KR20090056502A - Composition for forming organic insulating film and display device having organic insulating film made therefrom - Google Patents

Abstract

A composition for forming an organic insulating film is provided to form an organic insulating film with thermal, electrical, chemical and physical properties and to increase the reliability of s display device. A composition for forming an organic insulating film comprises a compound represented by chemical formula 1, wherein m+n = 1, 0 <= m <= 1, and 0 <= n <= 1; and R1 is one selected from the group consisting of the compounds (1)-(4) independently represented by chemical formula 2. The composition for forming an organic insulating film further comprises a photo-curable agent, a photopolymerization initiator and solvent.

Description

COMPOSITION FOR FORMING ORGANIC INSULATING FILM AND DISPLAY DEVICE HAVING ORGANIC INSULATING FILM MADE THEREFROM}

The present invention relates to a display device, and more particularly, to a display device including a composition for forming an organic insulating film and an organic insulating film formed therefrom.

Today, a display device is a device that informs a user through information. Examples of a display device widely used in recent years may be a liquid crystal display device, an organic light emitting diode display device, or the like.

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

Such a liquid crystal display includes a liquid crystal panel for displaying an image according to light transmittance 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. A passivation film is interposed between the thin film transistor and the pixel electrode. The passivation 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. As a result, in order to form the passivation layer including the contact hole, a deposition process and a photolithography process should be performed. As the deposition process is performed in a vacuum chamber, there is a problem that the process equipment is expensive as well as a limitation on the applicable substrate size. In addition, the photolithography process includes a film forming process, an exposure process, a developing process, and an etching process, so that the process is complicated. Accordingly, when the protective layer is formed of an inorganic layer, not only the process for forming the display device is complicated but also the process cost increases.

When the protective layer is formed of an organic layer, the organic layer may be formed through a coating process, thereby simplifying the process of the display device. However, the liquid crystal display device is easily exposed to harsh environmental conditions such as high temperature during or after the process, and there is a problem that the organic film is deformed or damaged in a harsh environment. In addition, the organic layer has a problem that the stability is low because the adhesion to the substrate on which the thin film transistor is formed.

In addition, the thin film transistor may be applied to an organic light emitting diode display device as well as a liquid crystal display device. Thus, applying the protective film as an organic film is not only a problem of the liquid crystal display device. In particular, the organic light emitting diode display has a problem in that the lifetime is reduced by the outgassing generated from the organic film. As a result, thermal stability of the organic film applied to the organic light emitting diode display is essentially required.

That is, the display device attempts to form the passivation layer as an organic layer in order to reduce the number of processes, but the organic layer has a problem of lowering the reliability of the display device due to lower thermal, electrical, chemical and physical characteristics than the inorganic layer.

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.

One object of the present invention is to provide a display device having a protective film formed from the organic insulating film forming composition, which can reduce the number of processes and ensure reliability.

In order to achieve the above technical problem, an aspect of the present invention provides a composition for forming an organic insulating film. The composition for forming an organic insulating layer includes a compound represented by Formula 1 below.

In Formula 1, m + n = 1, O ≦ m ≦ 1, and O ≦ n ≦ 1. R 1 is each independently selected from the group consisting of compounds (1) to (4) represented by the following formula (2).

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

In Formula 4, 1, 2, 3, 4, 5, 6, 7, 8 are any one selected from the group represented by the compound represented by the following formula (5) independently of each other.

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

In Chemical Formula 6, n is 0 to 10. In Formula 6, 1 and 2 are any one selected from the group represented by the following Formula 7.

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

In Formulas (3) and (4), n is 0 to 10. In (3) and (4) of the formula (2), 1, 2, 3, 4, 5 is any one selected from the group represented by the following formula (8) independently of each other.

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, CF3, and CH3.

In Formula 1, R2 and R3 are any one selected from the group represented by the following formula (9) independently of each other.

In Formula 9, m and n are each 0 to 10. In addition, in Formula 9, A and 1, 2, 3, 4, 5, 6, 7, 8 are independently selected from the group consisting of H, F, CN, CF3 and CH3.

In Formula 1, R 4 and R 5 are each independently selected from the group represented by the following Formula 10.

In Formula 10, m and n are each 0 to 10. In addition, in Formula 9, A and 1, 2, 3, 4, 5, 6, 7, 8 are independently selected from the group consisting of H, F, CN, CF3 and CH3.

In order to achieve the above technical problem, another aspect of the present invention provides a display device. The display device includes a first substrate on which a thin film transistor is formed, a first passivation layer formed on the first substrate including the thin film transistor, a passivation layer formed from the compound represented by Formula 1, and a pixel electrode on the passivation layer.

The display device according to the embodiment of the present invention has a protective film to which an organic insulating film formed from a polyamide-based compound or a polythioether compound into which a triazine group having a photoactive group is introduced, thereby providing heat resistance, chemical resistance and dimensional stability. Can be improved, the reliability of the display device can be ensured and can be formed through a simple process.

In addition, since the dielectric constant of the organic insulating layer is small, as the organic insulating layer is applied as the passivation layer, the thin film transistor and the pixel electrode arranged with the passivation layer interposed therebetween can be overlapped to improve the aperture ratio of the display device. Can be.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings of the liquid crystal display. The following embodiments are provided as examples to sufficiently convey the spirit of the present invention to those skilled in the art. Accordingly, the invention is not limited to the embodiments described below and may be embodied in other forms. In the drawings, the size and thickness of the device may be exaggerated for convenience. Like numbers refer to like elements throughout.

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

Referring to FIG. 1, a liquid crystal display device is interposed between a first substrate 100, a second substrate 200 facing the first substrate 100, a first substrate 100, and a second substrate 200. The liquid crystal layer 300 is included.

In detail, the first substrate 100 includes a plurality of pixels for representing an image. The pixels may be defined by gate lines and data lines (not shown) that cross each other on the first substrate 100. Each pixel includes a thin film transistor Tr electrically connected to a gate line and a data line. The thin film transistor Tr is disposed on the gate electrode 110 branched from the gate wiring, the gate insulating layer 120 covering the gate electrode 110, and the gate insulating layer 120 corresponding to the gate electrode 110. The semiconductor pattern 130 includes 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 covering the thin film transistor Tr is disposed on the first substrate 100. The passivation layer 150 includes a contact hole exposing a part of the drain electrode 140b of the thin film transistor Tr.

The passivation layer 150 may be formed from a composition including the compound represented by Chemical Formula 1.

[Formula 1]

In Formula 1, m + n = 1, O ≦ m ≦ 1, and O ≦ n ≦ 1. R1 may be any one selected from the group consisting of compounds (1) to (4) each independently represented by the following formula (2).

[Formula 2]

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

[Formula 3]

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

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

[Formula 4]

In Formula 4, 1, 2, 3, 4, 5, 6, 7, 8 may be any one selected from the group represented by the compound represented by the following formula (5) independently of each other.

[Formula 5]

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

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

[Formula 6]

In Chemical Formula 6, n is 0 to 10. In Formula 6, 1 and 2 may be any one selected from the group represented by Formula 7 below.

[Formula 7]

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

In Formulas (3) and (4), n is 0 to 10. In (3) and (4) of the formula (2), 1, 2, 3, 4, 5 may be any one selected from the group represented by the following formula (8) independently of each other.

[Formula 8]

In Formula 8, m and n are each 0 to 10, A and B may be any one selected from the group consisting of H, F, Cl, CN, CF3 and CH3 independently of each other.

In Chemical Formula 1, R2 and R3 may be any one selected from the group represented by the following Chemical Formula 9 independently of each other.

[Formula 9]

In Formula 9, m and n are each 0 to 10. In addition, in Formula 9, A and 1, 2, 3, 4, 5, 6, 7, 8 may be any one selected from the group consisting of H, F, CN, CF3 and CH3 independently of each other.

In Chemical Formula 1, R4 and R5 may be any one selected from the group represented by the following Chemical Formula 10 independently of each other.

[Formula 10]

In Formula 10, m and n are each 0 to 10. In addition, in Formula 9, A and 1, 2, 3, 4, 5, 6, 7, 8 may be any one selected from the group consisting of H, F, CN, CF3 and CH3 independently of each other.

The protective film 150 has a triazine ring having a photoactive group in the main chain of any one of a polyamide polymer and a polythioether 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 is any one of the compounds represented by Chemical Formula 2, and may cause a crosslinking reaction by light to improve physical properties such as heat resistance, dimensional stability, mechanical properties, and adhesion of the protective film 150 itself.

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

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

The pixel electrode 180 may overlap the thin film transistor Tr, the gate line, and the data line, and may be disposed on the passivation layer 150. This is because the passivation layer 150 is formed of an organic insulating layer having a lower dielectric constant than the silicon-based inorganic layer, so that parasitic capacitance is formed between the pixel electrode 180 and the thin film transistor Tr, the gate line, and the data line. This can be prevented. As a result, the aperture ratio of the liquid crystal display device can be improved.

On the other hand, the color filter pattern 220 for realizing the color on the inner surface of the second substrate 200 is disposed. In detail, a black matrix 210 is disposed on the inner surface of the second substrate 200 to prevent light leakage. The black matrix 210 has an opening that exposes a pixel for displaying an image. The color filter pattern 220 is disposed in the opening, that is, the pixel. An overcoat layer 230 may be further disposed on the entire surface of the second substrate 200 including the black matrix 210 and the color filter pattern 220. As the overcoat layer 230 has a flat upper surface, the step formed by the black matrix 210 and the color filter pattern 220 is removed.

The common electrode 240 is disposed on the overcoat layer 230. Here, the liquid crystal molecules of the liquid crystal layer 300 are driven by the electric fields 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 Chemical Formula 1.

Accordingly, the liquid crystal display according to the 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, thereby manufacturing the liquid crystal display device. It can simplify and secure the reliability of the liquid crystal display device.

In the first embodiment of the present invention, the organic insulating film represented by Chemical Formula 1 is limited to the liquid crystal display device, but the present invention is not limited thereto. That is, the organic insulating film represented by Chemical Formula 1 may be applied to another display device, for example, an organic light emitting diode display.

2A through 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 thin film transistor may be formed at a gate line and a data line crossing each other on a first substrate 100 in which a plurality of pixels are defined, and at an intersection of the gate line and the data line. Tr). The thin film transistor Tr may include a gate electrode 110 branched from a gate wiring, a gate insulating layer 120 covering the gate electrode 110, and a semiconductor pattern disposed on the gate insulating layer 120 corresponding to the gate electrode 110. 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.

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

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

The curing agent may serve to crosslink the compounds represented by Formula 1 with each other by light or heat. Examples of the material used as the curing agent include epoxy compounds, phenol compounds, amine compounds, maleic anhydride, tetrahydrophthalic anhydride, polyethylene glycol mono acrylate, polypropylene glycol mono acrylate, trimethylol propane triacrylate, and peta. Erythritol trimethacrylate, petaerythritol tetramethacrylate, phenoxy ethylacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate and the like.

The initiator serves to activate the crosslinking reaction of the curing agent. Examples of the material used as the initiator may be a sulfotium salt compound, an iodonium salt compound, a phosphine compound, a benzoin compound, a benzophenone compound, an acetophenone compound, or the like.

The solvent may be a material having excellent volatility. Examples of the material used as the solvent may be diethylene glycol, methyl ethyl ether, diethylene glycol dimethyl ether, triethylene glycol motomenyl ether, propylene glycol, menylethyl ketone, cyclohexane, toluene, xylene and the like.

The organic insulating layer composition may further include at least one of a filler, a surfactant, an antioxidant, and an anti-agglomerating agent.

Examples of the method of coating the organic insulating layer composition may be a spin coating method, a spray coating method, a slit coating method, an inkjet printing method, or the like.

Referring to FIG. 2C, a contact hole exposing a part of the drain electrode 140b is formed by performing an exposure and development process using a mask on the passivation layer 150.

The pixel electrode 180 is formed on the passivation layer 150 to be electrically connected to the drain electrode 140b. In order to form the pixel electrode 180, a transparent conductive film is formed on the passivation layer 150. The transparent conductive film can be formed by a vapor deposition method. An example of a material of the transparent conductive film may be ITO or IZO. The transparent conductive layer may be etched to form the pixel electrode 180.

In this case, the pixel electrode 180 may be formed to overlap the thin film transistor Tr, the gate line, and the data line with the passivation layer 150 therebetween, thereby improving the aperture ratio of the liquid crystal display.

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 exposing and developing the black resin film after forming a black resin film on the second substrate 200. In contrast, 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.

The color filter pattern 220 is formed in the opening. In order to form the color filter pattern 220, a color filter resin film is formed on the second substrate 200 including the black matrix 210, and then subjected to an exposure and development process to perform 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.

The 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, sealing members (not shown) are formed along edges of the first and second substrates. Thereafter, the liquid crystal is dropped on the first and second substrates, and then the first and second substrates are bonded to each other using the sealing member. In the embodiment of the present invention, the method of forming the liquid crystal layer has been described by the liquid crystal dropping method, but is not limited thereto. That is, the liquid crystal layer may be formed by the 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 compound or a polythioether compound into which a triazine group having a photoactive group is introduced, the heat resistance, chemical resistance, electrical properties and dimensional stability of the protective film are provided. Can be improved, and the aperture ratio and reliability of the liquid crystal display device can be ensured and can be formed through a simple process.

Hereinafter, a method of synthesizing the compound represented by Formula 1 included in the composition for forming an organic insulating film 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) cinnamate precursor formation

    14.8 g of cinnamic acid was added to a round bottom flask filled with nitrogen. Thereafter, 17.8 g of thionyl chloride (SOCl 2) was added to the flask containing cinnamic acid, followed by stirring. In addition, 0.5 ml of dimethylformamide (DMF) was further added to the flask, followed by reaction at room temperature for 24 hours. After the reaction was completed, distillation under reduced pressure was carried out to obtain 16 g of cinnamoyl chloride as a cinnamate precursor.

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

   In a round bottom flask filled with nitrogen, 18.4 g of cyanuric chloride was added and 200 ml of tetrahydrofuran from which water was removed was dissolved. After adding 15.2 g of triethylamine to this solution, the temperature was lowered to -5 ° C. Thereafter, 20 ml of tetrahydrofuran from which water was removed was diluted in cinnamoyl chloride obtained in (1) of Experimental Example 1. Thereafter, the diluted cinnamic chloride solution was slowly added dropwise to the flask, followed by vigorous stirring for 12 hours. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove tetrahydrofuran and dissolved in methylene chloride. Thereafter, the solution was passed through a filter filled with silica gel and distilled under reduced pressure again to remove the solvent. Finally, after recrystallization in a 1: 1 mixed solvent of methylene chloride and normal hexane, and filtered 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 Monomer Having Two Amine Functions

   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 dissolved in 3 g of cetyltrimethylammonium bromide, mixed with the first solution, and reacted vigorously for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water-removed solution was distilled under reduced pressure to remove chloroform, an organic solvent, and then recrystallized from a mixed solvent of methylene chloride and normal hexane. The precipitated crystals were filtered under reduced pressure and then dried in vacuo to obtain a triazine monomer having two amine functional groups.

(4) Polymerization of Polyamide Polymer Having Cinamate Photosensitive Functional Group

   44.144 g of a triazine monomer having two amine functional groups obtained in (3) of Experimental Example 1 was put in a round bottom flask filled with nitrogen and dissolved in 400 ml of tetrahydrofuran from which water was removed. 20.238 g of triethylamine was added to this solution to form a second solution. After dissolving 20.3 g of terephthaloyl chloride in 100 ml of tetrahydrofuran from which water was removed, the mixture was stirred vigorously while slowly dropping into the second solution to react for 12 hours. After completion of the reaction, the reaction solution was slowly poured into methanol, precipitated, and filtered to dry the precipitate in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran and then precipitated in methanol twice. After vacuum drying, a polyamide-based polymer having a cinnamate photosensitive functional group represented by Formula 11 was finally obtained using a triazine ring. .

(5) organic insulating film formation

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 including 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, and then baked at 80 to 90 ° C. for 3 minutes, followed by UV irradiation. The UV irradiation wavelength was 365nm, the amount of UV irradiation energy was 50mJ / ㎠. After the completion of the UV irradiation was baked for 1 hour at 220 ℃ to complete the organic insulating film.

Experimental Example  2

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

(1) Synthesis of N-hydroxy maleimide

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

(2) Synthesis of Triazine Compound Substituted with Maleimide

11.3 g of N-hydroxymaleimide obtained in (1) of Experimental Example 2 was dissolved in 100 ml of THF to form a first solution. After adding 3 g of NaH to the first solution and reacting for 2 hours, the reaction proceeded while slowly adding dropwise 18.4 g of triazine to THF in a solution dissolved in THF. Here, the reaction was further proceeded for about 1 hour after the dropwise addition of the reaction solution was completed. THF was removed from the reaction solution, and then the salt component was removed from the solid phase reaction product and recrystallized from a mixed solution of methylene chloride and normal hexane to prepare a triazine compound substituted with maleimide. The yield was 15.7 g as 60%. .

(3) Synthesis of Triazine Monomer

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 dissolved in 3 g of cetyltrimethylammonium bromide, mixed with the second solution, and reacted vigorously for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water-removed solution was distilled under reduced pressure to remove chloroform, an organic solvent, and then recrystallized from a mixed solvent of methylene chloride and normal hexane. The precipitated crystals were filtered under reduced pressure and dried in vacuo 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 was placed in a round bottom flask filled with nitrogen and dissolved in 400 ml of toluene from which water was removed. 20.238 g of triethylamine is added to this solution. After dissolving 20.3 g of terephthaloyl chloride in 100 ml of toluene, the mixture was stirred vigorously while slowly dropping into the solution of the previous triazine monomer and triethyl amine, followed by reaction for 12 hours. After completion of the reaction, the reaction solution was slowly poured into methanol, precipitated and filtered, and the precipitate was dried in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran and then precipitated in methanol. The procedure was repeated two times, followed by vacuum drying. Finally, the compound represented by the following formula (12) using a triazine ring, that is, a polyamide-based polymer having a maleimide functional group Was prepared.

(5) organic insulating film formation

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

Experimental Example  3

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

(1) Synthesis of Chalcone Photosensitive Functional Group

10 g of 4-methoxychalcone and 2.05 g of sodium cyanide were dissolved in 100 ml of dimethyl sulfoxide and allowed to react for 24 hours. After completion of the reaction, the reaction solution was mixed with chloroform and stirred with distilled water to extract impurities. After removing the aqueous phase, chloroform was removed under reduced pressure at room temperature. The remaining solid phase was recrystallized in methanol and dried in vacuo at 40 ° C. to obtain side chain 4-hydroxy chalcone for photoreaction.

(2) Introduction of Chalcone Photosensitive Functional Groups into Triazine Rings

23.8 g of 4-hydroxychalcone obtained in (1) of Experimental Example 3 were placed in a round bottom flask filled with nitrogen and dissolved in 240 ml of tetrahydrofuran from which moisture 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 the first solution was slowly added dropwise at −5 ° C. to a solution dissolved in 200 ml of tetrahydrofuran from which water was removed, and reacted with vigorous stirring for 24 hours. After completion of the reaction, the product was distilled under reduced pressure, and tetrahydrofuran was removed, and the obtained solid was dissolved in chloroform again. The solution was washed three times with distilled water in a separatory funnel to extract impurities, and then water was removed with calcium chloride. The solution was distilled under reduced pressure again to remove chloroform and recrystallized with a mixed solvent of methylene chloride and normal nucleic acid. The obtained material was filtered under reduced pressure and then dried in vacuo to give 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 in which 3 g of cetyltrimethylammonium bromide was dissolved, mixed with the previous triazine solution, and reacted vigorously for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water-removed solution was distilled under reduced pressure to remove chloroform, an organic solvent, and then recrystallized from a mixed solvent of methylene chloride and normal hexane. The precipitated crystals were filtered under reduced pressure and dried in vacuo to obtain a triazine monomer.

 (4) Synthesis of Polythioester Polymer Having Chalcon Photosensitive Functional Group

56.7 g of the triazine monomer obtained in (3) of Experimental Example 3 was added to 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 a nitrobenzene solution in which the triazine monomer was dissolved, and stirred vigorously for 24 hours. I was. After completion of the reaction, the reaction solution was slowly poured into methanol to precipitate, and the precipitate obtained by filtration was dried in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran and then precipitated in methanol. The procedure was repeated two times, followed by vacuum drying. Finally, a polythioether-based compound having a chalcon photosensitive functional group using a compound represented by the following formula (13), that is, a triazine ring, was used. 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 a polythioether polymer having a chalcon photosensitive functional group obtained in Experiment (3).

Experimental Example  4

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

(1) Synthesis of Triazine Having Coumarin Photosensitive Functional Group

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

(2) Synthesis of Triazine Monomer Having Two Halide Functional Groups

31.1 g of a triazine monomer having a 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 in which 3 g of cetyltrimethylammonium bromide was dissolved, mixed with the previous triazine solution, and reacted vigorously for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water-removed solution was distilled under reduced pressure to remove chloroform, an organic solvent, and then recrystallized from a mixed solvent of methylene chloride and normal hexane. The precipitated crystals were filtered under reduced pressure and then dried in vacuo to give 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 (2) of 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, mixed with a nitrobenzene solution in which the triazine monomer was dissolved, followed by vigorous stirring for 24 hours. Let. After completion of the reaction, the reaction solution was slowly poured into methanol, precipitated and filtered, and the precipitate was dried in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran and then precipitated in methanol twice. After vacuum drying, the compound represented by the following formula (14) using a triazine ring, that is, a polythioether polymer having a coumarin photosensitive functional group was finally used. 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 a polythioether polymer having a coumarin photosensitive functional group obtained in Experiment (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.

Hereinafter, Table 1 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 Fume production degree (capture weight) (mg) 2 0.2 0.3 0.2 0.3 Refractive index 1.55 1.5 1.51 1.51 1.52 Transmittance (3um, 400 ~ 800nm) 〉 90% 〉 91% 〉 92% 〉 92% 〉 93% Dielectric constant (@ 100 kHz) 3.4 3.2 3.2 3.3 3.2 Thickness change rate (@ 250 ℃, 2hr) -3.2% -1.3% -1.0% -1.1% -0.9% Hardness (H) 3 ~ 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 forming an organic insulating film from a polyamide polymer or a polythioether polymer having a triazine group according to the present invention as in Experimental Example 1, Experimental Example 2, Experimental Example 3, Experimental Example 4, It was confirmed that the dielectric constant is lowered and heat resistance, chemical resistance, and electrical properties such as low dielectric constant and insulation are improved.

Therefore, by using at least one of a protective film, a gate insulating film and an overcoat layer of the liquid crystal display device of the present invention as a organic insulating film from a polyamide polymer or a polythioether polymer having a triazine group, the number of steps can be reduced and the liquid crystal display device can be reduced. It is possible to secure the reliability of.

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

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

 (Explanation of reference numerals for the 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)

A composition for forming an organic insulating film comprising a compound represented by Formula 1 below. [Formula 1]

In Formula 1, m + n = 1, O ≦ m ≦ 1, and O ≦ n ≦ 1. R 1 is each independently selected from the group consisting of compounds (1) to (4) represented by the following formula (2). [Formula 2]

In the formula (1), X is any one of the compounds represented by the following formula (3). [Formula 3]

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

In Formula 4, 1, 2, 3, 4, 5, 6, 7, 8 are any one selected from the group represented by the compound represented by the following formula (5) independently of each other. [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) of the formula (2), Y is any one selected from the group represented by the following formula (6). [Formula 6]

In Chemical Formula 6, n is 0 to 10. In Formula 6, 1 and 2 are any one selected from the group represented by the following Formula 7. [Formula 7]

In Chemical Formula 7, A is any one selected from the group consisting of H, F, CH 3, CF 3, and CN. In Formulas (3) and (4), n is 0 to 10. In (3) and (4) of the formula (2), 1, 2, 3, 4, 5 is any one selected from the group represented by the following formula (8) independently of each other. [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, CF3, and CH3. In Formula 1, R2 and R3 are any one selected from the group represented by the following formula (9) independently of each other. [Formula 9]

In Formula 9, m and n are each 0 to 10. In addition, in Formula 9, A and 1, 2, 3, 4, 5, 6, 7, 8 are independently selected from the group consisting of H, F, CN, CF3 and CH3. In Formula 1, R 4 and R 5 are each independently selected from the group represented by the following Formula 10. [Formula 10]

In Formula 10, m and n are each 0 to 10. In addition, in Formula 9, A and 1, 2, 3, 4, 5, 6, 7, 8 are independently selected from the group consisting of H, F, CN, CF3 and CH3. The method of claim 1, The compound represented by Formula 1 is an organic insulating film forming composition, characterized in that represented by any one selected from the group represented by the formula (11) to (14). [Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

The method of claim 1, The organic insulating film-forming composition further comprises a photocuring agent, a photopolymerization initiator and a solvent. A first substrate on which a thin film transistor is formed; A protective film disposed on the first substrate including the thin film transistor and formed from a compound represented by Formula 1 below; And And a pixel electrode disposed on the passivation layer. [Formula 1]

In Formula 1, m + n = 1, O ≦ m ≦ 1, and O ≦ n ≦ 1. R 1 is each independently selected from the group consisting of compounds (1) to (4) represented by the following formula (2). [Formula 2]

In the formula (1), X is any one of the compounds represented by the following formula (3). [Formula 3]

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

In Formula 4, 1, 2, 3, 4, 5, 6, 7, 8 are any one selected from the group represented by the compound represented by the following formula (5) independently of each other. [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) of the formula (2), Y is any one selected from the group represented by the following formula (6). [Formula 6]

In Chemical Formula 6, n is 0 to 10. In Formula 6, 1 and 2 are any one selected from the group represented by the following Formula 7. [Formula 7]

In Chemical Formula 7, A is any one selected from the group consisting of H, F, CH 3, CF 3, and CN. In Formulas (3) and (4), n is 0 to 10. In (3) and (4) of the formula (2), 1, 2, 3, 4, 5 is any one selected from the group represented by the following formula (8) independently of each other. [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, CF3, and CH3. In Formula 1, R2 and R3 are any one selected from the group represented by the following formula (9) independently of each other. [Formula 9]

In Formula 9, m and n are each 0 to 10. In addition, in Formula 9, A and 1, 2, 3, 4, 5, 6, 7, 8 are independently selected from the group consisting of H, F, CN, CF3 and CH3. In Formula 1, R 4 and R 5 are each independently selected from the group represented by the following Formula 10. [Formula 10]

In Formula 10, m and n are each 0 to 10. In addition, in Formula 9, A and 1, 2, 3, 4, 5, 6, 7, 8 are independently selected from the group consisting of H, F, CN, CF3 and CH3. The method of claim 1, And a gate insulating film of the thin film transistor is formed from a composition including the compound represented by Chemical Formula 1. The method of claim 1, The display device may include 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 and formed from a composition including the compound represented by Formula 1; And And a liquid crystal layer interposed between the first and second substrates.

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