitated crystals were filtered under reduced pressure and vacuum dried to obtain a triazine monomer.

 (4) Synthesis of polythioester polymer having chalcone photosensitive functional group

56.7 g of the triazine monomer obtained in (3) of Experimental Example 3 was placed in a round bottom flask and dissolved in 600 ml of nitrobenzene. 14.2 g of 1,4-phenyldithiol, 8 g of sodium hydroxide and 0.3 g of cetyltrimethylammonium bromide were dissolved in 100 ml of water and mixed in a nitrobenzene solution in which the triazine monomer was dissolved, followed by vigorous stirring for 24 hours. . After completion of the reaction, the reaction solution was slowly poured into methanol to precipitate the precipitate. The precipitate obtained by filtration was vacuum dried. The resulting precipitate was dissolved again in tetrahydrofuran and then precipitated in methanol. This procedure was repeated twice, followed by vacuum drying. Finally, a compound represented by the following formula (13), that is, a polythioether-based compound having a chalcone photosensitive functional group The polymer was synthesized.

(5) Formation of organic insulating film

An organic insulating film was formed in the same manner as in (5) of Experimental Example 1, except that the binder resin was used as the polythioether polymer having a chalcone photosensitive functional group obtained in (4) of Experimental Example 3.

Experimental Example  4

Experimental Example 4 of the present invention relates to the synthesis of a polythioether polymer having a coumarin photosensitive functional group and a method for forming an organic insulating film using the same.

(1) Synthesis of triazine having a coumarin photosensitive functional group

16.2 g of 7-hydroxy coumarin and 2.4 g of sodium hydride (NaH) were placed in a round bottom flask filled with nitrogen and dissolved in 160 ml of tetrahydrofuran in which moisture was removed, followed by vigorous stirring and reaction for 6 hours. This solution was reacted vigorously for 24 hours while slowly dropping the solution at -5 ° C in a solution of 18.4 g of triazine in a round bottom flask and dissolving in 200 ml of tetrahydrofuran in which water was removed. After completion of the reaction, tetrahydrofuran was removed by distillation under reduced pressure, and the resulting solid was dissolved again in chloroform. The solution was washed three times with distilled water in a separating funnel to remove impurities, and water was removed with calcium chloride. This solution was again distilled under reduced pressure to remove chloroform, and recrystallized from a mixed solvent of methylene chloride and normal nucleic acid. The obtained material was filtered under reduced pressure and vacuum dried to obtain triazine having a coumarin photosensitive functional group.

(2) Synthesis of triazine monomers having two halide functional groups

31.1 g of the triazine monomer having the coumarin photosensitive functional group obtained in (1) of Example 3 was dissolved in 400 ml of chloroform. 25.6 g of 4-chlorophenol and 8 g of sodium hydroxide were dissolved in 300 ml of distilled water containing 3 g of cetyltrimethylammonium bromide, mixed with the above triazine solution, and vigorously reacted for 24 hours. After the reaction was terminated, the organic phase was separated, transferred to a separating funnel, washed three times with distilled water to remove impurities, and water was removed with calcium chloride. The water-free solution was distilled under reduced pressure to remove chloroform, which was an organic solvent, and recrystallized in a mixed solvent of methylene chloride and n-hexane. The precipitated crystals were filtered under reduced pressure and vacuum dried to obtain a triazine monomer having two halide functional groups

(3) Synthesis of polyimide photosensitive polymer having coumarin photosensitive functional group

49.1 g of the triazine monomer obtained in Example 3 (2) was placed in a round bottom flask and dissolved in 600 ml of nitrobenzene. 14.2 g of 1,4-phenyldithiol, 8 g of sodium hydroxide, and 0.3 g of cetyltrimethylammonium bromide were dissolved in 100 ml of water, mixed with the nitrobenzene solution in which the triazine monomer was dissolved, vigorously stirred, and reacted for 24 hours Lt; / RTI > After the completion of the reaction, the reaction solution was slowly poured into methanol, precipitated in water, filtered and the precipitate was vacuum dried. The obtained precipitate was dissolved again in tetrahydrofuran and then precipitated in methanol. This procedure was repeated twice, followed by vacuum drying. Finally, a compound represented by the following chemical formula 14, namely, a polythioether polymer having a coumarin photosensitive functional group Were synthesized.

(5) Formation of organic insulating film

An organic insulating film was formed in the same manner as in (5) of Experimental Example 1, except that the binder resin was used as a polythioether polymer having a coumarin photosensitive functional group obtained in (4) of Experimental Example 4.

Comparative Example  One

In Comparative Example 1, an organic insulating film was formed in the same manner as in (5) of Experimental Example 1, except that the binder resin was used as an acrylate compound.

Table 1 below shows the results of observing the characteristics of the organic insulating films formed from Experimental Example 1, Experimental Example 2, Experimental Example 3, Experimental Example 4 and Comparative Example 1, respectively.

Item Comparative Example 1 Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 Degree of fume generation
(Collecting weight) (mg) 2 0.2 0.3 0.2 0.3 Refractive index 1.55 1.5 1.51 1.51 1.52 Transmittance
(3 [mu] m, 400 to 800 nm) > 90% > 91% > 92% > 92% > 93% permittivity
(@ 100kHz) 3.4 3.2 3.2 3.3 3.2 Thickness change rate
(@ 250 C, 2 hr) -3.2% -1.3% -1.0% -1.1% -0.9% Hardness (H) 3 to 4 4 4 4 4 Resistivity (ΩhCm) 1.6 × 10 ¹⁵ 1.8 × 10 ¹⁵ 1.9 × 10 ¹⁵ 1.9 × 10 ¹⁵ 2.1 × 10 ¹⁵ Chemical resistance


NMP No change No change No change No change No change IPA No change No change No change No change No change Base solution No change No change No change No change No change Acid solution No change No change No change No change No change

As shown in Table 1, when an organic insulating film is formed from a polyamide polymer or polythioether polymer having a triazine group according to the present invention as in Experimental Examples 1, 2, 3, and 4, It is confirmed that the dielectric constant is lowered and the heat resistance, chemical resistance, electrical characteristics such as low dielectric constant and insulation property are improved.

Therefore, since at least one of the protective film, the gate insulating film and the overcoat layer of the liquid crystal display of the present invention is used as an organic insulating film from a polyamide polymer having a triazine group or a polythioether polymer, Can be secured.

1 is a cross-sectional view illustrating a liquid crystal display device according to a first embodiment of the present invention.

2A to 2D are cross-sectional views illustrating a method of manufacturing a liquid crystal display device according to a second embodiment of the present invention.

 (Description of Reference Numbers to Main Parts of the Drawings)

 100: first substrate

 112: gate insulating film

 150: Shield

 200: second substrate

 210: Black Matrix

 220: Color filter pattern

 230: Overcoat layer

Claims (6)

delete And a compound represented by any one of the following formulas (11) to (14) A photopolymerization initiator, a photopolymerization initiator, and a solvent. (11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

delete A first substrate on which a thin film transistor is formed; A protective film formed on the first substrate including the thin film transistor and formed from a compound represented by Chemical Formula 1; And And a pixel electrode disposed on the protective film, The thin- A gate electrode, a gate insulating film covering the gate electrode, a semiconductor pattern disposed on the gate insulating film, a source electrode and a drain electrode disposed on the semiconductor pattern, Wherein the gate insulating film of the thin film transistor is formed from a composition comprising a compound represented by the following formula (1). [Chemical Formula 1]

M + n = 1, O ≤ m ≤ 1 and O ≤ And R 1 are each independently selected from the group consisting of compounds (1) to (4) represented by the following formula (2). (2)

In (1) of the above formula (2), X is any one of the compounds represented by the following formula (3). (3)

In Formula 3, m and n are each 0 to 10. In the formula (1) of formula (2), Y is any one selected from the group represented by the following formula (4). [Chemical Formula 4]

In Formula 4, 1, 2, 3, 4, 5, 6, 7, and 8 are independently selected from the group consisting of compounds represented by Formula 5 below. [Chemical Formula 5]

In Formula 5, m and n are each 0 to 10. In Formula 5, A and B are each independently selected from the group consisting of H, F, Cl, CN, CF _3, and CH ₃ . In the formula (2), Y is any one selected from the group consisting of the following formula (6). [Chemical Formula 6]

In Formula 6, n is 0 to 10. In Formula 6, 1 and 2 are any one selected from the group consisting of Formula (7). (7)

In Formula 7, A is any one selected from the group consisting of H, F, CH ₃ , CF _3, and CN. In the above formulas (3) and (4), n is 0 to 10. In the above formulas (3) and (4), 1, 2, 3, 4, and 5 are independently selected from the group consisting of the following formula (8). [Chemical Formula 8]

In Formula 8, m and n are each 0 to 10, and A and B are each independently selected from the group consisting of H, F, Cl, CN, CF ₃ and CH ₃ . In the above formula (1), R 2 and R 3 are independently selected from the group represented by the following formula (9). [Chemical Formula 9]

In Formula 9, m and n are each 0 to 10. In Formula 9, A and 1, 2, 3, 4, 5, 6, 7 and 8 are each independently selected from the group consisting of H, F, CN, CF ₃ and CH ₃ . In formula (1), R4 and R5 are independently selected from the group consisting of the following formula (10). [Chemical formula 10]

In Formula 10, m and n are each 0 to 10. delete 5. The method of claim 4, A second substrate facing the first substrate and having a color filter pattern and a black matrix formed thereon; An overcoat layer disposed on a second substrate including the color filter and the black matrix, the overcoat layer formed from a composition comprising the compound represented by Formula 1; And And a liquid crystal layer interposed between the first and second substrates.

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