WO2021054515A1

WO2021054515A1 - Polyimide film, method for manufacturing same, and flexible metal foil laminate comprising same

Info

Publication number: WO2021054515A1
Application number: PCT/KR2019/014208
Authority: WO
Inventors: 김동영; 원동영; 최정열
Original assignee: 에스케이씨코오롱피아이 주식회사
Priority date: 2019-09-18
Filing date: 2019-10-25
Publication date: 2021-03-25
Also published as: CN112823181B; CN112823181A; KR102382019B1; JP7375176B2; KR20210033364A; JP2022548897A

Abstract

Disclosed are a polyimide film having a moisture absorption expansion coefficient of about 9 ppm/% RH or less in a relative humidity range of 20 to 80% at 25°C, a method for manufacturing same, and a flexible metal foil laminate comprising same.

Description

Polyimide film, manufacturing method thereof, and flexible metal clad laminate including same

It relates to a polyimide film, a method of manufacturing the same, and a flexible metal clad laminate including the same, and more particularly, to a polyimide film having a small moisture absorption expansion coefficient, a method of manufacturing the same, and a flexible metal clad laminate including the same.

Polyimide films have excellent mechanical and thermal dimensional stability and chemical stability, and are widely used in electric, electronic materials, space, aviation, and telecommunication fields. Polyimide film is a flexible printed circuit board (FPCB) material with a fine pattern due to the light and thinness of the component, such as tape automated bonding (TAB) or chip on film (COF). ), etc. It is widely used as a base film. A flexible circuit board generally has a structure in which a circuit including a metal foil is formed on a base film, and such a flexible circuit board is referred to as a flexible metal foil clad laminate in a broad sense. Unlike other polymer materials, such polyimide has a rather high coefficient of expansion of moisture absorption.If the coefficient of expansion of moisture absorption is high, dimensional change may occur by absorbing moisture during the FPCB process, resulting in a short circuit between circuits or a distance between patterns. Changing problems can arise. Therefore, it is necessary to lower the moisture absorption and expansion coefficient of the polyimide film.

An object of the present invention is to provide a polyimide film excellent in dimensional stability due to its low moisture absorption and expansion coefficient.

Another object of the present invention is to provide a method of manufacturing the above-described polyimide film.

Another object of the present invention is to provide a flexible metal foil laminate comprising the polyimide film described above.

1. According to one aspect, there is provided a polyimide film having a moisture absorption expansion coefficient of about 9ppm/%RH or less in a 25°C, 20 to 80% relative humidity section.

2. In 1 above, the polyimide film is derived from imidization of a polyamic acid formed from the reaction of a first dianhydride, a second dianhydride, a first diamine, and a second diamine,

The first dianhydride and the second anhydride are different from each other,

The first diamine and the second diamine are different from each other,

The first dianhydride includes 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, or a combination thereof,

The first diamine includes m-phenylenediamine, p-phenylenediamine, or a combination thereof,

In the polyimide film, a first binding ratio, which is a ratio in which the first dianhydride and the first diamine are bonded, may be about 40 to about 70%.

3. In the above 2, the polyamic acid may be formed by sequentially reacting the second anhydride and the second diamine with the pre-reactant of the first dianhydride and the first diamine to extend the ends of at least some of the pre-reactant.

4. In 2 or 3 above, the second dianhydride may include pyromellitic dianhydride.

5. In any one of 2 to 4 above, the second diamine may include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or a combination thereof.

6. In any one of the above 2 to 5, the first dianhydride is contained in an amount of about 40 to about 70 mol% based on the total number of moles of the first dianhydride and the second dianhydride, and the second dianhydride is It may be included in about 30 to about 60 mol%.

7. In any one of the above 2 to 6, based on the total number of moles of the first diamine and the second diamine, the first diamine is contained in an amount of about 70 to about 98 mol%, and the second diamine is about 2 to It may be included in about 30 mol%.

8. In any one of 2 to 7 above, based on the total number of moles of the first diamine and the second diamine, the first diamine is contained in an amount of about 80 to about 98 mol%, and the second diamine is 2 to 20 It is included in mole percent,

The polyimide film may have a moisture absorption expansion coefficient of less than or equal to about 8 ppm/%RH in a range of 25° C. and 20 to 80% relative humidity.

9. In any one of the above 1 to 8, the polyimide film may have a moisture absorption expansion coefficient of about 9ppm/%RH or less in a range of 25°C and 3 to 90% relative humidity.

10. According to another aspect, after mixing and reacting a first dianhydride and a first diamine in a solvent, adding and reacting a second dianhydride and a second diamine to form a polyamic acid solution; And

It is a method for producing a polyimide film comprising; imidizing the polyamic acid,

The first dianhydride and the second anhydride are different from each other,

The first diamine and the second diamine are different from each other,

The polyimide film is provided with a method of manufacturing a polyimide film having a moisture absorption expansion coefficient of about 9 ppm/% RH or less in a 25° C., 20 to 80% relative humidity range.

11. In the above 10, the first dianhydride is 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, or a combination thereof Including,

12. In 10 or 11, the second dianhydride may include pyromellitic dianhydride.

13. In any one of 10 to 12 above, the second diamine may include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or a combination thereof.

14. In any one of the above 10 to 13, the first dianhydride is contained in an amount of about 40 to about 70 mol% based on the total number of moles of the first dianhydride and the second dianhydride, and the second dianhydride is It may be included in about 30 to about 60 mol%.

15. In any one of the above 10 to 14, based on the total number of moles of the first diamine and the second diamine, the first diamine is contained in an amount of about 70 to about 98 mol%, and the second diamine is about 2 to It may be included in about 30 mol%.

16. In any one of 10 to 15, based on the total number of moles of the first diamine and the second diamine, the first diamine is contained in an amount of about 80 to about 98 mol%, and the second diamine is about 2 to It is contained in about 20 mol%,

17. In any one of the above 10 to 16, the polyimide film may have a moisture absorption expansion coefficient of less than or equal to about 9 ppm/%RH at 25° C. and 3 to 90% relative humidity.

18. According to another aspect, the polyimide film of any one of the above 1 to 9 or the polyimide film produced by any one of the manufacturing method of the above 10 to 17; And

A flexible metal foil laminated plate comprising a metal foil formed on the polyimide film is provided.

The present invention has an effect of providing a polyimide film having a small moisture absorption expansion coefficient and excellent dimensional stability, a method of manufacturing the same, and a flexible metal clad laminate including the same.

In describing the present invention, when it is determined that a detailed description of a related known technology may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

When'include','have', and'consist of' mentioned in the present specification are used, other parts may be added unless'only' is used. In the case of expressing the constituent elements in the singular, it includes the case of including the plural unless specifically stated otherwise.

In addition, in the interpretation of the constituent elements, it is interpreted as including an error range even if there is no explicit description.

Terms such as first and second used in the present specification may be used to describe various elements, but the elements should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from other components.

In the present specification, the term "first bonding ratio" refers to the first dianhydride and the first dianhydride among the polyimide films prepared from imidization of a polyamic acid formed from the reaction of a first dianhydride, a second dianhydride, a first diamine, and a second diamine. The first diamine may mean a bonded ratio, and the "second bonding ratio" may mean a bonded ratio of the second dianhydride and the first diamine, and the second bonding ratio may be determined according to the first bonding ratio. I can. For example, the total number of moles of the first dianhydride and the second dianhydride and the total number of moles of the first diamine and the second diamine are equal moles, and the molar ratio of the first dianhydride based on the total number of moles of the first dianhydride and the second dianhydride. Is A mol%, and when the molar ratio of the first diamine is B mol% based on the total number of moles of the first diamine and the second diamine, when A mol% is less than B mol%, the first bonding ratio is A %, the second binding ratio is BA%, and A mol% is greater than B mol%, the first binding ratio is B%, the second binding ratio is 0%, the first binding ratio, the second The binding ratio can be calculated.

In "a to b" representing a numerical range in the present specification, "to" is defined as ≥a and ≤b.

폴리이미드 필름Polyimide film

According to one aspect, a polyimide film is provided. The polyimide film has a moisture absorption expansion coefficient of about 9 ppm/% RH or less in the 25° C., 20 to 80% relative humidity section (eg, about 0, about 0.5, about 1, about 1.5, about 2, about 2.5, About 3, about 3.5, about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm/%RH). In the above range, dimensional stability may be excellent. In one embodiment, the lower limit of the moisture absorption expansion coefficient of the polyimide film in the range of 25° C. and 20 to 80% relative humidity is, for example, greater than 0, about 1, about 2, about 3, about 4, about 5, About 6 or about 6.2 ppm/%RH, with an upper limit of about 9, about 8.5, about 8, about 7.5, about 7, about 6.9, about 6.8, about 6.7, about 6.5, about 6.4, about 6.3 or about 6.2 ppm/%RH, and the lower and upper limits may be combined with each other. For example, the moisture absorption expansion coefficient of the polyimide film in the range of 25° C. and 20 to 80% relative humidity is greater than 0 to about 9 ppm/% RH, another example, about 4 to about 9 ppm/% RH, another example For example, it may be about 4 to about 8 ppm/%RH, but is not limited thereto.

According to one embodiment, the polyimide film may be derived from imidization of a polyamic acid formed from a reaction of a first dianhydride, a second dianhydride, a first diamine, and a second diamine. For example, in the polyimide film, from the imidization of a polyamic acid formed by sequentially reacting a second dianhydride and a second diamine with a pre-reactant of a first dianhydride and a first diamine to extend at least some of the ends of the pre-reactant. It may be induced, but is not limited thereto. In this case, the first dianhydride and the second anhydride may be different from each other, and the first diamine and the second diamine may be different from each other.

For example, the first dianhydride may include 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, or a combination thereof. have. According to one embodiment, the first dianhydride may be 3,3',4,4'-biphenyltetracarboxylic dianhydride, but is not limited thereto.

The type of the second anhydride is not particularly limited as long as it is different from the first anhydride. For example, the second anhydride may include pyromellitic dianhydride, but is not limited thereto.

For example, the first diamine may include m-phenylenediamine, p-phenylenediamine, or a combination thereof. According to one embodiment, the first diamine may be p-phenylenediamine, but is not limited thereto.

The type of the second diamine is not particularly limited as long as it is different from the first diamine. For example, the second diamine may include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or a combination thereof. According to one embodiment, the second diamine may be 4,4'-diaminodiphenyl ether, but is not limited thereto.

According to one embodiment, the first binding ratio, which is the ratio of the first dianhydride and the first diamine in the polyimide film, is about 40 to about 70% (e.g., about 40, about 41, about 42, about 43, About 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57, about 58, about 59, about 60 , About 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69 or about 70%). In the above range, the moisture absorption expansion coefficient of the polyimide film is small, so that dimensional stability may be excellent. The first binding ratio is, for example, about 45 to about 70%, another such as about 50 to about 70%, another such as about 40 to about 60%, another such as about 45 to about 55%. Can be According to one embodiment, the first binding ratio may be about 50 to about 70%. According to another embodiment, the first binding ratio may be about 45 to about 55%, but is not limited thereto.

According to one embodiment, the first binding ratio, which is the ratio of the first dianhydride and the first diamine in the polyimide film, is about 40 to about 70% (for example, about 50 to about 70%), and the second dianhydride is The second binding ratio, which is the ratio of water and first diamine bonded, is about 20 to about 50% (e.g., about 20, about 21, about 22, about 23, about 24, about 25, about 26, about 27, about 28, about 29, about 30, about 31, about 32, about 33, about 34, about 35, about 36, about 37, about 38, about 39, about 40, about 41, about 42, about 43, about 44, About 45, about 46, about 47, about 48, about 49 or about 50%). Within the above range, the polyimide film has a small coefficient of moisture absorption and excellent dimensional stability, as well as a predetermined physical property, for example, a predetermined coefficient of thermal expansion (CTE) (e.g., about 2 to about 5 μm/(m)). ·°C), so when manufacturing a flexible metal foil laminate using this, the adhesion between the polyimide film and the metal foil can be excellent.

According to one embodiment, the first dianhydride is about 40 to about 70 mol% based on the total moles of the first dianhydride and the second dianhydride (e.g., about 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57, about 58, about 59, about 60, About 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69 or about 70 mol%), and the second dianhydride is about 30 to about 60 mol% ( For example, about 30, about 31, about 32, about 33, about 34, about 35, about 36, about 37, about 38, about 39, about 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57, about 58, about 59 or about 60 mol%) Can be included. Within the above range, it is possible to lower the moisture absorption expansion coefficient of the polyimide film. For example, based on the total number of moles of the first dianhydride and the second dianhydride, the first dianhydride is, for example, about 45 to about 70 mol%, another example, about 50 to about 70 mol%, another example For example, about 40 to about 60 mol%, and for another example, about 45 to about 55 mol%, and the second dianhydride is, for example, about 30 to about 55 mol%, and for another example, about 30 to about 30 to about 55 mol%. It may be included in about 50 mol%, another example about 40 to about 60 mol%, another example about 45 to about 55 mol%, but is not limited thereto.

According to one embodiment, the first diamine is about 70 to about 98 mol% (e.g., about 70, about 71, about 72, about 73, about 74, based on the total number of moles of the first diamine and the second diamine) About 75, about 76, about 77, about 78, about 79, about 80, about 81, about 82, about 83, about 84, about 85, about 86, about 87, about 88, about 89, about 90, about 91 , About 92, about 93, about 94, about 95, about 96, about 97, or about 98 mol%), and the second diamine is about 2 to about 30 mol% (e.g., about 2, about 3 , About 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19, about 20, about 21, about 22, about 23, about 24, about 25, about 26, about 27, about 28, about 29, or about 30 mole%). Within the above range, it is possible to lower the moisture absorption expansion coefficient of the polyimide film. For example, based on the total number of moles of the first diamine and the second diamine, the first diamine is, for example, about 70 to about 92 mol%, another example, about 70 to about 90 mol%, another example About 70 to about 88 mole%, another example about 80 to about 98 mole%, another example about 80 to about 92 mole%, another example about 80 to about 90 mole%, another example For example, it is contained in about 80 to about 88 mol%, and the second diamine is, for example, about 8 to about 30 mol%, for example, about 10 to about 30 mol%, and another example, about 12 to about 30 mol%, another such as about 2 to about 20 mol%, another such as about 8 to about 20 mol%, another such as about 10 to about 20 mol%, another such as about 12 To about 20 mol%, but is not limited thereto.

According to one embodiment, the polyimide film has a moisture absorption expansion coefficient of about 9 ppm/%RH or less (eg, about 0, about 0.5, about 1, about 1.5, About 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm/%RH) have. In the above range, dimensional stability may be excellent. The lower limit of the moisture absorption expansion coefficient of the polyimide film in the range of 25°C and 3 to 90% relative humidity is, for example, greater than 0, about 1, about 2, about 3, about 4, about 5, about 6, about 7 or About 9, about 8.9, about 8.8, about 8.7, about 8.6, about 8.5, about 8.4, about 8.3 or about 8.2 ppm/%RH, and the upper limit can be about ppm/%RH, and the upper limit can be about 9, about 8.9, about 8.8, about 8.7, about 8.6, about 8.5, about 8.4, about 8.3 or about 8.2 ppm/%RH, wherein The lower limit and the upper limit may be combined with each other, but are not limited thereto.

The thickness of the polyimide film may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film. For example, the thickness of the polyimide film is about 10 to about 500 μm (e.g., about 10, about 50, about 100, about 150, about 200, about 250, about 300, about 350, about 400, about 450 Or about 500 µm), for example about 25 to about 50 µm, for another example, about 35 to about 50 µm, for another example, about 25 to about 35 µm, but is not limited thereto.

The coefficient of thermal expansion of the polyimide film may be appropriately selected in consideration of the use, environment of use, and physical properties of the polyimide film. For example, when a polyimide film is used for a flexible metal foil laminate, the coefficient of thermal expansion of the polyimide film may be lower than that of the metal foil. For example, the metal foil is about 16 to about 17 μm/m·° C. (e.g., about 16, about 16.1, about 16.2, about 16.3, about 16.4, about 16.5, about 16.6, about 16.7, about 16.8, about 16.9, or It has a coefficient of thermal expansion of about 17 μm/m·° C.), and the polyimide film has a coefficient of thermal expansion of about 2 to about 7 μm/m·° C. (for example, about 2, about 3, about 4, about 5, about 6 or about 7 Μm/m·°C, for example, about 2 to about 5µm/m·°C), but is not limited thereto. Here, the coefficient of thermal expansion of the polyimide film was heated from room temperature (25°C) to 420°C at a rate of 10°C/min under a load of 0.01 to 0.05N and nitrogen atmosphere using TA's TMA (thermal mechanical apparatus) Q400. It can be obtained, but is not limited thereto.

The glass transition temperature of the polyimide film may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film. For example, when a polyimide film is used for a flexible metal foil laminate, the polyimide film is about 370°C or higher (e.g., about 370, about 380, about 390, about 400, about 410 or about 420°C, other examples For example, it may have a glass transition temperature of about 370 to about 420°C, another example of about 380°C or more, another example of about 380 to about 420°C). Here, the glass transition temperature of the polyimide film can be obtained by heating at a rate of 5°C/min from room temperature (25°C) to 550°C in a nitrogen atmosphere using TA's DMA (dynamic mechanical analysis) Q800, but is limited thereto. It does not become.

폴리이미드 필름의 제조방법Manufacturing method of polyimide film

According to another aspect, a method of manufacturing a polyimide film is provided. The method includes mixing and reacting a first dianhydride and a first diamine in a solvent, and then adding and reacting a second dianhydride and a second diamine to form a polyamic acid solution, and imidizing the polyamic acid. In this case, the first dianhydride and the second anhydride are different from each other, the first diamine and the second diamine are different from each other, and the polyimide film is 25° C., 20 to 80% relative humidity. The moisture absorption expansion coefficient in the section is about 9ppm/%RH or less (e.g., about 0, about 0.5, about 1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5 , About 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm/%RH). The polyimide film prepared by the above method may have excellent dimensional stability.

First, a first dianhydride and a first diamine are mixed and reacted in a solvent, and then a second dianhydride and a second diamine are added and reacted to form a polyamic acid solution. At this time, after mixing and reacting the first dianhydride and the first diamine in a solvent, the second dianhydride is added and reacted, and then the second diamine is added and reacted to form a polyamic acid solution. Alternatively, after mixing and reacting the first dianhydride and the first diamine in a solvent, the second dianhydride and the second diamine may be added together and reacted to form a polyamic acid solution. In this case, due to the difference in reactivity, the first dianhydride and the first diamine are mixed and reacted. The prereactant of the dianhydride and the first diamine and the second dianhydride may react first, and then the second diamine may react.

The first dianhydride may include, for example, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, or a combination thereof. have. According to one embodiment, the first dianhydride may be 3,3',4,4'-biphenyltetracarboxylic dianhydride, but is not limited thereto.

The first diamine may include, for example, m-phenylenediamine, p-phenylenediamine, or a combination thereof. According to one embodiment, the first diamine may be p-phenylenediamine, but is not limited thereto.

According to one embodiment, the first dianhydride is about 40 to about 70 mol% based on the total moles of the first dianhydride and the second dianhydride (e.g., about 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57, about 58, about 59, about 60, About 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69 or about 70%), and the second dianhydride is about 30 to about 60 mol% (e.g. For example, about 30, about 31, about 32, about 33, about 34, about 35, about 36, about 37, about 38, about 39, about 40, about 41, about 42, about 43, about 44, about 45 , About 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57, about 58, about 59 or about 60 mole%) I can. Within the above range, it is possible to lower the moisture absorption expansion coefficient of the polyimide film. For example, based on the total number of moles of the first dianhydride and the second dianhydride, the first dianhydride is, for example, about 45 to about 70 mol%, another example, about 50 to about 70 mol%, another example For example, about 40 to about 60 mol%, and for another example, about 45 to about 55 mol%, and the second dianhydride is, for example, about 30 to about 55 mol%, and for another example, about 30 to about 30 to about 55 mol%. It may be included in about 50 mol%, another example about 40 to about 60 mol%, another example about 45 to about 55 mol%, but is not limited thereto.

The type of the solvent is not particularly limited as long as it is a solvent capable of dissolving the polyamic acid. For example, the solvent may be an aprotic polar solvent among organic solvents, such as amide solvents such as N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), phenolic solvents such as p-chlorophenol and o-chlorophenol, N-methyl-pyrrolidone (NMP), γ-butyrolactone (GBL), and Diglyme, and these may be used alone or It can be used in combination of two or more. If necessary, an auxiliary solvent such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water may be used to adjust the solubility of the polyamic acid.

According to one embodiment, the polyamic acid solution is about 10 to about 20% by weight (e.g., about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19 or about 20%) polyamic acid solids and about 80 to about 90% (e.g., about 80, about 81, about 82, about 83, about 84, about 85, about 86, about 87, about 88 , About 89 or about 90% by weight) of a solvent. For example, the polyamic acid solution may contain about 13 to about 17 weight percent (e.g., about 15 weight percent) polyamic acid solids and about 83 to about 87 weight percent (e.g., about 85 weight percent) solvent. It may include, but is not limited thereto.

According to one embodiment, the polyamic acid solution is about 90,000 to about 300,000 cP (e.g., about 90,000, about 100,000, about 110,000, about 120,000, about 130,000, about 140,000, about 150,000, about 160,000, about 170,000, about 180,000 , About 190,000, about 200,000, about 210,000, about 220,000, about 230,000, about 240,000, about 250,000, about 260,000, about 270,000, about 280,000, about 290,000 or about 300,000 cP). In the above range, processability may be excellent in manufacturing the polyimide film. Here, the viscosity of the polyamic acid can be obtained as an average value measured twice at 50 rpm through 7 scandals at 25° C. using a Brookfield viscometer (RVDV-II+P), but is not limited thereto. According to one embodiment, the viscosity of the polyamic acid solution may be about 100,000 to about 250,000 cP, but is not limited thereto.

According to one embodiment, the polyamic acid is about 150,000 to about 1,000,000 (e.g., about 150,000, about 200,000, about 250,000, about 300,000, about 350,000, about 400,000, about 450,000, about 500,000, about 550,000, about 600,000, about 650,000, about 700,000, about 750,000, about 800,000, about 850,000, about 900,000, about 950,000, or about 1,000,000). Within the above range, it is possible to improve the heat resistance and mechanical properties of the polyimide film. Here, the weight average molecular weight may mean a weight average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC). For example, the weight average molecular weight of the polyamic acid may be about 260,000 to about 700,000, for example, about 280,000 to about 500,000, but is not limited thereto.

According to one embodiment, the reaction may be performed at a temperature of about 0 to about 80° C. for about 10 minutes to about 30 hours, and the polymerization reaction may be controlled by adding a small amount of an end sealant before polymerization, but is limited thereto. It does not become.

According to one embodiment, additives may be added when preparing polyamic acid for the purpose of improving various properties of the film such as sliding properties, thermal conductivity, conductivity, corona resistance, and loop hardness of the polyimide film. Examples of such additives include fillers, and examples of such fillers include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like, but are not limited thereto. The content of the additive may be appropriately selected within a range that does not impair the object of the present invention.

Then, the polyamic acid in the solution can be imidized.

In order to imidize the polyamic acid, a dehydrating agent and an imidizing agent may be added to the polyamic acid. The dehydrating agent is not particularly limited as long as it can accelerate the ring closure reaction through the dehydration action of the polyamic acid, and examples of the dehydrating agent include acetic anhydride. The imidizing agent is not particularly limited as long as it can accelerate the ring closure reaction to the polyamic acid, and examples of the imidizing agent include tertiary amines such as quinoline, isoquinoline, β-picoline, pyridine, and the like. . The contents of the dehydrating agent and the imidizing agent are not particularly limited, but for example, the dehydrating agent is about 2.5 to about 5.0 molar ratio (e.g., about 2.5, about 2.6, about 2.7, about 2.8) to 1 mol of the amic acid group in the polyamic acid. , About 2.9, about 3, about 3.1, about 3.2, about 3.3, about 3.4, about 3.5, about 3.6, about 3.7, about 3.8, about 3.9, about 4.0, about 4.1, about 4.2, about 4.3, about 4.4, about 4.5, about 4.6, about 4.7, about 4.8, about 4.9 or about 5.0 molar ratio), and the imidizing agent is added in a molar ratio of about 0.7 to about 1.2 (e.g., about 0.7, about 0.8, about 0.9, about 1.0, about 1.1 or about 1.2 molar ratio).

According to one embodiment, the step of imidizing the polyamic acid may include preparing a composition for a polyimide film by mixing a dehydrating agent and an imidizing agent with the polyamic acid; And forming the composition. For film formation, polyamic acid is applied in the form of a film on a substrate (for example, a glass plate, aluminum foil, an endless stainless belt, or a stainless drum, etc.), and then about 30 to about 200°C (for example, about 50 to After the first heat treatment at a temperature of about 150° C. for about 15 seconds to about 30 minutes to prepare a gel film, the gel film from which the substrate was removed is prepared at a temperature of about 50 to about 650° C. (for example, about 20 to about 600° C.). It may be performed by performing a second heat treatment at a temperature for about 15 seconds to about 30 minutes, but is not limited thereto. The amic acid group can be rapidly converted to an imide group by the first heat treatment, and the amic acid group can be quickly converted to an imide group by the second heat treatment, and the solvent, dehydrating agent, imidizing agent, etc. remaining in the gel film can be removed. . Between the first heat treatment and the second heat treatment, the gel film may be selectively stretched to control the thickness of the polyimide film and improve orientation, but is not limited thereto. In some cases, the polyimide film may be further cured by heating the second heat-treated polyimide film at a temperature of about 400 to about 650° C. for a third heat treatment for about 5 to about 400 seconds, and the third heat treatment is In order to alleviate the internal stress that may remain in the polyimide film, it may be performed under a predetermined tension.

The polyimide film prepared by the above-described manufacturing method has a moisture absorption expansion coefficient of about 9 ppm/% RH or less in the range of 25° C. and 20 to 80% relative humidity (eg, about 0, about 0.5, about 1, about 1.5, About 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm/%RH) have. In the above range, dimensional stability may be excellent. In one embodiment, the lower limit of the moisture absorption expansion coefficient of the polyimide film in the range of 25° C. and 20 to 80% relative humidity is, for example, greater than 0, about 1, about 2, about 3, about 4, about 5, About 6 or about 6.2 ppm/%RH, with an upper limit of about 9, about 8.5, about 8, about 7.5, about 7, about 6.9, about 6.8, about 6.7, about 6.5, about 6.4, about 6.3 or about 6.2 ppm/%RH, and the lower and upper limits may be combined with each other. For example, the moisture absorption expansion coefficient of the polyimide film in the range of 25° C. and 20 to 80% relative humidity is greater than 0 to about 9 ppm/% RH, another example, about 4 to about 9 ppm/% RH, another example For example, it may be about 4 to about 8 ppm/%RH, but is not limited thereto.

According to one embodiment, the polyimide film prepared by the above-described manufacturing method has a first binding ratio of about 40 to about 70% (for example, a ratio of the first dianhydride and the first diamine bonded to each other in the polyimide film). 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, About 57, about 58, about 59, about 60, about 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69 or about 70%). In the above range, the moisture absorption expansion coefficient of the polyimide film is small, so that dimensional stability may be excellent. The first binding ratio is, for example, about 45 to about 70%, another such as about 50 to about 70%, another such as about 40 to about 60%, another such as about 45 to about 55%. Can be According to one embodiment, the first binding ratio may be about 50 to about 70%. According to another embodiment, the first binding ratio may be about 45 to about 55%, but is not limited thereto.

According to one embodiment, the polyimide film prepared by the above-described manufacturing method has a first binding ratio of about 40 to about 70% (for example, a ratio of the first dianhydride and the first diamine bonded to each other in the polyimide film). 50 to about 70%), and the second binding ratio, which is the ratio of the second dianhydride and the first diamine, is about 20 to about 50% (e.g., about 20, about 21, about 22, about 23, about 24 , About 25, about 26, about 27, about 28, about 29, about 30, about 31, about 32, about 33, about 34, about 35, about 36, about 37, about 38, about 39, about 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49 or about 50%). Within the above range, the polyimide film has a small coefficient of moisture absorption and excellent dimensional stability, as well as a predetermined physical property, for example, a predetermined coefficient of thermal expansion (CTE) (e.g., about 2 to about 5 μm/(m)). ·°C), so when manufacturing a flexible metal foil laminate using this, the adhesion between the polyimide film and the metal foil can be excellent.

According to one embodiment, the polyimide film manufactured by the above-described manufacturing method has a moisture absorption expansion coefficient of about 9 ppm/%RH or less (for example, about 0, about 0.5, About 1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm /%RH). In the above range, dimensional stability may be excellent. The lower limit of the moisture absorption expansion coefficient of the polyimide film in the range of 25°C and 3 to 90% relative humidity is, for example, greater than 0, about 1, about 2, about 3, about 4, about 5, about 6, about 7, About 8 or about 8.2 ppm/%RH, with an upper limit of about 9, about 8.9, about 8.8, about 8.7, about 8.6, about 8.5, about 8.4, about 8.3 or about 8.2 ppm/%RH The lower limit and the upper limit may be combined with each other, but are not limited thereto.

According to one embodiment, the thickness of the polyimide film manufactured by the above-described manufacturing method may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film. For example, the thickness of the polyimide film is about 10 to about 500 μm (e.g., about 10, about 50, about 100, about 150, about 200, about 250, about 300, about 350, about 400, about 450 Or about 500 µm), for example about 25 to about 50 µm, for another example, about 35 to about 50 µm, for another example, about 25 to about 35 µm, but is not limited thereto.

According to one embodiment, the coefficient of thermal expansion of the polyimide film manufactured by the above-described manufacturing method may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film. For example, when a polyimide film is used for a flexible metal foil laminate, the coefficient of thermal expansion of the polyimide film may be lower than that of the metal foil. For example, the metal foil is about 16 to about 17 μm/m·° C. (e.g., about 16, about 16.1, about 16.2, about 16.3, about 16.4, about 16.5, about 16.6, about 16.7, about 16.8, about 16.9, or It has a coefficient of thermal expansion of about 17 μm/m·° C.), and the polyimide film has a coefficient of thermal expansion of about 2 to about 7 μm/m·° C. (for example, about 2, about 3, about 4, about 5, about 6 or about 7 Μm/m·°C, for example, about 2 to about 5µm/m·°C), but is not limited thereto.

According to one embodiment, the glass transition temperature of the polyimide film manufactured by the above-described manufacturing method may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film. For example, when a polyimide film is used for a flexible metal foil laminate, the polyimide film is about 370°C or higher (e.g., about 370, about 380, about 390, about 400, about 410 or about 420°C, other examples For example, it may have a glass transition temperature of about 370 to about 420°C, another example of about 380°C or more, another example of about 380 to about 420°C).

연성금속박적층판Ductile metal foil laminated plate

According to another aspect, a flexible metal foil laminated plate including the polyimide film described above is provided. Such a flexible metal foil laminate may be formed of a metal foil on one side or both sides of a polyimide film. For example, the flexible metal foil laminate may include the above-described polyimide film or a polyimide film manufactured by the above-described manufacturing method; And a metal foil formed on the polyimide film.

The flexible metal foil laminate can be manufactured by various methods commonly used in the art. For example, the flexible metal foil laminate is (i) a casting method in which a polyamic acid solution is cast on a metal foil and then imidized, (ii) a metallization method in which a metal layer is directly formed on a polyimide film by sputtering, (iii) It can be produced by a method such as a lamination method in which a polyimide film and a metal foil are bonded by heat and pressure.

The flexible metal foil laminate of the present invention has a low coefficient of moisture absorption and expansion of the polyimide film, and may have excellent dimensional stability even in a high-temperature processing process.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this has been presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense.

실시예Example

실시예 1Example 1

Dimethylformamide (DMF) was added to the reactor, and 3,3',4,4'-biphenyltetracarboxylic dianhydride as the first dianhydride and p-phenylenediamine as the first diamine were added in a molar ratio of 7:9. After the addition, it was reacted at 25° C. for 2 hours. To the reactor, pyromellitic dianhydride as a second dianhydride and 4,4'-diaminodiphenyl ether as a second diamine were added in a molar ratio of 3:1 and reacted at 30° C. for 2 hours to obtain a solid content of polyamic acid. A polyamic acid solution having a content of 15% by weight was prepared. At this time, the total number of moles of the first dianhydride and the second dianhydride and the total number of moles of the first diamine and the second diamine were substantially equimolar.

To the thus prepared polyamic acid solution, 3.5 molar ratio of acetic anhydride and 1.1 molar ratio of isoquinoline per 1 mol of amic acid group were added to obtain a composition for preparing a polyimide film. The composition was cast on a SUS plate (100SA, Sandvik) using a doctor blade, and dried at 90° C. for 4 minutes to prepare a gel film. After separating the gel film from the SUS plate, heat treatment was performed at 250 to 380° C. for 14 minutes to prepare a polyimide film having an average thickness of 30 μm.

실시예 2 내지 4, 및 비교예 1 및 2Examples 2 to 4 and Comparative Examples 1 and 2

A polyimide film was prepared using the same method as in Example 1, except that the content of each component was changed as described in Table 1.

평가예: 흡습팽창계수 측정Evaluation Example: Measurement of moisture absorption expansion coefficient

After cutting the polyimide films prepared in Examples 1 to 4 and Comparative Examples 1 and 2 into 25 mm × 130 mm, and fastened to CHEmeter (BMA), the dimensional change from 20% to 80% relative humidity at 25°C Was measured, and the results are shown in Table 1.

	제1이무수물(몰%)First dianhydride (mol%)	제2이무수물(몰%)Second dianhydride (mol%)	제1디아민(몰%)First diamine (mol%)	제2디아민(몰%)Second diamine (mol%)	제1결합비율(%)1st binding ratio (%)	흡습팽창계수(ppm/%RH)Hygroscopic expansion coefficient (ppm/%RH)
실시예 1Example 1	7070	3030	9090	1010	70%70%	6.56.5
실시예 2Example 2	5050	5050	96.296.2	3.83.8	50%50%	6.96.9
실시예 3Example 3	5050	5050	7575	2525	50%50%	8.38.3
실시예 4Example 4	5050	5050	8787	1313	50%50%	6.26.2
비교예 1Comparative Example 1	3030	7070	6060	4040	30%30%	12.912.9
비교예 2Comparative Example 2	3030	7070	9090	1010	30%30%	11.711.7

As can be seen from Table 1, the polyimide films of Examples 1 to 4 of the present invention have a low coefficient of thermal expansion of 9 ppm/%RH or less in the 25°C, 20 to 80% relative humidity section, but not In the case of Comparative Examples 1 and 2, it can be seen that the coefficients of thermal expansion are as high as 12.9 and 11.7 ppm/% RH, respectively.

On the other hand, the polyimide film prepared in Example 4 was cut into 25 mm × 130 mm, and then fastened to CHEmeter (BMA) to measure the dimensional change from 3% to 90% relative humidity at 25°C. As a result, it was confirmed that the moisture absorption expansion coefficient at 25° C. and 3 to 90% relative humidity was as low as 8.2 ppm/% RH.

Simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims

A polyimide film having a moisture absorption expansion coefficient of about 9 ppm/%RH or less in a 25°C, 20 to 80% relative humidity range.
The method of claim 1,

The polyimide film is derived from imidization of a polyamic acid formed from the reaction of a first dianhydride, a second dianhydride, a first diamine, and a second diamine,

The first dianhydride and the second anhydride are different from each other,

The first diamine and the second diamine are different from each other,

The first dianhydride includes 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, or a combination thereof,

The first diamine includes m-phenylenediamine, p-phenylenediamine, or a combination thereof,

A polyimide film having a first binding ratio of about 40 to about 70%, which is a ratio of the first dianhydride and the first diamine of the polyimide film.
The method of claim 2,

The polyamic acid is a polyimide film formed by sequentially reacting a second dianhydride and a second diamine with a pre-reactant of a first dianhydride and a first diamine to extend the ends of at least some of the pre-reactants.
The method of claim 2,

The second dianhydride is a polyimide film containing pyromellitic dianhydride.
The method of claim 2,

The second diamine is a polyimide film comprising 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or a combination thereof.
The method of claim 2,

Polyyi containing about 40 to about 70 mol% of the first dianhydride and about 30 to about 60 mol% of the second dianhydride based on the total number of moles of the first dianhydride and the second dianhydride Mid film.
The method of claim 2,

A polyimide film containing about 70 to about 98 mol% of the first diamine and about 2 to about 30 mol% of the second diamine based on the total number of moles of the first diamine and the second diamine.
The method of claim 7,

The first diamine is contained in an amount of about 80 to about 98 mol%, and the second diamine is contained in an amount of about 2 to about 20 mol%, based on the total number of moles of the first diamine and the second diamine,

The polyimide film is a polyimide film having a moisture absorption expansion coefficient of about 8 ppm/%RH or less in a range of 25° C. and 20 to 80% relative humidity.
The method of claim 1,

The polyimide film is a polyimide film having a moisture absorption expansion coefficient of about 9 ppm/%RH or less in a range of 25° C. and 3 to 90% relative humidity.
Mixing and reacting the first dianhydride and the first diamine in a solvent, and then adding and reacting the second dianhydride and the second diamine to form a polyamic acid solution; And

It is a method for producing a polyimide film comprising; imidizing the polyamic acid,

The first dianhydride and the second anhydride are different from each other,

The first diamine and the second diamine are different from each other,

The polyimide film is a method of producing a polyimide film having a moisture absorption expansion coefficient of about 9ppm/%RH or less in a range of 25°C and 20 to 80% relative humidity.
The method of claim 10,

The first dianhydride includes 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, or a combination thereof,

The first diamine includes m-phenylenediamine, p-phenylenediamine, or a combination thereof,

A method for producing a polyimide film in which a first bonding ratio, which is a ratio of bonding of the first dianhydride and the first diamine among the polyimide films, is about 40 to about 70%.
The method of claim 10,

The second dianhydride is a method for producing a polyimide film containing pyromellitic dianhydride.
The method of claim 10,

The second diamine is a method for producing a polyimide film comprising 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or a combination thereof.
The method of claim 10,

Polyyi containing about 40 to about 70 mol% of the first dianhydride and about 30 to about 60 mol% of the second dianhydride based on the total number of moles of the first dianhydride and the second dianhydride Method for producing a mid film.
The method of claim 10,

Of the polyimide film containing about 70 to about 98 mol% of the first diamine and about 2 to about 30 mol% of the first diamine based on the total number of moles of the first diamine and the second diamine. Manufacturing method.
The method of claim 15,

The first diamine is contained in an amount of about 80 to about 98 mol%, and the second diamine is contained in an amount of about 2 to about 20 mol%, based on the total number of moles of the first diamine and the second diamine,

The polyimide film is a method of producing a polyimide film having a moisture absorption expansion coefficient of about 8 ppm/%RH or less in a range of 25° C. and 20 to 80% relative humidity.
The method of claim 10,

The polyimide film is a method of producing a polyimide film having a moisture absorption expansion coefficient of about 9 ppm/%RH or less in a range of 25° C. and 3 to 90% relative humidity.
The polyimide film of any one of claims 1 to 9; And

Flexible metal foil laminated plate comprising a metal foil formed on the polyimide film.