KR20220060476A - Polyimide film WITH HIGH DIMENSIONAL STABILTY and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a polyimide film with excellent dimensional stability which has a thermal expansion coefficient of 1 ppm/℃ or more and 5 ppm/℃ or less, an elastic modulus of 9 GPa or more and 11.5 GPa or less, and a glass transition temperature of 340 ℃ or more and 400 ℃ or less and a preparation manufacturing thereof.

Description

Polyimide film with high dimensional stability and manufacturing method thereof

The present invention relates to a polyimide film having high dimensional stability, and more particularly, to a polyimide film having high thermal dimensional stability and high dimensional stability against moisture, and a method for manufacturing the same.

Polyimide (PI) is a polymer material with the highest level of heat resistance, chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials based on an imide ring with excellent chemical stability along with a rigid aromatic main chain. am.

The polyimide film is spotlighted as a material for various electronic devices requiring the above-described properties.

Examples of microelectronic components to which the polyimide film is applied include thin circuit boards that have high circuit integration and are flexible to respond to weight reduction and miniaturization of electronic products. there is.

The thin circuit board generally has a structure in which a circuit including a metal foil is formed on an insulating film. In a broad sense, such a thin circuit board is called a Flexible Metal Foil Clad Laminate, and a thin copper plate is made of metal foil. When used, it is also referred to as Flexible Copper Clad Laminate (FCCL) in a narrower sense.

As a manufacturing method of a flexible metal foil laminate, for example, (i) a casting method in which polyamic acid, a precursor of polyimide, is cast or coated on a metal foil, and then imidized, (ii) sputtering a metallizing method in which a metal layer is directly provided on the polyimide film by the method;

In particular, the metallizing method produces a flexible metal foil laminate by sequentially depositing a tie layer and a seed layer by sputtering a metal such as copper on a polyimide film having a thickness of 20 to 38 μm, for example. This method has an advantage in forming ultra-fine circuits having a circuit pattern pitch of 35 μm or less, and is widely used in manufacturing flexible metal foil laminates for COF (chip on film).

The polyimide film used for the flexible metal foil laminate by the metallizing method should have high dimensional stability. In general, dimensional stability is measured by thermal dimensional stability expressed by thermal expansion coefficient, but dimensional stability to moisture expressed by hygroscopic expansion coefficient is increasingly important as well as thermal dimensional stability.

That is, there is an increasing demand for a polyimide film having both excellent thermal dimensional stability and dimensional stability against moisture. This lowering problem is emerging.

Therefore, there is an urgent need for a polyimide film capable of achieving both high thermal dimensional stability and high dimensional stability against moisture.

Matters described in the above background art are intended to help the understanding of the background of the invention, and may include matters that are not already known to those of ordinary skill in the art to which this technology belongs.

Republic of Korea Patent Registration No. 10-1375276 Republic of Korea Patent Publication No. 2016-0002402

Accordingly, an object of the present invention is to provide a polyimide film having both high thermal dimensional stability and high dimensional stability against moisture.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present invention for achieving the above object is that the coefficient of thermal expansion is 1 ppm / ℃ or more, 5 ppm / ℃ or less,

The modulus of elasticity is 9 GPa or more and 11.5 GPa or less,

The glass transition temperature is 340 ℃ or more and 400 ℃ or less,

A polyimide film is provided.

The polyimide film may have a coefficient of hygroscopic expansion of 4 ppm/RH% or more and 6 ppm/RH% or less.

Another aspect of the present invention is biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA) and benzophenonetetracarboxylic dianhydride (BTDA) A dianhydride component comprising two or more selected from the group consisting of, paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA), and 1,3-bisaminophenoxybenzene (TPE-R) obtained by imidation reaction of a polyamic acid solution containing a diamine component containing two or more selected from the group consisting of,

Based on 100 mol% of the total content of the diamine component, the content of paraphenylene diamine is 10 mol% or more and 70 mol% or less, and the content of m-tolidine is 25 mol% or more and 80 mol% or less,

A polyimide film is provided.

Based on 100 mol% of the total content of the dianhydride component, the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, and the content of the pyromellitic dianhydride is 40 mol% It may be more than 60 mol%.

In addition, based on 100 mol% of the total content of the dianhydride component, the content of the oxydiphthalic anhydride is 20 mol% or less, and the content of the benzophenonetetracarboxylic dianhydride is 30 mol% or less, Based on 100 mol% of the total content of the diamine component, the content of oxydianiline (ODA) may be 20 mol% or less, and the content of 1,3-bisaminophenoxybenzene may be 20 mol% or less.

The molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride may be 0.3 or more and 2.5 or less, and the molar ratio of the m-tolidine to the pyromellitic dianhydride may be 0.6 or more and 1.5 or less.

In addition, the reaction molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride is 1.05 or more and 1.2 or less, and the paraphenylene diamine and the m-tolidine to the pyromellitic dianhydride are The reaction molar ratio may be 0.9 or more and 0.99 or less.

Another aspect of the present invention is (a) biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA) and benzophenonetetracarboxylic dianhydride A dianhydride component comprising two or more selected from the group consisting of ride (BTDA), paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA), and 1,3-bis preparing a polyamic acid by polymerizing a diamine component including at least two selected from the group consisting of aminophenoxybenzene (TPE-R) in an organic solvent; and

(b) imidizing the polyamic acid;

Based on 100 mol% of the total content of the dianhydride component, the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, and the content of the pyromellitic dianhydride is 40 mol% or more and 60 mol% or less,

Based on 100 mol% of the total content of the diamine component, the content of paraphenylene diamine is 10 mol% or more and 70 mol% or less, and the content of m-tolidine is 25 mol% or more and 80 mol% or less,

A method for manufacturing a polyimide film is provided.

Another aspect of the present invention provides a flexible metal foil laminate comprising the polyimide film and an electrically conductive metal foil.

Another aspect of the present invention provides an electronic component comprising the flexible metal foil laminate.

The present invention provides a polyimide film excellent in both thermal dimensional stability and moisture dimensional stability by providing a polyimide film in which the composition ratio and reaction ratio of dianhydride and diamine components are controlled.

Such a polyimide film is applicable to various fields requiring a polyimide film having excellent dimensional stability properties, for example, a flexible metal foil laminate manufactured by a metallizing method or an electronic component including such a flexible metal foil laminate.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Accordingly, since the configuration of the embodiments described in the present specification is only one of the most preferred embodiments of the present invention and does not represent all the technical spirit of the present invention, various equivalents and modifications that can be substituted for them at the time of the present application It should be understood that examples may exist.

In this specification, the singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "have" are intended to designate the existence of an embodied feature, number, step, element, or a combination thereof, but one or more other features or It should be understood that the existence or addition of numbers, steps, elements, or combinations thereof, is not precluded in advance.

As used herein, “dianhydride” is intended to include precursors or derivatives thereof, which may not technically be dianhydride acids, but will nevertheless react with a diamine to form a polyamic acid, which in turn is a polyamic acid can be converted into mids.

As used herein, "diamine" is intended to include precursors or derivatives thereof, which may not technically be diamines, but will nevertheless react with dianhydrides to form polyamic acids, which in turn are polyamic acids. can be converted to mid

Where an amount, concentration, or other value or parameter is given herein as a range, a preferred range, or a recitation of a preferred upper value and a lower preferred value, any pair of any upper range limit, or any pair of upper range limits, whether or not ranges are separately disclosed. It is to be understood that the preferred values and any lower range limits or all ranges formed by the preferred values are specifically disclosed.

When a range of numerical values is recited herein, the range is intended to include the endpoints and all integers and fractions within the range, unless otherwise stated. It is intended that the scope of the invention not be limited to the particular values recited when defining the ranges.

The polyimide film according to an embodiment of the present invention is biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA) and benzophenonetetracarboxylic A dianhydride component comprising two or more selected from the group consisting of dianhydride (BTDA), paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA), and 1,3 -It is obtained by imidization reaction of a polyamic acid solution containing a diamine component including two or more selected from the group consisting of bisaminophenoxybenzene (TPE-R), and based on 100 mol% of the total content of the dianhydride component , wherein the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, the content of the pyromellitic dianhydride is 40 mol% or more and 60 mol% or less, and the total amount of the diamine component is Based on the content of 100 mol%, the content of the paraphenylene diamine may be 10 mol% or more and 70 mol% or less, and the content of m-tolidine may be 25 mol% or more and 80 mol% or less.

Preferably, based on 100 mol% of the total content of the dianhydride component, the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 55 mol% or less, and the content of the pyromellitic dianhydride is It may be 45 mol% or more and 55 mol% or less.

In addition, preferably, based on 100 mol% of the total content of the diamine component, the content of the paraphenylene diamine may be 15 mol% or more and 70 mol% or less.

The paraphenylene diamine of the present invention is a rigid monomer, and as the content of paraphenylene diamine increases, the synthesized polyimide has a more linear structure, contributing to the improvement of the mechanical properties of the polyimide.

In addition. Since m-tolidine has a particularly hydrophobic methyl group, it contributes to the low moisture absorption properties related to the dimensional stability of the polyimide film against moisture.

The polyimide chain derived from the biphenyltetracarboxylic dianhydride of the present invention has a structure called a charge transfer complex (CTC), that is, an electron donor and an electron acceptor. It has a regular linear structure positioned close to each other, and the intermolecular interaction is strengthened.

Since this structure has an effect of preventing hydrogen bonding with moisture, it is possible to maximize the effect of lowering the hygroscopicity of the polyimide film, which affects the dimensional stability of the polyimide film by affecting the lowering of the moisture absorption.

In addition, pyromellitic dianhydride is a dianhydride component having a relatively rigid structure, and is preferable in that it can impart appropriate elasticity to the polyimide film.

In order for the polyimide film to have excellent dimensional stability, the content ratio of dianhydride is important. For example, as the content ratio of biphenyltetracarboxylic dianhydride decreases, it is difficult to expect a low moisture absorption rate due to the CTC structure, and dimensional stability with respect to moisture is also reduced.

In addition, biphenyltetracarboxylic dianhydride contains two benzene rings corresponding to the aromatic moiety, whereas pyromellitic dianhydride contains one benzene ring corresponding to the aromatic moiety.

An increase in the pyromellitic dianhydride content in the dianhydride component can be understood as an increase in the imide group in the molecule based on the same molecular weight, which is a polyimide polymer chain derived from the pyromellitic dianhydride. It can be understood that the ratio of the group is relatively increased compared to the imide group derived from biphenyltetracarboxylic dianhydride.

That is, the increase in the content of pyromellitic dianhydride can be viewed as a relative increase in imide groups for the entire polyimide film, and therefore, it is difficult to expect high dimensional stability against moisture due to low moisture absorption.

Conversely, when the content ratio of pyromellitic dianhydride is reduced, a component having a relatively rigid structure is decreased, and thus the elasticity of the polyimide film may be lowered to a desired level or less.

For this reason, when the content of biphenyltetracarboxylic dianhydride exceeds the above range or the content of pyromellitic dianhydride is below the above range, dimensional stability of the polyimide film may be reduced.

Conversely, even when the content of biphenyltetracarboxylic dianhydride is less than the above range or the content of pyromellitic dianhydride exceeds the above range, the dimensional stability of the polyimide film may be adversely affected. .

On the other hand, based on 100 mol% of the total content of the dianhydride component, the content of the oxydiphthalic anhydride is 20 mol% or less, and the content of the benzophenonetetracarboxylic dianhydride is 30 mol% or less, Based on 100 mol% of the total content of the diamine component, the content of oxydianiline (ODA) may be 20 mol% or less, and the content of 1,3-bisaminophenoxybenzene may be 20 mol% or less.

In the composition of the polyimide film, the molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride (=mol% of paraphenylene diamine/mol% of biphenyltetracarboxylic dianhydride) ) is 0.3 or more and 2.5 or less, and the molar ratio of m-tolidine to the pyromellitic dianhydride (=mol% of m-tolidine/mol% of pyromellitic dianhydride) may be 0.6 or more and 1.5 or less there is.

In addition, in the reaction molar ratio of the dianhydride component and the diamine component of the polyimide film, the reaction molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride is 1.05 or more and 1.2 or less, and the pyromellitic A reaction molar ratio of the paraphenylene diamine and the m-tolidine to the dianhydride may be 0.9 or more and 0.99 or less.

That is, in the course of the reaction between the dianhydride component and the diamine component, 1 mole of biphenyltetracarboxylic dianhydride reacts with 1.05 moles or more and 1.2 moles or less of paraphenylene diamine, and 1 mole of pyromellitic dianhydride is It can react with 0.9 mol or more and 0.99 mol or less of paraphenylene diamine and m-tolidine.

Preferably, the reaction molar ratio of the paraphenylene diamine and the m-tolidine to the pyromellitic dianhydride may be 0.9 or more and 0.95 or less.

On the other hand, the polyimide film has a coefficient of thermal expansion of 1 ppm/℃ or more and 5 ppm/℃ or less, an elastic modulus of 9 GPa or more and 11.5 GPa or less, and a hygroscopic expansion coefficient of 4 ppm/RH% or more and 6 ppm/RH% or less. can

In addition, the glass transition temperature of the polyimide film may be 340 ℃ or more, 400 ℃ or less, preferably less than 390 ℃.

In the present invention, the preparation of the polyamic acid is, for example,

(1) a method in which the whole amount of the diamine component is placed in a solvent, and then the dianhydride component is added so as to be substantially equimolar with the diamine component, followed by polymerization;

(2) a method in which the entire amount of the dianhydride component is placed in a solvent, and then the diamine component is added so as to be substantially equimolar with the dianhydride component and polymerized;

(3) After putting some of the diamine components in the solvent, mixing some of the dianhydride components with respect to the reaction components in a ratio of about 95 to 105 mol%, then adding the remaining diamine components and successively with the remaining dianhydride acid a method of polymerization by adding a component so that the diamine component and the dianhydride component are substantially equimolar;

(4) After putting the dianhydride component in the solvent, mixing some components of the diamine compound in a ratio of 95 to 105 mol% with respect to the reaction component, adding another dianhydride component, and then adding the remaining diamine components, a method of polymerization such that the diamine component and the dianhydride component are substantially equimolar;

(5) reacting some diamine component and some dianhydride component in a solvent so that any one is in excess to form a first composition, and reacting some diamine component and some dianhydride component in another solvent so that any one is in excess After forming the second composition, the first and second compositions are mixed, and polymerization is completed. In this case, when the diamine component is excessive when the first composition is formed, the dianhydride component is excessively used in the second composition And, when the dianhydride component in the first composition is excessive, in the second composition, the diamine component is in excess, the first and second compositions are mixed and the total diamine component and the dianhydride component used in these reactions are substantially The method of superposing|polymerizing so that it may become equimolar, etc. are mentioned.

In one specific example, the method for producing a polyimide film according to the present invention,

(a) the group consisting of biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA) and benzophenonetetracarboxylic dianhydride (BTDA) A dianhydride component comprising two or more selected from, paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA) and 1,3-bisaminophenoxybenzene (TPE- R) preparing a polyamic acid by polymerizing a diamine component comprising two or more selected from the group consisting of in an organic solvent; and

(b) imidizing the polyamic acid;

Based on 100 mol% of the total content of the dianhydride component, the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, and the content of the pyromellitic dianhydride is 40 mol% or more and 60 mol% or less,

Based on 100 mol% of the total content of the diamine component, the content of paraphenylene diamine is 10 mol% or more and 70 mol% or less, and the content of m-tolidine is 25 mol% or more and 80 mol% or less,

It may be a method of manufacturing a polyimide film.

In the present invention, the polymerization method of the polyamic acid as described above can be defined as a random polymerization method, and the polyimide film prepared from the polyamic acid of the present invention prepared by the above process is the present invention that improves dimensional stability It can be preferably applied in terms of maximizing the effect of

However, in the polymerization method, since the length of the repeating unit in the above-described polymer chain is relatively short, there may be a limit in exhibiting excellent properties of the polyimide chain derived from the dianhydride component. Accordingly, the polymerization method of the polyamic acid that can be particularly preferably used in the present invention may be a block polymerization method.

On the other hand, the solvent for synthesize|combining a polyamic acid is not specifically limited, Any solvent can be used as long as it is a solvent in which a polyamic acid is dissolved, It is preferable that it is an amide type solvent.

Specifically, the organic solvent may be an organic polar solvent, specifically an aprotic polar solvent, for example, N,N-dimethylformamide (DMF), N,N -Dimethylacetamide, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), may be at least one selected from the group consisting of Diglyme (Diglyme), but is not limited thereto. Or it can be used in combination of 2 or more types.

In one example, as the organic solvent, N,N-dimethylformamide and N,N-dimethylacetamide may be particularly preferably used.

In addition, in the polyamic acid manufacturing process, a filler may be added for the purpose of improving various properties of the film, such as sliding properties, thermal conductivity, corona resistance, and loop hardness. The filler to be added is not particularly limited, but preferred examples thereof include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like.

The particle size of the filler is not particularly limited, and may be determined according to the characteristics of the film to be modified and the type of filler to be added. Generally, the average particle diameter is 0.05 to 100 μm, preferably 0.1 to 75 μm, more preferably 0.1 to 50 μm, particularly preferably 0.1 to 25 μm.

When the particle size is less than this range, the modifying effect becomes difficult to appear, and when the particle size exceeds this range, the surface properties may be greatly impaired or the mechanical properties may be greatly reduced.

Moreover, it is not specifically limited also about the addition amount of a filler, What is necessary is just to determine by the film characteristic to be modified|reformed, a filler particle diameter, etc. In general, the added amount of the filler is 0.01 to 100 parts by weight, preferably 0.01 to 90 parts by weight, and more preferably 0.02 to 80 parts by weight based on 100 parts by weight of polyimide.

When the filler addition amount is less than this range, the modifying effect by the filler is difficult to appear, and when it exceeds this range, the mechanical properties of the film may be greatly impaired. The method of adding a filler is not specifically limited, Any well-known method can also be used.

In the manufacturing method of the present invention, the polyimide film may be prepared by thermal imidization and chemical imidization.

Also, it may be prepared by a complex imidization method in which thermal imidization and chemical imidization are combined.

The thermal imidization method is a method in which a chemical catalyst is excluded and the imidization reaction is induced by a heat source such as hot air or an infrared dryer.

The thermal imidization method can imidize the amic acid group present in the gel film by heat-treating the gel film at a variable temperature in the range of 100 to 600 ° C., specifically 200 to 500 ° C., more specifically, The amic acid group present in the gel film can be imidized by heat treatment at 300 to 500 °C.

However, in the process of forming the gel film, some of the amic acid (about 0.1 mol% to 10 mol%) may be imidized, and for this purpose, the polyamic acid composition is dried at a variable temperature in the range of 50 ℃ to 200 ℃. and may also be included in the scope of the thermal imidization method.

In the case of chemical imidization, a polyimide film may be prepared by using a dehydrating agent and an imidizing agent according to a method known in the art.

As an example of the complex imidization method, after adding a dehydrating agent and an imidizing agent to a polyamic acid solution, heating at 80 to 200° C., preferably 100 to 180° C., partially curing and drying, at 200 to 400° C. for 5 to 400 seconds A polyimide film can be manufactured by heating.

The present invention provides a flexible metal foil laminate comprising the above-described polyimide film and an electrically conductive metal foil.

The metal foil to be used is not particularly limited, but when the flexible metal foil laminate of the present invention is used for electronic or electrical equipment applications, for example, copper or copper alloy, stainless steel or an alloy thereof, nickel or a nickel alloy (alloy 42) Also included), it may be a metal foil comprising aluminum or an aluminum alloy.

In general flexible metal foil laminates, copper foils such as rolled copper foils and electrolytic copper foils are often used, and they can be preferably used in the present invention as well. Moreover, the antirust layer, the heat-resistant layer, or the adhesive layer may be apply|coated on the surface of these metal foils.

In the present invention, the thickness of the metal foil is not particularly limited, and may have a thickness capable of exhibiting a sufficient function according to its use.

The flexible metal foil laminate according to the present invention may have a structure in which a metal foil is laminated on at least one surface of the polyimide film.

Hereinafter, the action and effect of the invention will be described in more detail through specific preparation examples and examples of the invention. However, these manufacturing examples and examples are only presented as examples of the invention, and the scope of the invention is not limited thereby.

Preparation Example: Preparation of polyimide film

The polyimide film of the present invention can be prepared by a conventional method known in the art as follows. First, a polyamic acid solution is obtained by reacting the above-described dianhydride acid with the diamine component in an organic solvent.

In this case, the solvent is generally an amide solvent, and an aprotic polar solvent, for example, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-pyrrolidone, or Combinations of these may be used.

The input form of the dianhydride and the diamine component may be in powder, lump, or solution form. At the beginning of the reaction, it is added in powder form to proceed with the reaction, and thereafter, it is preferable to input in the form of a solution to control polymerization viscosity. .

The obtained polyamic acid solution may be mixed with an imidization catalyst and a dehydrating agent and applied to a support.

Examples of the catalyst used include tertiary amines (eg, isoquinoline, β-picoline, pyridine, etc.), and examples of the dehydrating agent include, but are not limited to, acid anhydride. In addition, the support used in the above may include, but is not limited to, a glass plate, an aluminum foil, a circulation stainless belt or a stainless drum.

The film applied on the support is gelled on the support by dry air and heat treatment.

The gelled film is separated from the support and heat-treated to complete drying and imidization.

After the heat treatment, the film may be heat treated under a certain tension to remove residual stress inside the film generated during the film forming process.

Specifically, 500 ml of DMF was added while injecting nitrogen into a reactor equipped with a stirrer and nitrogen injection/discharge tube, and the temperature of the reactor was set to 30 ° C., then biphenyltetracarboxylic dianhydride (BPDA), fatigue Melitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA), benzophenone tetracarboxylic dianhydride (BTDA), paraphenylene diamine (PPD), m-tolidine (m-tolidine), jade Cydianiline (ODA) and 1,3-bisaminophenoxybenzene (TPE-R) are added in a controlled composition ratio and in a predetermined order to completely dissolve. Thereafter, stirring was continued for 120 minutes while heating the reactor by raising the temperature of the reactor to 40° C. under a nitrogen atmosphere to prepare a polyamic acid having a primary reaction viscosity of 1,500 cP.

The thus-prepared polyamic acid was stirred to have a final viscosity of 100,000 to 120,000 cP.

After the catalyst and dehydrating agent were added to the prepared final polyamic acid by adjusting the content, a polyimide film was prepared using an applicator.

Examples and Comparative Examples

As shown in Table 1 below, by controlling the contents of the dianhydride component and the diamine component in Examples 1 to 8 and Comparative Examples 1 to 7, polyimide films were prepared according to Preparation Examples.

In addition, in Examples 1 to 7, the reaction molar ratio of paraphenylene diamine to biphenyltetracarboxylic dianhydride is 1.05 or more and 1.2 or less, and paraphenylene diamine and m-tolidine to pyromellitic dianhydride. The reaction was controlled so that the reaction molar ratio of was 0.9 or more and 0.99 or less.

dianhydride diamine BPDA PMDA ODPA BTDA m-Tolidine PPD ODA TPE-R Example 1 50 50 - - 40 60 - - Example 2 50 50 - - 35 65 - - Example 3 47 53 - - 35 65 - - Example 4 47 53 - - 40 60 - - Example 5 40 50 10 - 70 30 - - Example 6 30 50 - 20 30 70 - - Example 7 50 50 - - 75 15 10 - Example 8 50 50 - - 75 15 - 10 Comparative Example 1 50 50 - - 0 100 - - Comparative Example 2 50 50 - - 15 85 - - Comparative Example 3 50 50 - - 60 40 - - Comparative Example 4 40 60 - - 100 0 - - Comparative Example 5 20 50 30 - 85 15 - - Comparative Example 6 50 50 - - 85 5 - 10 Comparative Example 7 50 50 - - 15 75 10 -

The elastic modulus, coefficient of thermal expansion (CTE), coefficient of hydroscopic expansion (CHE) and glass transition temperature (Tg) of the prepared polyimide film were measured and shown in Table 2 below.

Properties modulus of elasticity
(GPa) CTE
(ppm/℃) CHE
(ppm/RH%) Tg
(℃) Example 1 10.5 1.8 4.5 343 Example 2 9.5 4.4 5.3 353 Example 3 9.1 2.5 4.6 373 Example 4 10.3 1.6 4.3 382 Example 5 9.7 4.9 5.8 343 Example 6 9.3 2.2 5.7 370 Example 7 11.2 3.1 5.5 341 Example 8 11.1 3.5 5.8 342 Comparative Example 1 8.6 0.2 7.0 390 Comparative Example 2 9.0 1.5 6.5 410 Comparative Example 3 11.9 5.7 3.8 327 Comparative Example 4 11.7 6.0 5.9 295 Comparative Example 5 11.5 7.0 6.5 300 Comparative Example 6 12.2 2.1 5.0 310 Comparative Example 7 8.8 2.4 6.0 390

(1) Measurement of modulus of elasticity

The modulus of elasticity of the polyimide films prepared in all Examples and Comparative Examples was tested three times in accordance with ASTM D 882 regulations using a Standard Instron testing apparatus, and the average value was taken.

(2) Measurement of coefficient of thermal expansion

The coefficient of thermal expansion (CTE) was measured using a Q400 thermomechanical analyzer from TA, and after cutting a polyimide film to 4 mm in width and 20 mm in length, while applying a tension of 0.05 N under a nitrogen atmosphere, 10 °C/min After raising the temperature from room temperature to 400 °C at a rate of

(3) Measurement of hygroscopic expansion coefficient

The coefficient of hygroscopic expansion (CHE) is measured by adjusting the humidity to 3 %RH and absorbing moisture until completely saturated with the minimum weight applied to prevent the polyimide film from loosening (for a sample of 25 mm × 150 mm, about 1 g). After measuring, the humidity was adjusted to 90 %RH, and the size was measured after saturated moisture absorption in the same way, and the dimensional change rate was measured at 90%RH per 87% relative humidity difference from both results.

(4) Glass transition temperature measurement

The glass transition temperature (T _g ) was obtained by obtaining the loss modulus and storage modulus of each film using DMA, and the inflection point was measured as the glass transition temperature in their tangent graph.

As a result of the measurement, the polyimide films of Examples 1 to 8 have a coefficient of thermal expansion of 1 ppm/℃ or more and 5 ppm/℃ or less, an elastic modulus of 9 GPa or more and 11.5 GPa or less, and a hygroscopic expansion coefficient of 4 ppm/RH% or more, 6 ppm/RH% or less was exhibited.

In contrast, in Comparative Examples 1 and 2 containing no or a small amount (15% by weight) of m-tolidine at all, the thermal expansion coefficient properties were relatively excellent (1.5 ppm/℃ or less), but the hygroscopic expansion coefficient was 6.5 ppm/ It was measured at RH% or more, and it was found that the dimensional stability against moisture was lower than in the Examples.

On the other hand, in Comparative Example 7 in which oxydianiline and paraphenylene diamine were used together while using a small amount (15% by weight) of m-tolidine as the diamine component, it was confirmed that the elastic modulus was lowered to less than 9 GPa.

In addition, in the case of Comparative Examples 2 to 4, it was confirmed that the glass transition temperature was lower or higher than the glass transition temperature of Examples.

In addition, in the case of Comparative Examples 3 and 4 containing excessively m-tolidine, the coefficient of hygroscopic expansion property was relatively excellent (5.9 ppm/RH% or less), but the coefficient of thermal expansion was measured to be 5.7 ppm/°C or more. It was found that the thermal dimensional stability was lower than that of .

On the other hand, it can be seen that Comparative Example 5 including oxydiphthalic anhydride as a dianhydride component while excessively including m-tolidine has lowered thermal dimensional stability and lowered glass transition temperature compared to Examples. (coefficient of thermal expansion: 7.0 ppm/°C, glass transition temperature: 300°C).

Comparative Example 6 containing 1,3-bisaminophenoxybenzene as a diamine component while excessively containing m-tolidine had an excessively large elastic modulus compared to Examples (modulus of elasticity: 12.2 GPa), and a glass transition temperature It was confirmed that the lowering (glass transition temperature: 310 ℃).

Accordingly, the polyimide films of Examples 1 to 8 prepared within the appropriate range of the present application were excellent in both thermal dimensional stability and dimensional stability to moisture, but outside the appropriate range of the present application, thermal dimensional stability and dimensional stability to moisture It was confirmed that it was difficult to achieve both stability.

In addition, it was confirmed that the polyimide films of Examples 1 to 8 prepared within the appropriate range of the present application had appropriate ranges applicable to various fields in terms of elastic modulus and glass transition temperature.

That is, it was confirmed that the polyimide film that has excellent dimensional stability and satisfies all the various conditions applicable to the application field is a polyimide film manufactured within the appropriate range of the present application.

The embodiments of the polyimide film and the method of manufacturing the polyimide film according to the present invention are only preferred embodiments that enable those skilled in the art to easily practice the present invention, Since the present invention is not limited, the scope of the present invention is not limited thereto. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims. In addition, it will be apparent to those skilled in the art that various substitutions, modifications and changes are possible within the scope of the present invention, and it is apparent that parts easily changeable by those skilled in the art are also included in the scope of the present invention. .

Claims (15)

The coefficient of thermal expansion is 1 ppm/℃ or more and 5 ppm/℃ or less,
The modulus of elasticity is 9 GPa or more and 11.5 GPa or less,
The glass transition temperature is 340 ℃ or more and 400 ℃ or less,
polyimide film. According to claim 1,
The coefficient of hygroscopic expansion is 4 ppm/RH% or more and 6 ppm/RH% or less,
polyimide film. 2 selected from the group consisting of biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA) and benzophenonetetracarboxylic dianhydride (BTDA) With a dianhydride component containing more than one species, paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA) and 1,3-bisaminophenoxybenzene (TPE-R) It is obtained by imidizing a polyamic acid solution containing a diamine component containing two or more selected from the group consisting of,
Based on 100 mol% of the total content of the diamine component, the content of paraphenylene diamine is 10 mol% or more and 70 mol% or less, and the content of m-tolidine is 25 mol% or more and 80 mol% or less,
polyimide film. 4. The method of claim 3,
Based on 100 mol% of the total content of the dianhydride component, the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, and the content of the pyromellitic dianhydride is 40 mol% greater than or equal to 60 mol%,
polyimide film. 5. The method of claim 4,
Based on 100 mol% of the total content of the dianhydride component, the content of the oxydiphthalic anhydride is 20 mol% or less, and the content of the benzophenonetetracarboxylic dianhydride is 30 mol% or less,
Based on 100 mol% of the total content of the diamine component, the content of oxydianiline (ODA) is 20 mol% or less, and the content of 1,3-bisaminophenoxybenzene is 20 mol% or less,
polyimide film. 4. The method of claim 3,
The molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride is 0.3 or more and 2.5 or less,
polyimide film. 4. The method of claim 3,
The molar ratio of m-tolidine to the pyromellitic dianhydride is 0.6 or more and 1.5 or less,
polyimide film. 4. The method of claim 3,
The reaction molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride is 1.05 or more and 1.2 or less,
polyimide film. 4. The method of claim 3,
The reaction molar ratio of the paraphenylene diamine and the m-tolidine to the pyromellitic dianhydride is 0.9 or more and 0.99 or less,
polyimide film. (a) the group consisting of biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA) and benzophenonetetracarboxylic dianhydride (BTDA) A dianhydride component comprising two or more selected from, paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA), and 1,3-bisaminophenoxybenzene (TPE- R) preparing a polyamic acid by polymerizing a diamine component comprising at least two selected from the group consisting of in an organic solvent; and
(b) imidizing the polyamic acid;
Based on 100 mol% of the total content of the dianhydride component, the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, and the content of the pyromellitic dianhydride is 40 mol% or more and 60 mol% or less,
Based on 100 mol% of the total content of the diamine component, the content of paraphenylene diamine is 10 mol% or more and 70 mol% or less, and the content of m-tolidine is 25 mol% or more and 80 mol% or less,
A method for producing a polyimide film. 11. The method of claim 10,
Based on 100 mol% of the total content of the dianhydride component, the content of the oxydiphthalic anhydride is 20 mol% or less, and the content of the benzophenonetetracarboxylic dianhydride is 30 mol% or less,
Based on 100 mol% of the total content of the diamine component, the content of oxydianiline (ODA) is 20 mol% or less, and the content of 1,3-bisaminophenoxybenzene is 20 mol% or less,
A method for producing a polyimide film. 11. The method of claim 10,
The reaction molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride is 1.05 or more and 1.2 or less,
The reaction molar ratio of the paraphenylene diamine and the m-tolidine to the pyromellitic dianhydride is 0.9 or more and 0.99 or less,
A method for producing a polyimide film. 11. The method of claim 10,
The coefficient of thermal expansion of the polyimide film is 1 ppm/℃ or more and 5 ppm/℃ or less,
The modulus of elasticity is 9 GPa or more and 11.5 GPa or less,
The glass transition temperature is 340 °C or higher and 400 °C or lower;
The coefficient of hygroscopic expansion is 4 ppm/RH% or more and 6 ppm/RH% or less,
A method for producing a polyimide film. According to any one of claims 1 to 9, comprising a polyimide film and electrically conductive metal foil according to any one of claims 1 to 9,
Flexible metal foil laminates. Including the flexible metal foil laminate according to claim 14,
Electronic parts.