KR20150058835A - Separation Method of Multi-layered Polyimide Film, Analytical Method and System for Composition of Monomer in Multi-layered Polyimide Film - Google Patents

Abstract

The present invention relates to: a method for analyzing a composition of a monomer of a multi-layered polyimide film; and an analyzing system using the same. The method includes the steps of: (a) separating each layer by treating the multi-layered polyimide film with strong alkali; (b) hydrolyzing a first sample of one layer separated from the multi-layered polyimide film; (c) methanolyzing a second sample of the layer, same one for the first sample in step (b); (d) extracting organic layers from the samples by liquid-liquid extraction; and (e) analyzing an sample of the extracted organic layers by using GC/MS.

Description

TECHNICAL FIELD [0001] The present invention relates to a multilayer polyimide film, and more particularly, to a multilayer polyimide film,

TECHNICAL FIELD The present invention relates to a layer separation method for a multilayer polyimide film, a monomer composition analysis method, and an analysis system.

Polyimide (PI) film has excellent thermal stability and excellent mechanical properties and is widely used in industry. It is widely used as information electronic material. As shown in the reaction formula of FIG. 1, the polyimide film is prepared from a polyamic acid (PAA) obtained by polymerizing dianhydride and diamine as a precursor, followed by imidation reaction to form a film. In the research and development of the polyimide film , A method for analyzing the monomer composition of the polyimide film is indispensable to confirm the composition of the developed product. Particularly, in the case of the multilayer polyimide film, it is difficult to separate each layer, and after analyzing the total monomer composition of the multilayer polyimide film, the monomer composition is analyzed by FT-IR analysis while scratching the film surface in the depth direction. It is difficult to reveal a significant difference in analyzing the composition of the polyimide films of different layers composed of similar monomer components, so that it is difficult to obtain accurate composition analysis data.

In this regard, the conventional method of analyzing the composition of the polyimide film monomer composition is a method using Pyrolysis GC-MS or a method of analyzing a polyimide film by derivatization with tetramethylammonium hydroxide (TMAH) as disclosed in Korean Patent Publication No. 1995-0029297 However, it is difficult to analyze the data due to the generation of complicated pyrolysis products, and in the case of dianhydride, the derivatization is not easily performed, so that it is difficult to grasp the monomer components.

Korean Patent Publication No. 1995-0029297

The present invention provides a method for separating each polyimide layer in a multilayer polyimide film which is physically difficult to separate layers, and it is difficult to analyze the data due to a complicated thermal decomposition product and the derivatization of the dianhydride component does not progress, In order to improve conventional analytical methods which are not easy, the respective layers of the multilayered film are separated, and methanolysis and hydrolysis methods are then used as pretreatment methods, so that there is no interference effect due to complicated thermal decomposition products , And a method for analyzing monomer composition of a multilayer polyimide film in which desired monomer (dianhydride and diamine) is detected as a main component and the monomer composition of the PI film is easily analyzed.

For the above purpose,

(A) treating the multilayer polyimide film with a strong base to separate each layer;

(b) hydrolysis of the first sample of any one of the separated polyimide films;

(c) methanolysis of a second sample of the same layer as the first sample of step (b);

(d) extracting an organic layer from each of the samples through liquid-liquid extraction;

(e) GC / MS analysis of a sample of the extracted organic layer. The present invention also provides a method for analyzing the monomer composition of a multilayer polyimide film.

The present invention also relates to a separator module comprising: (a) a separation module for treating a multilayer polyimide film with a strong base to separate each layer;

(b) a hydrolysis module for hydrolysis of the first sample of the polyimide film;

(c) a methanol decomposition module for methanolysis of the second sample of the polyimide film;

(d) an extraction module for extracting the organic layer through liquid-liquid extraction, respectively;

(e) analyzing a sample of the extracted organic layer by GC / MS.

The present invention also provides a computer-readable recording medium on which a program for executing the above method is recorded.

According to the method for analyzing the monomer composition of the multilayer polyimide film of the present invention,

The multilayer polyimide film was treated with a strong base to separate each layer and methanolysis and hydrolysis methods were used as pretreatment methods to prevent the interference due to complicated thermal decomposition products and to obtain the desired monomers (dianhydride and diamine is detected as a main component, so that it is easy to analyze the monomer composition of each layer of the multilayer polyimide film.

1 is a view showing a reaction formula of a polyimide film.
2 is a SEM photograph showing a cross section of a multilayer polyimide film produced according to Synthesis Example 1 of the present invention.
3 is a SEM photograph showing a cross section of a multilayer polyimide film produced according to Synthesis Example 2 of the present invention.
4 is a SEM photograph showing a cross section of a multilayer polyimide film produced according to Synthesis Example 3 of the present invention.
5 is a photograph showing the multi-layered film separation process of Examples 1-1 and 1-2 of the present invention.
6 is a photograph showing the multi-layered film separation process of Examples 2-1 and 2-2 of the present invention.
7 is a photograph showing the multi-layered film separation process of Examples 3-1 and 3-2 of the present invention.
8 is a graph showing GC / MS data of Example 1-1 of the present invention.
9 is a graph showing GC / MS data of Example 1-2 of the present invention.
10 is a graph showing GC / MS data of Example 2-1 of the present invention.
11 is a graph showing GC / MS data of Example 2-2 of the present invention.
12 is a graph showing GC / MS data of Example 3-1 of the present invention.
13 is a graph showing GC / MS data of Example 3-2 of the present invention.
14 is a table showing the peaks of the comparative examples and examples of the present invention and the chemical formulas of the compounds.
15 is a graph showing GC / MS data showing the decrease of p-PDA according to the hydrolysis time of the present invention.
16 is a graph showing LC / MS data showing analysis of the amount of change of p-PDA according to the hydrolysis time of the present invention.
17 is a graph showing GC / MS data showing analysis of the change amount of p-PDA according to the hydrolysis time of the present invention.

Hereinafter, the present invention will be described in detail.

The method for analyzing the monomer composition of the multilayer polyimide film according to the present invention comprises:

(a) treating the multilayer polyimide film with a strong base to separate each layer;

(b) hydrolysis of the first sample of any one of the separated polyimide films;

(c) methanolysis of a second sample of the same layer as the first sample of step (b);

(d) extracting an organic layer from each of the samples through liquid-liquid extraction;

(e) GC / MS analysis of the extracted organic layer sample.

In the method of analyzing the monomer composition of the multilayer polyimide film according to the present invention, the multilayer polyimide film is treated with a strong base to separate each layer in step (a). Strong base may be used for the separation in the step (a). In the present invention, the strong base solution is added to the multi-layer polyimide film to separate each layer of the multi-layer polyimide film. The strong base is not particularly limited as long as it is a commonly used strong base, but NaOH or TMAH can be preferably used . The separation conditions may be a reaction at 100 to 150 ° C for 10 to 60 minutes. When the reaction is completed, the multilayer polyimide film is washed with methanol, and each layer is carefully scratched or pushed out to separate. Thereafter, the multilayer polyimide film is washed again with distilled water and then dried at room temperature to obtain a polyimide film of each layer.

Thereafter, the method for analyzing the monomer composition of the multilayer polyimide film according to the present invention hydrolyzes the first sample of one of the separated polyimide films in step (b).

The hydrolysis in step (b) is for analyzing the components of the diamine monomer in the polyimide film, and hydrolysis is carried out using a strong base. In the present invention, the strong base is not particularly limited as long as it is a commonly used strong base, but NaOH and the like can be preferably used. The amount of the strong base to be added in the hydrolysis is not particularly limited as long as sufficient hydrolysis can be carried out, but it is preferably 10 to 50 times as much as the total amount of the polyimide film.

The hydrolysis in step (b) is preferably carried out at 100 to 150 ° C. for 2 to 24 hours in order to obtain a sufficient hydrolysis effect. When the reaction temperature for hydrolysis is lower than 100 ° C., There is a problem, and when it is higher than 150 ° C, decomposition is promoted too much, and undesired compounds are produced. In the case that contains the p -PDA (p -Phenylene diamine) the structure of the polyimide film, and thus the longer the reaction time of hydrolysis to reduce the concentration of the p -PDA, not the detection of the p well -PDA . To this end, in contrast to the case where p- PDA is contained in the polyimide film, the hydrolysis in step (b) is preferably carried out by reacting two or more first samples at different reaction times. More specifically, It is preferable that the two first samples are reacted at a reaction time of 2 to 6 hours and 12 to 18 hours, respectively. Through this, there is an advantage that it can all the compositional analysis of the case does not include the composition analysis and p -PDA cases containing the p -PDA.

In the method for analyzing the monomer composition of the multilayer polyimide film according to the present invention, the second sample in the same layer as the first sample in step (b) is subjected to methanolysis in step (c).

The decomposition of methanol in step (c) is performed for analyzing the components of the dianhydride monomer in the polyimide film. Methanol decomposition is performed using strong acid and alcohol. In the present invention, the strong acid is not particularly limited as long as it is a commonly used strong acid, but sulfuric acid and the like can be preferably used. In the present invention, the alcohol is not particularly limited as long as it is a commonly used alcohol, but preferably it is selected from the group consisting of methanol, ethanol, n-propanol or isopropanol. The amount of strong acid to be added in the decomposition of methanol is not particularly limited as long as methanol decomposition is sufficient, but it is preferably 10 to 50 times as much as the total amount of the polyimide film. In addition, the amount of alcohol added in the decomposition of methanol is not particularly limited as long as sufficient hydrolysis can be carried out, but it is preferably 50 to 200 times as much as the total amount of the polyimide film.

The decomposition of methanol in step (c) is preferably carried out at 100 to 150 ° C for 2 to 12 hours in order to obtain a sufficient decomposition effect of methanol. If the reaction temperature of methanol decomposition is lower than 100 ° C, There is a problem, and when it is higher than 150 ° C, decomposition is promoted too much, and undesired compounds are produced.

Thereafter, in the method for analyzing the monomer composition of the multilayer polyimide film according to the present invention, the organic layer is extracted from each of the samples through liquid-liquid extraction in step (d).

In the step (d), the polyimide film mixture sample hydrolyzed in step (b) and the methanolic polyimide film mixture sample in step (c) are each subjected to liquid-liquid extraction. In the present invention, liquid-liquid extraction is carried out after the samples hydrolyzed in step (b) are cooled at room temperature so that the liquid-liquid extraction can proceed sufficiently, In the step (c), the methanol-decomposed samples are cooled at room temperature, and methanol is volatilized under nitrogen, followed by liquid-liquid extraction.

Liquid-Liquid Extraction can separate an organic layer using an organic solvent. The organic solvent is not particularly limited as long as it is ordinarily used, but chloroform, ethyl ether, ethyl Acetate can be used. In addition, in the liquid-liquid extraction of the methanol-decomposed sample in the step (c), in addition to the organic solvent, water is further added to the sample to remove strong acid.

Further, it is preferable that the organic solvent is added to the mixture and shaken for 30 minutes or more so that the liquid-liquid extraction can proceed sufficiently. Thereafter, when the liquid-liquid extraction is completed, the organic solvent layer is taken after allowing the layer separation to proceed completely.

Thereafter, in the method for analyzing the monomer composition of the multilayer polyimide film according to the present invention, a sample of the extracted organic solvent layer is subjected to GC / MS analysis in step (e).

For the GC / MS analysis of the sample, the mixture of the organic solvent layer obtained in the step (d) was completely dried at room temperature under nitrogen, and then the organic solvent was added to dissolve the extracted sample well. Analyze.

The analytical instrument used for the GC / MS analysis is not particularly limited as long as it is an analytical instrument used for gas chromatography and mass spectrometry. In the present invention, GC / MS (Agilent 7890A GC system with 5975C inert XL mass selective detector, Agilent Technologies Korea).

The method for analyzing the monomer composition of the multilayer polyimide film of the present invention involves hydrolysis to analyze the diamine component and GC / MS analysis after methanolysis to analyze the dianhydride component. After analyzing the monomer composition of the polyimide film through the above process, the samples subjected to the hydrolysis process are diamine components and the samples subjected to the methanolysis process are the methyl ester products of the dianhydride, .

The present specification provides a computer-readable recording medium on which a program for executing the above-described analysis method is recorded.

(A) a separation module for treating the multilayer polyimide film with a strong base to separate each layer;

(b) a hydrolysis module for hydrolysis of the first sample of the polyimide film;

(c) a methanol decomposition module for methanolysis of the second sample of the polyimide film;

(d) an extraction module for extracting the organic layer through liquid-liquid extraction, respectively;

(e) analyzing a sample of the extracted organic layer by GC / MS.

In the monomer composition analysis system of the multilayer polyimide film, the description of the structure overlapping with the method of analyzing the monomer composition of the multilayer polyimide film is the same.

Also, in the present invention, the term module refers to a unit for processing a specific function or operation, which can be realized by hardware, software, or a combination of hardware and software.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims.

Example

[Synthesis Example 1]

N, N-dimethylacetamide solution (100 ml) was added dianhydride and diamine compound so that the total molar amount of dianhydride and diamine was the same as shown in Table 1 below to form a middle layer, a first layer and a second layer A mixed acid sample solution was prepared.

Thereafter, the polyamic acid sample solution for forming the first layer was cast on a copper foil by a blade-coater and an air convection oven, and pre-dried at 100 ° C for 10 minutes. Baking (pre-baking) was carried out. Thereafter, an intermediate layer was formed on the first layer in the same manner as the first layer, and then the second layer was formed on the intermediate layer in the same manner. Thereafter, the resulting film was subjected to an imidization reaction at 350 DEG C for 20 minutes under a nitrogen atmosphere. The imidized film was removed from the copper foil with an etching solution, washed with distilled water, and dried to produce a three-layer polyimide film. The prepared film was stored in a desiccator. An SEM image for the cross-sectional analysis of the three-layered polyimide film prepared in Synthesis Example 1 is shown in FIG. As shown in Fig. 2, it was confirmed that the polyimide film was made of three layers.

[Synthesis Example 2]

Dianhydride and diamine compounds were added to N, N-dimethylacetamide solution (100 ml) as shown in Table 1 below to prepare a polyamic acid sample solution for forming the intermediate layer, the first layer and the second layer.

Thereafter, in the same manner as in Synthesis Example 1, a three-layer polyimide film was produced. An SEM image for the cross-sectional analysis of the three-layered polyimide film prepared in Synthesis Example 2 is shown in FIG. As shown in Fig. 3, it was confirmed that the polyimide film was made of three layers.

[Synthesis Example 3]

Dianhydride and diamine compounds were added to N, N-dimethylacetamide solution (100 ml) as shown in Table 1 below to prepare a polyamic acid sample solution for forming the first and second layers.

Thereafter, a two-layered polyimide film was produced in the same manner as in Synthesis Example 1 except that the second layer was formed on the first layer. An SEM image for the cross-sectional analysis of the two-layered polyimide film prepared in Synthesis Example 3 is shown in FIG. As shown in FIG. 4, it was confirmed that the polyimide film was made of two layers.

Dianhydride (input molar ratio) Diamine (input mole ratio) Synthesis Example 1 Middle layer PMDA: BTDA (1: 1) ODA: PDA: BAPP (1: 1: 1) The first layer BPDA (1) TPE-R (1) Second layer BPDA (1) TPE-R (1) Synthesis Example 2 Middle layer PMDA: BPDA (1: 1) mTB-HG: TPE-R (1: 1) The first layer PMDA: BPDA (1: 1) BAPP: mTB-HG (1: 1) Second layer PMDA: BPDA (1: 1) BAPP: mTB-HG (1: 1) Synthesis Example 3 The first layer PMDA: BPDA (1: 1) ODA: PDA (1: 1) Second layer PMDA: BPDA: BTDA (1: 1: 1) ODA: TPE-P (1: 1)

BPDA: 3,3'-4,4'-biphenyltetracarboxylic dianhydride

PMDA: pyromellitic dianhydride

BTDA: 3,3'-4,4'-benzophenone tetracarboxylic dianhydride

ODA: 4,4'-oxydianiline

PDA: p-phenylenediamine

TPE-R: 1,3-bis (4-aminophenoxy) benzene

TPE-P: 1,3-bis (3-aminophenoxy) benzene

mTB-HG: 2,2'-Dimethyl-4,4'-diaminobiphenyl

[Example 1-1]

As shown in FIG. 5, the 3-layer polyimide film prepared in Synthesis Example 1 was transferred to a 40 mL vial at a size of 2 x 2 cm, and a 25% TMAH solution was added to an 8.3% TMAH solution 3 mL, the lid was closed, and the film was allowed to stand at 120 ° C for 30 minutes. Then, the film was carefully washed with methanol, and each layer of the film was carefully scratched or pushed out. The separated three layers of polyimide film were washed with distilled water and dried at room temperature.

Thereafter, two separate polyimide films of three layers were prepared, transferred to 40 mL vials with 10 mg of sample, and 5 mL of 6N-NaOH solution was added thereto. The hydrolysis reaction was carried out for 14 hours. After completion of the hydrolysis reaction, the reaction mixture was cooled at room temperature, 20 mL of chloroform (CHCl ₃ ) was added thereto, and liquid-liquid extraction was performed by shaking for 30 minutes. Thereafter, when the liquid-liquid extraction was completed, the layer was left to be sufficiently separated, and then a chloroform layer located on the lower layer was taken. The obtained chloroform layer was dried at room temperature under nitrogen, and 100 μl of chloroform was further added to dissolve the extracted sample, followed by GC / MS analysis.

[Example 1-2]

As shown in FIG. 5, the 3-layer polyimide film prepared in Synthesis Example 1 was transferred to a 40 mL vial at a size of 2 x 2 cm, and a 25% TMAH solution was added to an 8.3% TMAH solution 3 mL, the lid was closed, and the film was allowed to stand at 120 ° C for 30 minutes. Then, the film was carefully washed with methanol, and each layer of the film was carefully scratched or pushed out. The separated three layers of polyimide film were washed with distilled water and dried at room temperature.

Thereafter, each of the separated three layers of polyimide films was transferred to a 40 mL vial with a cap, and 5 mL of H ₂ SO ₄ / MeOH (1/10, v / v%) solution was added Methanol decomposition reaction was carried out at 120 ° C for 6 hours. After methanol decomposition, the reaction mixture was cooled to room temperature, methanol was volatilized under nitrogen, 20 mL of chloroform (CHCl ₃ ) and 5 mL of distilled water were added, and liquid-liquid extraction was performed by shaking for 30 minutes. When the liquid-liquid phase extraction was completed, the layer separation was sufficient so that the chloroform layer located in the lower layer was taken. The obtained chloroform layer was dried at room temperature under nitrogen, and 100 μl of chloroform was further added to dissolve the extracted sample, followed by GC / MS analysis.

[Example 2-1]

As shown in FIG. 6, GC / MS analysis was performed in the same manner as in Example 1-1 except that the sample of Synthesis Example 2 was used.

 [Example 2-2]

As shown in FIG. 6, GC / MS analysis was performed in the same manner as in Example 1-2, except that the sample of Synthesis Example 2 was used.

[Example 3-1]

As shown in Fig. 7, the 2-layer polyimide film prepared in Synthesis Example 3 was transferred to a 40 mL vial at a size of 2 x 2 cm, and 3 mL of 6N NaOH solution was added. The lid was then closed and left at 120 DEG C for 30 minutes The film was then carefully washed with distilled water, and each layer of the film was carefully scratched or pushed off. The separated two layers of polyimide film were washed with distilled water and dried at room temperature.

Thereafter, two separated polyimide films were prepared, and 10 mg of the sample was transferred to a 40 mL vial with a lid. 5 mL of 6N-NaOH solution was added thereto, followed by heating at 120 ° C for 2 hours and The hydrolysis reaction was carried out for 14 hours. After completion of the hydrolysis reaction, the reaction mixture was cooled at room temperature, 20 mL of chloroform (CHCl ₃ ) was added thereto, and liquid-liquid extraction was performed by shaking for 30 minutes. Thereafter, when the liquid-liquid extraction was completed, the layer was left to be sufficiently separated, and then a chloroform layer located on the lower layer was taken. The obtained chloroform layer was dried at room temperature under nitrogen, and 100 μl of chloroform was further added to dissolve the extracted sample, followed by GC / MS analysis.

 [Example 3-2]

As shown in Fig. 7, the 2-layer polyimide film prepared in Synthesis Example 3 was transferred to a 40 mL vial at a size of 2 x 2 cm, and 3 mL of 6N NaOH solution was added. The lid was then closed and left at 120 DEG C for 30 minutes The film was then carefully washed with distilled water, and each layer of the film was carefully scratched or pushed off. The separated two layers of polyimide film were washed with distilled water and dried at room temperature.

Thereafter, each of the separated two layers of the polyimide film was transferred to a 40 mL vial with a lid, and 5 mL of a H ₂ SO ₄ / MeOH (1/10, v / v%) solution was added Methanol decomposition reaction was carried out at 120 ° C for 6 hours. After methanol decomposition, the reaction mixture was cooled to room temperature, methanol was volatilized under nitrogen, 20 mL of chloroform (CHCl ₃ ) and 5 mL of distilled water were added, and liquid-liquid extraction was performed by shaking for 30 minutes. When the liquid-liquid phase extraction was completed, the layer separation was sufficient so that the chloroform layer located in the lower layer was taken. The obtained chloroform layer was dried at room temperature under nitrogen, and 100 μl of chloroform was further added to dissolve the extracted sample, followed by GC / MS analysis.

Experimental Example

The samples of Examples 1-1 to 3-2 were subjected to GC / MS analysis under the following conditions.

Instrument: GC / MS (Agilent 7890A GC system with 5975C inert XL mass selective detector, Agilent Technologies Korea)

Experimental conditions

Column: HP-5ms capillary column (0.25mm ID X 30m L., 0.25μm d.f., Agilent Technologies, USA)

Injector temp .: 300 ° C

Carrier (He): 1.0 mL / min

                  40: 1 s / s ratio

Oven temp .: 50 ° C / 5min-10 ° C / min-320 ° C / 15min

MSD Source / Qd temp .: 230 ° C / 150 ° C

Scan range: 18 - 600m / z

Further, the analysis of p-PDA change according to hydrolysis time was performed by LC / MS analysis under the following conditions.

Instrument: Accela HPLC system with LTQ-Orbitrap Elite mass spectrometer (ThermoFisher, Bremen, Germany)

MS conditions:

Ionization method: APCI positive

Resolution: 240,000

Ion spray voltage: 6 kV

Discharge current: 5 μA

S-lens RF level: 50%

Capillary temperature: 275 ℃

APCI vaporizer temperature: 450 DEG C

Sheath gas flow: 50 (arbitrary units)

Aux. gas flow: 5 (arbitrary units)

Sweep gas: 5 (arbitrary units)

Sheath and auxiliary gas: N ₂

HPLC conditions:

Column: Capcellpak C18 (4.6 mm ID x 50 mm L., particle size: 3 m, Shiseido, Japan)

A: Acetonitrile / Trifluoroacetic acid = 100 / 0.1 (v / v,%)

B: H2O / Trifluoroacetic acid = 100 / 0.1 (v / v,%)

Time (min.) A (%) B (%) 0 One 99 10 50 50

Flow rate: 1 mL / min.

Column temperature: 40 ℃

Injection volume: 10 μ

Detection: 254 nm

LC / MS  Data analysis: p- PDA Difference in content

The inventors of the present invention found that the polyimide containing p-PDA was not detected in the GC / MS analysis after hydrolysis and that the p-PDA standard was dissolved in 6N-NaOH After the solution was prepared, the concentration change by hydrolysis time at 120 ℃ was examined. As shown in Fig. 15, as the hydrolysis time increased from 2 hours to 24 hours, the p-PDA decreased and the dimer of the p-PDA increased. Therefore, it is judged that the longer the hydrolysis reaction time, the more the p-PDA participates in the decomposition or other reactions. It was confirmed that the hydrolysis time was reduced by about 50% from the initial concentration after 14 hours. Therefore, it was judged that hydrolysis of 2 to 6 hours is suitable for analyzing only p-PDA.

Also, as a result of LC / MS analysis of a sample obtained by hydrolyzing the p-PDA standard for 24 hours, the compounds produced by the reaction between p-PDA including the dimer were detected as shown in Fig. Therefore, it can be seen that the detection of p-PDA is difficult due to the reaction between p-PDAs when the hydrolysis time is long.

The reduction in the amount of p-PDA by hydrolysis at 120 ° C was examined in the entire multilayer film without separation of the film of Synthesis Example 1 containing p-PDA and the film of Synthesis Example 3. As shown in FIG. 17, the longer the hydrolysis time was, the lower the p-PDA was, and was not detected after 24 hours. The results of the analysis show that hydrolysis of 14 hours is preferable for analyzing the total composition of diamine used in polyimide film, and 2 to 6 hours of hydrolysis is suitable for analyzing only p-PDA. In the hydrolysis of 14 hours, it is not easy to detect if the content of p-PDA is too small. Therefore, it is preferable to conduct the hydrolysis for 14 hours and the hydrolysis for 2 to 6 hours in parallel.

GC / MS  Analysis of the data: Example  1-1 to 3-2

GC / MS analysis was carried out using the polyimide film samples of Examples 1-1 to 3-2 as the analysis method of the present invention. The relationship between each analytical compound and the peak shown by the analysis is shown in FIG. 8 to FIG. The structural formulas of the compounds corresponding to the respective peaks detected in FIGS. 8 to 13 are shown in FIG.

As shown in Fig. 8, in the case of Example 1-1, p-PDA, ODA, TPE-R and BAPP were detected. TPE-R was detected in both the first and second layers in the case of 2 hours and 14 hours hydrolysis. In the case of hydrolysis for 2 hours, p-PDA and ODA were detected in the middle layer and ODA and BAPP were detected in the case of hydrolysis for 14 hours. Thus, it can be seen that TPE-R was used for the first layer and the second layer, and p-PDA, ODA and BAPP were used for the middle layer.

As shown in Fig. 9, in the case of Example 1-2, methylation products of PMDA, BPDA and BTDA were detected. The methylation product of BPDA was detected in the first layer and the second layer, and the methylation product of PMDA and BTDA was detected in the middle layer.

As shown in Fig. 10, in the case of Example 2-1, mTB-HG, TPE-R and BAPP were detected. MTB-HG and BAPP were detected in the first and second layers, and mTB-HG and TPE-R were detected in the middle layer.

As shown in Fig. 11, in the case of Example 2-2, the methylation product of PMDA and BPDA was detected. The methylation products of PMDA and BPDA were detected in the first, second and middle layers with layer separation

As shown in Fig. 12, in the case of Example 3-1, p-PDA, ODA and TPE-P were detected. In the first layer separated, ODA was detected in the 14-hour hydrolysis and in the 2-hour hydrolysis, p-PDA and ODA were detected. ODA and TPE-P were detected in the 2-hour and 14-hour hydrolysis in the layered second layer.

As shown in Fig. 13, in the case of Example 3-2, PMDA, BPDA and BTDA were detected. PMDA and BPDA were detected in the first layer and PMDA, BPDA and BTDA were detected in the second layer.

Through the above analysis, when the multilayer polyimide film is analyzed by the analysis method of the present invention of Examples 1-1 to 3-2, the dianhydride component is detected by tetramethylation and the diamine component is not deformed Was detected. Therefore, it is easy to analyze the monomer component used in the polyimide film through simple analysis.

In addition, for polyimide films composed of a plurality of layers, composition analysis data could be obtained without interfering with the composition of the polyimide films of different layers.

In addition, as the time for hydrolysis was controlled, the composition of the compounds with varying contents according to the hydrolysis reaction time could be analyzed together.

Claims (29)

(a) treating the multilayer polyimide film with a strong base to separate each layer;
(b) hydrolysis of the first sample of any one of the separated polyimide films;
(c) methanolysis of a second sample of the same layer as the first sample of step (b);
(d) extracting an organic layer from each of the samples through liquid-liquid extraction;
(e) GC / MS analysis of the sample of the extracted organic layer. The method according to claim 1,
Wherein the separation of step (a) is performed using NaOH or TMAH. The method of claim 2,
Wherein the separation in step (a) is carried out at 100 to 150 ° C for 10 to 60 minutes. A method for analyzing monomer composition of a multi-layer polyimide film, The method according to claim 1,
Wherein the hydrolysis of step (b) employs a strong base. The method of claim 4,
Wherein the strong base is NaOH. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the hydrolysis in step (b) is carried out at 100 to 150 ° C for 2 to 24 hours. The method according to claim 1,
Wherein the hydrolysis of step (b) comprises reacting two or more first samples at different reaction times. The method of claim 7,
Wherein the two first samples are reacted at a reaction time of 2 to 6 hours and 12 to 18 hours, respectively. The method according to claim 1,
Wherein the decomposition of methanol in step (c) is performed using a strong acid and an alcohol. The method of claim 9,
Wherein the strong acid is sulfuric acid. The method of claim 9,
Wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol and isopropanol. The method according to claim 1,
Wherein the decomposition of methanol in step (c) is carried out at 100 to 150 ° C for 2 to 12 hours. The method according to claim 1,
Wherein the liquid-liquid extraction of step (d) comprises using an organic solvent. 14. The method of claim 13,
Wherein the organic solvent is selected from the group consisting of chloroform, ethyl ether and ethyl acetate. (a) a separation module for treating the multilayer polyimide film with a strong base to separate each layer;
(b) a hydrolysis module for hydrolysis of the first sample of the polyimide film;
(c) a methanol decomposition module for methanolysis of the second sample of the polyimide film;
(d) an extraction module for extracting the organic layer through liquid-liquid extraction, respectively;
(e) analyzing a sample of the extracted organic layer by GC / MS. 16. The method of claim 15,
Wherein the separation of the separation module is performed using NaOH or TMAH. 18. The method of claim 16,
Wherein the separation of the separation module is carried out at 100 to 150 ° C for 10 to 60 minutes. 16. The method of claim 15,
Wherein the hydrolysis of the hydrolysis module uses a strong base. 19. The method of claim 18,
Wherein the strong base is NaOH. ≪ RTI ID = 0.0 > 15. < / RTI > 16. The method of claim 15,
Wherein the hydrolysis of the hydrolysis module is carried out at 100 to 150 DEG C for 2 to 24 hours. 16. The method of claim 15,
Wherein the hydrolysis of the hydrolysis module comprises reacting two or more first samples at different reaction times. 23. The method of claim 21,
Wherein the two first samples are reacted at a reaction time of 2 to 6 hours and 12 to 18 hours, respectively. 16. The method of claim 15,
Wherein the methanol decomposition module of the methanol decomposition module utilizes a strong acid and alcohol. 24. The method of claim 23,
Wherein the strong acid is sulfuric acid. 24. The method of claim 23,
Wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol and isopropanol. 16. The method of claim 15,
Wherein the methanol decomposition of the methanol decomposition module is performed at 100 to 150 ° C for 2 to 12 hours. 16. The method of claim 15,
Wherein the liquid-liquid extraction of the extraction module uses an organic solvent. 28. The method of claim 27,
Wherein the organic solvent is selected from the group consisting of chloroform, ethyl ether and ethyl acetate. A computer-readable recording medium on which a program for executing the analysis of the monomer composition of the multilayer polyimide film of claim 1 is recorded.

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