KR102249475B1 - manufacturing method of polyamic acid composition comprising novel dicarbonyl compounds, polyamic acid composition, manufacturing method of polyamide-imide film using the polyamic acid composition and polyamide-imide film using the same - Google Patents

Abstract

The present invention relates to a method for preparing a polyamic acid composition, a polyamic acid composition, a method for preparing a polyamide-imide film using the same, and a polyamide-imide film prepared through the method, and more precisely, a novel dicarbonyl Method for producing a polyamic acid composition having excellent optical properties, high glass transition temperature and low coefficient of thermal expansion through the application of a compound, a dicarbonyl compound containing an aromatic and alicyclic ring, a polyamic acid composition, and a polyamide-imide using the same It relates to a method of manufacturing a film and a polyamide-imide film manufactured through the manufacturing method.

Description

A method for preparing a polyamic acid composition containing a novel dicarbonyl compound, a polyamic acid composition, a method for preparing a polyamide-imide film using the same, and a polyamide-imide film prepared through the method. {manufacturing method of polyamic acid composition comprising novel dicarbonyl compounds, polyamic acid composition, manufacturing method of polyamide-imide film using the polyamic acid composition and polyamide-imide film using the same}

The present invention relates to a method for preparing a polyamic acid composition, a polyamic acid composition, a method for preparing a polyamide-imide film using the same, and a polyamide-imide film prepared through the method, and more precisely, a novel dicarbonyl Method for producing a polyamic acid composition having excellent optical properties, high glass transition temperature and low coefficient of thermal expansion through the application of a compound, a dicarbonyl compound containing an aromatic and alicyclic ring, a polyamic acid composition, and a polyamide-imide using the same It relates to a method of manufacturing a film and a polyamide-imide film manufactured through the manufacturing method.

The substrate material of a flexible display, which is attracting attention as a next-generation display device, should be light, unbreakable, bendable, and should have no shape restrictions due to easy processability. A polymer material that is lighter than a glass substrate used as a material for a display substrate, is not broken, and is easy to manufacture, and thus capable of manufacturing a thin film, is attracting attention as the most suitable material for realizing a flexible display.

Conventional flexible devices generally use an organic light emitting diode (OLED) display, and a TFT process having a high process temperature (300 to 500°C) is used. Polymeric materials that can withstand these high process temperatures are extremely limited. Therefore, in recent years, the use of polyimide resins having excellent heat resistance and dimensional stability as candidate plastic substrates for transparent flexible displays has been increasing.

For the application of a flexible display substrate, excellent heat resistance and dimensional stability, as well as excellent transmittance, low refractive index, and phase delay characteristics for securing a display viewing angle are essential. However, the color of a typical polyimide is brown or yellow, and this is mainly due to the charge transfer complex (CTC) caused by intra-molecular or inter-molecular interactions of the polyimide. .

In order to impart excellent optical properties to the brown or yellow polyimide as described above, a linkage group (- COO-, -O-, SO ₂ -, -CO-) can be introduced to minimize the formation of electron transfer complexes due to intramolecular or intermolecular interactions, thereby providing optical properties.

However, the polyimide improved by the above method has a disadvantage in that the optical properties are superior to that of the conventional polyimide, but the thermal and mechanical properties are low.This is a flexible material introduced in the main chain of the polyimide to improve the optical properties. This is because a group having a large structure or electronegativity deteriorates the thermal and mechanical properties.

In order to solve the above problems, a polyamide-imide structure including an amide group in the polyimide main chain has been proposed, which has high thermal stability and mechanical properties due to the synergistic effect of polyamide and polyimide. Compared with, it has higher thermal properties due to interchain hydrogen bonds, and is known to have good solubility in amide-based polar solvents. Based on these advantages, polyamide-imide is used in various electronic material applications.

The present invention is to solve the above problems, the specific purpose of which is as follows.

In the present invention, by applying a dicarbonyl compound having a specific structure including an aromatic and alicyclic ring, including a novel dicarbonyl compound, to invent a high heat-resistant polyamide-imide having excellent optical properties, a glass transition temperature, and a low coefficient of thermal expansion. do.

According to the present invention, one selected from the group consisting of a dicarbonyl compound, a diamine compound, an acid dianhydride compound, and a combination thereof is included, and the dicarbonyl compound is represented by the following Chemical Formulas 1, 2, 3, 4, It provides a polyamic acid comprising one compound selected from the group consisting of Chemical Formula 5, Chemical Formula 6, Chemical Formula 7, and combinations thereof.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

The diamine compound may include one selected from the group consisting of a fluorinated aromatic diamine monomer, a non-fluorinated aromatic dimine monomer, and a combination thereof.

The diamine compound is 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p-methylenedianiline (pMDA), m-methylenedianiline (mMDA), p-cyclohexanediamine (pCHDA), p -Xylylenediamine (pXDA), m-xylylenediamine (mXDA), m-cyclohexanediamine (mXDA), 4,4'-diaminodiphenylsulfone (DDS), 2,2-bis[4-(4) -Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoro propane (BAFP), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane (BAMF), 2,2'-bis(3-aminophenyl)-hexafluoropropane (BAPF), 3,5-diamino Benzotrifluoride (DABF), 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (BTDE), 2,2-bis (3-amino-4-hydroxy) It may include one selected from the group consisting of phenyl) hexafluoropropane (BAHH) and combinations thereof.

The acid dianhydride compound may include one selected from the group consisting of a fluorinated aromatic acid dianhydride, a non-fluorinated aromatic acid dianhydride, and a combination thereof.

The fluorinated aromatic acid dianhydride is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 6FDA)), 4,4'-(4,4'- One selected from the group consisting of hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride)(4,4'-(4,4'-Hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride, 6-FDPDA) and combinations thereof It may include.

The non-fluorinated aromatic acid dianhydride is pyromellitic dianhydride, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3'4). ,4'-biphenyltetracarboxylic acid dianhydride, BPDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3',4,4'-benzophenonetetracarboxylic dianhydride, BTDA), 4,4' -Oxydiphthalic anhydride (4,4′-oxydiphthalic anhydride, ODPA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane anhydride (2,2-Bis[4-(3 ,4-dicarboxyphenoxy) phenyl]propane dianhydride, BPADA), 3,3',4,4'-diphenyl sulfone tetracarboxylic anhydride, ethylene glycol bis(4-trimelitate anhydride) (3,3',4 ,4'-Diphenyl sufone tetracarboxylic dianhydride, DSDA), cyclobutanetetracarboxylic dianhydride (CBDA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4- Tetrahydronaphthalene-1,2-dicarboxylic acid dihydrate (TDA), pyromellitic acid dihydrate (PMDA), benzophenone tetracarboxylic acid dihydride (BTDA), oxydiphthalic dihydride (ODPA), bicyclo [2.2.2] Oct-7ene-2,3,5,6-tetracarboxylic acid dihydride (BTDA), 3,3',4,4-biphenyretracarboxylic acid dihydride (s-BPDA ) And may include one selected from the group consisting of a combination thereof.

Any one of the polyamic acid may have a viscosity of 1,000 to 10,000 cp at 23°C.

According to the present invention, a polyamide-imide film comprising any one of the above polyamic acids is provided.

When the polyamide-imide film has a thickness of 10 to 15 μm, a yellow index (YI) of 10 or less, a coefficient of thermal expansion (CTE) of 20 ppm/℃ or less at 100 to 250°C, glass transition Transmittance at a temperature of 360° C. or higher and a wavelength of 550 nm may be 85% or higher.

According to the present invention, preparing a mixture by mixing a diamine compound and a solvent; And preparing a polyamic acid solution by adding and polymerizing a dicarbonyl compound and an acid dianhydride to the mixture, wherein the dicarbonyl compound includes the following Chemical Formulas 1, 2, 3, 4, and 5 , Formula 6, Formula 7, and a method for producing a polyamic acid, characterized in that it comprises one compound selected from the group consisting of a combination thereof.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In the step of preparing the mixture, the solvent is selected from the group consisting of a polar solvent, a low boiling point solvent, a low absorption solvent, a spreading solvent, and a combination thereof, and the polar solvent is m-cresol, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), diethyl acetate (DEA), 3-methoxy-N,N-dimethyl propanamide (DMPA) ), N,N-dimethyl propinoamide (DPA), N,N-dimethyllactamide (DML), and combinations thereof, and the low boiling point solvent is tetrahydrofuran (THF), trichloromethane (Chloroform, TCM) and a combination thereof, and the low absorption solvent is gamma-butyrolactone (GBL), 3-methoxy-N,N-dimethylpropanamide (DMPA), N,N- It is selected from the group consisting of dimethyl propinoamide (DPA), N,N-dimethyllactamide (DML), N-methyl-2-pyrrolidone (NMP), and combinations thereof, and the spreadable solvent is ethylene glycol mono One selected from the group consisting of butyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene glycol diethyl ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and combinations thereof Can be

A first low-absorption solvent mixture containing 30 to 70 mol% of gamma butyrolactone and 30 to 70 mol% of N-methyl-2-pyrrolidone as the low-absorption solvent, 30 to 70 mol% of gamma-butyrolactone, and A second low-absorption solvent mixture comprising 30 to 70 mole percent of N,N-dimethyl propinoamide, 30 to 70 mole percent gamma-butyrolactone and 30 to 70 moles of 3-methoxy-N,N-dimethyl propanamide The third low-absorption solvent mixture comprising %, 100 mol% of N,N-dimethyl propinoamide or 100 mol% of 3-methoxy-N,N-dimethyl propanamide may be included.

The solvent is ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene glycol diethyl ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and combinations thereof It may include one spreading solvent selected from the group consisting of.

In the step of preparing a polyamic acid solution, the dicarbonyl compound may contain 20 to 100 mol% based on the diamine compound.

In the step of preparing the mixture, the mixing may be performed for 30 to 60 minutes in a nitrogen atmosphere and at a temperature of 25 to 30°C.

In the step of preparing the polyamic acid solution, one selected from the group consisting of a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, a leveling agent, and a combination thereof may be further added to the mixture.

In the step of preparing a polyamic acid solution, the polymerization may be performed at a temperature of 10 to 70° C. for 6 to 48 hours.

In the step of preparing a polyamic acid solution, the diamine compound, dicarbonyl compound, and acid dianhydride constitute a solid content of the polyamic acid solution, and the content of the solid content may be 10 to 40% by weight based on the polyamic acid solution. .

In the step of preparing a polyamic acid solution, the acid dianhydride compound and the dicarbonyl compound may contain 100 to 105 mol% based on the diamine compound.

According to the present invention, in any one of the polyamic acid manufacturing method, the steps of forming a transparent coating layer by coating the polyamic acid solution on a substrate; And heat-treating the transparent coating layer, wherein the heat treatment is performed for 30 to 120 minutes at a temperature of 100 to 450° C. in a nitrogen atmosphere.

According to the present invention, a polyamide-imide film having transparent and excellent mechanical properties, high heat resistance and low coefficient of thermal expansion that can be usefully used for a cover substrate for a flexible display, an optical film, a touch panel substrate material, a semiconductor material, etc. Can provide.

The effects of the present invention are not limited to the above-mentioned effects. It should be understood that the effects of the present invention include all effects that can be inferred from the following description.

The above objects, other objects, features, and advantages of the present invention will be easily understood through the following preferred embodiments related to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In describing each drawing, similar reference numerals have been used for similar elements. In the accompanying drawings, the dimensions of the structures are shown to be enlarged than actual for clarity of the present invention. Terms such as first and second may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element. Singular expressions include plural expressions unless the context clearly indicates otherwise.

In the present specification, terms such as "comprise" 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 the possibility of being added. Further, when a part such as a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where the other part is "directly above", but also the case where there is another part in the middle. Conversely, when a part such as a layer, a film, a region, or a plate is said to be "under" another part, this includes not only the case where the other part is "directly below" but also the case where there is another part in the middle.

Unless otherwise specified, all numbers, values, and/or expressions expressing quantities of ingredients, reaction conditions, polymer compositions, and formulations used herein are those that occur in obtaining these values, among other things essentially. Since they are approximations that reflect the various uncertainties of the measurement, it should be understood as being modified in all cases by the term "about". In addition, when numerical ranges are disclosed herein, such ranges are continuous and, unless otherwise indicated, include all values from the minimum value of this range to the maximum value including the maximum value. Furthermore, where this range refers to an integer, all integers from the minimum to the maximum value including the maximum value are included, unless otherwise indicated.

In the present specification, where a range is described for a variable, it will be understood that the variable includes all values within the stated range, including the stated endpoints of the range. For example, a range of “5 to 10” includes values of 5, 6, 7, 8, 9, and 10, as well as any subranges such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc. Inclusive, and it will be understood to include any values between integers that are reasonable in the scope of the stated range, such as 5.5, 6.5, 7.5, 5.5 to 8.5 and 6.5 to 9, and the like. Also, for example, the range of "10% to 30%" is 10% to 15%, 12% to 10%, 11%, 12%, 13%, etc., as well as all integers including up to 30%. It will be understood to include any subranges, such as 18%, 20% to 30%, and the like, and include any values between reasonable integers within the scope of the stated range, such as 10.5%, 15.5%, 25.5%, and the like.

The present invention relates to a method for preparing a polyamic acid composition containing a novel dicarbonyl compound, a polyamic acid composition, a method for preparing a polyamide-imide film using the same, and a polyamide-imide film prepared through the method As described above, the polyamic acid composition and a polyamide-imide film including the same, and a method of preparing a polyamic acid composition and a polyamide-imide film will be described.

Polyamic acid composition

The polyamic acid of the present invention includes one selected from the group consisting of a dicarbonyl compound, a diamine compound, an acid dianhydride compound, and a combination thereof, and the dicarbonyl compound is represented by the following Chemical Formulas 1, 2, 3, and 4 , Formula 5, Formula 6, Formula 7 and one compound selected from the group consisting of a combination thereof; characterized by including.

Each component constituting the polyamic acid will be described.

Dicarbonyl compound

The dicarbonyl compound of the present invention is a novel dicarbonyl compound, 4,4'-{2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-bis (Iminocarbonyl)}bis(benzoyl chloride) (BTBC), benzophenone-4,4'-dicarboxyl chloride (BPDC), 2,2'-bis(trifluoromethyl)-[1,1 '-Biphenyl]-4,4'-dicarboxyl chloride (TFBC), 4,4'-[4,4'-(hexafluoroisopropidine) diphthalimide]bis(benzoyl chloride) (BHIC ), [2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-bis(imide)]bis(phthalyl chloride) (BTIC), 4, 4'-[1,2,4,5-cyclohexanetetracarboxylimide]bis(benzoyl chloride) (BHCC), 1,4-cyclohexyl-bis(imide)]bis(phthalyl chloride) ( It is characterized by including one selected from the group consisting of CHIC) and combinations thereof.

The dicarbonyl compound is represented by the following formulas 1, 2, 3, 4, 5, 6, and 7.

[Formula 1]

4,4'-{2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-bis(iminocarbonyl)}bis(benzoyl chloride) (BTBC)

[Formula 2]

Benzophenone-4,4'-dicarboxyl chloride (BPDC)

[Formula 3]

2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-dicarboxyl chloride (TFBC)

[Formula 4]

4,4'-[4,4'-(hexafluoroisopropidine) diphthalimide]bis(benzoyl chloride) (BHIC)

[Formula 5]

[2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-bis(imide)]bis (phthalyl chloride) (BTIC)

[Formula 6]

4,4'-[1,2,4,5-cyclohexanetetracarboxylimide]bis(benzoyl chloride) (BHCC)

[Formula 7]

1,4-cyclohexyl-bis(imide)]bis(phthalyl chloride) (CHIC)

In the present invention, the dicarbonyl compound of Formula 1 is obtained through a specific synthesis process, and the synthesis process of Formula 1 will be described in the following Preparation Example.

Diamine compound

The diamine compound of the present invention includes one selected from the group consisting of a fluorinated aromatic diamine monomer, a non-fluorinated aromatic diamine monomer, and a combination thereof.

The fluorinated aromatic diamine monomer is 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]- 1,1,1,3,3,3-hexafluoro propane (BAFP), 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane (BAMF), 2,2'-bis ( 3-aminophenyl)-hexafluoropropane (BAPF), 3,5-diaminobenzotrifluoride (DABF), 2,2'-bis(trifluoromethyl)-4,4'-diaminodi It is preferable to use one selected from the group consisting of phenyl ether (BTDE), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHH), and combinations thereof.

The non-fluorinated aromatic diamine monomer is 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p -Methylenedianiline (pMDA), m-methylenedianiline (mMDA), p-cyclohexanediamine (pCHDA), p-xylylenediamine (pXDA), m-xylylenediamine (mXDA), m-cyclohexanediamine ( mXDA), 4,4'-diaminodiphenylsulfone (DDS), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and combinations thereof desirable.

Acid dianhydride compounds

The acid dianhydride compound of the present invention is characterized by including one selected from the group consisting of fluorinated aromatic acid dianhydrides, non-fluorinated aromatic acid dianhydrides, and combinations thereof.

The fluorinated aromatic acid dianhydride is an aromatic acid dianhydride into which a fluorine substituent is introduced, for example, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 6FDA )), 4,4'-(4,4'-hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride)(4,4'-(4,4'-Hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride, 6-FDPDA) and combinations thereof.

The non-fluorinated aromatic acid dianhydride is an aromatic acid dianhydride to which a fluorine substituent is not introduced, for example, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxyl Acid dianhydride (3,3'4,4'-biphenyltetracarboxylic acid dianhydride, BPDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3',4,4'-benzophenonetetracarboxylic dianhydride, BTDA), 4,4'-oxydiphthalic anhydride (ODPA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane anhydride (2 ,2-Bis[4-(3,4-dicarboxyphenoxy) phenyl]propane dianhydride, BPADA), 3,3',4,4'-diphenyl sulfone tetracarboxylic anhydride, ethylene glycol bis(4-trimelitate Anhydride) (3,3',4,4'-Diphenyl sufone tetracarboxylic dianhydride, DSDA), cyclobutanetetracarboxylic dianhydride (CBDA), 4-(2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dihydrate (TDA), pyromellitic acid dihydride (PMDA), benzophenone tetracarboxylic acid dihydrate (BTDA), oxydiph Talic dihydrate (ODPA), bicyclo[2.2.2]oct-7ene-2,3,5,6-tetracarboxylic acid dihydride (BTDA), 3,3',4,4-bifeniretra It may be one selected from the group consisting of carboxylic acid dihydride (s-BPDA) and combinations thereof.

The acid dianhydride of the present invention is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(4,4'-hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride ), cyclobutanetetracarboxylic acid dihydride, 3,3',4,4'-biphenyltetracarboxylic acid dihydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6 -Tetracarboxylic acid dihydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dihydride, fatigue It is preferable to include one selected from the group consisting of melitic acid dihydride, benzophenone tetracarboxylic acid dihydride, oxydiphthalic dihydride, and combinations thereof.

The viscosity of the polyamic acid of the present invention including the dicarbonyl compound, diamine compound and acid dianhydride compound is 1,000 to 10,000 cp at 23°C. At this time, when the viscosity of the polyamic acid is less than 1,000 cp, it may be difficult to obtain an appropriate level of film thickness when manufacturing a polyamide-imide film, and when it is more than 10,000 cp, uniform coating and effective solvent removal cannot be achieved. Occurs.

Method for preparing polyamic acid composition

In the description of the method for preparing the polyamic acid composition of the present invention, a matter that overlaps with the characteristics of the composition previously described in the configuration of the polyamic acid composition will be partially excluded and described.

In order to obtain the polyamide-imide film of the present invention, a polyamic acid (this is the same expression as a polyamic acid solution) is prepared. Specifically, the method for preparing a polyamic acid includes preparing a mixture by mixing a diamine compound and a solvent; And preparing a polyamic acid solution by adding and polymerizing a dicarbonyl compound and an acid dianhydride compound to the mixture.

Steps of preparing the mixture

In this step, a diamine compound is added and mixed in a prepared solvent to form a mixture.

The diamine compound includes one selected from the group consisting of a fluorinated aromatic diamine monomer, a non-fluorinated aromatic diamine monomer, and a combination thereof.

The fluorinated aromatic diamine monomer is 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]- It is preferable to use one selected from the group consisting of 1,1,1,3,3,3-hexafluoro propane (BAFP) and combinations thereof.

The non-fluorinated aromatic diamine monomer is 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p -Methylenedianiline (pMDA), m-methylenedianiline (mMDA), p-cyclohexanediamine (pCHDA), p-xylylenediamine (pXDA), m-xylylenediamine (mXDA), m-cyclohexanediamine ( mXDA), 4,4'-diaminodiphenylsulfone (DDS), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and combinations thereof desirable.

The mixing is carried out for 30 to 60 minutes at a temperature of 25 to 30 ℃ under a nitrogen atmosphere.

The solvent into which the diamine compound is added may be selected from the group consisting of a polar solvent, a low boiling point solvent, a low absorption solvent, a spreading solvent, and a combination thereof. A more specific example will be described below. (However, in the case of a solvent including two or more characteristics of the solvents listed below, it may be repeatedly described.)

The polar solvent is m-cresol, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), diethyl acetate ( DEA), 3-methoxy-N,N-dimethyl propanamide (DMPA), N,N-dimethyl propinoamide (DPA), N,N-dimethyllactamide (DML) and combinations thereof I can.

The low boiling point solvent may be selected from the group consisting of tetrahydrofuran (THF), trichloromethane (chloroform, TCM), and combinations thereof. The low boiling point solvent has high volatility, so it is easy to remove the solvent during film production, and this makes it possible to improve the physical properties of the produced film.

The low-absorption solvent is gamma-butyrolactone (GBL), 3-methoxy-N,N-dimethylpropanamide (DMPA), N,N-dimethyl propinoamide (DPA), N,N-dimethyllactamide ( DML), N-methyl-2-pyrrolidone (NMP), and combinations thereof.

The low-absorption solvent plays an important role in improving the clouding phenomenon by minimizing water absorption during film production.In order to improve the clouding phenomenon when casting the solution at room temperature, gamma-butyrolactone (GBL) and N-methyl-2-pi A first low absorption solvent mixture of rolidone (NMP), a second low absorption solvent mixture of gamma-butyrolactone (GBL) and N,N-dimethyl propinoamide (DPA), gamma-butyrolactone (GBL) and Select a third low absorption solvent mixture of 3-methoxy-N,N-dimethyl propanamide (DMPA), or 3-methoxy-N,N-dimethyl propanamide (DMPA) and N,N-dimethyl propino It is preferred to select each amide (DPA) alone.

When using the mixture of gamma-butyrolactone and N-methyl-2-pyrrolidone as the low water absorption solvent, gamma-butyrolactone 30 to 70 mol% and N-methyl-2-pyrrolidone 70 to 30 It is preferred to use mole %. More preferably, 50 to 70 mol% of gamma-butyrolactone and 30 to 50 mol% of N-methyl-2-pyrrolidone are used.

When the mixture of gamma-butyrolactone and N,N-dimethyl propinoamide is used as the low-absorption solvent, 30 to 70 mol% of gamma-butyrolactone and 30 to 70 mol% of N,N-dimethyl propinoamide Use. Preferably, 50 to 70 mol% of gamma-butyrolactone and 30 to 50 mol% of N,N-dimethyl propinoamide are used.

When using a mixture of the gamma-butyrolactone and 3-methoxy-N,N-dimethyl propanamide as the low-absorption solvent, 30 to 70 mol% of gamma-butyrolactone and 3-methoxy-N,N- It is preferred to use 70 to 30 mol% of dimethyl propanamide. More preferably, 50 to 70 mol% of gamma-butyrolactone and 30 to 50 mol% of 3-methoxy-N,N-dimethyl propanamide are used.

When selecting the N,N-dimethyl propinoamide alone or 3-methoxy-N,N-dimethyl propanamide alone as the low-absorption solvent, it is preferable to use 100 mol% alone without the addition of other solvents.

Examples of the spreadable solvent include ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene glycol diethyl ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and these One selected from the group consisting of a combination of can be used.

The spreadable solvent plays an important role in improving wetting, and improves spreadability of the solution when casting the solution, thereby preventing shrinkage of the solution and obtaining a film having excellent uniformity. For this, ethylene glycol monobutyl ether may be used in an amount of 10 to 40 mol%, preferably 10 to 30 mol%.

Preparing a polyamic acid solution

In this step, a dicarbonyl compound and an acid dianhydride compound are added to the prepared mixture, and a polyamic acid solution is prepared through polymerization.

The added dicarbonyl compound is 4,4'-{2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-bis(iminocarbonyl)} Bis(benzoyl chloride) (BTBC), benzophenone-4,4'-dicarboxyl chloride (BPDC), 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4 ,4'-dicarboxyl chloride (TFBC), 4,4'-[4,4'-(hexafluoroisopropidine) diphthalimide]bis(benzoyl chloride) (BHIC), [2,2' -Bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-bis(imide)]bis(phthalyl chloride) (BTIC), 4,4'-[1,2 ,4,5-cyclohexanetetracarboxylimide]bis(benzoyl chloride) (BHCC), 1,4-cyclohexyl-bis(imide)]bis(phthalyl chloride) (CHIC) and combinations thereof It is characterized by including one selected from the group consisting of.

The amount of the dicarbonyl compound and the acid dianhydride compound added is 100 to 105 mol% based on the diamine compound.

Preferably, the amount of the dicarbonyl compound added is 20 mol% to 100 mol% based on the total content of the diamine compound. At this time, if the input amount is less than 20 mol%, the optical characteristics increase, but there is a limit to the improvement of the heat resistance, and if the amount exceeds 100 mol%, does the optical characteristics deteriorate?

The acid dianhydride compound to be added may include one selected from the group consisting of a fluorinated aromatic acid dianhydride, a non-fluorinated aromatic acid dianhydride, and a combination thereof, and specific examples are omitted because they are already overlapped with the contents described in the polyamic acid composition. Do it.

In the present invention, the dicarbonyl compound, the diamine compound, and the acid dianhydride compound constitute a solid content in the polyamic acid solution, wherein the content of the solid content is preferably 10 to 40% by weight based on the polyamic acid solution. More preferably, the solid content is included in 10 to 25% by weight. At this time, when the solid content is less than 10% by weight, there is a limitation in increasing the thickness of the film during the production of the polyamide-imide film, and when the solid content is more than 40% by weight, there is a problem that there is a limitation in controlling the viscosity of the polyamic acid solution. Occurs.

In the case of the diamine compound and the acid dianhydride compound constituting the solid content, the diamine compound is contained in an amount of 95 to 100 mol%, and the acid dianhydride compound is contained in an amount of 100 to 105 mol%.

In the case of the polymerization, it is preferably carried out for 6 to 48 hours at a temperature of 10 to 70 ℃.

In this step, a catalyst may be further added to increase reactivity other than the acid dianhydride. The catalyst used at this time is not particularly limited as long as it does not violate the object of the present invention and can improve the reactivity within a range not significantly impairing the effect. For example, it may be selected from the group consisting of trimethylamine, xylene, pyridine, quinoline, and combinations thereof. In the present invention, in addition to the catalyst, any one selected from the group consisting of a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, a leveling agent, and a combination thereof may be further included. It can be selected and used as needed within the range that does not damage it.

Method for producing polyamide-imide film

The prepared polyamic acid solution is coated on a substrate to form a transparent coating layer, and the transparent coating layer is heat-treated to prepare a polyamide-imide film of the present invention.

Looking specifically at the manufacturing method of the polyamide-imide film of the present invention, the polyamic acid solution of the present invention having a specific viscosity is coated on a prepared substrate such as glass, and the coating method used at this time is not particularly limited. . For example, it may be selected from the group consisting of spin coating, dip coating, solvent casting, slot die coating, spray coating, and combinations thereof.

The heat treatment may be performed in a convection manner through a general oven, and the heat treatment conditions are performed at 100 to 450° C. for 30 to 120 minutes. Preferably, the heat treatment may be performed under temperature and time conditions at 100° C. for 30 minutes and 350° C. for 30 minutes. This is a condition capable of maximizing the properties of the polyamide-imide film of the present invention used as an optical film while removing an appropriate solvent.

Polyamide-imide film

The polyamic acid composition of the present invention has excellent heat resistance, optical properties, and high transparency by optimizing the composition of a dicarbonyl compound, a diamine compound, and an acid dianhydride and a solvent (organic solvent) that does not cause cloudiness and their usage. It is characterized by providing a polyamide-imide film having. Specifically, the polyamide-imide film of the present invention is produced through the method of manufacturing the polyamide-imide film. When the polyamide-imide film has a thickness of 10 to 15 μm, the yellow index , YI) 5 or less, a glass transition temperature of 360°C or more and a transmittance of 85% or more at a wavelength of 550 nm, and high transparency. At this time, the glass transition temperature of the polyamide-imide film of the present invention is more preferably 380% or more, and may have a value of 20 ppm/°C or less at a coefficient of thermal expansion (C.T.E.) of 100 to 250°C.

The polyamide-imide film of the present invention can be used in various fields. In particular, flexible devices, tablet PCs, wearable devices, and flexible OLED lighting substrate materials that require high-efficiency light sources that require high transparency and high refractive index characteristics. It can be usefully used.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are only examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

Preparation Example (Method for preparing dicarbonyl compound of Formula 1)

Method for preparing dicarbonyl compound of formula 1

The dicarbonyl compound of Formula 1, 4,4'-{2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-bis(iminocarbonyl)} Bis(benzoyl chloride) (BTBC) is a methyl benzoate intermediate synthesis step; Carboxylic acid intermediate synthesis step; And BTBC synthesis step; It is synthesized through

Step 1. Methyl benzoate intermediate synthesis step

100 ml of dried NMP was added to a 1000 ml round flask in a nitrogen atmosphere. Here, TFMB (20.15g, 62.94mmol) and Triethylamine (14.0g, 138.5mmol) were added and completely dissolved and then cooled to 0°C. After dissolving methyl 4-(chloroformyl)benzoate (25g, 125.9mmol) in 100ml of NMP, it was slowly added to the TFMB solution. After the addition, the reaction solution was heated to 50° C. and stirred for 2 hours. Subsequently, 200 ml of water was added, the contents were cooled to room temperature (20° C.), and the precipitate was filtered. The filtered precipitate was washed with 300 ml of water and further washed with 50 ml of dichloromethane. Vacuum-dried at 60° C. for 12 hours to obtain a white target compound. (38.5g, 94.9%) The ^{results of 1} H-NMR for the obtained white target compound are as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.84 (s, 2H), 8.35 (s, 2H), 8.14-8.12 (d, 8H), 8.12-8.10 (d, 2H), 7.42-7.40 (d, 2H), 2.70 (s, 6H)

Step 2. Carboxylic acid intermediate synthesis step

To a 1000ml round flask was added methyl benzoate (20g, 31.0mmol), KOH (3.8g, 68.2 mmol), 200ml of ethanol, and 100ml of water. The reaction solution was heated to 80° C. and stirred for 4 hours. After the reaction, 500 ml of water was added to the completely dissolved solution and cooled to room temperature (20° C.). After cooling, 50 ml of 1M HCl was slowly added and the pH was dropped to 2 or less. The precipitate was stirred for 30 minutes and then filtered. The filtered precipitate was washed with 1000 ml of water. Vacuum-dried at 60° C. for 12 hours to obtain a white target compound. (15.45g, 80.9%) The ^{results of 1} H-NMR for the obtained white target compound are as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 13.3 (brs, 2H), 10.81 (s, 2H), 8.36 (s, 2H), 8.13-8.12 (d, 2H), 8.11-8.10 (d) , 8H), 7.42-7.40 (d, 2H)

Step 3. BTBC synthesis step

In a 250ml round flask, carboxylic acid (14.3g, 23.2mmol), oxalyl chloride (14.7g, 116mmol), and 50ml of CHCl3 were added, and the reaction solution was heated to 50°C and stirred for 5 hours. After the reaction, the solvent was removed by vacuum concentration. After concentration, 60 ml of CHCl3 was added, stirred for 30 minutes, and filtered. The filtered precipitate was washed with 40 ml of CHCl3. Vacuum-dried at 60° C. for 12 hours to obtain an off-white target compound. ^{(9.5g, 62.9%) The results of 1} H-NMR, ¹³ C-NMR and FT-IR for the obtained off-white target compound are as follows.

¹ H-NMR (500 MHz, DMSO-d6): δ 10.83 (s, 2H), 8.36 (s, 2H), 8.13 (d, 2H), 8.12-8.10 (d, 8H), 7.41-7.40 (d,) 2H)

¹³ C-NMR (500 MHz, DMSO-d6): δ 163.73, 162.38, 136.29, 135.15, 130.64, 129.57, 128.57, 126.41, 125.08, 121.91, 119.76, 119.58, 114.26

FT-IR (KBr, cm-1): 3320, 1690, 1590, 1520, 725, 553

Comparative Example 1

As a composition shown in Table 1 below, 3.22 g (0.01 mole) of TFMB as a diamine compound was dissolved in 44.01 g of DMPA as a solvent, and dissolved for 30 minutes at room temperature in a nitrogen atmosphere. Thereafter, 4.54 g (0.01 mole) of 6FDA, an acid dianhydride compound, was added, followed by stirring and polymerization for 24 hours to prepare a polyamic acid solution. The polymerization temperature was maintained at 30°C, and the solid content was maintained to be 15% by weight based on the total weight of the polyamic acid solution. At this time, as a result of measuring with a viscosity measuring device (Brookfield DV2T, SC4-27), the viscosity was 4,800cp.

Example 1

As a composition shown in Table 1 below, as a diamine compound, 2.96g (0.009mole) of TFMB was dissolved in 42.5g of DMPA as a solvent and dissolved for 30 minutes at room temperature in a nitrogen atmosphere. Thereafter, 0.41g (0.001 mole) of 6FDA and 1.09g (0.004 mole) of BPDA, which are acid dianhydride compounds, were added, followed by stirring at room temperature for 1 hour. Then, 3.05 g (0.005 mole) of the compound of Formula 1 (BTBC) prepared in Preparation Example was added, followed by stirring and polymerization at room temperature for 3 hours to prepare a polyamic acid solution. A solution obtained by mixing acetone and water in a ratio of 2:1 to the prepared polyamic acid solution was titrated and dried in vacuum at 80° C. for 12 hours to obtain 7.5 g of polyamic acid as a solid powder.

The polyamic acid powder was added to 42.5 g of DMPA and stirred for 4 hours to prepare a polyamic acid solution. The polymerization temperature was maintained at 30°C, and the solid content was maintained to be 15% by weight based on the total weight of the polyamic acid solution. At this time, as a result of measuring with a viscosity measuring device (Brookfield DV2T, SC4-27), the viscosity was 4,900cp.

Example 2

As a composition shown in Table 1 below, as a diamine compound, 3.77 g (0.012 mole) of TFMB was dissolved in 42.5 g of DMPA as a solvent, and dissolved for 30 minutes at room temperature in a nitrogen atmosphere. Thereafter, 0.52g (0.001 mole) of 6FDA and 1.39g (0.005 mole) of BPDA, which are acid dianhydride compounds, were added, followed by stirring at room temperature for 1 hour. Thereafter, 1.82g (0.006 mole) of the compound of Formula 2 (BPDC) was added, followed by stirring and polymerization at room temperature for 3 hours to prepare a polyamic acid solution. A solution obtained by mixing acetone and water in a ratio of 2:1 to the prepared polyamic acid solution was titrated and dried in vacuum at 80° C. for 12 hours to obtain 7.5 g of polyamic acid as a solid powder.

The polyamic acid powder was added to 42.5 g of DMPA and stirred for 4 hours to prepare a polyamic acid solution. The polymerization temperature was maintained at 30°C, and the solid content was maintained to be 15% by weight based on the total weight of the polyamic acid solution. At this time, as a result of measuring with a viscosity measuring device (Brookfield DV2T, SC4-27), the viscosity was 6,000 cp.

Example 3

As a composition shown in Table 1 below, as a diamine compound, 3.47 g (0.011 mole) of TFMB was dissolved in 42.5 g of DMPA as a solvent and dissolved for 30 minutes at room temperature in a nitrogen atmosphere. Thereafter, 0.48g (0.001 mole) of 6FDA and 1.28g (0.004 mole) of BPDA, which are an acid dianhydride compound, were added, followed by stirring at room temperature for 1 hour. Thereafter, 2.27g (0.005 mole) of the compound of Formula 3 (TFBC) was added, followed by stirring and polymerization at room temperature for 3 hours to prepare a polyamic acid solution. A solution obtained by mixing acetone and water in a ratio of 2:1 to the prepared polyamic acid solution was titrated and dried in vacuum at 80° C. for 12 hours to obtain 7.5 g of polyamic acid as a solid powder.

The polyamic acid powder was added to 42.5 g of DMPA and stirred for 4 hours to prepare a polyamic acid solution. The polymerization temperature was maintained at 30°C, and the solid content was maintained to be 15% by weight based on the total weight of the polyamic acid solution. At this time, as a result of measuring with a viscosity measuring device (Brookfield DV2T, SC4-27), the viscosity was 4,700cp.

Example 4

As a composition shown in Table 1 below, as a diamine compound, 2.39 g (0.007 mole) of TFMB was dissolved in 42.5 g of DMPA as a solvent and dissolved for 30 minutes at room temperature in a nitrogen atmosphere. Thereafter, 5.38g (0.007 mole) of the compound of Formula 4 (BHIC) was added, followed by stirring and polymerization at room temperature for 3 hours to prepare a polyamic acid solution. A solution obtained by mixing acetone and water in a ratio of 2:1 to the prepared polyamic acid solution was titrated and dried in vacuum at 80° C. for 12 hours to obtain 7.5 g of polyamic acid as a solid powder.

The polyamic acid powder was added to 42.5 g of DMPA and stirred for 4 hours to prepare a polyamic acid solution. The polymerization temperature was maintained at 30°C, and the solid content was maintained to be 15% by weight based on the total weight of the polyamic acid solution. At this time, as a result of measuring with a viscosity measuring device (Brookfield DV2T, SC4-27), the viscosity was 5,600cp.

Example 5

As a composition shown in Table 1 below, as a diamine compound, 2.42g (0.008mole) of TFMB was dissolved in 42.5g of DMPA as a solvent and dissolved for 30 minutes at room temperature in a nitrogen atmosphere. Thereafter, 5.34g (0.008 mole) of the compound of Formula 5 (BTIC) was added, followed by stirring and polymerization at room temperature for 3 hours to prepare a polyamic acid solution. A solution obtained by mixing acetone and water in a ratio of 2:1 to the prepared polyamic acid solution was titrated and dried in vacuum at 80° C. for 12 hours to obtain 7.5 g of polyamic acid as a solid powder.

The polyamic acid powder was added to 42.5 g of DMPA and stirred for 4 hours to prepare a polyamic acid solution. The polymerization temperature was maintained at 30°C, and the solid content was maintained to be 15% by weight based on the total weight of the polyamic acid solution. At this time, as a result of measuring with a viscosity measuring device (Brookfield DV2T, SC4-27), the viscosity was 4,700cp.

Example 6

As a composition shown in Table 1 below, as a diamine compound, 3.27 g (0.01 mole) of TFMB was dissolved in 42.5 g of DMPA as a solvent and dissolved for 30 minutes at room temperature in a nitrogen atmosphere. Thereafter, 0.45g (0.001 mole) of 6FDA and 1.20g (0.004 mole) of BPDA, which are acid dianhydride compounds, were added, followed by stirring at room temperature for 1 hour. Thereafter, 2.57 g (0.005 mole) of the compound of Formula 6 (BHCC) was added, followed by stirring and polymerization at room temperature for 3 hours to prepare a polyamic acid solution. A solution obtained by mixing acetone and water in a ratio of 2:1 to the prepared polyamic acid solution was titrated and dried in vacuum at 80° C. for 12 hours to obtain 7.5 g of polyamic acid as a solid powder.

The polyamic acid powder was added to 42.5 g of DMPA and stirred for 4 hours to prepare a polyamic acid solution. The polymerization temperature was maintained at 30°C, and the solid content was maintained to be 15% by weight based on the total weight of the polyamic acid solution. At this time, as a result of measuring with a viscosity measuring device (Brookfield DV2T, SC4-27), the viscosity was 4,100cp.

Example 7

As a composition shown in Table 1 below, as a diamine compound, 3.27 g (0.01 mole) of TFMB was dissolved in 42.5 g of DMPA as a solvent and dissolved for 30 minutes at room temperature in a nitrogen atmosphere. Thereafter, 0.45g (0.001 mole) of 6FDA and 1.20g (0.004 mole) of BPDA, which are acid dianhydride compounds, were added, followed by stirring at room temperature for 1 hour. Thereafter, 2.57g (0.005 mole) of the compound of Formula 7 (CHIC) was added, followed by stirring and polymerization at room temperature for 3 hours to prepare a polyamic acid solution. A solution obtained by mixing acetone and water in a ratio of 2:1 to the prepared polyamic acid solution was titrated and dried in vacuum at 80° C. for 12 hours to obtain 7.5 g of polyamic acid as a solid powder.

The polyamic acid powder was added to 42.5 g of DMPA and stirred for 4 hours to prepare a polyamic acid solution. The polymerization temperature was maintained at 30°C, and the solid content was maintained to be 15% by weight based on the total weight of the polyamic acid solution. At this time, as a result of measuring with a viscosity measuring device (Brookfield DV2T, SC4-27), the viscosity was 3,900cp.

division Example Comparative example One 2 3 4 5 6 7 One Composition Dicarbonyl *BTBC 50 - - - - - - - *BPDC - 50 - - - - - - *TFBC - - 50 - - - - - *BHIC - - - 100 - - - - *BTIC - - - - 100 - - - *BHCC - - - - - 50 - - *CHIC - - - - - - 50 - Acid dianhydride *6 FDA 10 10 10 - - 10 10 100 *BPDA 40 40 40 - - 40 40 - Diamine *TFMB 100 100 100 100 100 100 100 100 Organic solvent DMPA = 100 (Unit: mol%) *BTBC: 4,4'-{2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-bis(iminocarbonyl)}bis(benzoyl chloride)
*BPDC: Benzophenone-4,4'-dicarboxyl chloride
*TFBC: 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-dicarboxyl chloride
*BHIC: 4,4'-[4,4'-(hexafluoroisopropidine) diphthalimide]bis(benzoyl chloride)
*BTIC: [2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-bis(imide)]bis(phthalyl chloride)
*BHCC: 4,4'-[1,2,4,5-cyclohexanetetracarboxylimide]bis(benzoyl chloride)
*CHIC: 1,4-cyclohexyl-bis(imide)]bis(phthalyl chloride)
*6FDA: 4,4'-(Hexafluoroisopropylidene) diphthalic anhydride (4,4'-(Hexafluoroisopropylidene) diphthalic anhydride)
*BPDA: 3,3,4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride)
*TFMB: 2,2'-bis(trifluoromethyl)-benzidine (2,2'-bis(trifluoromethyl)benzidine)

Experimental example

(1) Evaluation of polyamide-imide film properties

The polyamic acid solutions prepared in Examples 1 to 7, Comparative Example 1 were coated on a glass plate using a spin coater, and then heat treated in a high-temperature convection oven. The heat treatment was performed under a nitrogen atmosphere, and a final film was obtained under conditions of temperature and time of 100°C/30min and 350°C/30min. The polyamide-imide films prepared in each were measured for physical properties through the following method, and the results are shown in Table 2 below.

(a) Transmittance

Transmittance was measured at 550 nm using a UV-Vis NIR Spectrophotometer (Shimadsu, UV-1800).

(b) Yellowness Index (YI)

It was measured using a color difference meter (LabScan XE).

(c) haze

It was measured using a Haze meter (TOYOSEIKI, HAZE-GARD).

(d) thermal properties

The glass transition temperature (T _g ) and coefficient of thermal expansion (CTE) of the film were measured using TMA 402 F3 manufactured by Netzsch. The force of the tension mode was set to 0.1N, and the measurement temperature was increased from 30°C to 350°C at a rate of 5°C/min, and the coefficient of linear thermal expansion was measured as an average value in the range of 100 to 250°C. The thermal decomposition temperature (T _d , 1%) was measured using TG 209 F3 manufactured by Netzsch.

Physical property measurement Target value Example Comparative example One 2 3 4 5 6 7 One Properties
Measure Viscosity
(cp, 23℃) 1000
~
7000 4900 6000 4700 5600 4700 4100 3900 4800 thickness
(㎛) 10 10 10 10 10 10 10 10 10 Transmittance (%, @550nm) >85 89 90 88 90 88 85 85 91 Haze <1 0.6 0.4 0.4 0.3 0.5 0.9 0.9 0.3 Y.I. <10 7 4 4 3 7 8 8 4 CTE
(100 ~
250℃) ppm/℃ <30 16 17 15 18 17 20 20 56 Tg ℃ >400 383 380 386 376 371 369 364 333 Td 1% ℃ >400 463 461 461 445 454 447 431 459

As shown in Table 2 above, if the dicarbonyl compound having the structures of Chemical Formulas 1 to 7 is properly used, it can have excellent optical properties and have a high glass transition temperature and a low coefficient of thermal expansion.

Accordingly, the polyamic acid solution prepared according to the present invention has a film thickness of 10 to 15 μm, a yellowness of 10 or less, a thermal expansion coefficient of 20 ppm or less in the range of 100 to 250°C, and a glass transition temperature (Tg) of 360 It may be provided as a transparent polyamide-imide film having a transmittance of 88% or more at a wavelength of 550 nm or more.

Therefore, the polyamide-imide film manufactured according to the present invention satisfies excellent optical properties and heat resistance characteristics, and thus, displays for OLEDs, displays for liquid crystal devices, TFT substrates, flexible printed circuit boards, flexible OLED surface-illuminated substrates, and electronic devices. It can be widely applied to substrates and protective films for flexible displays such as paper substrate materials.

Claims (20)

Including a dicarbonyl compound, a diamine compound and an acid dianhydride compound,
The dicarbonyl compound includes one compound selected from the group consisting of the following Formulas 1, 3, 5, 6, 7, and combinations thereof,
The dicarbonyl compound and the acid dianhydride compound are contained in an amount of 100 to 105 mol% based on the diamine compound,
The dicarbonyl compound is a polyamic acid, characterized in that contained 50 to 100 mol% based on the diamine compound.
[Formula 1]

[Formula 3]

[Formula 5]

[Formula 6]

[Formula 7]

The method of claim 1,
The diamine compound is a polyamic acid comprising one selected from the group consisting of a fluorinated aromatic diamine monomer, a non-fluorinated aromatic dimine monomer, and a combination thereof. The method of claim 1,
The diamine compound is 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p-methylenedianiline (pMDA), m-methylenedianiline (mMDA), p-cyclohexanediamine (pCHDA), p -Xylylenediamine (pXDA), m-xylylenediamine (mXDA), m-cyclohexanediamine (mXDA), 4,4'-diaminodiphenylsulfone (DDS), 2,2-bis[4-(4) -Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoro propane (BAFP), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane (BAMF), 2,2'-bis(3-aminophenyl)-hexafluoropropane (BAPF), 3,5-diamino Benzotrifluoride (DABF), 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (BTDE), 2,2-bis (3-amino-4-hydroxy) Phenyl) polyamic acid comprising one selected from the group consisting of hexafluoropropane (BAHH) and combinations thereof. The method of claim 1,
The acid dianhydride compound is a polyamic acid comprising one selected from the group consisting of a fluorinated aromatic acid dianhydride, a non-fluorinated aromatic acid dianhydride, and a combination thereof. The method of claim 4,
The fluorinated aromatic acid dianhydride is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 6FDA)), 4,4'-(4,4'- One selected from the group consisting of hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride)(4,4'-(4,4'-Hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride, 6-FDPDA) and combinations thereof Polyamic acid comprising a. The method of claim 5,
The non-fluorinated aromatic acid dianhydride is pyromellitic dianhydride, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3'4). ,4'-biphenyltetracarboxylic acid dianhydride, BPDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3',4,4'-benzophenonetetracarboxylic dianhydride, BTDA), 4,4' -Oxydiphthalic anhydride (4,4′-oxydiphthalic anhydride, ODPA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane anhydride (2,2-Bis[4-(3 ,4-dicarboxyphenoxy) phenyl]propane dianhydride, BPADA), 3,3',4,4'-diphenyl sulfone tetracarboxylic anhydride, ethylene glycol bis(4-trimelitate anhydride) (3,3',4 ,4'-Diphenyl sufone tetracarboxylic dianhydride, DSDA), cyclobutanetetracarboxylic dianhydride (CBDA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4- Tetrahydronaphthalene-1,2-dicarboxylic acid dihydrate (TDA), pyromellitic acid dihydrate (PMDA), benzophenone tetracarboxylic acid dihydride (BTDA), oxydiphthalic dihydride (ODPA), bicyclo [2.2.2] Oct-7ene-2,3,5,6-tetracarboxylic acid dihydride (BTDA), 3,3',4,4-biphenyretracarboxylic acid dihydride (s-BPDA ) And a polyamic acid comprising one selected from the group consisting of a combination thereof. The polyamic acid of claim 1 has a viscosity of 1,000 to 10,000 cp at 23°C. A polyamide-imide film comprising the polyamic acid of any one of claims 1 to 7. The method of claim 8,
When the polyamide-imide film has a thickness of 10 to 15 μm,
Yellow Index (YI) 10 or less,
Coefficient of thermal expansion (CTE) 20ppm/℃ or less at 100 to 250℃,
The glass transition temperature is more than 360℃ and
A polyamide-imide film having a transmittance of 85% or more at a wavelength of 550 nm. Preparing a mixture by mixing a diamine compound and a solvent; And
Including; adding and polymerizing a dicarbonyl compound and an acid dianhydride to the mixture to prepare a polyamic acid solution; Including,
The dicarbonyl compound includes one compound selected from the group consisting of the following Formulas 1, 3, 5, 6, 7, and combinations thereof,
In the step of preparing a polyamic acid solution, the dicarbonyl compound and the acid dianhydride compound are contained in an amount of 100 to 105 mol% based on the diamine compound,
The method for producing a polyamic acid, wherein the dicarbonyl compound is contained in an amount of 50 to 100 mol% based on the diamine compound.
[Formula 1]

[Formula 3]

[Formula 5]

[Formula 6]

[Formula 7]

The method of claim 10,
In the step of preparing a mixture, the solvent is selected from the group consisting of a polar solvent, a low boiling point solvent, a low absorption solvent, a spreading solvent, and a combination thereof,
The polar solvent is m-cresol, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), diethyl acetate ( DEA), selected from the group consisting of 3-methoxy-N,N-dimethyl propanamide (DMPA), N,N-dimethyl propinoamide (DPA), N,N-dimethyllactamide (DML), and combinations thereof Become,
The low boiling point solvent is selected from the group consisting of tetrahydrofuran (THF), trichloromethane (chloroform, TCM), and combinations thereof,
The low-absorption solvent is gamma-butyrolactone (GBL), 3-methoxy-N,N-dimethylpropanamide (DMPA), N,N-dimethyl propinoamide (DPA), N,N-dimethyllactamide ( DML), is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), and combinations thereof,
Examples of the spreadable solvent include ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene glycol diethyl ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and these Polyamic acid production method, characterized in that one selected from the group consisting of a combination of. The method of claim 11,
A first low-absorption solvent mixture containing 30 to 70 mol% of gamma butyrolactone and 30 to 70 mol% of N-methyl-2-pyrrolidone as the low-absorption solvent, 30 to 70 mol% of gamma-butyrolactone, and A second low-absorption solvent mixture comprising 30 to 70 mole percent of N,N-dimethyl propinoamide, 30 to 70 mole percent gamma-butyrolactone and 30 to 70 moles of 3-methoxy-N,N-dimethyl propanamide A method for producing a polyamic acid, comprising: a third low-absorption solvent mixture containing %, 100 mol% of N,N-dimethyl propinoamide or 100 mol% of 3-methoxy-N,N-dimethyl propanamide. The method of claim 10,
The solvent is ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene glycol diethyl ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and combinations thereof Polyamic acid production method comprising one spreading solvent selected from the group consisting of. delete The method of claim 10,
In the step of preparing a mixture, the mixing is performed for 30 to 60 minutes in a nitrogen atmosphere and at a temperature of 25 to 30°C. The method of claim 10,
In the step of preparing a polyamic acid solution, one selected from the group consisting of a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, a leveling agent, and a combination thereof is further added to the mixture. The method of claim 10,
In the step of preparing a polyamic acid solution, the polymerization is performed at a temperature of 10 to 70° C. for 6 to 48 hours. The method of claim 10,
In the step of preparing a polyamic acid solution, the diamine compound, dicarbonyl compound, and acid dianhydride constitute a solid content of the polyamic acid solution,
Polyamic acid production method, characterized in that the content of the solid content is 10 to 40% by weight based on the polyamic acid solution. delete In the polyamic acid solution prepared by the method for producing a polyamic acid of any one of claims 10 to 13 and 15 to 18,
Coating the polyamic acid solution on a substrate to form a transparent coating layer; And
Heat-treating the transparent coating layer; further comprising,
The heat treatment is performed for 30 to 120 minutes at a temperature of 100 to 450°C in a nitrogen atmosphere.