WO2017111300A1 - Polyamic acid solution to which diamine monomer having novel structure is applied, and polyimide film comprising same - Google Patents

Abstract

The present invention provides: a novel monomer applicable as a diamine component of a polyamic acid; a polyamic acid composition containing the same; and a polyimide prepared from the composition. The polyamic acid composition provided by the present invention, having excellent optical, thermal and mechanical characteristics, can be applied as a flexible display material.

Description

Polyamic acid solution to which a diamine monomer of a novel structure is applied and a polyimide film comprising the same

The present invention relates to a diamine monomer having a novel structure, a polyamic acid composition for producing a transparent polyimide resin including such a diamine monomer, and a transparent polyimide resin prepared from the composition and applicable to a flexible display substrate or a protective film.

As the thinning and miniaturization of flat panel displays (FPDs) proceeds, transparent plastic substrates are required instead of glass substrates in the manufacture of flat panel displays.

According to such a demand, a transparent plastic substrate manufactured by film-forming a polymer resin such as polyethylene terephthalate (PET) or polyether sulfone (PES) has been developed. The transparent plastic substrate using a polymer resin such as PET or PES has a good ductility compared to the glass substrate, but has a low heat resistance because the glass transition temperature (Tg) is low. In addition, since the coefficient of thermal expansion (CTE) is higher than that of the glass substrate, there is also a problem that deformation is easily caused by a process (for example, a TFT process of 220 ° C or higher) at a high temperature in the display manufacturing process.

On the other hand, a technique for producing a transparent plastic substrate using a polyimide resin having excellent heat resistance and a relatively low coefficient of thermal expansion has attracted attention. Polyimide resin (PI) has a limitation in showing high transparency like a glass substrate because it is colored in brown or yellow due to the effect of a charge transfer complex (CTC) and thus has low transmittance in the visible region. . Therefore, a lot of research is in progress to solve this problem. In general, a polyimide (PI) resin refers to a high heat-resistant resin prepared by solution polymerization of an aromatic acid dianhydride and an aromatic diamine or an aromatic diisocyanate to produce a polyamic acid derivative, and then imidization by ring closure dehydration at a high temperature.

As the component of the aromatic acid dianhydride for producing the polyimide resin, pyromellitic dianhydride (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) is used, and as the aromatic diamine component, oxydianiline (ODA) ), p-phenylene diamine (p-PDA), m-methylene diamine (m-MDA), methylene diamine (MDA), bisaminophenylhexafluoropropane (HFDA), etc. are mainly used. Since the acid dianhydride or diamine component has a trade-off relationship between optical properties, thermal properties, and mechanical properties, it is necessary to develop a compound of a component suitable for each property, that is, a monomer for transparent PI. Accordingly, development of a transparent polyamic acid composition for a flexible display having high transparency, excellent heat resistance, low thermal expansion coefficient, and excellent mechanical properties is required.

The present invention is directed to the introduction of a monomer having a specific chemical structure and substituents improve the optical, mechanical and thermal properties compared to the conventional.

More specifically, in the present invention, in order to obtain a polyimide resin having high transparency, excellent mechanical and thermal properties, it is judged to be effective to introduce a rigid chemical monomer, and a diamine monomer derivative having a specific chemical structure Designed and synthesized, by adjusting the content of the new diamine monomer synthesized in a specific range, a transparent polyamic acid composition and a polyimide film that can simultaneously implement a low YI (high Yellow Index), high light transmittance, mechanical and thermal properties For the purpose of manufacturing.

In addition, the present invention is a transparent polyamic acid applicable to a plastic transparent substrate, a TFT substrate, a flexible printed circuit board, a flexible OLED surface lighting substrate, and an electronic paper substrate material for LCD and OLED flexible displays. It is to provide a composition and a transparent polyimide film.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1).

In Chemical Formula 1,

Y is a C ₆ ~ C ₄₀ arylene group, the C ₆ ~ C ₄₀ arylene group may be substituted with a halogen or a C ₁ ~ C ₆ alkyl group substituted with a halogen atom,

X ₁ and X ₂ are the same or different, are each independently selected from hydrogen, halogen, the group consisting of an alkyl group of C ₁ ~ C ₆ alkyl, and C ₁ ~ in which one or more hydrogen substituted with halogen atoms C _6, the Provided that at least one of X ₁ , X ₂ and Y has a halogen or a C ₁ to C ₆ alkyl group substituted with a halogen atom,

n is an integer of 0-3.

In the present invention, it is preferable that each of X ₁ and X ₂ is an electron-withdrawing group (EWG) which is independently F or CF ₃ .

In addition, the present invention (a) a diamine containing a compound of the formula (1); (b) acid dianhydrides; And (c) an organic solvent, wherein the compound represented by Chemical Formula 1 provides a polyamic acid composition that is included in the range of 10 to 90 mol% based on 100 mol% of the total diamine.

In the present invention, the diamine is fluorinated first diamine; It may further comprise one or more selected from the group consisting of sulfone-based second diamine, hydroxy-based third diamine, ether-based fourth diamine and alicyclic fifth diamine.

In the present invention, the content of the fluorinated first diamine, sulfone-based second diamine, hydroxy-based third diamine, ether-based fourth diamine and cycloaliphatic fifth diamine are each 10 to 90 mol based on 100 mol% total diamine May be%.

In the present invention, the acid dianhydride may include one or more selected from the group consisting of fluorinated aromatic first acid dianhydride, alicyclic diacid dianhydride and non-fluorinated aromatic tertiary dianhydride.

In the present invention, the content of the at least one compound selected from the group consisting of the first acid dianhydride, the second acid dianhydride and the third acid dianhydride may be in the range of 10 to 100 mol% based on 100 mol% of the total acid dianhydride.

In the present invention, the ratio (a / b) of the number of moles of the diamine (a) and the acid dianhydride (b) may range from 0.7 to 1.3.

In addition, the present invention provides a transparent polyimide film prepared by imidizing the polyamic acid composition described above.

In the present invention, the transparent polyimide film may satisfy the physical property conditions of the following (i) to (v), more specifically (i) the glass transition temperature (Tg) is 320 to 400 ℃ range, (ii ) The light transmittance of wavelength 550nm is 88% or more based on film thickness of 50㎛, (iii) Yellowness is 4.0 or less according to ASTM E313 standard, (iv) Tensile strength is 110 MPa or more, and (v) Tensile modulus is May be at least 3.5 GPa.

In the present invention, the transparent imide film may be used as a substrate and / or protective film for a flexible display.

In the present invention, it is possible to provide a polyamic acid composition having excellent optical properties, mechanical properties, thermal properties, etc. by adopting a diamine monomer having a specific structure and a substituent and adjusting the weight percentage thereof.

In the present invention, by applying the polyamic acid composition having excellent optical properties, mechanical properties, thermal properties and the like as a substrate, it is possible to provide a flexible display substrate exhibiting excellent physical properties and product reliability.

Hereinafter, the present invention will be described in detail. However, this is presented by way of example, whereby the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

<New diamine compound>

The present invention provides a compound represented by Chemical Formula 1, preferably a diamine compound.

[Formula 1]

In Chemical Formula 1,

Y is a C ₆ ~ C ₄₀ arylene group, the C ₆ ~ C ₄₀ arylene group may be substituted with a halogen or a C ₁ ~ C ₆ alkyl group substituted with a halogen atom,

X ₁ and X ₂ are the same or different, are each independently selected from hydrogen, halogen, the group consisting of an alkyl group of C ₁ ~ C ₆ alkyl, and C ₁ ~ in which one or more hydrogen substituted with halogen atoms C _6, the Provided that at least one of X ₁ , X ₂ and Y has a halogen or a C ₁ to C ₆ alkyl group substituted with a halogen atom,

n is an integer of 0-3.

In the present invention, the compound represented by Formula 1 is a conventional 2,2'-bis (trifluoromethyl) -4,4'- diaminobiphenyl (2,2'-Bis (trifluoromethyl) -4,4'- Basic structure is similar to Diaminobiphenyl (hereinafter referred to as TFDB), but has a more rigid structure as a divalent arylene linker is introduced between the diamine-substituted moieties in the compound. . Therefore, since it is not decomposed by heat or light and is more stable against external impact, optical properties, thermal properties, and mechanical properties (Modulus, Strength) of the polyamic acid composition including the same may be significantly improved.

In the present invention, by introducing at least one electron-withdrawing group (EWG) such as fluorine (F) or CF ₃ in the above formula (1), it is possible to further increase the above-described optical and thermal properties. More specifically, the polyimide film is dark brown rather than colorless because of the Charge Transfer Complex (CTC) of π electrons present in the imide chain. Since -F, -CF ₃ and the like introduced in Chemical Formula 1 are strong electron withdrawing groups, the CT-Complex does not occur through the movement between π electrons, thereby exhibiting high transparency of polyimide.

According to a preferred embodiment of the present invention, X ₁ and X ₂ may be a conventional electron withdrawing group (EWG) known in the art, each independently fluorine (F) or CF ₃ It is preferred.

In addition, the Y may be a conventional C ₆ ~ C ₄₀ arylene group known in the art, specific examples thereof include phenylene, biphenylene, triphenylenyl and the like. In particular, the Y is preferably selected from the group of substituents represented by the following formula.

,

,

,

,

,

,

In the above substituents, R ₁ to R ₃ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, F, and CF ₃ . Preferably, R ₁ to R ₃ are each independently F or CF ₃ .

The compound represented by Formula 1 according to the present invention may be more specific to any one of a compound group consisting of Compound 1 to Compound 26, but is not particularly limited thereto.

<Transparent Polyamic Acid Composition>

The transparent polyamic acid composition of the present invention is for producing a transparent polyimide film, characterized in that it comprises a compound represented by the formula (1) as a diamine (diamine) component.

More specifically, the polyamic acid composition comprises (a) a diamine containing the compound of Formula 1; (b) acid dianhydrides; And (c) an organic solvent.

The diamine (a) monomer used in the preparation of the transparent polyamic acid of the present invention may include a compound represented by Chemical Formula 1, and may be mixed with a conventional diamine compound known in the art.

The amount of the diamine monomer represented by Chemical Formula 1 is not particularly limited, and may be, for example, in the range of 10 to 90 mol% based on 100 mol% of the total acid dianhydride, and preferably in the range of 20 to 80 mol%. .

In the present invention, the diamine compound mixed with the compound of Formula 1 may be used without particular limitation as long as the compound has a diamine structure in the molecule. An example is an aromatic, alicyclic, or aliphatic compound having a diamine structure.

Diamines usable in the present invention include optical properties such as high transmittance, low Y.I, low haze, and the like; Thermal properties such as high glass transition temperature (High Tg) and low coefficient of thermal expansion (Low CTE); Considering mechanical properties such as high modulus and high surface hardness, linear structures having fluorinated substituents or sulfone based, hydroxy based, ether based, etc. Appropriate combinations of structures to include are required. Accordingly, in the present invention, as the diamine compound, fluorinated aromatic first diamine, sulphonated second diamine, hydroxy third diamine, ether fourth diamine and alicyclic fifth diamine each having a fluorine substituent introduced therein alone. It may be used or in a form in which two or more thereof are mixed.

Non-limiting examples of diamine monomer (a) that can be used include oxydianiline (ODA), 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-TFDB ), 2,2'-bis (trifluoromethyl) -4,3'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -4,3'-Diaminobiphenyl), 2,2'-bis ( Trifluoromethyl) -5,5'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -5,5'-Diaminobiphenyl), 2,2'-bis (trifluoromethyl) -4,4 '-Diaminophenyl ether (2,2'-Bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 6-FODA), bis aminohydroxy phenyl hexafluoropropane (DBOH), bis amino phenoxy phenyl hexafluoro Lopropanane (4BDAF), bis amino phenoxy phenylpropane (6HMDA), bis aminophenoxy diphenylsulfone (DBSDA), bis (4-aminophenyl) sulfone (4,4'-DDS), bis (3-aminophenyl ) sulfone (3,3'-DDS), sulfonyl deep Talic anhydride (SO ₂ DPA), bis (dicarboxyphenyl) dimethylsilane, or one kind of these addition This mixture of two or more of the like is applicable.

Given high transparency, high glass transition temperature, and low yellowness, the fluorinated first diamine is a 2,2'-bis (trifluoromethyl) -4,4'-dia which may lead to linear polymerisation. Preference is given to using minobiphenyl (2,2'-TFDB). In addition, it is preferable to use bis (4-aminophenyl) sulfone (4,4'-DDS) as the sulfone-based second diamine. In addition, the hydroxy tertiary diamine is 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane (2,2-Bis (3-amino-4-methylphenyl) -hexafluoropropane, BIS-AT- AF) is preferred. In addition, it is preferable to use 2,2'-bis (trifluoromethyl) -4,4'- diaminophenyl ether (6-FODA) as said ether type 4 diamine.

In the diamine monomer (a) of the present invention, the content of the fluorinated first diamine, sulfonated second diamine, hydroxy third diamine, ether fourth diamine, alicyclic fifth diamine, and the like are not particularly limited. It may be 10 to 90 mol% based on 100 mol% of the total diamine, preferably in the range of 20 to 80 mol%.

Acid dianhydride (b) monomers used in the preparation of the transparent polyamic acid of the present invention can be used without limitation, acid dianhydrides such as fluorinated, non-fluorinated, alicyclic and the like known in the art having an acid dianhydride structure in the molecule. For example, the fluorinated first acid dianhydride, alicyclic diacid dianhydride, and non-fluorinated triacid dianhydride may be used alone or in a mixed form of two or more thereof.

In the present invention, the fluorinated first acid dianhydride monomer is not particularly limited as long as it is an aromatic acid dianhydride into which a fluorine substituent is introduced.

Examples of fluorinated first dianhydrides that can be used include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydrid, 6-FDA), 4- (trifluoromethyl) pyromellitic dianhydride (4- (trifluoromethyl) pyromellitic dianhydride, 4-TFPMDA). These may be used alone or in combination of two or more thereof. In fluorinated acid dianhydrides, 6-FDA is a very suitable compound for clearing due to its very high property of limiting the formation of change transfer complexes (CTCs) between and within molecular chains.

In addition, the alicyclic diacid dianhydride that can be used in the present invention is not particularly limited as long as it is a compound having an acid dianhydride structure having an alicyclic ring instead of an aromatic ring in the compound.

Examples of the alicyclic second dianhydride usable in the present invention include cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride (CPDA) , Bicyclo [2,2,2] -7-octene-2,3,5,6-tetracarboxylic dianhydride (BCDA), or mixtures of one or more thereof, but are not particularly limited thereto. .

The non-fluorinated tertiary acid dianhydride monomer is not particularly limited as long as it is a non-fluorinated aromatic acid dianhydride to which a fluorine substituent is not introduced.

Non-limiting examples of non-fluorinated tertiary dianhydride monomers that can be used include pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (3, 3 ′, 4,4′-Biphenyl tetracarboxylic acid dianhydride (BPDA). These may be used alone or in combination of two or more thereof.

In the present invention, the content of at least one compound selected from the group consisting of the first acid dianhydride, the second acid dianhydride and the third acid dianhydride is not particularly limited. In one example, they may each range from 10 to 100 mole percent, based on 100 mole percent total acid dianhydride, preferably in the range from 10 to 90 mole percent, more preferably 20 to 80 mole percent.

According to a preferred embodiment of the present invention, when the fluorinated first acid dianhydride and the non-fluorinated third acid dianhydride are mixed as the acid dianhydride (b), the ratio thereof may be 40 to 90: 60 to 10 mol%.

According to another preferred embodiment of the present invention, when the fluorinated first acid dianhydride and alicyclic second acid dianhydride are mixed as the acid dianhydride (b), the ratio thereof may be 30 to 70:70 to 30 mol%. have.

According to another preferred embodiment of the present invention, when the alicyclic dianhydride and non-fluorinated tertiary dianhydride are mixed as the acid dianhydride (b), the ratio of their use is 40 to 90: 60 to 10 mol% ratio. Can be.

In the transparent polyamic acid composition of the present invention, the ratio (a / b) of the number of moles of the diamine component (a) to the number of moles of the dianhydride component (b) may be 0.7 to 1.3, preferably 0.8 to 1.2. And more preferably 0.9 to 1.1.

The solvent (c) for solution polymerization of the aforementioned monomers included in the polyamic acid composition of the present invention may use any organic solvent known in the art without limitation.

Examples of solvents that can be used include m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl One or more polar solvents selected from acetate, and dimethyl phthalate (DMP) can be used. In addition, low boiling point solutions such as tetrahydrofuran (THF), chloroform or low absorbing solvents such as γ-butyrolactone may be used.

The content of the solvent is not particularly limited, but in order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, the content of the solvent for polymerization (the first solvent) may range from 50 to 95 wt% based on the total weight of the polyamic acid composition. It is preferably in the range of 70 to 90% by weight, more preferably in the range of 75 to 85% by weight.

The polyamic acid composition of the present invention may be prepared by adding the above-described acid dianhydride and diamine into an organic solvent and reacting. In one example, the diamine of Formula 1, at least one or more diamine components of the first to fifth diamine, and acid dianhydride, diamine (a) and acid dianhydride (b) to improve the glass transition temperature and yellowness Transparent polyamic acid compositions can be formed with an equivalent ratio of approximately 1: 1.

The composition of the polyamic acid composition is not particularly limited, and for example, based on 100% by weight of the total weight of the polyamic acid composition, 2.5 to 25.0% by weight of the acid dianhydride, 2.5 to 25.0% by weight of diamine, and the remaining amount to satisfy 100% by weight of the composition It may be configured to include an organic solvent of. In one example, the content of the organic solvent may be 75 to 85% by weight. Meanwhile, in the composition of the polyamic acid composition according to the present invention, based on 100% by weight of solids, the acid dianhydride may be in the range of 30 to 70% by weight, and diamine 30 to 70% by weight. However, this is not particularly limited.

Such transparent polyamic acid compositions of the present invention may have a viscosity in the range of about 1,000 to 50,000 cps, preferably about 3,000 to 15,000 cps. When the viscosity of the polyamic acid solution falls within the above-described range, the thickness of the polyamic acid solution may be easily adjusted when the solution is coated, and the coating surface may be uniformly exhibited.

In addition, the polyamic acid solution of the present invention may contain a small amount of additives such as plasticizers, antioxidants, flame retardants, dispersants, viscosity regulators, leveling agents and the like within the range that does not significantly impair the object and effect of the present invention if necessary. .

<Polyimide film>

The present invention provides a polyimide film prepared by imidizing and heat treating the polyamic acid solution described above at high temperature.

The polyimide resin is a polymer material containing an imide ring, and is excellent in heat resistance, chemical resistance, abrasion resistance, and electrical properties. In this case, the polyimide resin may be in the form of a random copolymer or a block copolymer.

Meanwhile, in order to apply a polyimide resin film to a flexible display, it should basically have characteristics such as high transparency, low thermal expansion coefficient, and high glass transition temperature. More specifically, a light transmittance of 550 nm is 90% or more based on a film thickness of 10 μm, a yellowness value of 550 nm is 3 or less, a glass transition temperature (Tg) of 300 ° C. or more is required.

Indeed, the polyimide film of the present invention prepared by imidizing the polyamic acid composition described above has a rigid chemical structure in a repeating unit and exhibits high transparency while having low yellowness, thermal expansion coefficient, and high glass transition temperature. (Tg), high tensile strength and elastic modulus. More specifically, the polyimide film has a physical property condition of the following (i) to (v), such as (i) the glass transition temperature (T _g ) is in the range of 320 to 400 ℃, (ii) the film thickness 50㎛ reference The light transmittance of 500 nm is 88% or more, (iii) the yellowness according to ASTM E313 standard is 4.0 or less (50 micrometers basis), (iv) tensile strength is 110-150 MPa, (v) tensile elasticity modulus is 3.5- The 5.0 GPa range can all be met.

The polyimide film according to the present invention may be prepared by exothermic solution polymerization of a transparent polyamic acid solution according to conventional methods known in the art. For example, the transparent polyamic acid composition may be prepared by coating (casting) a glass substrate and inducing an imide cyclization reaction (Imidazation) for 0.5 to 8 hours while gradually raising the temperature in the range of 30 to 350 ° C. It is preferable to react in inert atmosphere, such as argon and nitrogen at this time.

In this case, the coating method may be used without limitation conventional methods known in the art, for example, spin coating (dip coating), dip coating (Dip coating), solvent casting (Solvent casting), slot die coating (Slot die coating) ) And at least one method selected from the group consisting of spray coating. The colorless transparent polyimide layer may be coated at least once with a transparent polyamic acid composition such that the thickness of the colorless and transparent polyimide layer is several hundreds of micrometers.

The thickness of the polyimide film thus formed is not particularly limited and may be appropriately adjusted according to the field to be applied. For example, it may be in the range of 10 to 150㎛, preferably in the range of 10 to 80㎛.

In the present invention, the transparent polyimide film manufactured as described above may be used in various fields, and particularly, displays for organic EL devices (OLEDs), displays for liquid crystal devices, TFT substrates, flexible printed circuit boards that require high transparency and heat resistance. It can be used as a flexible display substrate and a protective film such as a flexible OLED surface lighting substrate, a substrate material for electronic paper.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are merely examples to help understanding of the present invention, but the scope of the present invention is not limited thereto.

[Diamine Monomer Synthesis of Chemical Formula 1]

Synthesis Example 1 Synthesis of Compound 1

1-1. Synthesis of Intermediate 2

1-bromo-4-nitro-2- (trifluoromethyl) benzene (54g, 200mmol), 2,2 '-(2- (trifluoromethyl) -1,4-phenylene) bis (4,4,5,5-tetramethyl- 1,3,2-dioxaborolane) (39.8 g, 100 mmol) and Pd (PPh ₃ ) ₄ (13.5 g, 10 mol%) were added to the flask. 300 ml of Toluene and 150 ml of THF were added thereto, an aqueous solution of K ₂ CO ₃ (83 g, 600 mmol) dissolved in 200 ml of distilled water was added thereto, followed by heating and stirring for 13 hours.

After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 100 ml of ethyl acetate. The solvent was removed with a rotary evaporator and then crystallized with MeOH to obtain Compound 2 (34.13 g, yield 65%).

Elemental Analysis: C, 48.11; H, 1.73; F, 32.61; N, 5.34; O, 12.21

HRMS [M] ⁺ : 524

1-2. Synthesis of Compound 1

34.13 g (65 mmol) of the intermediate 2 was added to a mixed solvent of 200 ml of ethanol and 200 ml of distilled water and stirred. 44 g of Fe powder was added thereto, followed by heating and stirring at 80 ° C. After 10 minutes, 15 ml of 3 M HCl was slowly added and stirred by heating for 7 hours. After confirming that the reaction was terminated by TLC, the reaction solution was cooled to room temperature. The reaction solution was filtered and extracted twice with 100 ml of ethyl acetate. The solvent was removed with a rotary evaporator and crystallized with HX to obtain 27.2 g of Compound 1 compound (yield 90%).

Elemental Analysis: C, 54.32; H, 2. 82; F, 36.82; N, 6.03

HRMS [M] ⁺ : 464

Synthesis Example 2 Synthesis of Compound 4

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 55.57; H, 2.80; F, 35.16; N, 6.48

HRMS [M] ⁺ : 432

Synthesis Example 3 Synthesis of Compound 5

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 51.30; H, 2. 15; F, 40.57; N, 5.98

HRMS [M] ⁺ : 468

Synthesis Example 4 Synthesis of Compound 7

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 60.61; H, 3.56; F, 28.76; N, 7.07

HRMS [M] ⁺ : 396

Synthesis Example 5 Synthesis of Compound 9

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 54.32; H, 2. 82; F, 36.82; N, 6.03

HRMS [M] ⁺ : 464

Synthesis Example 6 Synthesis of Compound 10

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 51.30; H, 2. 15; F, 40.57; N, 5.98

HRMS [M] ⁺ : 468

Synthesis Example 7 Synthesis of Compound 12

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 57.98; H, 3. 16; F, 32.10; N, 6.76

HRMS [M] ⁺ : 414

Synthesis Example 8 Synthesis of Compound 13

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 55.27; H, 2.65; F, 37.47; N, 4.60

HRMS [M] ⁺ : 608

Synthesis Example 9 Synthesis of Compound 15

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 50.67; H, 1. 64; F, 43.15; N, 4.55

HRMS [M] ⁺ : 616

Synthesis Example 10 Synthesis of Compound 16

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 61.42; H, 3. 17; F, 29.89; N, 5.51

HRMS [M] ⁺ : 508

Synthesis Example 11 Synthesis of Compound 18

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 55.27; H, 2. 65; F, 37.47; N, 4.60

HRMS [M] ⁺ : 608

Synthesis Example 12 Synthesis of Compound 20

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 61.42; H, 3. 17; F, 29.89; N, 5.51

HRMS [M] ⁺ : 508

Synthesis Example 13 Synthesis of Compound 21

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 55.86; H, 2.54; F, 37.87; N, 3.72

HRMS [M] ⁺ : 752

Synthesis Example 14 Synthesis of Compound 23

Synthesis was carried out using the same method as the synthesis of Compound 1 of Example 1.

Elemental Analysis: C, 55.86; H, 2.54; F, 37.87; N, 3.72

HRMS [M] ⁺ : 752

[Synthesis of Transparent Polyamic Acid Composition and Production of Polyimide Film]

Example 1

1-1. Preparation of Polyamic Acid Compositions

A 500 ml three-necked round bottom flask was charged with 216.366 g (85.0 wt%) of N, N-dimethylacetamide (denoted as N, N-Dimethylacetamide, hereinafter referred to as DMAc), and the temperature of the reactor was increased to 50 ° C. , 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -4,4'-Diaminobiphenyl, hereinafter referred to as TFDB) 15.0 g (90 mol%) After 30 minutes, 2.417 g (10 mol%) of Compound (1) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (1). Thereafter, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (denoted 2,2-bis (3,4-dicarboxyphenyl) Hexa fluoropropane dianhydride, hereinafter referred to as 6FDA) and pyromelli Pyromellitic dianhydride (hereinafter referred to as PMDA) was sequentially added to 18.495 g (80 mol%) and 2.270 g (20 mol%), respectively, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

1-2. Preparation of Transparent Polyimide Film

After coating the transparent polyamic acid solution on the glass plate for LCD using a bar coater (Bar Coater) in nitrogen convection oven 30 minutes at 80 ℃, 30 minutes at 150 ℃, 1 hour at 200 ℃, 1 at 300 ℃ Drying and imid ring closure (Imidazation) were performed while gradually raising the temperature step by step. This produced the transparent polyimide film with a film thickness of 52 micrometers whose imidation ratio is 85% or more. Then, the polyimide film was separated and taken from the glass plate.

Example 2

1. Preparation of Polyamic Acid Composition

After filling 210.028 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as mentioned in Example 1, the reactor was heated to 50 ° C., 7.5 g (50 mol%) of TFDB was added, and 30 minutes later. 10.875 g (50 mol%) was added to Compound (1). Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (1). Thereafter, 16.646 g (80 mol%) and 2.043 g (20 mol%) of 6FDA and PMDA were sequentially added, and then cooled to 30 ° C to be dissolved. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 3

1. Preparation of Polyamic Acid Composition

After filling 214.361 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., 15.0 g (90 mol%) was added thereto, and 30 minutes later. , 2.063 g (10 mol%) of Compound (2) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (2). Thereafter, 18.495 g (80 mol%) and 2.270 g (20 mol%) of 6FDA and PMDA were sequentially added, and then cooled to 30 ° C to be dissolved. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 4

1. Preparation of Polyamic Acid Composition

After filling 214.403 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as mentioned in Example 1, the reactor was heated to 50 ° C., 8.0 g (50 mol%) of TFDB was added, and 30 minutes later. And 9.901 g (50 mol%) of compound (2) were added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (2). Thereafter, 6FDA and PMDA were sequentially added to 17.755 g (80 mol%) and 2.180 g (20 mol%), respectively, and then cooled to 30 ° C to be dissolved. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 5

1. Preparation of Polyamic Acid Composition

After filling 12.732 g (85.0 wt%) of DMAc in a round-bottomed flask under the same conditions as described in Example 1, the temperature of the reactor was raised to 50 ° C., and 13.5 g (80 mol%) of TFDB was added thereto for 30 minutes. Thereafter, 5.610 g (20 mol%) of compound (5) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (5). Subsequently, 9.302 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (denoted as 3,3', 4,4'-Biphenyltetracarboxylic dianhydride, hereinafter referred to as BPDA) and 6FDA were respectively sequentially (60 mol%) and 9.363 g (40 mol%) were added, followed by cooling to 30 ° C to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 6

1. Preparation of Polyamic Acid Composition

After filling DM12 212.732 g (85.0 wt%) in a round bottom flask under the same conditions as mentioned in Example 1, the reactor was heated to 50 ° C., 9.5 g (60 mol%) of TFDB was added, and 30 minutes later. 10.528 g (40 mol%) of Compound (5) were added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (5). Thereafter, 8.728 g (60 mol%) and 8.785 g (40 mol%) of BPDA and 6FDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 7

1. Preparation of Polyamic Acid Composition

After filling DMAc 212.732 g (85.0 wt%) in a round bottom flask under the same conditions as described in Example 1, the temperature of the reactor was raised to 50 ° C., 14.0 g (80 mol%) of TFDB was added, and 30 minutes later. , 5.118 g (20 mol%) of compound (6) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (6). Thereafter, 9.647 g (60 mol%) and 9.710 g (40 mol%) were added to BPDA and 6FDA sequentially, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 8

1. Preparation of Polyamic Acid Composition

After filling 216.375 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., TFDB 10.0 g (60 mol%) was added, and after 30 minutes 9.749 g (40 mol%) of Compound (6) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (6). Thereafter, 9.187 g (60 mol%) and 9.248 g (40 mol%) were added to BPDA and 6FDA sequentially, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 9

1. Preparation of Polyamic Acid Composition

After filling 216.031 g (85.0 wt%) of DMAc in a round-bottomed flask under the same conditions as described in Example 1, the temperature of the reactor was raised to 50 ° C., thereby yielding 2,2′-bis (trifluoromethyl)- 8.0 g (70 mol%) of 4,4'-diaminodiphenyl ether (2,2'-Bis (trifluoromethyl) -4,4'-diamin odiphenyl ether, hereinafter referred to as 6FODA) was added, and after 30 minutes, the compound (10) 8.286 g (30 mol%) were added. Thereafter, the monomer was stirred for 1 hour to completely dissolve 6FODA and compound (10). Subsequently, 8.166 g of cyclobutane-1,2,3,4-tetracarboxylic dianhydride (hereinafter referred to as CBDA) and 6FDA were sequentially 70 mol%) and 7.927g (30mol%) were added, and it cooled to 30 degreeC and dissolved. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 10

1. Preparation of Polyamic Acid Composition

After filling 216.031 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., and 7.5 g (40 mol%) of 6FODA was added thereto, and 30 minutes later. 15.536 g (60 mol%) was added to Compound (10). Thereafter, the monomer was stirred for 1 hour to completely dissolve 6FODA and compound (10). Thereafter, 7.655 g (70 mol%) and 7.432 g (30 mol%) of CBDA and 6FDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 11

1. Preparation of Polyamic Acid Composition

After filling 212.422 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as mentioned in Example 1, the temperature of the reactor was raised to 50 ° C., and 14.0 g (70 mol%) of 6FODA was added thereto, followed by 30 minutes. 7.394 g (30 mol%) was added to the compound (13). Thereafter, the monomer was stirred for 1 hour to completely dissolve 6FODA and compound (13). Thereafter, 8.166 g (70 mol%) and 7.927 g (30 mol%) of CBDA and 6FDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 12

1. Preparation of Polyamic Acid Composition

After filling 220.319 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as mentioned in Example 1, the reactor was heated to 50 ° C., 8.0 g (40 mol%) of 6FODA was added, and 30 minutes later. 14.787 g (60 mol%) of Compound (13) were added. Thereafter, the monomer was stirred for 1 hour to completely dissolve 6FODA and compound (13). Thereafter, 8.166 g (70 mol%) and 7.927 g (30 mol%) of CBDA and 6FDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 13

1. Preparation of Polyamic Acid Composition

After filling 220.807 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as mentioned in Example 1, the temperature of the reactor was increased to 50 ° C., thereby obtaining 2,2-bis (3-amino-4-methylphenyl ) -Hexafluoropropane (2,2-Bis (3-amino-4-methylphenyl) -hexafluoropropane, hereinafter referred to as BIS-AT-AF) 1.8 g (10 mol%) was added thereto, and 30 minutes later, a compound (15 27.204 g (90 mol%) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve BIS-AT-AF and Compound (15). Thereafter, 7.794 g (80 mol%) and 2.167 g (20 mol%) of CBDA and PMDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 14

1. Preparation of Polyamic Acid Composition

After filling 210.783 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., and 5.5 g (30 mol%) of BIS-AT-AF was added thereto. After 30 minutes, 21.551 g (70 mol%) of Compound (15) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve BIS-AT-AF and Compound (15). Thereafter, 7.939 g (80 mol%) and 2.207 g (20 mol%) of CBDA and PMDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 15

1. Preparation of Polyamic Acid Composition

After filling 210.783 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the temperature of the reactor was raised to 50 ° C. to give 4,4′-diaminodiphenylsulfone (4, 1.1 g (10 mol%) of 4'-Diaminodiphenylsulfone (hereinafter referred to as 4,4'-DDS) was added, and after 30 minutes, 20.271 g (90 mol%) of compound (19) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve 4,4'-DDS and Compound (19). Thereafter, 7.821 g (60 mol%) and 7.872 g (40 mol%) of BPDA and 6FDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 16

1. Preparation of Polyamic Acid Composition

After filling 208.903 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the temperature of the reactor was raised to 50 ° C., and 3.5 g (30 mol%) of 4,4′-DDS was added. After 30 minutes, 16.722 g (70 mol%) of compound (19) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve 4,4'-DDS and Compound (19). Thereafter, 8.295 g (60 mol%) and 8.349 g (40 mol%) of BPDA and 6FDA were sequentially added, and then cooled to 30 ° C to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 17

1. Preparation of Polyamic Acid Composition

After filling 208.903 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as mentioned in Example 1, the temperature of the reactor was raised to 50 ° C., 15.0 g (90 mol%) was added thereto, and 30 minutes later. , 3.166 g (10 mol%) of Compound (21) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (21). Thereafter, 13.871 g (60 mol%) and 6.125 g (40 mol%) of 6FDA and BPDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 18

1. Preparation of Polyamic Acid Composition

After filling 210.212 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as mentioned in Example 1, the reactor was heated to 50 ° C., 7.0 g (50 mol%) of TFDB was added, and 30 minutes later. And 13.299 g (50 mol%) of compound (21) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (21). Thereafter, 11.652 g (60 mol%) and 5.145 g (40 mol%) of 6FDA and BPDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 19

1. Preparation of Polyamic Acid Composition

After filling 210.212 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., TFDB 15.0 g (90 mol%) was added, and 30 minutes later. , 3.916 g (10 mol%) of Compound (24) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (24). Then, 16.183 g (70 mol%) of 6FDA and 1,2,3,4-cyclopentanetetracarbolic dianhydride (denoted as 1,2,3,4-Cyclopentanetetracarboxylic Dianhydride, hereinafter CPDA) were sequentially 3.281g (30mol%) was added, and it cooled to 30 degreeC and dissolved. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Example 20

1. Preparation of Polyamic Acid Composition

After filling 209.418 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as mentioned in Example 1, the temperature of the reactor was increased to 50 ° C., 6.5 g (50 mol%) of TFDB was added, and 30 minutes later. 15.274 g (50 mol%) of Compound (24) was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve TFDB and compound (24). Thereafter, 6FDA and CPDA were sequentially added to 12.623 g (70 mol%) and 2.599 g (30 mol%), respectively, and then cooled to 30 ° C to be dissolved. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Comparative Example 1

1. Preparation of Polyamic Acid Composition

After filling 216.359 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., and 17.0 g (100 mol%) of TFDB was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve the TFDB. Thereafter, 6FDA and PMDA were each sequentially added 18.865 g (80 mol%) and 2.316 g (20 mol%), and then cooled to 30 ° C to be dissolved. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Comparative Example 2

1. Preparation of Polyamic Acid Composition

After filling 214.823 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., and 18.0 g (100 mol%) of TFDB was added thereto. Thereafter, the monomer was stirred for 1 hour to completely dissolve the TFDB. Thereafter, 9.922 g (60 mol%) and 9.987 g (40 mol%) were added to BPDA and 6FDA sequentially, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Comparative Example 3

1. Preparation of Polyamic Acid Composition

After filling 214.752 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., and 21.0 g (100 mol%) of 6FODA was added thereto. Thereafter, the monomer was stirred for 1 hour to completely dissolve 6FODA. Thereafter, 8.574 g (70 mol%) and 8.323 g (30 mol%) of CBDA and 6FDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

[Comparative Example 4]

1. Preparation of Polyamic Acid Composition

After filling 211.266 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the temperature of the reactor was increased to 50 ° C., and 24.0 g (100 mol%) of BIS-AT-AF was added. It was. Thereafter, the monomer was stirred for 1 hour to completely dissolve the BIS-AT-AF. Thereafter, 10.393 g (80 mol%) and 2.890 g (20 mol%) of CBDA and PMDA were sequentially added, and then cooled to 30 ° C. to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

[Comparative Example 5]

1. Preparation of Polyamic Acid Composition

After filling 206.259 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., and 15.0 g (100 mol%) of 4,4′-DDS was added. Was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve the 4,4'-DDS. Thereafter, 10.664 g (60 mol%) and 10.734 g (40 mol%) of BPDA and 6FDA were sequentially added, and then cooled to 30 ° C to dissolve. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Comparative Example 6

1. Preparation of Polyamic Acid Composition

After filling 208.837 g (85.0 wt%) of DMAc in a round bottom flask under the same conditions as described in Example 1, the reactor was heated to 50 ° C., and 17.0 g (100 mol%) of TFDB was added. Thereafter, the monomer was stirred for 1 hour to completely dissolve the TFDB. Thereafter, 6FDA and CPDA were sequentially added to 16.507 g (70 mol%) and 3.347 g (40 mol%), respectively, and then cooled to 30 ° C to be dissolved. Solid content at this time was 15%, and then stirred for 3 hours. After the reaction of the monomer was completed, it was naturally cooled to obtain a polyamic acid composition.

2. Preparation of Transparent Polyimide Film

Colorless and transparent polyimide film production process was carried out in the same manner as in Example 1.

Compositions of the polyamic acid composition prepared in Examples 1 to 20 and Comparative Examples 1 to 6 are as shown in Table 1 below. At this time, mol% represents the mole ratio of each monomer in diamine and the whole acid dianhydride.

	Diamine (mol%)		Acid dianhydride (mol%)
	First Monomer	Second Monomer	First Monomer	Second Monomer
Example 1	TFDB (90)	Compound 1 (10)	6FDA (80)	PMDA (20)
Example 2	TFDB (50)	Compound 1 (50)	6FDA (80)	PMDA (20)
Example 3	TFDB (90)	Compound 2 (10)	6FDA (80)	PMDA (20)
Example 4	TFDB (50)	Compound 2 (50)	6FDA (80)	PMDA (20)
Example 5	TFDB (80)	Compound 5 (20)	BPDA (60)	6FDA (40)
Example 6	TFDB (60)	Compound 5 (40)	BPDA (60)	6FDA (40)
Example 7	TFDB (80)	Compound 6 (20)	BPDA (60)	6FDA (40)
Example 8	TFDB (60)	Compound 6 (40)	BPDA (60)	6FDA (40)
Example 9	6FODA (70)	Compound 10 (30)	CBDA (70)	6FDA (30)
Example 10	6FODA (40)	Compound 10 (60)	CBDA (70)	6FDA (30)
Example 11	6FODA (70)	Compound 13 (30)	CBDA (70)	6FDA (30)
Example 12	6FODA (40)	Compound 13 (60)	CBDA (70)	6FDA (30)
Example 13	BIS-AT-AF (10)	Compound 15 (90)	CBDA (80)	PMDA (20)
Example 14	BIS-AT-AF (30)	Compound 15 (70)	CBDA (80)	PMDA (20)
Example 15	4,4-DDS (10)	Compound 19 (90)	BPDA (60)	6FDA (40)
Example 16	4,4-DDS (30)	Compound 19 (70)	BPDA (60)	6FDA (40)
Example 17	TFDB (90)	Compound 21 (10)	6FDA (60)	BPDA (40)
Example 18	TFDB (50)	Compound 21 (50)	6FDA (60)	BPDA (40)
Example 19	TFDB (90)	Compound 24 (10)	6FDA (70)	CPDA (30)
Example 20	TFDB (50)	Compound 24 (50)	6FDA (70)	CPDA (30)
Comparative Example 1	TFDB 100	-	6FDA (80)	PMDA (20)
Comparative Example 2	TFDB 100	-	BPDA (60)	6FDA (40)
Comparative Example 3	6FODA (100)	-	CBDA (70)	6FDA (30)
Comparative Example 4	BIS-AT-AF 100	-	CBDA (80)	PMDA (20)
Comparative Example 5	4,4-DDS (100)	-	BPDA (60)	6FDA (40)
Comparative Example 6	TFDB (10)		6FDA (7)	CPDA (3)

[Property evaluation]

Physical properties of the polyimide films prepared in Examples 1 to 20 and Comparative Examples 1 to 6 were evaluated in the following manner, and the results are shown in Table 2 below.

<Property evaluation method>

(1) Light transmittance measurement

Measurement was performed using a UV-Vis NIR Spectrophotometer (Shimadzu, model name: UV-3150) at a wavelength of 550 nm.

(2) yellowness measurement

Yellowness was measured according to ASTM E313 using a spectrophotometer (Konica Minolta, model name: CM-3700d).

(3) Measurement of tensile strength and elastic modulus

Tensile strength (MPa) and elastic modulus (GPa) were measured according to ISO 527-3 using UTM (Instron, Model Name: 5942).

(4) film thickness measurement

The thickness of the film was measured by a thickness gauge (Mitutoyo, model name: 293-140).

(5) Glass Transition Temperature (Tg)

Glass transition temperature was measured using a DMA (TA Instrument, model name: Q800).

	Thickness (㎛)	Permeability (%)	Yellow road	Glass transition temperature (℃)	Tensile Strength (Mpa)	Modulus of elasticity (Gpa)
Example 1	52	90	3.2	340	129	4.2
Example 2	50	90	2.9	345	144	4.6
Example 3	51	90	3.3	339	128	4.0
Example 4	49	90	3.1	342	141	4.4
Example 5	51	90	2.7	330	137	4.6
Example 6	52	91	2.5	337	142	4.8
Example 7	50	90	2.9	329	140	4.7
Example 8	50	90	2.8	331	144	4.9
Example 9	49	91	2.7	321	127	3.9
Example 10	51	91	2.5	336	132	4.2
Example 11	49	91	2.9	327	129	4.0
Example 12	50	91	2.7	339	136	4.4
Example 13	52	90	2.9	341	133	4.3
Example 14	48	90	2.9	338	129	4.1
Example 15	50	90	3.2	349	128	3.9
Example 16	51	90	3.7	347	124	3.7
Example 17	51	90	2.9	330	135	4.5
Example 18	50	91	2.9	337	144	4.9
Example 19	51	88	3.8	329	112	3.6
Example 20	49	89	3.5	334	124	3.9
Comparative Example 1	51	90	3.3	337	124	3.9
Comparative Example 2	50	90	2.9	325	130	4.3
Comparative Example 3	50	91	3.1	307	117	3.7
Comparative Example 4	52	88	2.9	321	109	3.6
Comparative Example 5	49	85	5.7	332	97	3.2
Comparative Example 6	51	87	4.2	319	107	3.4

As a result of looking at Table 2, in the case of the films of Examples 1 to 20 to which the new diamine monomer of Formula 1 was added according to the present invention, the light transmittance was increased in comparison with the films of Comparative Examples 1 to 6 containing no new diamine monomer. And it was found that not only has excellent optical properties of yellowishness reduction, but also excellent mechanical properties such as thermal properties due to glass transition temperature rise, tensile strength and elastic modulus increase.

Accordingly, it can be seen that the polyimide film of the present invention improves the optical, thermal, and mechanical properties of the conventional polyimide film, and the polyimide film is usefully applied as a transparent plastic substrate instead of a glass substrate when manufacturing a flat panel display. It could be confirmed.

Claims (13)

1. Compound represented by the following formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   Y is a C ₆ ~ C ₄₀ arylene group, the C ₆ ~ C ₄₀ arylene group may be substituted with a halogen or a C ₁ ~ C ₆ alkyl group substituted with a halogen atom,

   X ₁ and X ₂ are the same or different, are each independently selected from hydrogen, halogen, the group consisting of an alkyl group of C ₁ ~ C ₆ alkyl, and C ₁ ~ in which one or more hydrogen substituted with halogen atoms C _6, the Provided that at least one of X ₁ , X ₂ and Y has a halogen or a C ₁ to C ₆ alkyl group substituted with a halogen atom,

   n is an integer of 0-3.
2. The method of claim 1,

   X ₁ and X ₂ are each independently an electron-withdrawing group (EWG) which is F or CF ₃ .
3. The method of claim 1,

   In Formula 1, Y is selected from the group of substituents represented by the following formula:

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   In the above substituents,

   R ₁ to R ₃ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, F, and CF ₃ .
4. The method of claim 1,

   Compound represented by Formula 1 is selected from the group of compounds represented by the following formula.

   

   

   

   
5. (a) a diamine containing a compound of formula 1 according to any one of claims 1 to 4;

   (b) acid dianhydrides; And

   (c) comprises an organic solvent,

   Compound represented by the formula (1) is a polyamic acid composition, characterized in that included in 10 to 90 mol% range based on 100 mol% total diamine.
6. The method of claim 5,

   The diamine is fluorinated first diamine; A polyamic acid composition further comprising at least one member selected from the group consisting of sulfonated second diamine, hydroxy third diamine, ether fourth diamine, and alicyclic fifth diamine.
7. The method of claim 6,

   The content of the fluorinated first diamine, sulfone-based second diamine, hydroxy-based third diamine, ether-based fourth diamine and cycloaliphatic fifth diamine are each 10 to 90 mol% based on 100 mol% of all diamines. Polyamic acid composition to be.
8. The method of claim 5,

   The acid dianhydride is a polyamic acid composition, characterized in that it comprises one or more selected from the group consisting of fluorinated aromatic first acid dianhydride, alicyclic second acid dianhydride and non-fluorinated aromatic third acid dianhydride.
9. The method of claim 8,

   The content of at least one compound selected from the group consisting of the first acid dianhydride, the second acid dianhydride and the third acid dianhydride is 10 to 100 mol% based on 100 mol% of the total acid dianhydride. .
10. The method of claim 5,

    A ratio (a / b) of the number of moles of diamine (a) and acid dianhydride (b) is in the range of 0.7 to 1.3.
11. The transparent polyimide film manufactured by imidating the polyamic-acid composition of Claim 5.
12. The method of claim 11,

    Transparent polyimide film, characterized by satisfying the following physical property conditions of (i) to (v):

    (i) the glass transition temperature (T _g ) ranges from 320 to 400 ° C.,

    (ii) the light transmittance of wavelength 550nm is 88% or more based on the film thickness of 50 micrometers,

    (iii) the yellowness according to ASTM E313 is 4.0 or less;

    (iv) tensile strength is 110 MPa or more,

    (v) the tensile modulus is 3.5 GPa or more.
13. The method of claim 11,

    A transparent polyimide film, which is used as a substrate or a protective film for a flexible display.