KR101138800B1 - Transparent and highly heat resistant polymer resin and preparation method thereof - Google Patents

Abstract

The present invention relates to a high heat-resistant transparent polymer resin and a method of manufacturing the same, and more particularly to a high heat-resistant transparent polymer resin and a method of manufacturing the same that can be used stably in the manufacturing process of the flexible LCD panel. The high heat-resistant transparent polymer resin of the present invention has excellent optical and mechanical properties and has a low coefficient of thermal expansion and can be used in a manufacturing process of an LCD panel using an existing glass substrate. It is possible to minimize the phase difference change of the pattern cell can be used in the manufacture of a flexible LCD panel (flexible LCD panel).

High heat resistant transparent polymer resin, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (aminophenyl) fluorene, 5-hydroxy isophthalic acid, terephthalic acid, epichlorohydrin, LCD panel

Description

High heat resistant transparent polymer resin and its manufacturing method {TRANSPARENT AND HIGHLY HEAT RESISTANT POLYMER RESIN AND PREPARATION METHOD THEREOF}

The present invention relates to a high heat-resistant transparent polymer resin and a method of manufacturing the same, and more particularly to a high heat-resistant transparent polymer resin and a method of manufacturing the same that can be used stably in the manufacturing process of the flexible LCD panel.

Liquid crystal display (LCD) uses the principle that the liquid crystal's molecular arrangement is disturbed and does not pass through the light when a certain voltage is applied, and it has better visibility and the same power consumption than the color cathode ray tube. Compared with the plasma display device (PDP) or the field emission display device (FED) in recent years, mobile phones and computer monitors are not only small, but also have a small amount of heat generation and can be manufactured thinner, which makes them easier to flatten. Is emerging as a next-generation display device such as a television.

 Such liquid crystal displays generally include an LCD panel and a backlight unit. The LCD has excellent color reproducibility, high color temperature and white balance. In order to satisfy the characteristics of the LCD, the substrate of the LCD panel is transparent and the substrate is deformed even at the high temperature of the LCD manufacturing process over 200 ° C. It is required to be made of a material having high heat resistance so as to minimize the phase difference change of the pattern cell.

As a resin excellent in heat resistance, it is disclosed in the following published document and is explained in full detail below.

US Patent Publication No. 2006-0276616 discloses a polyester obtained from a mixture of 9,9-bis- (4-hydroxyphenyl) fluorene derivatives, terephthalic acid and isophthalic acid derivatives, and Japanese Patent Publication No. 2007-246668 No. discloses a polyimide compound composed of aromatic diamine (fluorene-9-ylidenediphenylene group) and dicarboxylic acids (phthalic acid, isophthalic acid, and petephthalic acid) as raw materials.

In addition, Japanese Patent Application Laid-Open No. 1998-060312 discloses a resin composition in which a glycylated terephthalate is used as a curing agent, and Japanese Patent No. 4314845 discloses a resin composition in which glycidylated hydroterephthalic acid is used as a reactive monomer. Is disclosed.

 The present inventors earnestly studied to develop a polymer resin having superior optical and mechanical properties and high heat resistance than the resin disclosed in the above-mentioned document, and as a result, 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) Alternatively, a high heat-resistant transparent polymer resin prepared by reacting 9,9-bis (aminophenyl) fluorene (BAPF) with 5-hydroxy isophthalic acid and terephthalic acid and a starting polymer synthesized with epichlorohydrin may be used. When used in the manufacture of a substrate, it was found that even in a high temperature LCD process, it is possible to minimize the phase difference change of the pattern cell of the LCD panel due to misalignment of the active matrix due to the deformation of the substrate. The invention has been completed.

An object of the present invention is to provide a high heat-resistant transparent polymer resin that can be used as a display material that requires transparency and heat resistance, and a method of manufacturing the same.

In order to achieve the above object, the present invention provides a high heat-resistant transparent polymer resin composition prepared by reacting a fluoroene derivative, 5-hydroxy isophthalic acid and terephthalic acid with a synthesized starting polymer and epichlorohydrin.

In one embodiment of the present invention, the high heat resistant transparent polymer resin composition of the present invention may be a high heat resistant transparent polymer resin composition represented by the following formula (1).

[Formula 1]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, Repeat unit can be adjusted in 0.1 unit.

 The high heat resistant transparent polymer resin composition represented by Chemical Formula 1 is synthesized by reacting 9,9-bis (aminophenyl) fluorene (BAPF), 5-hydroxy isophthalic acid and terephthalic acid, represented by the following Chemical Formula 3, a fluorene derivative: Can be prepared by reacting the epipolymer with epichlorohydrin.

(3)

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Is selected from the group consisting of.

In another embodiment of the present invention, the high heat resistant transparent polymer resin composition of the present invention may be a high heat resistant transparent polymer resin composition represented by the following formula (2).

[Formula 2]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, Repeat unit can be adjusted in 0.1 unit.

The high heat-resistant transparent polymer resin composition represented by the formula (2) is 9,9-bis (4-hydroxyphenyl) fluorene (BHPF), 5-hydroxy isophthalic acid and terephthalic acid represented by the following formula (4) which is a fluorene derivative It can be prepared by reacting epichlorohydrin with the starting polymer synthesized by the reaction.

[Formula 4]

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Is selected from the group consisting of.

In addition, the present invention comprises the steps of synthesizing the starting polymer by dissolving the fluorene derivative in a solvent with 5-hydroxy isophthalic acid and terephthalic acid (step 1);

Preparing a high heat-resistant transparent polymer resin composition by dissolving the starting polymer synthesized in Step 1 and epichlorohydrin in a basic solvent, then mixing and reacting (step 2); And

It provides a method for producing a high heat resistant transparent polymer resin comprising the step (step 3) of curing the high heat resistant transparent polymer resin composition prepared in step 2 using a curing agent.

Hereinafter will be described in detail step by step for the manufacturing method of a high heat-resistant transparent polymer resin according to the present invention.

 First, the fluorene derivative is dissolved in a solvent together with 5-hydroxy isophthalic acid and terephthalic acid, followed by reaction to synthesize a starting polymer (step 1).

As a fluorene derivative in the manufacturing method of the high heat resistant transparent polymer resin of the present invention, 9,9-bis (aminophenyl) fluorene (BAPF) represented by the above-mentioned formula (3) or 9,9-bis (represented by the formula (4) 4-hydroxyphenyl) fluorene (BHPF) can be used.

As the solvent that may be used in the step 1, one or two or more mixed solutions selected from the group consisting of N-methylpyrrolidone, pyridine and tripryl phosphate may be used.

 Next, the starting polymer synthesized in Step 1 and epichlorohydrin are dissolved in a basic solvent, mixed, and reacted to prepare a high heat-resistant transparent polymer resin composition (step 2).

When the starting polymer synthesized in step 1 and epichlorohydrin are dissolved in a basic solvent and then mixed and reacted, the hydroxy group of 5-hydroxy isophthalic acid of the starter polymer reacts with epichlorohydrin to form an epoxy group, thereby forming a crosslinked structure. To form.

As the basic solvent used in step 2, a basic solvent obtained by dissolving potassium hydroxide (KOH), sodium hydroxide (NaOH) and K ₂ CO ₃ (potassium carbonate) in a solvent such as dimethyl sulfoxide (DMSO) may be used. .

In one embodiment of the present invention, the high heat resistant transparent high molecular resin composition prepared in step 2 may be a high heat resistant transparent polymer resin composition represented by the formula (1).

In another embodiment of the present invention, the high heat resistant transparent polymer resin composition prepared in Step 2 may be a high heat resistant transparent polymer resin composition represented by Formula 2.

 Finally, the high heat resistant transparent polymer resin composition prepared in Step 2 is cured using a curing agent to prepare the high heat resistant transparent polymer resin of the present invention.

In the present invention, the curing agent may be an amine curing agent, an anhydride curing agent, an alcohol curing agent and the like, but is not limited thereto. As the curing agent, for example, 9,9-bis (aminophenyl) fluorene, diethylene triamine, triethylene tetramine, diethylamino propyl amine, methane Menthane diamine, N-aminoethyl piperazine, M-xylene diamine, isophorone diamine, meta phenylene diamine, 4.4 '4.4' dimethyl aniline, diamino diphenyl sulfone, dodecenyl succinic anhydride, cyclo aliphatic anhydride, methyl tetrahydrophthalic Methyl tetrahydrophthalic anhydride, methyl hymic anhydride, hexa hydrophthalic anhydride, tetrahydrophthalic Can be used for dry high DE (tetratrahydrophthalic anhydride), phthalic anhydride (phthalic anhydride), trimethyl rigs anhydride (trimethylic anhydride), fatigue methyl anhydride (pyromethylic anhydride) and the like.

As such, the method of curing the polymer resin composition using a curing agent can be easily carried out by those skilled in the art to which the present invention pertains, and thus a detailed description thereof will be omitted.

The present invention can be used in the manufacturing process of the LCD panel using the existing glass substrate by providing a polymer resin having excellent optical and mechanical properties and high heat resistance, and the LCD panel by shrinking and expanding the substrate in the high temperature LCD manufacturing process Since the phase difference of the pattern cell can be minimized, it can be used for manufacturing the flexible LCD panel.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

< Example >

< Example  1> Preparation of high heat resistant transparent polymer resin

In a 3-neck separate reactor equipped with a stirrer, a nitrogen inlet, and a condenser, 7.5 g of 9,9-bis (aminophenyl) fluorene, 3.13 g of 5-hydroxy isophthalic acid and 0.714 g of terephthalic acid were 120 ml of N-methylpyrrolidone. After dissolving in a mixed solvent of 30 ml of pyridine and 40 ml of triferyl phosphate, the mixture was stirred at room temperature for 2 hours and stirred at 100 ° C. overnight. The obtained reaction was then precipitated in methanol, filtered, washed and dried for 8 hours at 55 ° C. in a vacuum oven to give a starting polymer. 1 g of the starting polymer thus obtained, 0.319 ml of epichlorohydrin, 8 mg of potassium hydroxide, and 20 ml of dimethyl sulfoxide were mixed in a reactor and reacted at room temperature for 12 hours. After precipitation and distillation using distilled water and then washed twice with methanol and dried for 8 hours at 55 ℃ in a vacuum oven to prepare a high heat-resistant polymer resin composition. The high heat-resistant transparent polymer resin of the present invention was cured by using the high heat-resistant transparent polymer resin composition of the present invention obtained by curing with 1% by weight of BAPF curing agent (based on the total weight of the polymer resin composition). The coefficient of thermal expansion (CTE) was measured using a TMA instrument, and the results are shown in FIG. 1.

< Example  2> Preparation of high heat resistant transparent polymer resin

The high heat resistant transparent polymer resin composition was prepared in the same manner as in Example 1 except that the high heat resistant transparent polymer resin composition was cured using 5 wt% of BAPF curing agent (based on the total weight of the polymer resin composition), thereby preparing a high heat resistant transparent polymer resin of the present invention. The coefficient of thermal expansion (CTE) was measured using a TMA apparatus for the heat resistant transparent polymer resin, and the results are shown in FIG. 2.

< Example  3> Preparation of high heat resistant transparent polymer resin

A high heat resistant transparent polymer resin composition was prepared in the same manner as in Example 1 except that the high heat resistant transparent polymer resin composition was cured using 10 wt% of BAPF curing agent (based on the total weight of the polymer resin composition). For the high heat resistant transparent polymer resin, the coefficient of thermal expansion (CTE) was measured using a TMA instrument, and the results are shown in FIG. 3.

< Comparative example  1>

21.02 g of 9,9-bis (4-hydroxyphenyl) fluorene, 6.09 g of isophthalic acid and 6.09 g of terephthalic acid were added to a reactor with 240 ml of toluene solvent. While maintaining the rpm of the stirrer installed in the reactor at 400 to 500 level, the solids were completely melted while heating to 45 ° C. and then cooled to 25 ° C. Thereafter, 13.4 g of triethylamine was added to remove the acid generated during the reaction, the rpm of the stirring apparatus was increased to 600, and the mixture was mixed for 30 minutes, and then the reaction product was filtered using acetone and washed twice with distilled water. And washed again with acetone. Thereafter, the final product was dried in a vacuum oven for 8 hours to obtain a linear polymer resin in 80% yield. For the polymer resin thus prepared, the coefficient of thermal expansion (CTE) was measured using a TMA apparatus, and the results are shown in FIG. 4.

1 to 4 show the results of measuring the coefficient of thermal expansion (CTE) of the polymer resins prepared in Examples 1, 2, 3 and Comparative Example 1, respectively. In Figures 1 to 4, after the polymer resins prepared in Examples 1, 2, 3 and Comparative Example 1 were attached to the jig, the heating and cooling processes were repeatedly performed at least 5 times from 30 degrees to the required temperature section. The calculated change in length (dt / d) is shown on the Y-axis, the change in temperature is shown on the X-axis, and the slope value represents the coefficient of thermal expansion (CTE).

1 to 4, in Comparative Example 1, the CTE of the linear polymer polymer prepared using BHPF, isophthalic acid and terephthalic acid was 60 to 65 ppm, but was prepared in Examples 1 to 3 The high heat resistant transparent polymer resin of the present invention shows a CTE of 20-25 ppm level, it can be seen that the CTE of the high heat resistant transparent polymer resin of the present invention is improved.

1 is a graph showing the results of measuring the coefficient of thermal expansion (CTE) of the high heat-resistant transparent polymer resin prepared in Example 1 of the present invention.

Figure 2 is a graph showing the results of measuring the coefficient of thermal expansion (CTE) for the high heat-resistant transparent polymer resin prepared in Example 2 of the present invention.

3 is a graph showing the results of measuring the coefficient of thermal expansion (CTE) of the high heat-resistant transparent polymer resin prepared in Example 3 of the present invention.

4 is a graph showing the results of measuring the coefficient of thermal expansion (CTE) of the high heat-resistant transparent polymer resin prepared in Comparative Example 1 of the present invention.

Claims (17)

A method of preparing a high heat resistant transparent polymer resin composition represented by the following Chemical Formula 1 or Chemical Formula 2 comprising reacting a fluorene derivative with 5-hydroxy isophthalic acid and terephthalic acid to react the synthesized starting polymer with epichlorohydrin. : [Formula 1]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, The repeat unit is adjusted to 0.1 unit; [Formula 2]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, The repeat unit is adjusted to 0.1 unit. delete A high heat resistant transparent polymer resin composition represented by Formula 2 below: [Formula 2]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, The repeat unit is adjusted to 0.1 unit. The method of claim 1, The fluorene derivative is 9,9-bis (aminophenyl) fluorene (BAPF) or 9,9-bis (hydroxyphenyl) fluorene (BHPF) method of producing a high heat resistant transparent polymer resin. The method of claim 1, The fluorene derivative is a method for producing a high heat resistant transparent polymer resin, characterized in that the compound represented by the following formula (3): (3)

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Selected from the group consisting of. The method of claim 1, The fluorene derivative is a method for producing a high heat resistant transparent polymer resin, characterized in that the compound represented by the following formula (4): [Formula 4]

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Selected from the group consisting of. delete A high heat resistant transparent polymer resin prepared by curing the high heat resistant transparent polymer resin composition represented by Formula 2 below: [Formula 2]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, The repeat unit is adjusted to 0.1 unit. Dissolving the fluorene derivative in a solvent together with 5-hydroxy isophthalic acid and terephthalic acid, followed by reaction to synthesize a starting polymer (step 1); Preparing a high heat-resistant transparent polymer resin composition by dissolving the starting polymer and epichlorohydrin obtained in step 1 in a basic solvent, then mixing and reacting (step 2); And Method for producing a high heat resistant transparent polymer resin represented by the following formula (1) or formula (2) comprising the step (step 3) of curing the high heat resistant transparent polymer resin composition prepared in step 2 using a curing agent: [Formula 1]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, The repeat unit is adjusted to 0.1 unit; [Formula 2]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, The repeat unit is adjusted to 0.1 unit. The method of claim 9, The fluorene derivative is a method of producing a high heat-resistant transparent polymer resin, characterized in that the compound represented by the formula (3) or a compound represented by the following formula (4): (3)

[Formula 4]

In Formula 3 and Formula 4, R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Selected from the group consisting of. 10. The method of claim 9, The solvent used in step 1 is one or two or more mixed solutions selected from the group consisting of N-methylpyrrolidone, pyridine and tripryl phosphate, and the basic solvent used in step 2 is potassium hydroxide (KOH), Method for producing a high heat-resistant transparent polymer resin, characterized in that the solvent containing sodium hydroxide (NaOH) and K ₂ CO ₃ (potassium carbonate): 10. The method of claim 9, The high heat-resistant transparent polymer resin composition prepared in step 2 is a high heat-resistant transparent polymer resin composition represented by the following formula (1): [Formula 1]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, The repeat unit is adjusted to 0.1 unit. 10. The method of claim 9, The high heat-resistant transparent polymer resin composition prepared in Step 2 is a high heat-resistant transparent polymer resin composition represented by the following formula (2) [Formula 2]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, The repeat unit is adjusted to 0.1 unit. 10. The method of claim 9, The curing agent is an amine-based curing agent, an anhydride-based curing agent or an alcohol-based curing agent characterized in that the manufacturing method of high heat-resistant transparent polymer resin. 10. The method of claim 9, The curing agent is 9,9-bis (aminophenyl) fluorene, diethylene triamine, triethylene tetraamine, diethylamino propyl amine, methane diamine, N-aminoethyl piperazine, M-xylene diamine, isophorone diamine , Meta phenylene diamine, 4.4 'dimethyl aniline, diamino diphenyl sulfone, dodecyl succine unhydride, cyclo aliphatic anhydride, methyl tetrahydrophthalic unhydride, methyl hymic unhydride, hexa hydrophthalic A method for producing a high heat resistant transparent polymer resin, characterized in that it is selected from the group consisting of an unhydride, tetrahydrophthalic unhydride, phthalic unhydride, trimethyl anhydride and pyromethyl unhydride. delete An LCD panel manufactured by using a high heat resistant transparent polymer resin prepared by curing the high heat resistant transparent polymer resin composition represented by Formula 2 as a substrate: [Formula 2]

R1 to R23 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) A: B is a number representing repeating units in the main chain of the high heat resistant transparent polymer resin composition, A + B = 1, A: B is 0.1: 0.9 to 0.9: 0.1, The repeat unit is adjusted to 0.1 unit.

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