KR101301399B1 - Colorless polyimide resin and method for preparing thereof - Google Patents

Abstract

The present invention relates to a colorless polyimide resin and a method of manufacturing the same, having a repeating unit represented by the following formula (1), and providing a colorless transparent polyimide resin and a method for producing the same, which is colorless and transparent, and has barrier properties, mechanical properties and thermal stability. It is possible to provide a polyimide resin having excellent physical properties and a production method thereof.

≪ Formula 1 >

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Polyimide, colorless, transparent

Description

Colorless polyimide resin and method for preparing the same

1 is a photograph taken with the polyimide film prepared in the embodiment of the present invention on the back of the transparent film is printed document,

Figure 2 is a graph showing the results of measuring the tensile strength and initial modulus of the polyimide film prepared in the embodiment of the present invention,

3 is a graph showing the results of measuring the elongation at break of the polyimide film prepared in Examples of the present invention,

Figure 4 is a graph showing the measurement of the glass transition temperature of the polyimide film prepared in the embodiment of the present invention using a differential scanning calorimeter (DSC),

5 is a graph evaluating the initial weight loss temperature and the 800 ℃ remaining amount of the polyimide film prepared in the embodiment of the present invention using thermogravimetric analysis (TGA),

6 is a graph measured by an X-ray diffractometer for the polyimide film prepared in the embodiment of the present invention,

Figure 7 is a graph measuring the maximum absorption wavelength of the polyimide film prepared in the embodiment of the present invention using UV-vis.

The present invention relates to a colorless polyimide resin and a method for producing the same.

In general, the polyimide (PI) resin refers to a high heat-resistant resin prepared by condensation polymerization of aromatic dianhydride and aromatic diamine or aromatic diisocyanate followed by imidization. In order to prepare a polyimide resin, pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), or the like is used as an aromatic dianhydride component, and as the aromatic diamine component, oxydianiline (ODA) or p -Phenylene diamine (p-PDA) and the like are used.

 In addition to excellent heat resistance, polyimide resins have excellent properties in mechanical properties, flame retardancy, chemical resistance, low dielectric constant, and the like, and thus have a wide range of uses in coating materials, molding materials, and composite materials.

However, polyimide resins are colored brown or yellow due to the high aromatic ring density, and thus have a low transmittance in the visible light range, making them difficult to use as optical materials.

Accordingly, an object of the present invention is to provide a polyimide resin and a method for producing the same, which are colorless and maintain excellent physical properties.

The present invention for achieving the above object has a repeating unit of the formula (1), and provides a colorless transparent polyimide resin.

≪ Formula 1 >

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The number average molecular weight is 4,000-200,000.

The polyimide resin is characterized in that the intrinsic viscosity is 0.5 ~ 0.8.

In another aspect, the present invention comprises the steps of preparing a polyamic acid solution by copolymerizing the compound of Formula 2, the compound of Formula 3 and the compound of Formula 4; And it provides a method for producing a polyimide resin comprising the step of imidizing the polyamic acid solution.

<Formula 2>

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The compound of Formula 3 and the compound of Formula 4 are characterized in that the reaction in a molar ratio of 1 to 9: 9 to 1 of the total diamine component.

The present invention provides a polyimide film containing the polyimide resin.

The polyimide film is characterized in that the L value of the color coordinate is 85 or more, b value is 0.7 or less.

Hereinafter, the present invention will be described in more detail.

The polyimide resin of the present invention is obtained by copolymerizing a diamine component and a dianhydride component, and is particularly a colorless and transparent polyimide resin.

The dianhydride component used for this purpose is a compound of formula (2).

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As the diamine component, a compound of Formula 3 and a compound of Formula 4 may be used. At this time, it is preferable to use the compounds of the formulas (3) and (4) in a molar ratio of 1-9: 9-1 in the total diamine components.

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The polyimide resin prepared according to the following preparation method using the dianhydride component and the diamine component described above has the structure of Formula 1, and has a colorless and transparent performance.

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The number average molecular weight is 4,000-200,000.

The polyimide resin according to the present invention described above has an intrinsic viscosity of 0.5 to 0.8.

Hereinafter, the manufacturing method of the polyimide resin will be described.

First, the dianhydride component and the diamine component are reacted in an organic solvent to prepare a polyamic acid. Dianehydride and diamine used here are as described above.

One or more polar solvents selected from m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc) and the like are known reaction solvents. Use In order to prevent the deterioration of physical properties, the water content of the solvent used for the polymerization of the polyimide is preferably 1000 ppm or less, and preferably 400 ppm or less.

In addition, an imidization catalyst may be used. The imidization catalyst may be selected from organic acids and organic amine derivatives such as p-toluenesulfonic acid, hydroxybenzoic acid, crotonic acid, and the like based on the total amount of the reaction mixture. Add in the range of 10% by weight.

The reaction temperature of the present invention for preparing a polyamic acid solution as described above is preferably 0 ~ 50 ℃, stirred for 30 to 90 minutes.

This may be filmed in a conventional manner to prepare a colorless transparent polyimide film.

The thickness of the film is preferably 50 to 100 microns in consideration of mechanical properties and transparency.

The produced polyimide nanocomposite film is characterized in that the L value of the color coordinate is 85 or more, b value is 7.0 or less. The L value is a white-black value. If the value is 100, the value is white, and if the value is 0, the value is black. On the other hand, the b value is a yellow-blue value, the positive direction is yellow, the negative direction is a blue value, and when the b value is 7.0 or less, the film is transparent.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

&Lt; Example 1 >

0.0162 moles of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFB) in 250 ml reactor, 2,2-bis [4 (4-aminophenoxy) phenyl] hexafluoro After adding 0.0041 mol of lopropan (BAPP) and dimethylacetamide (DMAc) as a solvent and dissolving for 30 minutes at 0 ° C. under a nitrogen stream, 2,2-bis (3,4-dicarboxyphenyl) -hexafluoropropane ( FDA) 40 ml of a solution in which 0.0203 mol was dissolved in DMAc was added thereto. The solution was stirred vigorously at 0 ° C. for 1 hour to prepare a polyamic acid solution.

After casting this solution on a glass plate, the solvent was evaporated at 110 degreeC for 30 minutes and 140 degreeC for 1 hour in the oven, and the film was obtained. The obtained film was washed three times for 5 minutes in an ultrasonic cleaner, and further heat-treated at 170 ° C. for 1 hour, 195 ° C. for 1 hour, 220 ° C. for 1 hour, and 235 ° C. for 1 hour.

<Example 2>

0.0102 mol of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFB) in Example 1, 2,2-bis [4 (4-aminophenoxy) phenyl] hexa A polyimide nanocomposite film was prepared in the same manner except that 0.0102 mole of fluoropropane (BAPP) was added.

<Example 3>

0.0041 moles of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFB) in Example 1, 2,2-bis [4 (4-aminophenoxy) phenyl] hexa A polyimide nanocomposite film was prepared in the same manner except that 0.0162 mole of fluoropropane (BAPP) was added.

<Comparative Example>

2,2-bis [4 (4-aminophenoxy) phenyl without adding 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFB) in Example 1 above ] Polyimide nanocomposite film was prepared in the same manner except that 0.0203 mol of hexafluoropropane (BAPP) was added.

The physical properties of the polyimide nanocomposite film prepared in the above example were measured and shown in the following table and drawing.

(1) color coordinates

The chromaticity was measured by using a colorimeter using the film prepared in Example, and the results are shown in Table 1 below. A value of 100 means white, and 0 means black. A value means red in the positive direction and green in the negative direction. On the other hand, the b value represents a yellow value in the positive direction and a blue value in the negative direction. In particular, the b value is transparent when it is 7 or less, indicating transparency.

division Film thickness (㎛) L (White-Black) a (Red-Green) b (Yellow-Blue) Example 1 80 89.90 -2.37 5.32 Example 2 80 89.70 -3.20 6.80 Example 3 90 90.67 -3.77 7.84 Comparative Example 80 85.06 -3.56 21.55

As a result of the measurement, Examples 1 and 2 of the present invention are colorless and transparent, it can be seen that the transparency decreases as the content of BAPP increases. In the case of the comparative example without adding TAB, it can be seen that transparency is lowered.

In order to confirm this more clearly and easily, the photograph is shown in FIG. 1 with the polyimide film prepared in each example and comparative example on the back of the transparent film on which the document is printed.

(2) tensile strength

Tensile strength, initial modulus and elongation at break of the film prepared in Example were measured using an Instron tensile tester (model Instron-5564), and the results are shown in FIGS. 2 and 3, which are summarized in Table 2. .

division Tensile Strength (MPa) Initial Modulus (GPa) Elongation at Break (%) Example 1 79 2.57 4 Example 2 94 2.40 6 Example 3 98 2.28 7 Comparative Example 100 1.82 12

As a result of the measurement, it can be seen that the embodiments of the present invention have excellent tensile strength and elongation at break, and thus have excellent mechanical properties. In the comparative example, it can be seen that the initial modulus of tensile strength and elongation at break is excellent.

(3) intrinsic viscosity

0.1 g of polyamic acid powder was dissolved in 100 ml of N, N'-dimethylacetamide, and the intrinsic viscosity was measured by a Ubbeload viscometer in a thermostat maintained at 30 ° C. The results are shown in Table 3 below.

(4) thermal properties

Differential scanning calorimetry (DSC) was used to measure the glass transition temperature (Tg), and the thermogravimetric analyzer (TGA) was used to evaluate the initial weight loss temperature and the residual temperature of 800 ℃. This is shown in Figures 3 and 4, respectively, summarized in Table 3 below.

division Intrinsic viscosity Tg (占 폚) Td ⁱ (℃) wt _R ⁸⁰⁰ Example 1 0.54 243 534 52 Example 2 0.57 236 535 53 Example 3 0.55 233 536 54 Comparative Example 0.55 228 536 55

In the case of the polyimide nanocomposite film, it can be seen that there is little change in the inherent thermal properties of the general polyimide film.

(5) XRD analysis

Rigaku D / Max-IIIB was used as an X-ray diffractometer, and the results are shown in FIG. 6.

(6) Analysis by UV Spectrophotometry

The maximum absorption wavelengths of the films prepared in Examples and Comparative Examples were measured using UV-vis, and the results are shown in FIG. 7.

As described above, the present invention can provide a polyimide resin, a method of preparing the same, and a polyimide film using the same, which are colorless and transparent, and have excellent barrier properties, mechanical properties, and thermal stability.

Claims (6)

Next, a compound of Formula 2, a compound of Formula 3, and a compound of Formula 4 are copolymerized, wherein the compound of Formula 3 and compound 4 are copolymerized at a molar ratio of 1 to 9: 9 to 1 in a total diamine component, and then imidized. A colorless transparent polyimide resin having a repeating unit represented by the following Chemical Formula 1 and having a color coordinate L of 85 or more and a b value of 7.0 or less based on a thickness of 50 to 100 μm. &Lt; Formula 1 >

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