WO2021060616A1

WO2021060616A1 - Polyamic acid composition, method for preparing polyamic acid composition, and polyimide comprising same

Info

Publication number: WO2021060616A1
Application number: PCT/KR2019/015409
Authority: WO
Inventors: 황인환; 이익상; 최정열
Original assignee: 피아이첨단소재 주식회사
Priority date: 2019-09-27
Filing date: 2019-11-13
Publication date: 2021-04-01
Also published as: KR20210037333A; KR102260038B1

Abstract

The present invention relates to a polyamic acid composition capable of simultaneously implementing a low dielectric dissipation factor, high adhesive strength, and mechanical characteristics at high temperature, a method for preparing the polyamic acid composition, and a polyimide and polyimide film comprising the polyamic acid composition.

Description

Polyamic acid composition, method for preparing polyamic acid composition, and polyimide containing same

Mutual citation with related applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0119867 filed on September 27, 2019, and all contents disclosed in the documents of the Korean patent application are included as part of this specification.

Technical field

The present invention relates to a polyamic acid composition, a method of preparing the polyamic acid composition, and a polyimide comprising the polyamic acid composition.

In general, a polyimide (PI) resin is a high heat-resistant resin prepared by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, followed by imidization at a high temperature.

Polyimide resin is an insoluble, infusible, ultra-high heat-resistant resin, and is used in the fields of electric, electronic, automobile and aerospace industries due to its high glass transition temperature, excellent heat oxidation resistance, heat resistance, radiation resistance, low temperature characteristics, chemical resistance and electrical properties. It is used in various forms such as films, resins, molded parts, adhesives, and insulators. In particular, as a material for the electronics industry, its use is expanding into interlayer insulating films of semiconductor chips due to its excellent insulation, thermal and chemical stability.

In recent years, the need for improvement of polyimide, development of new compositions, and development of new processing technology is gradually increasing due to the increase in demand for ultra-insulating properties and functionality. In particular, in order to be used in electronic devices of highly integrated multilayer structures, a lower dielectric constant, High glass transition temperature and low thermal expansion characteristics are required, and development of a polyimide satisfying this is required.

In this regard, in the prior art, Van der Waals (Van der Waals) is prepared using an aromatic dianhydride monomer or an aromatic amine monomer containing a fluorine substituent having a small radius, a large electronegativity and a large binding energy between heterogeneous elements. It has been found that polyimide exhibits a low dielectric constant. It is known that the use of 4,4'-(hexafluoroisopropylidene)bis(phthalic acid) (hereinafter referred to as 6FDA), a representative fluorinated monomer, can effectively lower the dielectric constant of polyimide. However, in the case of polyimide using 6FDA, the polyimide produced due to the unique flexible structure of 6FDA has a high coefficient of thermal expansion, resulting in poor heat resistance and poor adhesion. Therefore, it is an important technical task to provide a polyimide that simultaneously satisfies dielectric properties, adhesion, heat resistance, and mechanical properties.

The present invention provides a polyamic acid composition capable of simultaneously realizing low dielectric loss tangent, high adhesion, and mechanical properties at high temperatures, a method for preparing a polyamic acid composition, and a polyimide and a polyimide film including the polyamic acid composition.

In order to solve the above problem,

In one embodiment of the present invention, a first polyamic acid resin containing a fluorine-based monomer; And it provides a polyamic acid composition comprising a second polyamic acid resin containing a hydrophilic monomer, and having a dielectric loss tangent of 0.004 or less measured at a frequency of 1.0 GHz after curing, and an adhesive strength of 0.1 N/cm or more according to ASTM D3359.

In one embodiment, the present invention provides a method for preparing the above-described polyamic acid composition including mixing the first polyamic acid resin and the second polyamic acid resin.

In addition, in one embodiment, the present invention provides a polyimide that is a cured product of the polyamic acid composition.

In addition, in one embodiment, the present invention provides a polyimide film including the polyimide in a film or sheet form.

The present invention provides a polyamic acid composition capable of simultaneously realizing low dielectric constant, high adhesive force, and mechanical properties at high temperature, a method of preparing a polyamic acid composition, and a polyimide and a polyimide film including the polyamic acid composition.

Specifically, the polyamic acid composition comprising the fluorine-based polyamic acid and the hydrophilic polyamic acid of the present invention can achieve high heat resistance and low dielectric constant, low dielectric loss tangent, low thermal expansion, moisture absorption resistance, and high insulation strength by the fluorine-based polyamic acid. In addition, excellent mechanical strength and high interfacial adhesion can be realized by the hydrophilic polyamic acid.

In the present invention, various modifications may be made and various embodiments may be provided, and specific embodiments will be illustrated in the drawings and described in detail in the detailed description.

However, this is not intended to limit the present invention to a specific embodiment, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

In the present invention, terms such as "comprises" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof does not preclude in advance.

In the present invention, "dianhydride (dianhydride)" is intended to include a precursor or derivative thereof, which may not be technically dianhydride, but nevertheless react with diamine to form polyamic acid. This polyamic acid can be converted back to polyimide.

In the present invention, "diamine" is intended to include precursors or derivatives thereof, which may not technically be diamines, but nevertheless will react with dianhydride to form polyamic acid, which polyamic acid is again It can be converted to polyimide.

In the present invention, the "hydrophilic" monomer may mean a compound containing a polar functional group in the molecular structure. The polar functional group may be a functional group exhibiting polarity relative to carbon in addition to the amine group or anhydride group of the diamine monomer or dianhydride monomer. In one example, the hydrophilic monomer of the present application may mean a compound including a carbonyl group, a sulfone group, an oxy group, an ester group, or an ether group in the molecular structure.

Hereinafter, the present invention will be described in detail.

The present invention is a first polyamic acid resin containing a fluorine-based monomer; And a second polyamic acid resin containing a hydrophilic monomer, and having a dielectric loss tangent (loss coefficient) of 0.004 or less measured at a frequency of 1.0 GHz after curing, and an adhesion of 0.1 N/cm or more according to ASTM D3359. do.

Specifically, the polyimide film of the present invention includes a first polyamic acid resin containing a fluorine-based diamine monomer and a fluorine-based dianhydride monomer as a polymerization unit; And by including a second polyamic acid resin comprising a hydrophilic diamine monomer and a hydrophilic dianhydride monomer as a polymerized unit, mechanical properties including low dielectric constant, low dielectric loss tangent (loss coefficient), and high adhesion can be simultaneously realized. That the first polyamic acid resin and the second polyamic acid resin contain the monomer as a polymerized unit means a state in which a polymerization reaction has occurred between each monomer before curing with polyimide.

The dielectric loss tangent measured at a frequency of 1.0 GHz after curing of the polyamic acid composition of the present invention may be 0.004 or less, for example, the upper limit of the dielectric loss tangent is 0.004, 0.0039, 0.0038, 0.0037, 0.0036, 0.0035, 0.0034, 0.0033, 0.0032 Alternatively, it may be 0.003 or less, and the lower limit may be 0.001 or 0.0025 or more. In this case, after curing the polyamic acid composition, the adhesion according to ASTM D3359 may be 0.1 N/cm or more. For example, the lower limit of the adhesion may be 0.11 N/cm, 0.13 N/cm, 0.15 N/cm, or 0.17 N/cm or more, and the upper limit may be 0.25 N/cm or 0.21 N/cm or less. In the present application, by adjusting the physical properties of the polyamic acid composition after curing, the dielectric loss tangent (loss coefficient) can be sufficiently lowered, and desired adhesive properties and mechanical properties can be realized.

The dielectric constant measured at a frequency of 1.0 GHz after curing of the polyamic acid composition of the present invention may be 3.0 or less, for example, the dielectric constant is 2.0 to 3.0, 2.0 to 2.9, 2.0 to 2.8, 2.0 to 2.7, 2.0 to 2.6, 2.0 To 2.5 or 2.5 to 3.0. At this time, after curing the polyamic acid composition, the breaking strength according to ASTM D882 may be 220 to 280 MPa, and the breaking elongation may be 15 to 25%. For example, the breaking strength is 220 to 275 MPa, 220 to 260 MPa, 220 to 255 MPa, 220 to 245 MPa, 220 to 240 MPa, 220 to 230 MPa, 235 to 242 MPa, 242 to 245 MPa or 270 to It may be 280 MPa, and the elongation at break may be 15 to 22%, 15 to 20%, 15 to 18%, 15 to 16%, 16 to 20%, 16 to 18%, or 18 to 20%. In the present application, by adjusting the physical properties after curing of the polyamic acid composition, the dielectric constant may be sufficiently lowered, and desired adhesive properties and mechanical properties may be realized.

In addition, the decomposition temperature of 1% by weight of the polyamic acid composition after curing may be 470°C or higher. For example, the lower limit of the decomposition temperature may be 475°C, 480°C, 485°C, 490°C, 495°C, or 500°C or higher, and the upper limit may be 520°C or 550°C or lower.

The present application may realize desired adhesive properties, mechanical properties, and thermal properties having a high thermal decomposition temperature while sufficiently lowering the dielectric loss tangent (loss coefficient) by adjusting the properties of the polyamic acid composition after curing.

In one example, the dielectric constant and dielectric loss tangent are obtained by curing the polyamic acid composition to prepare a polyimide film. The polyimide film may be measured for a 1 GHz frequency using SPDR (Split Post Dielecric Resonator) technology.

In one example, the adhesive strength is after curing the polyamic acid composition to prepare a polyimide film For the polyimide film, the adhesion to the substrate may be measured using a tensile tester according to ASTM D3359.

In one example, the breaking strength and breaking elongation may be obtained by curing the polyamic acid composition to prepare a polyimide film, and then measuring the polyimide film by the ASTM D882 method.

In one example, the thermal decomposition temperature is heated to 150°C at a rate of 10°C/min in a nitrogen atmosphere by curing the polyamic acid composition to cure the polyimide film using a thermogravimetric analysis equipment, and then isothermal for 30 minutes. Retained to remove moisture. Thereafter, the temperature at which the temperature is raised to 600° C. at a rate of 10° C./min may be measured to measure the temperature at which a weight loss of 1% occurs.

The polyamic acid composition according to the present application may include a first polyamic acid resin and a second polyamic acid resin in an amount of 35 to 75 parts by weight and 25 to 65 parts by weight, respectively. For example, the first polyamic acid resin is 38 to 73 parts by weight, 43 to 68 parts by weight, 48 to 63 parts by weight, 52 to 58 parts by weight, or 58 to 62 parts by weight may be included, and the second polyamic acid resin is 28 to 63 parts by weight, 33 to 58 parts by weight Parts, 38 to 53 parts by weight, 38 to 43 parts by weight, or 42 to 48 parts by weight. The content ratio is more specifically, based on 100 parts by weight of the first polyamic acid resin, the second polyamic acid resin is 30 to 180 parts by weight, 35 to 160 parts by weight, 40 to 145 parts by weight, 45 to 153 parts by weight Parts, 55 to 130 parts by weight, 60 to 100 parts by weight, 63 to 90 parts by weight, 65 to 80 parts by weight, or 70 to 90 parts by weight. The present application may provide a polyamic acid composition capable of simultaneously realizing high adhesive strength and mechanical properties at high temperature with low dielectric constant by adjusting the weight ratio of each resin.

The first polyamic acid resin may be included in the range of 30 to 80% by weight in the total polyamic acid composition. For example, the first polyamic acid resin may be included in the range of 35 to 75% by weight, 40 to 70% by weight, 40 to 60% by weight, 50 to 60% by weight, or 55 to 70% by weight in the total polyamic acid composition. have. In addition, the second polyamic acid resin may be included in the range of 20 to 70% by weight in the total polyamic acid composition. For example, the second polyamic acid resin is 25 to 65% by weight, 30 to 60% by weight, 30 to 50% by weight, 30 to 45% by weight, 40 to 60% by weight, 50 to 65% by weight of the total polyamic acid composition % Or 55 to 70% by weight.

In one example, the fluorine-based monomer may be included in the range of 25 to 75 mol% in the total polyamic acid resin. For example, the fluorine-based monomer is 30 to 70 mol%, 30 to 60 mol%, 30 to 45 mol%, 40 to 70 mol% 40 to 60 mol%, 40 to 55 mol%, 45 in the total polyamic acid resin It may be included in the range of 60 to 60 mol%, 55 to 75 mol%, or 60 to 70 mol%. In addition, the hydrophilic monomer may be included in the range of 25 to 75 mol% in the total polyamic acid resin. For example, the hydrophilic monomer is 30 to 70 mol%, 30 to 60 mol%, 30 to 45 mol%, 40 to 70 mol% 40 to 60 mol%, 40 to 55 mol%, 45 in the total polyamic acid resin It may be included in the range of 60 to 60 mol%, 55 to 75 mol%, or 60 to 70 mol%.

In addition, in one example, the fluorine-based monomer may be included in the range of 70 to 100 mol% in the first polyamic acid resin. For example, the fluorine-based monomer is 70 to 90 mol%, 70 to 80 mol%, 79 to 100 mol%, 80 to 100 mol%, 85 to 100 mol%, or 90 to 100 mol% in the first polyamic acid resin It may be included in the range of, and the first polyamic acid resin may include a hydrophilic monomer or other monomer in addition to the fluorine-based monomer. In addition, the hydrophilic monomer may be included in the range of 70 to 100 mol% in the second polyamic acid resin. For example, the hydrophilic monomer is 70 to 90 mol%, 70 to 80 mol%, 79 to 100 mol%, 80 to 100 mol%, 85 to 100 mol%, or 90 to 100 mol% in the second polyamic acid resin It may be included in the range of, and the second polyamic acid resin may include a fluorine-based monomer or other monomers in addition to the hydrophilic monomer.

The present application describes the weight ratio of the first polyamic acid resin and the second polyamic acid resin in the polyamic acid composition, and the mol% of the fluorine-based monomer and/or the hydrophilic monomer contained in the first polyamic acid resin and/or the second polyamic acid resin. It can be adjusted, and the content ratio of the fluorine-based or hydrophilic monomer in the total resin can be adjusted. The present application can prevent degradation of adhesive properties and mechanical properties at high temperatures caused by the inclusion of a fluorine-based monomer while sufficiently lowering the dielectric constant by adjusting the ratio of each of the above compositions, and the compatibility of two resins with different properties can be achieved. Can be improved.

In the present specification, the fluorine-based diamine monomer and the fluorine-based dianhydride monomer may refer to a monomer including a fluorine atom in a molecular structure. The fluorine atom may be included in various positions and structures in the monomer, and this is not particularly limited. For example, the fluorine-based diamine monomer and the fluorine-based dianhydride monomer may include at least one perfluoroalkyl group in the molecular structure. The perfluoroalkyl group may be, for example, a perfluoromethyl group. In the present invention, by including the fluorine-based monomer as a polymerization unit, unlike conventionally containing fluorine-based particles as an additive, the dielectric constant can be lowered without the additive without problems of compatibility and dispersibility of the particles, thereby improving heat resistance and mechanical properties. Can be implemented together.

The fluorine-based diamine monomer is 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 2,2 -Bis(4-aminophenyl)hexafluoropropane (BAHF), 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 4,4'-bis(4-amino-) It may include at least one selected from the group consisting of 2-trifluoromethylphenoxy)biphenyl and 4,4'-bis(4-amino-2-trifluoromethylphenoxy)phenyl.

The fluorine-based dianhydride monomer is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) and 9,9-bis(trifluoromethyl)-2,3,4,7-c It may include one or more selected from the group consisting of xanthine tetracarboxylic anhydride.

In one example, the fluorine-based diamine monomer and the fluorine-based dianhydride monomer may have two or more benzene rings. In one example, the fluorine-based diamine monomer may have, for example, a perfluoroalkyl group by substituting hydrogen of the benzene ring. In addition, in one example, the fluorine-based diamine monomer may have the aforementioned perfluoroalkyl group in an alkylene group connecting two benzene rings. In addition, in one example, the fluorine-based dianhydride monomer may have a perfluoroalkyl group by substituting hydrogen of the benzene ring, and in one example, the perfluoroalkyl group described above in the alkylene group connecting the two benzene rings Can have.

In the specific example of the present application, as described above, the hydrophilic monomer may mean a compound including a polar functional group in the molecular structure. The polar functional group may be a functional group exhibiting polarity relative to carbon in addition to the amine group or anhydride group of the diamine monomer or dianhydride monomer. In one example, the hydrophilic diamine monomer of the present application may be a diamine monomer including a carbonyl group, a sulfone group, an oxy group, an ester group, or an ether group in a molecular structure, and the hydrophilic dianhydride monomer is a carbonyl group, a sulfone group, It may be a dianhydride monomer containing an oxy group, an ester group or an ether group.

The hydrophilic diamine monomer is 4,4'-diaminodiphenylether (ODA), 2,2-bis(4,-(4-aminophenoxy)phenyl)propane (BAPP), 4,4-diaminobenzanyl Lead (4,4-DABA), 3,3-diaminobenzanilide (3,3-DABA), 1,3-bis (4-aminophenoxy) benzene (TPE-R) and 1,4-bis It may include one or more selected from the group consisting of (4-aminophenoxy)benzene (TPE-Q).

The hydrophilic dianhydride monomer is 4,4'-oxydiphthalic dianhydride (ODPA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), 3,3 ,4,4-benzophenonetetracarboxylic dianhydride (BTDA), paraphenylene bistrimethyltate anhydride (TAHQ) may be one containing at least one selected from the group consisting of.

In one specific example, the polyamic acid composition may contain 15 to 40% by weight of solid content based on the total weight. In the present invention, by controlling the solid content of the polyamic acid composition, it is possible to prevent an increase in manufacturing cost and process time required to remove a large amount of solvent in the curing process while controlling viscosity increase.

The polyamic acid composition of the present invention may be a composition having low viscosity properties. The polyamic acid composition of the present invention may have a viscosity of 10,000 cP or less and 9,000 cP or less as measured under conditions of a ^{temperature of 23° C. and a shear rate of 1 s −1.} The lower limit is not particularly limited, but may be 500 cP or more or 1000 cP or more. The viscosity may be measured using, for example, Haake's Rheostress 600, and may be measured under conditions of a shear rate of 1/s, a temperature of 23° C., and a 1 mm plate gap. The present invention provides a precursor composition having excellent processability by adjusting the viscosity range, so that a film or substrate having desired physical properties can be formed when forming a film or substrate.

In one embodiment, the polyamic acid composition of the present invention has a weight average molecular weight after curing of 10,000 to 100,000 g/mol, 15,000 to 80,000 g/mol, 18,000 to 70,000 g/mol, 20,000 to 60,000 g/mol, 25,000 to 55,000 g /mol or 30,000 to 50,000 g/mol. In the present invention, the term weight average molecular weight refers to a value converted to standard polystyrene measured by GPC (Gel permeation Chromatograph).

In the present invention, the polyamic acid composition may include an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent in which polyamic acid can be dissolved, but may be an aprotic polar solvent as an example.

The aprotic polar solvent is, for example, N,N'-dimethylformamide (DMF), N,N'-diethylformamide (DEF), N,N'-dimethylacetamide (DMAc), dimethylpropane. Amide solvents such as amide (DMPA), phenolic solvents such as p-chlorophenol and o-chlorophenol, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL) and Diglyme, etc. These may be mentioned, and these may be used alone or in combination of two or more.

According to the present invention, the solubility of the polyamic acid may be adjusted by using auxiliary solvents such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water in some cases.

In one example, the organic solvent may be, for example, N-methyl-pyrrolidone (NMP).

On the other hand, the polyamic acid composition of the present invention may contain a filler for the purpose of improving various properties of the film such as sliding property, thermal conductivity, conductivity, corona resistance, and loop hardness. The filler to be added is not particularly limited, and examples thereof include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.

The particle diameter 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. The average particle diameter may be 0.05 to 20 µm, 0.1 to 10 µm, 0.1 to 5 µm, or 0.1 to 3 µm. In the present specification, unless otherwise specified, the average particle diameter may be an average particle diameter measured according to D50 particle size analysis.

According to the present invention, by adjusting the particle diameter range, it is possible to sufficiently maintain the modification effect and not to deteriorate the mechanical properties without impairing the surface properties.

In addition, the present invention is not particularly limited to the amount of the filler added, and can be determined by the film properties to be modified, the filler particle size, and the like. In the present invention, the amount of the filler added may be 0.01 to 10 parts by weight, 0.01 to 5 parts by weight, or 0.02 to 1 part by weight based on 100 parts by weight of the polyimide resin. According to the present invention, by adjusting the content, the mechanical properties of the film may not be impaired while sufficiently maintaining the modifying effect of the filler.

The method of adding the filler is not particularly limited, and a method known in the same industry may be used.

The polyamic acid composition comprising the fluorine-based polyamic acid and the hydrophilic polyamic acid of the present invention can realize a low dielectric constant, low dielectric loss tangent, low thermal expansion, moisture absorption resistance, and high insulation strength with high heat resistance by the fluorine-based polyamic acid, Excellent mechanical strength and high interfacial adhesion can be realized by the hydrophilic polyamic acid.

In addition, the present invention relates to a method of manufacturing a polyamic acid composition, and the manufacturing method may be a method of manufacturing the above-described polyamic acid composition.

Specifically, the present invention provides a method for preparing a polyamic acid composition comprising the step of mixing a first polyamic acid resin and a second polyamic acid resin.

In one example, the method for preparing a polyamic acid composition of the present invention is to prepare a first polyamic acid resin by polymerizing a fluorine-based diamine monomer and a fluorine-based dianhydride monomer in a molar ratio of 1:0.8 to 1:2 in a first organic solvent. The step of doing; Preparing a second polyamic acid resin by polymerizing a hydrophilic diamine monomer and a hydrophilic dianhydride monomer in a molar ratio of 1:0.8 to 1:2 in a second organic solvent; And mixing the first polyamic acid resin and the second polyamic acid resin. The order of preparing the first polyamic acid resin and the second polyamic acid resin is not particularly limited, and the first polyamic acid resin may be prepared after the second polyamic acid resin is first prepared.

The step of mixing the first polyamic acid resin and the second polyamic acid resin may be performed at a high temperature of 50 to 80°C. For example, the step of mixing the first polyamic acid resin and the second polyamic acid resin may be performed at 50 to 70°C, 50 to 60°C, 60 to 80°C, 60 to 70°C, or 70 to 80°C. have.

The present invention can realize a low dielectric constant, low dielectric loss tangent, low thermal expansion, moisture absorption resistance, and high insulation strength with high heat resistance by means of a fluorine-based polyamic acid (first polyamic acid resin) through the preparation of the polyamic acid composition. , Excellent mechanical strength and high interfacial adhesion can be realized by the hydrophilic polyamic acid (second polyamic acid resin).

The first organic solvent and the second organic solvent are not particularly limited as long as they are organic solvents in which polyamic acid can be dissolved independently, but may be an aprotic polar solvent as an example.

In addition, the present invention provides a polyimide that is a cured product of the polyamic acid composition. In one example, the polyimide may be a cured product of the above-described polyamic acid composition or a precursor composition prepared by the method.

In addition, the present invention provides a polyimide film comprising the polyimide in the form of a film or sheet.

In one example, the present application relates to a method of manufacturing a polyimide film. The present invention comprises the steps of preparing a gel film by forming a film of the polyamic acid composition on a support and drying it; And it may provide a method for producing a polyimide film comprising the step of curing the gel film.

Specifically, for a method of imidizing the polyamic acid composition to prepare a polyimide film, a conventionally known method may be used.

As a specific method of such imidization, a thermal imidation method, a chemical imidization method, or a composite imidization method in which the thermal imidation method and the chemical imidization method are used in combination may be exemplified.

Hereinafter, the present invention will be described in more detail through examples according to the present invention, but the scope of the present invention is not limited by the examples presented below.

<실시예 1><Example 1>

폴리아믹산 조성물의 제조Preparation of polyamic acid composition

N-methyl-pyrrolidone (NMP) was introduced into a 500 ml reactor equipped with a stirrer and a nitrogen injection/discharging pipe, and the temperature of the reactor was set to 30°C. As a fluorine-based diamine monomer of the first polyamic acid resin. 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6- FDA) was added and completely dissolved, and then the temperature was raised to 40°C and stirring was continued for 120 minutes while heating. Subsequently, stirring was continued for 2 hours while heating by raising the temperature to 80° C. in a nitrogen atmosphere, and then a first polyamic acid resin was prepared. In addition, 2,2-bis(4,-(4-aminophenoxy)phenyl)propane (BAPP) as a hydrophilic diamine monomer of the second polyamic acid resin and 3,3,4,4-benzo as a hydrophilic dianhydride monomer. After phenonetetracarboxylic dianhydride (BTDA) was added and completely dissolved, the temperature was raised to 40°C and stirring was continued for 120 minutes while heating. Subsequently, stirring was continued for 2 hours while heating by raising the temperature to 80° C. in a nitrogen atmosphere, and then a second polyamic acid resin was prepared. The first polyamic acid resin and the second polyamic acid resin were mixed in a weight ratio of Table 1 to prepare a polyamic acid composition.

폴리이미드 필름의 제조Preparation of polyimide film

Air bubbles were removed from the prepared polyimide precursor composition through high-speed rotation of 1,500 rpm or more. Thereafter, the defoamed polyimide precursor composition was applied to the glass substrate using a spin coater. Thereafter, a gel film was prepared by drying in a nitrogen atmosphere and at a temperature of 120° C. for 30 minutes, and the gel film was heated to 450° C. at a rate of 2° C./min, heat-treated at 450° C. for 60 minutes, and then until 30° C. It cooled at a rate of 2° C./min to obtain a polyimide film. Thereafter, the polyimide film was peeled off from the glass substrate by dipping in distilled water. The thickness of the prepared polyimide film was 15 µm. The thickness of the prepared polyimide film was measured using an Anritsu's Electric Film thickness tester.

<실시예 2 내지 4 및 비교예 1 내지 7><Examples 2 to 4 and Comparative Examples 1 to 7>

In Example 1, a polyamic acid composition and a polyimide film of Examples 2 to 4 and Comparative Examples 1 to 7 were prepared in the same manner as in Example 1, except that the monomer and the content ratio thereof were changed as shown in Table 1 below. I did.

실험예 1: 두께 측정Experimental Example 1: Thickness measurement

The thickness of the prepared polyimide film was measured using an Anritsu's Electric Film thickness tester. The results are shown in Table 2 below.

실험예 2: 유전정접(손실계수) 측정Experimental Example 2: Dielectric loss tangent (loss coefficient) measurement

The dielectric loss tangent at 1 GHz of the polyimide films prepared in the above Examples and Comparative Examples was measured using an SPDR meter of Keysight. As a result, the measured dielectric loss tangent values are shown in Table 2 below.

The dielectric loss tangent can be evaluated as excellent below 0.0050 and very good below 0.0040 or 0.0036.

실험예 3: 접착력 측정Experimental Example 3: Measurement of adhesion

For the polyimide films prepared in Examples and Comparative Examples, adhesion to the substrate was measured using a tensile tester (Instron5564) according to ASTM D3359, and the results are shown in Table 2 below.

Specifically, with respect to the polyimide film obtained in Examples, before peeling the polyimide film from the substrate, cut into 10 mm width using a cutter knife, under conditions of 23°C and 55%RH, at a tensile speed of 50 m/min. When peeled off by 50 mm, the average value of the 180° peel strength was measured.

Claims

A first polyamic acid resin containing a fluorine-based monomer; And

Including a second polyamic acid resin containing a hydrophilic monomer,

A polyamic acid composition having a dielectric loss tangent of 0.004 or less, measured at a frequency of 1.0 GHz after curing, and an adhesive strength of 0.1 N/cm or more according to ASTM D3359.
The method of claim 1,

A polyamic acid composition comprising the first polyamic acid resin and the second polyamic acid resin in a ratio of 35 to 75 parts by weight and 25 to 65 parts by weight, respectively.
The method of claim 1,

The first polyamic acid resin is a polyamic acid composition contained in the range of 30 to 80% by weight in the total polyamic acid composition.
The method of claim 1,

The first polyamic acid resin is a polyamic acid composition contained in the range of 30 to 80% by weight in the total polyamic acid composition.
The method of claim 1,

In the total polyamic acid resin, the fluorine-based monomer is a polyamic acid composition contained in the range of 25 to 75 mol%.
The method of claim 1,

In the total polyamic acid resin, the hydrophilic monomer is a polyamic acid composition contained in the range of 25 to 75 mol%.
The method of claim 1,

The first polyamic acid resin is a polyamic acid composition comprising a fluorine-based diamine monomer and a fluorine-based dianhydride monomer.
The method of claim 1,

The fluorine-based monomer is a polyamic acid composition contained in the range of 70 to 100 mol% in the first polyamic acid resin.
The method of claim 7,

The fluorine-based diamine monomer is 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 2,2- Bis(4-aminophenyl)hexafluoropropane (BAHF), 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 4,4'-bis(4-amino-2) Polyamic acid composition comprising at least one selected from the group consisting of -trifluoromethylphenoxy)biphenyl and 4,4'-bis(4-amino-2-trifluoromethylphenoxy)phenyl.
The method of claim 7,

The fluorine-based dianhydride monomer is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) and 9,9-bis(trifluoromethyl)-2,3,4,7-xanthine Polyamic acid composition comprising at least one selected from the group consisting of tetracarboxylic anhydride.
The method of claim 1,

The second polyamic acid resin is a polyamic acid composition comprising a hydrophilic diamine monomer and a hydrophilic dianhydride monomer.
The method of claim 1,

The hydrophilic monomer is a polyamic acid composition contained within the range of 70 to 100 mol% in the second polyamic acid resin.
The method of claim 11,

Hydrophilic diamine monomers are 4,4'-diaminodiphenylether (ODA), 2,2-bis(4,-(4-aminophenoxy)phenyl)propane (BAPP), 4,4-diaminobenzanilide (4,4-DABA), 3,3-diaminobenzanilide (3,3-DABA), 1,3-bis (4-aminophenoxy) benzene (TPE-R) and 1,4-bis ( A polyamic acid composition comprising at least one selected from the group consisting of 4-aminophenoxy)benzene (TPE-Q).
The method of claim 11,

Hydrophilic dianhydride monomers include 4,4'-oxydiphthalic dianhydride (ODPA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), 3,3, A polyamic acid composition comprising at least one selected from the group consisting of 4,4-benzophenonetetracarboxylic dianhydride (BTDA) and paraphenylene bistrimethyltate anhydride (TAHQ).
A method for producing a polyamic acid composition according to claim 1, comprising mixing the first polyamic acid resin and the second polyamic acid resin.
The method of claim 15,

The step of mixing the first polyamic acid resin and the second polyamic acid resin is carried out at 50 to 80 ℃ method for producing a polyamic acid composition.
A polyimide that is a cured product of the polyamic acid composition according to claim 1.
A polyimide film comprising the polyimide according to claim 17 in the form of a film or sheet.