WO2011013904A2

WO2011013904A2 - Polyimide film

Info

Publication number: WO2011013904A2
Application number: PCT/KR2010/004018
Authority: WO
Inventors: 원동영; 김성원
Original assignee: 에스케이씨코오롱피아이 주식회사
Priority date: 2009-07-31
Filing date: 2010-06-22
Publication date: 2011-02-03
Also published as: KR20110012753A; KR101142723B1; WO2011013904A3

Abstract

The present invention relates to a polyimide film, and discloses a polyimide film having a low degree of thermal expansion and little difference in the degree of expansion in the widthwise direction and in the degree of expansion in the mechanical direction of the film, so as to retain dimensional stability even under extreme heat conditions.

Description

Polyimide film

The present invention relates to a polyimide film useful as a flexible circuit board, a base film such as TAB or COF.

Polyimide films are widely used in electrical / electronic materials, aerospace / aviation and telecommunications because of their excellent mechanical and thermal dimensional stability and chemical stability.

In particular, the polyimide film has been widely used as a base film of a flexible circuit board material having a fine pattern, for example, TAB (tape automated bonding) or COF (chips on film) due to the thin and short size of parts.

TAB or COF technology is a kind of technology to seal IC chip or LSI chip. Specifically, it is a technology that creates a conductive pattern on a flexible tape and seals it by mounting the chip on it. It is advantageous for light and thin product.

In order to use a polyimide film as a base film for TAB or COF, high dimensional stability is required. This is because a dimensional change may occur due to heat shrinkage or a dimensional change may occur due to residual stress in the cooling process after the TAB or COF manufacturing process for bonding the polyimide film in a heated state or after the sputtering process for laminating the metal layer. As a result, positional errors can occur during the bonding of ICs or LSI chips to TABs or COFs.

The TAB tape is then exposed to high temperatures (about 300 ° C.) during a solder reflow process to electrically connect the chip to the substrate. At this time, the moisture is released, the gas is generated, which causes a dimensional change of the film and also forms a foam between the conductive pattern and the polyimide film. In order to solve this problem, the moisture absorption rate should be small.

In addition, in consideration of economical aspects along with miniaturization and advancement of the product, flexible circuit boards such as TAB and COF have tended to be miniaturized. To cope with this trend, polyimide films have improved performance. It requires something to be done.

As an example of a conventional polyimide film, U.S. Patent No. 5,166,308 uses pyromellitic dianhydride and biphenyltetracarboxylic dianhydride as aromatic tetracarboxylic acid components, and p-phenylenediamine and diaminodiphenyl ether are aromatic. Disclosed is a polyimide film comprising a diamine component, the polyimide film obtained therefrom has a high moisture absorption rate, the degree of expansion with respect to heat is large for a specific direction and the degree of expansion in the width direction of the film and the mechanical direction The difference in degree of expansion is large.

In one embodiment of the present invention to provide a polyimide film having a degree of expansion with respect to the heat across the film direction. In particular, to provide a polyimide film having a uniform degree of thermal expansion along the film direction.

In one embodiment of the present invention to provide a polyimide film with improved thermal dimensional stability.

In one embodiment of the present invention also to provide a polyimide film that satisfies low hygroscopicity.

In one embodiment of the present invention to provide a polyimide film useful as a base film such as TAB or COF according to the miniaturization of the line width.

In one embodiment of the present invention, a polyamic acid comprising an aromatic tetracarboxylic acid component containing a biphenyltetracarboxylic acid or a functional derivative thereof and an aromatic diamine component containing p-phenylenediamine and diaminodiphenylether. Obtained by imidizing; In the 50 to 200 ℃ section, the thermal expansion coefficient for the mechanical direction may be 9.9ppm / ℃ or less, the thermal expansion coefficient for the width direction may be 9.9ppm / ℃ or less.

In the polyimide film according to one embodiment of the present invention, a polyimide film having a thermal expansion coefficient of 3.0 to 9.9 ppm / ° C in the mechanical direction and a thermal expansion coefficient of 3.0 to 9.9 ppm / ° C in the width direction is provided. Preferably, the coefficient of thermal expansion deviation defined by the ratio of the coefficient of thermal expansion (CTE _MD ) in the mechanical direction to the coefficient of thermal expansion (CTE _TD ) in the width direction (CTE _MD / CTE _TD ) is 1.55 or less, in particular the coefficient of thermal expansion is 0.5 to 1.55. It provides a polyimide film.

In the polyimide film according to the preferred embodiment, the aromatic diamine component may include diaminodiphenyl ether at 20 mol% or less in the total aromatic diamine component.

The polyimide film according to a preferred embodiment may include biphenyltetracarboxylic acid or a functional derivative thereof in an amount of 90 mol% or more in the total aromatic tetracarboxylic acid component.

Polyimide film according to a preferred embodiment is 100 mol% aromatic tetracarboxylic acid component of biphenyltetracarboxylic acid; It can be obtained by imidating the polyamic acid which consists of 100 mol% of aromatic diamine components which consist of 80-99 mol% of p-phenylenediamine and 1-20 mol% of diamino diphenyl ether.

The polyimide film according to one embodiment of the present invention also has a moisture absorption expansion coefficient of 3.0 to 9.0 ppm /% RH in a mechanical direction at a temperature of 25 ° C. and a relative humidity of 20 to 80% RH, and a moisture absorption expansion in a width direction. The coefficient may be between 3.0 and 9.0 ppm /% RH.

In the polyimide film according to one embodiment of the present invention, the imidation may be accompanied by chemical conversion by a conversion agent including an imidization catalyst and a dehydrating agent.

According to one embodiment of the present invention, the thermal dimensional stability is excellent, and in particular, the thermal expansion coefficient according to the direction of the film is all small, and the circuit during the process of bonding the driver driver IC which realizes the image during the LCD manufacturing process onto the TAB or COF circuit Due to the heat received, dimensional change of the circuit occurs, which can prevent mis-matching with the Drive IC which has a relatively small dimensional change. Such a polyimide film can be used as base films, such as TAB and COF, and can respond especially to the demand of a fine line width. In addition, the polyimide film according to the embodiment of the present invention has low hygroscopicity, and thus, dimensional stability may be secured even in a process such as a wet process in a flexible circuit board manufacturing process such as TAB or COF.

The present invention will be described in more detail as follows.

The present invention relates to a polyimide film, and in particular, provides a polyimide film having a thermal expansion coefficient of 9.9 ppm / ° C. or less in the mechanical direction and a thermal expansion coefficient of 9.9 ppm / ° C. or less in the width direction.

In this case, the coefficient of thermal expansion was measured by cutting a portion of the finished film into a width of 6mm × length of 30mm to measure the coefficient of thermal expansion (Coefficient of thermal expansion, CTE) by using a TA thermal mechanical apparatus (Q400). The sample was hooked to a quartz hook and subjected to a force of 0.010 N and then heated at a rate of 10 ° C./minute from 30 ° C. to 420 ° C. in a nitrogen atmosphere. The coefficient of thermal expansion was determined within the range of 50 ° C to 200 ° C.

In general, in the process of manufacturing a flexible circuit board using a polyimide film, a metal layer is directly laminated on a polyimide film, for example, by deposition or plating, or a metal layer is laminated on a polyimide film using an adhesive. Thereby providing a polyimide / metal laminate, followed by etching the metal portion to obtain a patterned polyimide / metal laminate.

In particular, with the recent increase in the demand for small, high-performance electrical devices, flexible circuit boards are used more frequently under severe high temperature and high humidity.

In this regard, the polyimide film must ensure thermal dimensional stability, and in particular, dimensional stability in all directions of the film.

Thus, in one embodiment of the present invention provides a polyimide film having a thermal expansion coefficient of 9.9 ppm / ° C. or less in the width direction of the film and a thermal expansion coefficient of 9.9 ppm / ° C. or less of the mechanical direction of the film. Preferably, the thermal expansion coefficient in the width direction of the film is 4.0 to 9.0 ppm / 占 폚, and the thermal expansion coefficient in the mechanical direction of the film is 4.0 to 9.0 ppm / 占 폚.

On the other hand, even if the coefficient of thermal expansion in the width and mechanical directions of the film is small, if the difference in the coefficient of thermal expansion in the width direction and the coefficient of thermal expansion in the mechanical direction is large, deformation of the film occurs due to asymmetry of the coefficient of thermal expansion when heat is received from the surroundings. Problems may arise. In this regard, the polyimide film according to the embodiment of the present invention has a coefficient of thermal expansion deviation defined as the ratio (CTE _MD / CTE _TD ) of the thermal expansion coefficient (CTE _MD ) in the mechanical direction and the thermal expansion coefficient (CTE _TD ) in the width direction. It is less than 1.55. Preferably the variation in coefficient of thermal expansion is 0.8 to 1.4.

As such, the polyimide film having thermal dimensional stability may not only have excellent mechanical strength but also have a low hygroscopic expansion coefficient.

If the film absorbs moisture during the wet process during the manufacturing of the flexible circuit board using the polyimide film, volume expansion occurs, distorting the dimensions of the flexible circuit board, and due to vapor evaporated at a high temperature process This may cause delamination.

In particular, the polyimide film according to the embodiment of the present invention has a hygroscopic expansion coefficient of 3.0 to 9.0 ppm /% RH, and thus has a low hygroscopic expansion coefficient, thereby ensuring dimensional stability in a humid environment.

Here, the hygroscopic expansion coefficient was measured by fastening the specimen 25mm x 150mm to a CHE meter (manufactured by BMA Co.) and measuring the dimensional change from 20% to 80% relative humidity at 25 ° C.

Therefore, when the polyimide film according to one embodiment of the present invention is applied to a flexible printed circuit board, particularly a base film for TAB or COF, which is a semiconductor mounted flexible printed circuit board, it may contribute to fine line width and in a severe flexible printed circuit board manufacturing process There may be no dimensional change or adhesive layer separation.

The method for satisfying the coefficient of thermal expansion and the coefficient of thermal expansion within the above range is not limited, but the method considered in the present invention is biphenylcar as an aromatic tetracarboxylic dianhydride component used to prepare polyamic acid. A method containing an acid dianhydride or a functional derivative thereof, and containing p-phenylenediamine and diaminophenyl ether as an aromatic diamine component is mentioned.

Particularly preferably, the aromatic diamine component contains diaminophenyl ether at 20 mol% or less in the total aromatic diamine component. The molecular chain has a rigid structure with an appropriate degree, and thus the thermal expansion coefficient value and the hygroscopic expansion are satisfied. The coefficient can be lowered.

Preferably, the aromatic tetracarboxylic acid component may contain at least 90 mol% of biphenyltetracarboxylic acid or a functional derivative thereof in the total aromatic tetracarboxylic acid component to lower the coefficient of thermal expansion and absorption coefficient. have.

The most preferable polyimide film in terms of satisfying the above-described coefficient of thermal expansion and coefficient of thermal expansion is 100 mol% of an aromatic tetracarboxylic acid component of biphenyltetracarboxylic acid; It can be obtained by imidating the polyamic acid which consists of 100 mol% of aromatic diamine components which consist of 80-99 mol% of p-phenylenediamine and 1-20 mol% of diamino diphenyl ether.

On the other hand, another method to reduce the coefficient of thermal expansion is a method of holding both ends with a tenter clip or pin in the tenter step after obtaining the gel film.

As an example of another method, imidation is preferably accompanied by chemical conversion by a conversion agent including an imidization catalyst and a dehydrating agent in that the thermal expansion coefficient value can be lowered and the hygroscopic expansion coefficient can be lowered.

In order to facilitate understanding of the preparation of the polyimide film for achieving the present invention, the composition and the film forming method are specifically described below, but are not limited thereto.

[Aromatic Tetracarboxylic Anhydride]

The aromatic tetracarboxylic dianhydride that can be used in the present invention is biphenyltetracarboxylic dianhydride or functional derivatives thereof, such as 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, pyromelli Benzophenonetetracarboxylic dianhydride or a functional derivative thereof, such as triacid dianhydride or a functional derivative thereof, 3,3 ', 4,4'-benzophenonetetracarboxylic anhydride, p-phenylene-bistri Mellitic dianhydride and the like can be used, but as described above, it is preferable to use biphenyltetracarboxylic dianhydride in 90% or more of the total aromatic tetracarboxylic dianhydride.

The polyimide film containing an excessive amount of biphenyltetracarboxylic acid units has excellent mechanical properties, low coefficient of thermal expansion, and low coefficient of hygroscopic expansion, and excellent dimensional stability under high temperature and high humidity.

[Aromatic Diamine Component]

Diamines usable in the present invention include p-phenylene diamine and diaminophenyl ethers such as 4,4'-diaminophenyl ether, 3,4-diaminophenyl ether or 2,4-diaminophenyl ether. Can be mentioned.

Preferably the proportion of diaminophenyl ether in the total diamine is 20 mol% or less, preferably 1-20 mol%, more preferably 5-15 mol% in the total aromatic diamine component. Diaminophenyl ether is a monomer having flexibility compared to p-phenylenediamine. When the content thereof is increased, the polyimide molecular chain may become soft and dimensional stability may be inferior. In this regard, it is preferable to use an excessive amount of p-phenylenediamine in terms of lowering the coefficient of thermal expansion and lowering the hygroscopic expansion coefficient.

[Polyimide Film Film Forming Method]

In general, the method for forming a polyimide film is not particularly noticeable to those skilled in the art, but provides an example; First, the aromatic tetracarboxylic dianhydride and the aromatic diamine component are reacted with an organic solvent to obtain a polyamic acid solution. In this case, the solvent is generally preferably an aprotic polar solvent (Aprotic solvent) as the amide solvent, for example, N, N'- dimethylformamide, N, N'- dimethylacetamide, N-methyl- Pyrrolidone etc. can be mentioned and can also be used in combination of 2 types as needed.

The input form of the monomer may be added in the form of powder, lump, and solution. In the initial stage of the reaction, the monomer may be added in the form of powder, and the reaction may be performed in the form of a solution to control the polymerization viscosity.

The weight of the monomer added in the total polyamic acid solution in the state in which the equimolar amount of the aromatic diamine component and the aromatic tetracarboxylic dianhydride are added is called a solid content, and the solid content is in the range of 10-30% or 12-23%. It is preferable to proceed with polymerization.

In addition, as described above, the order of the monomers may be controlled so that the polyamic acid contains a large amount of a molecular chain whose terminal is an amine.

On the other hand, a filler may be added to the polyimide film to improve various properties such as sliding properties, thermal conductivity, conductivity, and corona resistance. Although the type of filler may not be limited, preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like.

The particle size of the filler depends on the thickness or type of the film and may be a modified surface of the filler. 0.1-100 micrometers is preferable and, as for the average particle diameter of a filler, 0.1-25 micrometers is more preferable.

The addition amount of the filler is not particularly limited, and may vary depending on the film to be modified, the type and particle size of the particles, the particle surface, and the like. The addition amount of the filler is preferably used in the range of 10ppm to 5% based on the solids content of the polymerized polyamic acid solution. If the amount of the filler is used in the above range, the physical properties of the polyimide film may be impaired. If the filler is used in the range below, the modification effect is hardly seen.

The dosing method can be added at the beginning of the reactants or after the reaction is over. Alternatively, in order to prevent contamination of the reactor, it may be added in a catalyst mixing step, and the addition method and timing are not particularly limited.

The obtained polyamic acid solution may be applied to the support by mixing with a converting agent, preferably an imidization catalyst and a dehydrating agent. Examples of the catalyst used may include tertiary amines, and anhydrides may be cited as the dehydrating agent. Examples of anhydrous acid include acetic anhydride, and tertiary amines include isoquinoline, β-picolin, pyridine and the like.

The amount of anhydrous acid can be calculated by the molar ratio of o-carboxylic amide functional group in the polyamic acid solution, and it is preferable to use 1.0-5.0 molar ratio.

The amount of tertiary amine can be calculated by the molar ratio of o-carboxylic amide groups in the polyamic acid solution, and it is appropriate to add between 0.2 and 3.0 molar ratios.

The conversion agent may be used in the form of a mixture of anhydrous acid / amines or anhydrous acid / amine / solvent mixture.

The film applied on the support is gelled on the support by dry air and heat treatment. The gelation temperature of the coated film is preferably 100 ~ 250 ℃ and may be used as a support, such as glass plate, aluminum foil, circulating stainless belt or stainless drum, but is not limited thereto.

The treatment time required for gelation depends on the temperature, the type of the support, the amount of the polyamic acid solution applied, and the mixing conditions of the conversion agent, and is not limited to a certain time, but is preferably performed within a range of 5 minutes to 30 minutes. It is good.

The gelled film is separated from the support and heat treated to complete drying and imidization. The heat treatment temperature is between 100 ~ 500 ℃ and the treatment time is between 1 ~ 30 minutes. As part of reducing the coefficient of thermal expansion relative to the width direction and the mechanical direction of the film, the gelled film may be fixed to the support during heat treatment. Gel film can be fixed using a pin type frame or a clip type.

The residual volatile content of the film after heat treatment is 5% or less and preferably 3% or less.

After the heat treatment, the film is heat treated under a constant tension to remove residual stress in the film. Since the tension and temperature conditions are correlated with each other, the tension conditions may vary with temperature. Temperature is preferably maintained between 100 ~ 500 ℃, tension is 50N or less, the time is preferably maintained for 1 minute to 1 hour.

Hereinafter, the present invention will be described in detail with reference to the following Examples, the present invention is not limited by the Examples.

Example 1

192 kg of N, N'-dimethylformamide (DMF) was added to the 400 L jacket reactor. The temperature was 40 ° C, 10.6 kg of p-phenylenediamine (p-PDA) and 0.2 kg of 4,4'-diaminophenyl ether (ODA) were added and stirred until complete dissolution.

After dissolution is completed, 29.16 kg of 3,4,3 ', 4'-biphenyl tetracarboxylic dianhydride (BPDA) is slowly added to adjust the aromatic tetracarboxylic dianhydride component and the aromatic diamine component to an equimolar amount. Stirring for time gave a DMF solution of polyamic acid.

The completed polyamic acid solution had a solid content of 17 wt% and a viscosity of 2,000 poise. The molar ratio of the introduced monomer is BPDA 100%, ODA 99%, PDA 1%.

The polyamic acid solution was mixed with 5 molar equivalents of acetic anhydride (based on polyamic acid) and 1 molar equivalent of isoquinoline (based on polyamic acid), and the mixed solution was cast on an endless type steel belt and held at 100 to 150 ° C. for about 10 minutes. After drying to peel off to prepare a gel film.

After fixing both ends of the gel film with a pin, the film is put into a tenter capable of adjusting the tension received in the width direction (TD), heated at 250 to 450 ° C. for about 10 minutes, and finally dried by dehydration ring drying. A polyimide film having a thickness of 38 μm was prepared.

However, in this embodiment, the dehydration ring drying process was performed with both ends of the gel film fixed without tension adjustment in the TD direction.

A portion of the obtained film was cut out and stored in a chamber of 100% RH (Relative Humidity) atmosphere for 48 hours and analyzed using Thermal gravimetric analysis. The temperature was heated at a rate of temperature increase of 10 ° C./min from 35 ° C. to 250 ° C. to analyze the change in weight to calculate water absorption.

Then, a portion of the finished film was cut into a width of 6 mm × length of 30 mm, and the coefficient of thermal expansion (CTE) was measured using a TA thermal mechanical apparatus Q400. The sample was hooked to a quartz hook and subjected to a force of 0.010 N and then heated at a rate of 10 ° C./minute from 30 ° C. to 420 ° C. in a nitrogen atmosphere. The coefficient of thermal expansion was determined within the range of 50 ° C to 200 ° C.

The hygroscopic expansion coefficient (CHE) was measured by measuring a dimensional change of 5% to 90% relative humidity at 25 ° C by fastening a 25mm x 150mm specimen to a CHE meter (BMA Co.).

Tensile strength, modulus and elongation were averaged using three standard Instron testing apparatus in accordance with ASTM D 882.

Heat shrinkage was measured by IPC 650.2.2.4 method.

All the above properties were obtained for the width direction and the mechanical direction of the film. In particular, the coefficient of thermal expansion (CTE _MD / CTE _TD ) was calculated from the thermal expansion coefficient (CTE _MD ) and the thermal expansion coefficient (CTE _TD ) in the mechanical direction. It was.

The results are shown in Table 2 below.

Examples 2-5

To prepare a polyimide film in the same manner as in Example 1, but when the polyamic acid polymerization, the monomer composition ratio was different as shown in Table 1 below.

After the reaction, the polyamic acid solution was formed into a film as in Example 1 and measured for physical properties. The results are shown in Table 2 below.

Example 6

192 kg of N, N'-dimethylformamide (DMF) was added to the 400 L jacket reactor. The temperature was 40 ° C, 10.2 kg of p-phenylenediamine (p-PDA) and 1.0 kg of 4,4'-diaminophenyl ether (ODA) were added and stirred until complete dissolution.

After dissolution was completed, 28.2 kg of 3,4,3 ', 4'-biphenyl tetracarboxylic dianhydride (BPDA) and 0.8 kg of pyromellitic dianhydride (PMDA) were added to substantially add the aromatic tetracarboxylic dianhydride component and the aromatic. The diamine component was adjusted to an equimolar amount and stirred for 2 hours to obtain a DMF solution of polyamic acid.

The completed polyamic acid solution had a solid content of 17 wt% and a viscosity of 2,000 poise. The molar ratio of injected monomer is BPDA 97%, PMDA 3%, ODA 5%, PDA 95%.

Comparative Example 1

304 kg of N, N'-dimethylformamide (DMF) was added to the 400 L jacket reactor as a solvent. The temperature was 40 ° C, and 3.4 kg of p-phenylenediamine (p-PDA) and 18.9 kg of diaminophenyl (ODA) were added thereto. Into this was added 14.8 kg of biphenyl tetracarboxylic dianhydride (BPDA) and 16.5 kg of pyromellitic dianhydride. After the addition, the mixture was stirred for 2 hours while maintaining the temperature at 40 ℃.

The reaction solution was mixed with 5 molar equivalents of acetic anhydride (based on polyamic acid) and 1 molar equivalent of isoquinoline (based on polyamic acid), and the mixed solution was cast on an endless steel belt and subjected to about 10 at 100 to 150 ° C. The gel film was prepared by drying for 2 minutes and then peeling off.

In this comparative example, the tension | tensile_strength which a film receives in the tenter was adjusted by adjusting the position of both ends of a tenter so that TD CTE of the film finally obtained may be 10 ppm / degrees C or less. When an additional tension is applied to the TD, the film is pulled to the TD, thereby decreasing the CTE value of the TD while increasing the CTE value of the machine direction (MD).

Comparative Example 2

After the reaction, the polyamic acid solution was formed into a film as in Comparative Example 1 and measured for physical properties. The results are shown in Table 2 below.

Table 1

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative Example 1	Comparative Example 2
BPDA	100	100	100	100	100	97	40	100
PMDA	-	-	-	-	-	3	60	-
PDA	99	95	90	85	80	95	25	75
ODA	One	5	10	15	20	5	75	25

TABLE 2

		Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative Example 1	Comparative Example 2
Tensile Modulus (GPa)	MD	10.1	9.5	8.7	7.8	7.3	9.4	4.5	6.1
Tensile Modulus (GPa)	TD	11.0	10.1	9.3	8.7	8.2	10.3	5.6	7.2
Tensile Strength (MPa)	MD	430	425	430	420	425	415	380	400
Tensile Strength (MPa)	TD	435	430	430	415	430	413	375	400
Elongation (%)	MD	40	43	45	51	55	44	60	58
Elongation (%)	TD	38	40	44	48	53	40	51	55
Coefficient of Thermal Expansion (CTE, ppm / ℃)	MD	4.8	6.8	6.5	9.0	9.8	7.0	15.3	16.1
Coefficient of Thermal Expansion (CTE, ppm / ℃)	TD	4.2	4.8	7.8	7.5	8.5	5.1	9.7	9.5
Coefficient of thermal expansion (CTE _MD / CTE _TD )		1.1	1.4	0.8	1.2	1.2	1.4	1.6	1.7
Hygroscopicity (%)	-	1.3	1.3	1.3	1.3	1.3	1.3	1.6	1.4
Hygroscopic expansion coefficient (ppm / RH%)	MD	5.5	5.8	6.5	7.6	8.7	5.9	10.5	9.7
Hygroscopic expansion coefficient (ppm / RH%)	TD	5.6	5.8	6.3	7.7	8.5	6.1	11.3	10.4
Heat Shrinkage (%)	MD	0.02	0.02	0.03	0.03	0.04	0.03	0.03	0.04
Heat Shrinkage (%)	TD	0.03	0.02	0.03	0.03	0.03	0.02	0.03	0.03

From the results in Table 2, the polyimide films obtained in Examples 1 to 6 had thermal expansion coefficients of 9.9 ppm / ° C or less in the width direction of the film and thermal expansion coefficients of 9.9 ppm / ° C or less in the mechanical direction. It can be seen that the coefficient deviation is 1.55 or less, and the hygroscopic expansion coefficient is 3.0 to 9.0 ppm /% RH, which is excellent in dimensional stability under high temperature and high humidity environment.

On the other hand, it can be seen that the polyimide film according to Comparative Example 1 has both a large coefficient of thermal expansion and a large coefficient of thermal expansion variation in the width direction and the mechanical direction. In addition, the hygroscopic expansion coefficient is also remarkably large.

In addition, in the case of the polyimide film according to Comparative Example 2, it can be seen that the coefficient of thermal expansion and the coefficient of hygroscopic expansion increase as the content of diaminophenyl (ODA) increases.

In particular, in Comparative Examples 1 and 2, in order to lower the CTE value in the width direction (TD), an additional tension was given to the TD in the tenter during the film forming process, but this increased the CTE value in the machine direction (MD). As a result, it can be seen that the CTE deviation in both directions of the film is further intensified.

Claims

Obtained by imidizing a polyamic acid comprising an aromatic tetracarboxylic acid component containing a biphenyltetracarboxylic acid or a functional derivative thereof and an aromatic diamine component containing p-phenylenediamine and diaminodiphenylether;

In the 50 to 200 ℃ section, the coefficient of thermal expansion in the mechanical direction is 9.9ppm / ℃ or less, the polyimide film having a coefficient of thermal expansion in the width direction of 9.9ppm / ℃ or less.
The polyimide film according to claim 1, wherein the coefficient of thermal expansion in the mechanical direction is 3.0 to 9.9 ppm / 占 폚, and the coefficient of thermal expansion in the width direction is 3.0 to 9.9 ppm / 占 폚.
The polyimide film of claim 1, wherein a coefficient of thermal expansion deviation defined as a ratio (CTE MD / CTE TD ) of the thermal expansion coefficient (CTE MD ) in the mechanical direction and the thermal expansion coefficient (CTE TD ) in the width direction is 1.55 or less.
The thermal expansion coefficient deviation according to claim 1 or 2, defined as the ratio (CTE MD / CTE TD ) of the thermal expansion coefficient (CTE MD ) in the mechanical direction and the thermal expansion coefficient (CTE TD ) in the width direction, is 0.5 to 1.55. Polyimide film.
2. The polyimide film of claim 1, wherein the aromatic diamine component comprises diaminodiphenyl ether in 20 mol% or less in the total aromatic diamine component.
The polyimide film according to claim 1 or 2, comprising biphenyltetracarboxylic acid or a functional derivative thereof in an amount of 90 mol% or more in the total aromatic tetracarboxylic acid component.
The method of claim 1, wherein 100 mol% of an aromatic tetracarboxylic acid component comprising biphenyltetracarboxylic acid; A polyimide film obtained by imidating a polyamic acid comprising 100 mol% of an aromatic diamine component comprising 80 to 99 mol% of p-phenylenediamine and 1 to 20 mol% of diaminodiphenyl ether.
According to claim 1 or 6, in the 25 ℃ temperature, relative humidity 20 to 80% RH section, the moisture absorption expansion coefficient in the mechanical direction is 3.0 to 9.0ppm /% RH, the moisture absorption expansion coefficient in the width direction 3.0 To 9.0 ppm /% RH polyimide film.
The polyimide film of claim 1, wherein the imidation involves chemical conversion by a conversion agent comprising an imidization catalyst and a dehydrating agent.