KR20230055111A - Novel Polymer, composition comprising the same and film prepared therefrom - Google Patents

Abstract

One embodiment of the present invention relates to a novel polymer, a composition for film formation containing the same, and a film prepared therefrom. Specifically, the present disclosure relates to a novel polymer containing a structural unit derived from diamine of a specific structure and a polyimide-based film prepared therefrom, wherein the polyimide-based film can realize high modulus and excellent optical properties.

Description

Novel polymer, composition comprising the same and film prepared therefrom {Novel Polymer, composition comprising the same and film prepared therefrom}

The present disclosure relates to a novel polymer, a composition for forming a film comprising the same, and a film made therefrom.

More specifically, the present disclosure relates to a novel polymer including a structural unit derived from a diamine having a specific structure and a polyimide-based film prepared therefrom.

Recently, as light weight, slimness, and flexibility of display devices are considered important, research is being actively conducted to replace glass substrates, cover glasses, and the like, which have been widely used in conventional displays, with polyimide. In order to apply it to next-generation display devices, it is necessary to secure excellent optical properties as well as improve mechanical properties, so the performance requirements of polyimide-based polymers for display devices are gradually increasing.

To this end, research is being conducted to improve mechanical properties by combining monomers with strong linearity and rigidity or by introducing an amide group into colorless polyimides (CPI). However, the optical properties and mechanical properties of the polyimide-based resin are in a trade-off relationship, and this attempt has a limit in that the optical properties deteriorate even if the mechanical properties of the polyimide-based resin are improved. In addition, there is a problem of deteriorating solution handling of the polyimide-based resin, and there is a limit in that the difficulty of the process increases or the resin cannot be obtained.

Accordingly, there is a demand for the development of a polyimide-based film capable of further widening the application range by realizing improved mechanical properties, particularly excellent modulus, without deteriorating colorless and transparent performance.

One embodiment is to provide a polymer capable of preparing a polyimide-based film that simultaneously satisfies excellent mechanical and optical properties.

In addition, one embodiment is to provide a high-strength, colorless and transparent polyimide-based film using the polymer.

In addition, one embodiment provides a laminate including the polyimide-based film and an optoelectronic device including the same.

A polymer according to an embodiment of the present invention includes a structural unit derived from diamine represented by Formula 1 below; and a structural unit derived from a dianhydride, a structural unit derived from an aromatic diacid dichloride, or a combination thereof.

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are each independently (C2-C20)alkyl, (C1-C20)alkoxy, halo(C1-C20)alkyl, (C1-C20)alkylcarbonyl, (C1-C20)alkoxycarbonyl, ( C6-C20)arylcarbonyl, tri(C1-C20)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;

R ₃ is (C1-C20)alkyl, (C1-C20)alkoxy, halo(C1-C20)alkyl, (C1-C20)alkylcarbonyl, (C1-C20)alkoxycarbonyl, (C6-C20)arylcarbo yl, tri(C1-C20)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;

R ^a is hydrogen, (C1-C20)alkyl or (C6-C20)aryl;

a and b are each independently an integer of 1 to 4;

c is an integer from 0 to 4;

When a, b, and c are integers of 2 or more, each of R ₁ , R ₂ and R ₃ may be the same as or different from each other;

p is an integer from 1 to 3.)

Diamine represented by Chemical Formula 1 according to an embodiment may be represented by Chemical Formula 2 or Chemical Formula 3 below.

[Formula 2]

[Formula 3]

(In Chemical Formulas 2 and 3,

R ₁ and R ₂ are each independently (C2-C7)alkyl, (C1-C7)alkoxy, halo(C1-C7)alkyl, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, tri(C1-C7)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;

R ₃ and R ₄ are each independently (C1-C7)alkyl, (C1-C7)alkoxy, halo(C1-C7)alkyl, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, tri(C1-C7)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;

R ^a and R ^b are each independently hydrogen, (C1-C7)alkyl or (C6-C12)aryl;

a and b are each independently an integer of 1 to 3;

c and d are each independently an integer from 0 to 3;

Where a, b, c, and d are integers greater than or equal to 2, each R ₁ , R ₂ , R ₃ and R ₄ may be the same as or different from each other.)

Diamine represented by Chemical Formula 1 according to an embodiment may be represented by Chemical Formula 4 or Chemical Formula 5 below.

[Formula 4]

[Formula 5]

(In Chemical Formulas 4 and 5,

R ₃ and R ₄ are each independently (C1-C7)alkyl, (C1-C7)alkoxy, halo(C1-C7)alkyl, carboxyl, hydroxy, amino or halogen;

R ₁₁ and R ₁₂ are each independently (C2-C7)alkyl, halo(C1-C7)alkyl or halogen;

n and m are each independently an integer of 1 to 5;

x, y, c and d are each independently an integer from 0 to 2;

When x, y, c, and d are 2, each R ₁₁ , R ₁₂ , R ₃ and R ₄ may be the same as or different from each other.)

Diamine represented by Chemical Formula 1 according to an embodiment may be represented by Chemical Formula 6 or Chemical Formula 7 below.

[Formula 6]

[Formula 7]

(In Chemical Formulas 6 and 7,

R ₃ and R ₄ are each independently (C1-C5)alkyl, (C1-C5)alkoxy, halo(C1-C5)alkyl, carboxyl, hydroxy, amino or halogen;

R ₁₁ and R ₁₂ are each independently (C2-C5)alkyl, halo(C1-C5)alkyl or halogen;

x, y and d are each independently 0 or 1;

c is an integer from 0 to 2, and when x, y, c and d are 2, each R ₁₁ , R ₁₂ , R ₃ and R ₄ may be the same as or different from each other.)

Diamine represented by Chemical Formula 1 according to an embodiment may be selected from the following.

The polymer according to one embodiment may further include a structural unit derived from aromatic diamine including 2,2-bis(trifluoromethyl)benzidine.

The dianhydride according to one embodiment may include an aromatic dianhydride, an alicyclic dianhydride, or a combination thereof.

The dianhydride according to an embodiment may include a fluorine-based aromatic dianhydride and an alicyclic dianhydride.

The aromatic diacid dichloride according to one embodiment is terephthaloyl dichloride, isophthaloyl dichloride, 1,1'-biphenyl-4,4'-dicarbonyl dichloride, 1,4-naphthalenedicarboxyl It may include ric dichloride, 2,6-naphthalenedicarboxylic dichloride and 1,5-naphthalenedicarboxylic dichloride, 4,4'-oxybis(benzoylchloride), or a combination thereof. .

In addition, one embodiment of the present invention provides a composition for forming a film containing the polymer.

In addition, one embodiment of the present invention provides a film made of the composition for forming the film.

The film according to one embodiment may include polyimide, polyamide, or a combination thereof.

The film according to one embodiment may have a thickness of 1 to 500 um.

According to one embodiment, the film may have a YI of 10 or less according to ASTM E313, a haze of 2.0% or less according to ASTM D1003, and a total light transmittance of 80% or more according to ASTM D1003.

The film according to one embodiment may have a modulus of 5 GPa or more according to ASTM D882.

In addition, one embodiment of the present invention provides a laminate comprising the film.

In addition, one embodiment of the present invention provides an optoelectronic device including the film.

The polymer according to one embodiment of the present invention may provide a polyimide-based film capable of simultaneously implementing excellent optical and mechanical properties by employing a diamine having a specific structure.

Specifically, the diamine according to one embodiment of the present invention has a structure that simultaneously has a unit capable of improving mechanical properties and a unit capable of reducing the charge transfer complex (CTC) effect, polyi Mechanical properties can be more effectively improved without deterioration of yellowness and transparency of the mid-based film.

In addition, the polymer according to one embodiment of the present invention has excellent solution handling properties, so that manufacturing processability can be improved, and a film having a sufficient thickness can be manufactured.

That is, the polymer according to one embodiment of the present invention not only can provide a polyimide-based film that is colorless and transparent and has excellent mechanical strength, but also has excellent manufacturing processability, so it can be applied to various industrial fields including displays.

Unless the present invention is defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms used in the description in the present invention are merely to effectively describe specific embodiments and are not intended to limit the present invention.

The singular form used herein may be intended to include the plural form as well, unless the context dictates otherwise.

Further, as used herein, numerical ranges include lower and upper limits and all values within that range, increments logically derived from the shape and breadth of the defined range, all values defined therebetween, and the upper limit of the numerical range defined in a different form. and all possible combinations of lower bounds. Unless otherwise specifically defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

The term "comprises" in the present specification is an open description having the same meaning as expressions such as "comprises", "includes", "has" or "characterized by", elements not additionally listed, No materials or processes are excluded.

As used herein, the term “A and/or B” may mean an aspect including A and B at the same time, or may mean an aspect selected from A and B.

As used herein, the term “polymer” includes oligomers, and includes homopolymers and copolymers, wherein the copolymers include alternating polymers, block copolymers, random copolymers, branched copolymers, crosslinked copolymers, or both. it may be

As used herein, the term “polyamic acid” refers to a polymer including a structural unit having an amic acid moiety, and “polyimide” refers to a polymer including a structural unit having an imide moiety. , "Polyamide" may mean a polymer including a structural unit having an amide moiety, and "polyamideimide" may mean a polymer including a structural unit having an imide moiety and an amide moiety. As used herein, the term "polyimide precursor solution" may have the same meaning as "polyamic acid solution" and may mean a solution containing polyimide and/or polyamic acid. In addition, the "polyimide" may be used as a meaning including polyimide or polyamideimide, and "polyamic acid" may be used as a meaning including polyamic acid or polyamic acid amide.

As used herein, the term "polyimide-based film" may be used as a meaning including a polyimide film or a polyamideimide film.

As used herein, the term "halogen" may mean a fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) atom.

As used herein, the term "alkyl" is an organic radical derived from an aliphatic hydrocarbon by removing one hydrogen, and may include both straight-chain and branched forms. The alkyl may have 1 to 20 carbon atoms, specifically 1 to 15 carbon atoms, specifically 1 to 10 carbon atoms, specifically 1 to 7 carbon atoms, specifically 1 to 5 carbon atoms. Examples of the alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, ethylhexyl, and the like.

As used herein, the term "alkoxy" is represented by *-O-alkyl, where alkyl has the same definition as above. Examples of the alkoxy include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, and the like.

As used herein, the term "haloalkyl" may mean that at least one hydrogen in the alkyl is substituted with a halogen.

The term "alkylcarbonyl" as used herein refers to a *-C(=O)alkyl radical, where alkyl has the same meaning as previously defined. By way of example, examples of alkylcarbonyl radicals include, but are not limited to, methylcarbonyl, ethylcarbonyl, isopropylcarbonyl, propylcarbonyl, butylcarbonyl, isobutylcarbonyl, t-butylcarbonyl, and the like.

As used herein, the term "alkoxycarbonyl" refers to a *-C(=O)alkoxy radical, wherein alkoxy has the same definition as above. Examples include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, and the like. It doesn't work.

As used herein, the term "trialkylsilyl" refers to a *-Si(alkyl)(alkyl)(alkyl) radical, where alkyl has the same definition as above.

As used herein, the term "aryl" is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, either singly or fused, containing preferably 4 to 7, preferably 5 or 6, ring atoms in each ring. It includes a ring system and may even include a form in which a plurality of aryls are connected by single bonds. Examples include, but are not limited to, phenyl, naphthyl, biphenyl, terphenyl, and the like.

As used herein, the term "arylcarbonyl" refers to a *-C(=O)aryl radical, where aryl has the same definition as above. Examples include, but are not limited to, phenylcarbonyl, naphthylcarbonyl, anthrylcarbonyl, and the like.

As used herein, the term "cyano" means -CN, "nitro" means -NO ₂ , "hydroxy" means -OH, "amino" means -NH 2 , and "amino" means -NH ₂ . "Carboxyl" may mean -COOH.

As the polymer according to one embodiment of the present invention includes a structural unit derived from diamine having a specific structure, a film having both excellent optical and mechanical properties, specifically a film comprising polyimide, polyamide, or a combination thereof can provide.

Specifically, the diamine according to one embodiment can improve the mechanical strength of the film by including a plurality of aromatic rings, and at the same time has an asymmetric structure, thereby reducing the crystallinity and electron transfer complex (Charge Transfer Complex, CTC) effect can make it

For example, the aromatic ring is a single ring; an unfused ring in which two or more aromatic rings are linked by a single bond, a substituted or unsubstituted C1 to C5 alkylene group, O or C(=O); or a combination thereof. Specifically, the aromatic ring may include benzene, biphenyl, or a combination thereof.

For example, in the diamine, the aromatic ring may include at least one benzene and at least one biphenyl, and the aromatic rings may be connected to each other by an amide group.

Specifically, the diamine may be diamine represented by Formula 1 below.

A polymer according to an embodiment of the present invention includes a structural unit derived from diamine represented by Formula 1 below; and a structural unit derived from a dianhydride, a structural unit derived from an aromatic diacid dichloride, or a combination thereof.

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are each independently (C2-C20)alkyl, (C1-C20)alkoxy, halo(C1-C20)alkyl , (C1-C20)alkylcarbonyl, (C1-C20)alkoxycarbonyl, ( C6-C20) arylcarbonyl, tri(C1-C20)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen ;

R ₃ is (C1-C20)alkyl, (C1-C20)alkoxy, halo(C1-C20)alkyl , (C1-C20)alkylcarbonyl, (C1-C20)alkoxycarbonyl, (C6-C20)arylcarbo yl, tri(C1-C20)alkylsilyl, carboxyl, hydroxy, amino , nitro, cyano or halogen ;

R ^a is hydrogen , (C1-C20)alkyl or (C6-C20)aryl;

a and b are each independently an integer of 1 to 4;

c is an integer from 0 to 4;

When a, b, and c are integers of 2 or more, each of R ₁ , R ₂ and R ₃ may be the same as or different from each other;

p is an integer from 1 to 3.)

The polymer may include, for example, a polyamic acid moiety and/or an imide moiety by including a structural unit derived from the diamine represented by Formula 1 and a structural unit derived from the dianhydride adjacent to each other. acid-based polymers and/or polyimide-based polymers; For example, it may be a polyamide-based polymer containing an amide moiety by including a structural unit derived from the diamine represented by Chemical Formula 1 and a structural unit derived from the aromatic diacid dichloride adjacent to each other; For example, a structural unit derived from the diamine represented by Chemical Formula 1 and a structural unit derived from the dianhydride are adjacent to each other, and the structural unit derived from the diamine represented by Chemical Formula 1 and the aromatic diacid dichloride are included. It may be a polyamic acid amide-based polymer and/or a polyamide-imide-based polymer by including structural units derived from adjacent to each other.

For example, in Formula 1, when p is an integer of 2 or more, each of R ^a , R ₃ and c may be the same as or different from each other.

Diamine represented by Chemical Formula 1 according to an embodiment of the present invention has the above-mentioned structural characteristics, for example, a biphenyl group structure, an asymmetric structure and an amide bond, and thus yellowness, haze, transmittance, etc. It is possible to manufacture a film with remarkably improved mechanical properties while maintaining excellent optical properties.

In another embodiment of the present invention, p may be, for example, an integer of 1 or 2, and more specifically, the diamine of Formula 1 may be represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

(In Chemical Formulas 2 and 3,

R ₁ and R ₂ are each independently (C2-C7)alkyl, (C1-C7)alkoxy, halo(C1-C7)alkyl, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, tri(C1-C7)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;

R ₃ and R ₄ are each independently (C1-C7)alkyl, (C1-C7)alkoxy, halo(C1-C7)alkyl, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, tri(C1-C7)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;

R ^a and R ^b are each independently hydrogen, (C1-C7)alkyl or (C6-C12)aryl;

a and b are each independently an integer of 1 to 3;

c and d are each independently an integer from 0 to 3;

Where a, b, c, and d are integers greater than or equal to 2, each R ₁ , R ₂ , R ₃ and R ₄ may be the same as or different from each other.)

For example, in Chemical Formulas 1 to 3, at least one of R ₁ to R ₄ may include an alkyl group substituted with fluoro, and for example, at least one of R ₁ and R ₂ is substituted with fluoro. For example, at least one of R ₁ may include an alkyl group substituted with fluoro and at least one of R ₂ may include an alkyl group substituted with fluoro. Accordingly, it is possible to more effectively improve the deterioration of the optical properties of the film. Here, the alkyl group may be as described above, and the fluoro-substituted alkyl group may be a perfluoroalkyl group, and more specifically, -CF _{3 ,} -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , C ₅ F ₁₁ , but is not limited thereto.

For example, in Chemical Formulas 1 to 3, R ₁ to R ₄ may be the same as or different from each other, for example, R ₁ and R ₂ and R ₃ may be the same as or different from each other, for example, R ₁ And R ₂ and R ₄ may be different from each other, for example, R ₁ and R ₂ may be the same as each other, and for example, R ₃ and R ₄ may be the same as or different from each other.

For example, in Chemical Formulas 1 to 3, a and b may each independently be 1 or 2, for example, 1.

For example, in Chemical Formulas 1 to 3, c and d may each independently be an integer of 0 to 2. For example, c may be an integer from 0 to 2, d may be 0 or 1, and for example, c and d may each independently be 0 or 1.

For example, in Chemical Formulas 1 to 3, a and b may be 1 or 2, c may be an integer from 0 to 2, and d may be 0 or 1, but is not limited thereto.

According to an embodiment of the present invention, R ^a and R ^b may each independently be hydrogen or (C1-C7)alkyl, for example, hydrogen .

By introducing a fluoro-substituted alkyl group capable of reducing the charge transfer complex (CTC) effect to the biphenyl group, the deterioration of the optical properties of the film can be more effectively improved. Here, the fluoro-substituted alkyl group may be as described above. More specifically, the diamine of Formula 1 may be represented by Formula 4 or Formula 5 below.

[Formula 4]

[Formula 5]

(In Chemical Formulas 4 and 5,

R ₃ and R ₄ are each independently (C1-C7)alkyl, (C1-C7)alkoxy, halo(C1-C7)alkyl, carboxyl, hydroxy, amino or halogen;

R ₁₁ and R ₁₂ are each independently (C2-C7)alkyl, halo(C1-C7)alkyl or halogen;

n and m are each independently an integer of 1 to 5;

x, y, c and d are each independently an integer from 0 to 2;

When x, y, c, and d are 2, each R ₁₁ , R ₁₂ , R ₃ and R ₄ may be the same as or different from each other.)

In Formula 5, R ₃ and R ₄ may be the same as or different from each other.

In Chemical Formulas 4 and 5, R ₁₁ and R ₁₂ may be the same as or different from each other, and for example, R ₁₁ and R ₁₂ may each independently represent (C2-C7)alkyl.

The n and m may each independently be an integer of 1 to 3, for example, an integer of 1 or 2, for example, 1.

In addition, the x and y may be the same as or different from each other, for example, the x and y may each independently be 0 or 1, and for example, the x and y may be 0, but are not limited thereto does not

More specifically, the fluoro-substituted alkyl group may be substituted at the ortho position of the biphenyl group. While not wishing to be bound by any particular theory, substitution of an alkyl group with fluoro at the ortho position of the biphenyl group can lead to a torsion structure of the two aryl groups in the biphenyl, and the steric hindrance effect can lead to distortion in the polyimide structure or chain. It can reduce liver packing density and CTC effect. Accordingly, the optical properties of the film, for example, yellowness and haze, can be further improved.

Specifically, the diamine of Formula 1 may be represented by Formula 6 or Formula 7 below.

[Formula 6]

[Formula 7]

(In Chemical Formulas 6 and 7,

R ₃ and R ₄ are each independently (C1-C5)alkyl, (C1-C5)alkoxy, halo(C1-C5)alkyl, carboxyl, hydroxy, amino or halogen;

R ₁₁ and R ₁₂ are each independently (C2-C5)alkyl, halo(C1-C5)alkyl or halogen;

x, y and d are each independently 0 or 1;

c is an integer from 0 to 2, and when x, y, c and d are 2, each R ₁₁ , R ₁₂ , R ₃ and R ₄ may be the same as or different from each other.)

In Formula 7, R ₃ and R ₄ may be the same as or different from each other.

Also, in Chemical Formulas 6 and 7, x and y may be 0 or 1, and R ₁₁ and R ₁₂ may be the same as or different from each other, for example, R ₁₁ and R ₁₂ may each independently (C2 -C7) alkyl.

The diamine according to one embodiment of the present invention, for example, may be selected from the following, but is not limited thereto.

The polymer according to one embodiment of the present invention may further include a structural unit derived from a known diamine in addition to the structural unit derived from the diamine represented by Formula 1 above.

The known diamine is not particularly limited, but, for example, PDA (p-Phenylenediamine, p-phenylenediamine), m-PDA (m-Phenylenediamine, m-phenylenediamine), 4,4'-ODA ( 4,4'-Oxydianiline, 4,4'-oxydianiline), 3,4'-ODA (3,4'-Oxydianiline, 3,4'-oxydianiline), BAPP (2,2-Bis[4 -(4-aminophenoxy)phenyl] propane, 2,2-bis(4-[4-aminophenoxy]-phenyl)propane), TPE-Q(1,4-Bis(4-aminophenoxy)benzene, 1,4 -Bis(4-aminophenoxy)benzene), TPE-R(1,3-Bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene), BAPB(4,4'- Bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl), BAPS(2,2-Bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis( 4-[4-aminophenoxy]phenyl)sulfone), m-BAPS(2,2-Bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis(4-[3-aminophenoxy] phenyl) sulfone), HAB (3,3'-Dihydroxy-4,4'-diamino-biphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl), TB (3,3'- Dimethylbenzidine, 3,3'-dimethylbenzidine), m-TB (2,2'-Dimethylbenzidine, 2,2'-dimethylbenzidine), TFMB (2,2'-bis(trifluoromethyl)benzidine, 2,2-bis( trifluoromethyl)benzidine), 6FAPB (1,4-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene), 6FODA ( 2,2'-Bis(trifluoromethyl)-4,4'- Diaminodiphenyl Ether, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether), APB(1,3'- Bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene), 1,4-ND (1,4-Naphthalenediamine, 1,4-naphthalenediamine), 1,5-ND ( 1,5-Naphthalenediamine, 1,5-naphthalenediamine), DABA (4,4'-Diaminobenzanilide, 4,4'-diaminobenzanilide), 6-amino-2-(4-aminophenyl)benzoxazole (6-Amino-2-(4-aminophenyl)benzoxazole) and 5-amino-2-(4-aminophenyl)benzoxazole, one or two selected from 5-Amino-2-(4-aminophenyl)benzoxazole Any of the above may be used, but is not limited thereto. Specifically, the diamine compound may be a fluorine-based aromatic diamine having a fluorine substituent introduced therein, and may be selected from, for example, TFMB, 6FAPB, 6FODA, or a combination thereof, and more specifically, TFMB may be used.

As the fluorine-based aromatic diamine is additionally used as described above, as the charge transfer effect is suppressed due to the fluorine substituent, more excellent optical properties can be imparted to the film. In addition, the mechanical strength of the film can be further improved.

Specifically, when the diamine of Chemical Formula 1 and the known diamine described above are used together, the diamine of Chemical Formula 1 and the known diamine may be used in a molar ratio of 1:1 to 1:100, specifically 1:1 to 80 A molar ratio, more specifically, 1:1 to 1:50 molar ratio may be used, but is not limited thereto. As the above range is satisfied, the mechanical properties of the film may be further improved.

The dianhydride according to one embodiment of the present invention may be any compound having an acid dianhydride functional group, but may be, for example, an aromatic dianhydride, an alicyclic dianhydride, or a combination thereof. The aromatic dianhydride is, for example, BPAF (9,9-Bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride), 6FDA (4 ,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)-diphthalic (acid) anhydride), BPDA(3,3',4,4'-Biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-biphenyltetracarboxylic dianhydride), ODPA (4,4'-Oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride), SO ₂ DPA (Sulfonyldiphthalic anhydride, sulfonyl diphthalic anhydride), 6HDBA ((isopropylidenediphenoxy)bis(phthalic anhydride), isopropylidenediphenoxy)bis(phthalic anhydride)), TDA(4-(2,5-Dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride), PMDA (1,2,4,5-Benzenetetracarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride) and BTDA (Benzophenone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride) may be used, but is not limited thereto.

Specifically, the aromatic dianhydride may be a fluorine-based aromatic dianhydride, for example, BPAF, 6FDA, or a combination thereof, and more specifically, 6FDA may be used. By using the fluorine-based aromatic dianhydride, not only the optical properties of the film but also the mechanical strength, particularly the modulus, can be more effectively improved.

The alicyclic dianhydride means a dianhydride containing at least one aliphatic ring, wherein the aliphatic ring is a single ring, a fused ring in which two or more aliphatic rings are fused, or two or more aliphatic rings are single bonded; It may be a substituted or unsubstituted (C1-C5) alkylene group, or an unfused ring linked by O or C(=O). For example, CBDA (1,2,3,4-Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride), DOCDA (5-(2,5-Dioxotetrahydrofuryl)-3- methyl-3-cyclohexene-1,2-dicarboxylic anhydride 5-(2,5-dioxotetrahydrofuryl)-3-methylcyclohexene-1,2-dicarboxylic anhydride), BTA (Bicyclo[2.2 .2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride), BODA (Bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, Bicyclooctene-2,3,5,6-tetracarboxylic dianhydride), CPDA (1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1 ,2,3,4-cyclopentanetetracarboxylic dianhydride), CHDA (1,2,4,5-Cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride), TMDA (1,2,4-tricarboxy-3-methylcarboxycyclopentane dianhydride, 1,2,4-tricarboxy-3-methylcarboxycyclopentane dianhydride), TCDA (1,2,3,4-tetracarboxycyclopentane dianhydride, 1, 2,3,4-tetracarboxycyclopentane dianhydride) and any one or two or more selected from the group consisting of derivatives thereof, but is not limited thereto. Specifically, the alicyclic dianhydride may be CBDA.

More specifically, the dianhydride according to one embodiment of the present invention may use a combination of an aromatic dianhydride and an alicyclic dianhydride, for example, a combination of a fluorine-based aromatic dianhydride and an alicyclic dianhydride. For example, a combination of 6FDA and CBDA may be used.

In addition, when preparing a polymer according to an embodiment of the present invention, diamine; The equivalent ratio of dianhydride, aromatic diacid dichloride, or a combination thereof is not particularly limited, but may be 1:0.9 to 1.1, specifically 1:0.9 to 1:1. As the above range is satisfied, physical properties of the film including film forming properties may be further improved.

The aromatic diacid dichloride reacts with the aforementioned diamine to form an amide structure in the polymer chain, so that mechanical properties including modulus can be further improved within a range that does not degrade the optical properties of the film.

The aromatic diacid dichloride is, for example, IPC (isophthaloyl dichloride, isophthaloyl dichloride), TPC (Terephthaloyl dichloride, terephthaloyl dichloride), BPC ([1,1'-Biphenyl] -4,4'- dicarbonyl dichloride, [1,1'-biphenyl]-4,4'-dicarbonyl dichloride), NPC (1,4-naphthalene dicarboxylic dichloride, 1,4-naphthalenedicarboxylic dichloride), NTC ( 2,6-naphthalene dicarboxylic dichloride, 2,6-naphthalenedicarboxylic dichloride), NEC (1,5-naphthalene dicarboxylic dichloride, 1,5-naphthalenedicarboxylic dichloride), DEDC (4,4' One or two or more selected from the group consisting of -Oxybis (benzoylchloride), 4,4'-oxybis (benzoylchloride)) and their derivatives may be used, but for example, TPC may be used, which is limited thereto It is not.

In one embodiment of the present invention, when the polymer includes a structural unit derived from aromatic diacid dichloride, the content of the aromatic diacid dichloride is not particularly limited, but is, for example, 50 to 100 moles of aromatic diamine. It may be included in mol or less, and may be included in 50 mol or more. Even if the aromatic diacid dichloride is included in an amount of 50 moles or more with respect to 100 moles of the aromatic diamine, as it is combined with the diamine of Chemical Formula 1, mechanical properties may be further improved while maintaining excellent optical properties.

In addition, one embodiment of the present invention provides a composition comprising the polymer described above.

Specifically, the composition according to one embodiment of the present invention, the polymer described above; And it may be a composition for forming a film containing an organic solvent.

As the composition according to one embodiment of the present invention includes the above-described polymer, a film having significantly improved optical and mechanical properties, specifically, a polyimide-based film including polyimide, polyamide, or a combination thereof can provide Here, the combination of polyimide and polyamide may mean polyamideimide or a mixture of polyimide and polyamide. In particular, the composition according to one embodiment of the present invention has high transparency and low yellowness value, and can provide a film with significantly improved modulus value.

The organic solvent included in the composition according to an embodiment of the present invention is gamma-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy ketones such as oxy-4-methyl-2-pentanone; Aromatic hydrocarbons, such as toluene, xylene, and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , glycol ethers such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether (Cellosolve); acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and dipropylene glycol monomethyl ether acetate; alcohols such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, and carbitol; N,N-Dimethylpropionamide (DMPA), N,N-Diethylpropionamide (DEPA), N,N-Dimethylacetamide (DMAc), N,N-Diethylacetamide (DEAc), N,N- Dimethylformamide (DMF), N,N-diethylformamide (DEF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N,N-dimethylmethoxyacetamide, etc. amides; It may be one or a mixture of two or more selected from the like.

Specifically, the organic solvent may be one or a mixture of two or more selected from the above-mentioned amides. For example, the organic solvent may be amides having a boiling point of 300° C. or less, specifically, N,N-diethylformamide (DEF), N,N-diethylacetamide (DEAc), N-ethylpyrroly It may be don (NEP), N,N-dimethylpropionamide (DMPA), N,N-diethylpropionamide (DEPA), or a combination thereof.

The film-forming composition according to one embodiment of the present invention may have a solid content of 5% by weight or more, for example, 10% by weight or more, for example, 20% by weight or less, for example, 15% by weight or less, based on the total weight of the composition. may be less than or equal to weight percent. Solid content here means the said polymer.

Specifically, the film-forming composition according to one embodiment of the present invention may have a viscosity of 2,000 cps or more, for example, 5,000 cps or more, and for example, 50,000 cps or less, for example, 30,000 cps or less. Thus, a more uniform surface can be realized. At this time, the viscosity is measured by stabilizing the sample at room temperature (25 ℃) using Brookfield (RVDV-III) viscometer spindle No. 52 and stabilizing when the torque value reaches 80% can mean

Hereinafter, a method for preparing a composition for forming a film according to an embodiment of the present invention will be described in detail.

A method for preparing a composition for forming a film according to an embodiment of the present invention includes (A) dissolving a diamine compound in an organic solvent and then reacting dianhydride to prepare a polyimide precursor solution; and (B) preparing a composition for forming a film by adjusting the solid content.

Specifically, the step (A) is to polymerize the polyimide precursor by mixing diamine and dianhydride in an equivalent ratio of 1:0.9 to 1:1.1. At this time, the polymerization condition is not particularly limited, but the polymerization reaction is carried out under an inert gas atmosphere. It can be carried out, for example, while nitrogen or argon gas is refluxed in the reactor. In addition, the reaction temperature may be carried out at 20 ℃ to 70 ℃ or 30 ℃ to 70 ℃, the reaction time may be carried out for 5 hours to 30 hours, or 5 hours to 20 hours, but is not necessarily limited thereto.

In addition, the step (A) may further include introducing an aromatic diacid dichloride. In this case, polymerization may be performed by adding diamine, dianhydride and aromatic diacid dichloride together, or by reacting diamine and aromatic diacid dichloride to prepare an oligomer having an amine terminal, and then adding the oligomer and additional diamine and dianhydride It may be prepared by reacting, but is not necessarily limited thereto. When an oligomer having an amine terminal is prepared and then additional diamine and dianhydride are reacted, block-type polyamideimide can be prepared, and mechanical properties of the film can be further improved.

Specifically, in the case of preparing an oligomer having an amine terminal, the step (A) includes (i) reacting diamine with an aromatic diacid dichloride; (ii) purifying and drying the obtained oligomer; (ii) preparing a polyimide precursor solution by reacting the purified oligomer, the diamine compound, and the dianhydride; may include. In this case, an amine-terminated polyamide oligomer may be prepared by adding the diamine compound at a molar ratio of 1.01 to 2 relative to the aromatic diacid dichloride. The molecular weight of the oligomer is not particularly limited, but may be, for example, a weight average molecular weight of 1,000 to 3,000 g/mol.

In addition, after preparing the polyimide precursor solution in step (A), imidizing the polyimide precursor and obtaining a polyimide-based resin; may be further included. At this time, it may be carried out through chemical imidization, and may be imidization by further including any one or two or more selected from an imidization catalyst and a dehydrating agent. Any one or two or more selected from pyridine, isoquinoline, and β-quinoline may be used as the imidation catalyst. In addition, as the dehydrating agent, any one or two or more selected from acetic anhydride, phthalic anhydride, and maleic anhydride may be used, but is not necessarily limited thereto. At this time, after imidization of the polyimide precursor, it is precipitated and purified in a solvent to obtain a solid content (polyimide powder), which is dissolved in an organic solvent to adjust the solid content to obtain a composition for film formation.

In one embodiment, when chemical imidization is not performed as described above, the composition for forming a film according to an embodiment of the present invention may include polyimide and/or polyamic acid and an organic solvent.

In addition, one embodiment of the present invention provides a film prepared using the composition for forming the film. Specifically, the film may be a polyimide-based film including polyimide, polyamide, or a combination thereof.

The film according to one embodiment of the present invention may have low yellowness and excellent transparency, as well as high modulus and excellent mechanical strength.

The film according to one embodiment of the present invention has a thickness of 1 to 500 um, for example, 10 to 500 um, for example, 20 to 500 um, for example, 30 to 300 um, for example, 40 to 100 can be um.

The film according to one embodiment of the present invention may have a YI of 20 or less, or 10 or less, or 7 or less, or 5 or less according to ASTM E313.

The film according to one embodiment of the present invention may have a haze of 2.0% or less, or 1.5 or less, or 1.0 or less according to ASTM D1003.

The film according to one embodiment of the present invention may have a total light transmittance of 80% or more, or 85% or more, or 87% or more according to ASTM D1003.

The film according to one embodiment of the present invention may have a modulus of 5 GPa or more, 6 GPa or more, or 7 GPa or more, or 7.3 GPa or more, or 7.5 GPa or more according to ASTM D882.

The film according to one embodiment of the present invention has a YI of 10 or less according to ASTM E313, a haze of 2.0% or less according to ASTM D1003, a total light transmittance of 80% or more according to ASTM D1003, and a modulus of 5 according to ASTM D882. It can be more than GPa. Specifically, YI may be 15 or less, haze may be 1.5 or less, total light transmittance may be 85% or more, and modulus may be 6 GPa or more. More specifically, YI may be 10 or less, haze may be 1.0 or less, total light transmittance may be 87% or more, and modulus may be 7 GPa or more.

The film according to one embodiment of the present invention is prepared from diamine into which a trifluoromethyl group, which is a specific functional group, is introduced at a specific backbone and a specific position, so that excellent optical and mechanical properties as described above can be implemented. Specifically, one embodiment of the present invention includes a structural unit derived from diamine represented by Chemical Formula 1, and thus can provide a film excellent in optical properties, mechanical strength and flexibility. Therefore, the film according to one embodiment of the present invention is a device substrate, a display cover substrate, an optical film, an IC (integrated circuit) package, an electrodeposited film, a multilayer FRC (flexible printed circuit), a tape, a touch panel, and protection for an optical disk. It can be applied to various fields such as films.

Hereinafter, a method for manufacturing a film according to an embodiment of the present invention will be described in detail.

The film according to one embodiment of the present invention may be prepared by coating a composition including the polymer and a solvent according to one embodiment of the present invention on a substrate, followed by drying and/or stretching.

Specifically, the film according to one embodiment of the present invention may be prepared through chemical curing or thermal curing.

The chemical curing may include preparing a polyimide-based resin by imidizing the polyimide precursor solution according to an embodiment of the present invention; It may be prepared by including the step of forming a film by applying a resin composition (film-forming composition) obtained by dissolving the polyimide-based resin in an organic solvent.

Since the imidation is the same as described above, it is omitted.

The film forming step is a step of forming a film through drying through heat treatment after applying a composition for forming a film to a substrate. The substrate may be, for example, glass, stainless steel, or a film, and coating may be performed by a die coater, air knife, reverse roll, spray, blade, casting, gravure, spin coating, or the like.

The heat treatment may be performed in stages, for example. For example, it may be carried out by stepwise heat treatment by first drying at 70 °C to 160 °C for 1 minute to 2 hours, and secondarily drying at 150 °C to 350 °C for 1 minute to 2 hours. However, it is not necessarily limited to the temperature and time conditions, and, for example, the primary drying is performed at 80 °C to 150 °C, 70 °C to 110 °C, 130 °C to 150 °C, 90 °C, 120 °C or 140 °C. , 10 minutes to 90 minutes, 10 minutes to 60 minutes, 20 minutes to 50 minutes, or may be carried out for 30 minutes, and the secondary drying is 200 ℃ to 300 ℃, 220 ℃ to 300 ℃ or 250 ℃ to 300 ℃ In, it can be performed for 10 minutes to 90 minutes, 30 minutes to 90 minutes, or 40 minutes to 80 minutes. At this time, stepwise heat treatment may preferably raise the temperature in the range of 1 to 20 ℃ during each step movement. In addition, the heat treatment may be performed in a separate vacuum oven or an oven filled with an inert gas, but is not necessarily limited thereto.

In addition, the thermal curing according to an embodiment of the present invention may be performed at 100 to 450 °C, or 120 to 450 °C, or 150 to 450 °C. More specifically, the thermal curing may be performed at 80 to 100 ° C. for 1 minute to 2 hours, or at greater than 100 ° C. to 200 ° C. for 1 minute to 20 hours, or greater than 200 ° C. to 450 ° C. for 1 minute to 2 hours, Stepwise thermal curing may be performed under two or more temperature conditions selected from these. In addition, thermal curing may be performed in a separate vacuum oven or an oven filled with an inert gas, but is not necessarily limited thereto. In addition, a drying step may be additionally performed before the thermal curing step, if necessary. . The drying step may be performed at a temperature of 50 °C to 150 °C, 50 °C to 130 °C, 60 °C to 100 °C or about 80 °C, but is not necessarily limited thereto.

In addition, one or two or more additives selected from flame retardants, adhesion enhancers, inorganic particles, antioxidants, UV inhibitors, and plasticizers may be further mixed with the polyimide precursor solution.

In addition, the film according to one embodiment of the present invention may be provided as a laminate in which two or more layers are laminated.

Specifically, the laminate may further include a functional coating layer on at least one other surface of the film or substrate, if necessary. Non-limiting examples of the functional coating layer include a hard coating layer, an antistatic layer, an anti-fingerprint layer, an antifouling layer, an anti-scratch layer, a low refractive index layer, an antireflection layer, and an impact absorbing layer. At least one or two or more functional coating layers may be provided. can

In addition, in one embodiment of the present invention, various types of molded articles can be manufactured using the film. As an example of the molded article, it can be applied to a printed wiring board, a flexible circuit board, etc. including a film, a protective film or an insulating film, but is not limited thereto. Specifically, it can be applied to a protective film that can replace cover glass, and has the advantage of a wide range of applications in various industrial fields including displays.

More specifically, it can be used as a window cover film for flexible displays and the like.

As the film according to one embodiment of the present invention includes a structural unit derived from the diamine represented by Chemical Formula 1, it can implement excellent optical properties such as high transparency and low yellowness and excellent modulus. Accordingly, the film according to one embodiment of the present invention can be used as a window cover film such as a flexible display panel. A window cover including a film according to an embodiment of the present invention has superior optical properties and excellent visibility, as well as high modulus and excellent mechanical strength, so that it can be used as an alternative material for tempered glass.

Hereinafter, an embodiment will be described for detailed description of the present invention, but the present invention is not limited to the following embodiment.

Physical properties of the present invention were measured as follows.

<Yellowness Index (YI)>

It was measured using a Spectrophotometer (Nippon Denshoku Co., COH-5500) in accordance with the ASTM E313 standard, and the measurement results were evaluated according to the following criteria.

O: Yellowness 5 or less, X: Yellowness 5 or more

<Total light transmittance>

Total light transmittance (%) of the film was measured in the entire wavelength range of 400 nm to 700 nm using a light transmittance meter (Nippon Denshoku Co., COH-5500) according to ASTM D1003 standard.

<Haze>

In order to measure the transparency of the film, the haze (%) value was measured using a spectrophotometer (Nippon Denshoku Co., COH-5500) according to ASTM D1003 standard.

<modulus>

Modulus (GPa) was measured according to the ASTM D882 standard using Instron's UTM 3365 under the condition that a film having a length of 50 mm and a width of 10 mm was stretched at 50 mm/min at 25 °C.

[Preparation Example 1] Preparation of diamine 1

Preparation of Compound 1-A

In a nitrogen environment, 15.0 g of 2,2-bistrifluoromethylbenzidine (TFMB), 50.0 ml of tetrahydrofuran (THF), and 9.79 ml of triethylamine (TEA) were added and cooled to 0°C. A solution of 8.69 g of 4-nitrobenzoyl chloride dissolved in 50.0 ml of THF was prepared and added dropwise to the TFMB solution over 2 hours in a nitrogen environment. After completion of the dropwise addition, 100 ml of Na ₂ CO ₃ solution was added after additional stirring at room temperature (25° C.) for 2 hours. Thereafter, after washing with ethyl acetate and distilled water, the solvent was removed by distillation under reduced pressure to obtain Compound 1-A (20.6 g) as a yellow solid.

Preparation of Diamine 1

15.0 g of ammonium chloride (NH ₄ Cl) and 15.7 g of Fe powder were added to 20.6 g of Compound 1-A prepared above, and 160 ml of tetrahydrofuran (THF), 80 ml of methanol (MeOH), and 80 ml of distilled water were added. After reacting at 60 ° C. for 20 hours while vigorously stirring the mixture, residual Fe powder was removed through Celite pad filtration. Thereafter, after extraction using ethyl acetate and distilled water, diamine 1 (10.8 g, 53%) was obtained through column purification after removing the solvent by purification under reduced pressure.

^1H -NMR (DMSO-d ₆ , 500MHz, ppm): 10.19 (s, 1H), 8.26 (d, 1H, J=2.0 Hz), 7.99 (dd, 1H, J=8.5, 2.0 Hz), 7.74 ( d, 2H, J=8.5 Hz), 7.22 (d, 1H, J=8.0 Hz), 6.94 (m, 2H), 6.78 (dd, 2H, J=8.5, 2.0 Hz), 6.62 (d, 1H, J =8.5 Hz), 5.81 (s, NH ₂ ), 5.65 (s, NH ₂ ).

[Preparation Example 2] Preparation of diamine 2

Preparation of compound 2-A

After dissolving 13 g of 4-[(4-nitrobenzyl)amino]benzoic acid in 260ml of tetrahydrofuran (THF) in a nitrogen environment, the mixture was cooled to 0°C. After slowly adding 8.7 g of oxalyl chloride to the solution, 0.1 ml of dimethylformamide (DMF) was added and stirred at room temperature (25° C.) for 6 hours. Thereafter, the solvent was removed by distillation under reduced pressure to obtain 13 g of compound 2-A, 4-[(4-nitrobenzyl)amino]benzoic chloride.

Preparation of compound 2-B

In a nitrogen environment, 11.8 g of 4'-Nitro-2,2'-bis(trifluoromethyl)[1,1'-biphenyl]-4-amine HCl, 60 ml of acetone, and 8.4 g of pyridine were added. . 11.1 g of Compound B prepared above was dissolved in another 150 ml of acetone and added dropwise to the solution over 1 hour. After completion of the dropwise addition, 200 ml of distilled water was added after additional stirring at room temperature (25° C.) for 2 hours. Thereafter, after washing with ethyl acetate and distilled water, the solvent was removed by distillation under reduced pressure to obtain Compound 2-B (18.3 g) as a white solid.

Preparation of Diamine 2

15.8 g of ammonium chloride (NH ₄ Cl) and 16.5 g of Fe powder were added to 18.9 g of Compound 2-B prepared above, and 180 ml of tetrahydrofuran (THF), 90 ml of methanol (MeOH), and 90 ml of distilled water were added. After reacting at 60 ° C. for 20 hours while vigorously stirring the mixture, residual Fe powder was removed through Celite pad filtration. Thereafter, after extraction using ethyl acetate and distilled water, diamine 2 (11.2 g, 68%) was obtained through column purification after removing the solvent by purification under reduced pressure.

^1H -NMR (DMSO-d ₆ , 500MHz, ppm): 10.44 (s, 1H), 10.05 (s, 1H), 8.29 (s, 1H), 8.04 (d, 1H, J=8.0 Hz), 8.00- 7.94 (m, 4H), 7.76 (d, 2H, J=8.5 Hz), 7.28 (d, 1H, J=8.5 Hz), 6.96-6.95 (m, 2H), 6.79 (d, 1H, J=8.0 Hz) ), 6.63 (d, 2H, J=8.5 Hz), 5.82 (s, NH ₂ ), 5.66 (s, NH ₂ ).

[Preparation Example 3] Preparation of diamine 3

Preparation of compound 3-A

After dissolving 10.0 g of 4-nitro-2-fluorobenzoic acid in 100 ml of dichloromethane (DCM) in a nitrogen environment, the mixture was cooled to 0°C. After slowly adding 12.3 g of oxalyl chloride to the solution, 0.1 ml of dimethylformamide (DMF) was added and stirred at room temperature (25° C.) for 6 hours. Thereafter, the solvent was removed by distillation under reduced pressure to obtain 11.2 g of compound 3-A, 4-nitro-2-fluorobenzoyl chloride.

Preparation of compound 3-B

22.7 g of 4'-Nitro-2,2'-bis(trifluoromethyl)[1,1'-biphenyl]-4-amine HCl, 120 ml of tetrahydrofuran (THF) and 16.2 g of pyridine were prepared in a nitrogen environment. put in. 11.2 g of the compound 3-A (4-nitro-2-fluorobenzoyl chloride) was dissolved in another 100 ml of tetrahydrofuran (THF), and the solution was added over 1 hour. it was added After completion of the dropwise addition, 200 ml of distilled water was added after additional stirring at room temperature (25° C.) for 2 hours. Thereafter, after washing with ethyl acetate and distilled water, the solvent was removed by distillation under reduced pressure to obtain compound 3-B (28.8 g) as a white solid.

Preparation of Diamine 3

8.3 g of ammonium chloride (NH ₄ Cl) and 8.6 g of Fe powder were added to 10.0 g of Compound 3-B prepared above, and 100 ml of tetrahydrofuran (THF), 50 ml of methanol (MeOH), and 50 ml of distilled water were added. After reacting at 60 ° C. for 20 hours while vigorously stirring the mixture, residual Fe powder was removed through Celite pad filtration. Thereafter, after extraction using ethyl acetate and distilled water, diamine 3 (7.5 g, 85%) was obtained through column purification after removing the solvent by purification under reduced pressure.

MS: m/z: M ⁺ calculated for C ₂₁ H ₁₅ F ₇ N ₃ O ⁺ , 458.11, found 458.18

[Preparation Example 4] Preparation of diamine 4

In Example 3, 4-nitro-2,6-difluorobenzoic acid (4-nitro-2,6-fluorobenzoic acid) was used instead of 4-nitro-2-fluorobenzoic acid. Diamine 4 (6.8 g, 77%) was obtained in the same manner except for using difluorobenzoic acid).

MS: m/z: M ⁺ calculated for C ₂₁ H ₁₄ F ₈ N ₃ O ⁺ , 476.10, found 476.19

[Preparation Example 5] Preparation of diamine 5

In Example 3, 4-nitro-2-trifluoromethylbenzoic acid was used instead of 4-nitro-2-fluorobenzoic acid. ) Diamine 5 (7.9 g, 88%) was obtained in the same manner except for using.

^1H -NMR (DMSO-d ₆ , 500MHz, ppm): 10.55 (s, 1H), 8.15 (s, 1H), 7.81 (d, 1H, J=8.5 Hz), 7.38 (d, 1H, J=8.5 Hz), 7.19 (d, 1H, J=8.5 Hz), 6.90 (m, 3H), 6.77 (d, 1H, J=8.5 Hz), 6.72 (d, 1H, J=8.5 Hz), 5.95 (s, NH ₂ ), 5.62 (s, NH ₂ ).

[Preparation Example 6] Preparation of diamine 6

In Example 3, 4-nitro-2-methylbenzoic acid was used instead of 4-nitro-2-fluorobenzoic acid. Diamine 6 (8.1 g, 92%) was obtained in the same manner except for the above.

^1H -NMR (DMSO-d ₆ , 500MHz, ppm): 10.09 (s, 1H), 8.25 (s, 1H), 8.01 (d, 1H, J=8.5 Hz), 7.64 (m, 2H), 7.23 ( d, 1H, J=8.5 Hz), 6.94 (m, 2H), 6.66 (d, 1H, J=8.0 Hz), 5.66 (s, NH ₂ ), 5.60 (s, NH ₂ ), 3.35 (s, CH ₃ ).

[Preparation Example 7] Preparation of diamine 7

In Example 3, 4-nitro-2-methoxybenzoic acid was used instead of 4-nitro-2-fluorobenzoic acid. Diamine 7 (7.2 g, 81%) was obtained in the same manner except for the use.

MS: m/z: M ⁺ calculated for C ₂₂ H ₁₈ F ₆ N ₃ O ₂ ⁺ , 470.13, found 470.19

[Preparation Example 8] Preparation of diamine 8

Preparation of compound 8-A

10.0 g of 4-[(4-nitrobenzoyl)amino]-2-methyl-benzoic acid (4-[(4-nitrobenzoyl)amino]-2-methyl-benzoic acid) in a nitrogen environment After dissolving in 50 ml of THF) and 50 ml of dichloromethane (DCM), the mixture was cooled to 0°C. After slowly adding 6.34 g of oxalyl chloride to the solution, 0.1 ml of dimethylformamide (DMF) was added and stirred at room temperature (25° C.) for 8 hours. Then, the solvent was removed by distillation under reduced pressure to obtain compound 8-A (4-[(4-nitrobenzoyl)amino]-2-methyl-benzoyl chloride (4-[(4-nitrobenzoyl)amino]-2-methyl -benzoyl chloride) 10.6 g was obtained.

Preparation of compound 8-B

11.7 g of 4'-Nitro-2,2'-bis(trifluoromethyl)[1,1'-biphenyl]-4-amine HCl, 60 ml of tetrahydrofuran (THF) and 8.4 g of pyridine were mixed in a nitrogen environment. put in. 10.6 g of (4-[(4-nitrobenzoyl)amino]-2-methyl-benzoyl chloride (4-[(4-nitrobenzoyl)amino]-2-methyl-benzoyl chloride) was added to another tetrahydrofuran (THF) Dissolved in 50 ml and added dropwise to the solution over 1 hour After completion of the dropwise addition, stirring was conducted at room temperature (25 ° C) for 2 hours and 200 ml of distilled water was added Then, washing with ethyl acetate and distilled water Then, the solvent was removed by distillation under reduced pressure to obtain Compound 8-B (18.2 g) as a white solid.

Preparation of Diamine 8

6.8 g of ammonium chloride (NH ₄ Cl) and 7.1 g of Fe powder were added to 10.0 g of Compound 8-B prepared above, and 100 ml of tetrahydrofuran (THF), 50 ml of methanol (MeOH), and 50 ml of distilled water were added. . The mixture was strongly stirred and reacted at 60 ° C. for 24 hours, and then residual Fe powder was removed through Celite pad filtration. Thereafter, after extraction using ethyl acetate and distilled water, diamine 8 (8.6 g, 95%) was obtained through column purification after removing the solvent by purification under reduced pressure.

MS: m/z: M ⁺ calculated for C ₂₉ H ₂₃ F ₆ N ₄ O ₂ ⁺ , 573.17, found 573.21

[Preparation Example 9] Preparation of diamine 9

In Example 8, instead of 4-[(4-nitrobenzoyl)amino]-2-methyl-benzoic acid (4-[(4-nitrobenzoyl)amino]-2-methyl-benzoic acid) (4- [(4-nitrobenzoyl)amino]-2-trifluoromethyl-benzoic acid (4-[(4-nitrobenzoyl)amino]-2-trifluoromethyl-benzoic acid) Diamine 9 (8.4 g, 92%) was prepared.

MS: m/z: M ⁺ calculated for C ₂₉ H ₂₀ F ₉ N ₄ O ₂ ⁺ , 627.14, found 627.20

[Example 1]

N,N-dimethylacetamide (DMAc), 2,2'-bis(trifluoromethyl)benzidine (TFMB), and diamine 1 of Preparation Example 1 were put into a reactor under a nitrogen atmosphere and sufficiently dissolved. After adding cyclobutanetetracarboxylic dianhydride (CBDA) to the solution of TFMB/diamine 1 and sufficiently dissolving, 4,4'-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA) and Terephthaloyl dichloride (TPC) was added and stirred for 6 hours to dissolve and react to prepare a polyimide precursor solution. At this time, as shown in the composition ratio of Table 1 below, the amount of each monomer is 50:50 and 35:15:50 based on the molar ratio of TFMB: diamine 1: TPC: 6FDA: CBDA to 100 of diamine raw material and 100 of other raw materials And, the solid content was adjusted to 13% by weight, and the temperature of the reactor was maintained at 40 ° C. Subsequently, pyridine and acetic anhydride were added in an amount of 2.5 times the total amount of dianhydride to the polyimide precursor solution, and the mixture was stirred at 60° C. for 12 hours. Thereafter, the solution was precipitated in an excess of methanol and then filtered, and the obtained solid content was vacuum dried at 50° C. for 12 hours or more to obtain a powder. 10.45 g of the powder obtained above was dissolved in 89.55 g of N,N-dimethylacetamide (DMAc) to prepare a composition for forming a film having a solid content of 10.45% by weight. The viscosity of the prepared composition was 64,000 cps.

Solution casting of the film-forming composition was performed on a glass substrate using an applicator. Thereafter, after primary drying at 90 ° C for 30 minutes using a convection oven, additional heat treatment at 280 ° C for 1 hour under nitrogen air flow conditions, cooling to room temperature, and separating the film formed on the glass substrate from the substrate to a thickness of 51 μm A phosphorus film was obtained. The physical properties are listed in Tables 2 and 3 below.

[Example 2]

After putting N,N-dimethylacetamide (DMAc) and 2,2'-bis(trifluoromethyl)-benzidine (TFMB) in a reactor under a nitrogen atmosphere and stirring sufficiently, terephthaloyl dichloride (TPC) was added and Stir for 6 hours to dissolve and react. Thereafter, the reaction product obtained by precipitation and filtration using an excess of water was vacuum dried at 90 ° C. for 6 hours or more to obtain a polyamide oligomer.

Again, DMAc, the polyamide oligomer, additional TFMB, and diamine 1 obtained in Preparation Example 1 were put into the reactor under a nitrogen atmosphere, so that the total amount of diamine used was TFMB:diamine 1 = 50:50 molar ratio. Then, cyclobutanetetracarboxylic dianhydride (CBDA) and 4,4'-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA) were sequentially added and stirred for 12 hours to dissolve and react. to prepare a polyimide precursor solution. At this time, the amount of each monomer is 50:50 and 35:20:45 based on the molar ratio of TFMB: diamine 1: TPC: 6FDA: CBDA, based on the ratio of 100 diamine raw materials and 100 other raw materials, as shown in the composition ratio of Table 1 below. , The solid content was adjusted to be 13% by weight, and the temperature of the reactor was maintained at 40 ° C. Subsequently, pyridine and acetic anhydride were added in an amount of 2.5 times the total dianhydride mole to the polyimide precursor solution and stirred at 60° C. for 12 hours to prepare a composition for forming a film. The viscosity of the prepared composition was 48,000 cps.

Solution casting of the film-forming composition was performed on a glass substrate using an applicator. Thereafter, after primary drying at 90 ° C for 30 minutes using a convection oven, additional heat treatment at 280 ° C for 1 hour under nitrogen air flow conditions, cooling to room temperature, and separating the film formed on the glass substrate from the substrate to a thickness of 50 μm A phosphorus film was obtained. The physical properties are listed in Tables 2 and 3 below.

[Examples 3 to 14]

A film was obtained in the same manner as in Example 1, except that the addition amount of the monomer was changed as shown in Table 1 below. The physical properties of the prepared samples were measured and listed in Tables 2 and 3 below.

[Comparative Examples 1 to 7]

A film was obtained in the same manner as in Example 1, except that the addition amount of the monomer was changed as shown in Table 1 below. The physical properties of the prepared samples were measured and listed in Tables 2 and 3 below.

[Comparative Example 8]

A film was obtained in the same manner as in Example 1, except that diamine of C1 was used instead of diamine 1 and the addition amount of the monomer was changed as shown in Table 1 below. The physical properties of the prepared samples were measured and listed in Tables 2 and 3 below.

[Comparative Examples 9 and 10]

A film was obtained in the same manner as in Example 1, except that diamine of C2 was used instead of diamine 1 and the addition amount of the monomer was changed as shown in Table 1 below. The physical properties of the prepared samples were measured and listed in Tables 2 and 3 below.

[Comparative Examples 11 and 12]

A film was obtained in the same manner as in Example 1, except that diamine of C3 was used instead of diamine 1 and the addition amount of the monomer was changed as shown in Table 1 below. The physical properties of the prepared samples were measured and listed in Tables 2 and 3 below.

composition ratio (molar ratio) TFMB diamine 1 C1 C2 C3 TPC 6FDA CBDA BPAF BPDA thickness
(μm) Example 1 50 50 - - - 35 15 50 - - 51 Example 2 50 50 - - - 35 20 45 - - 50 Example 3 70 30 - - - 50 15 35 - - 50 Example 4 77 23 - - - 55 15 30 - - 48 Example 5 80 20 - - - 55 15 30 - - 48 Example 6 80 20 - - - 55 10 35 - - 48 Example 7 90 10 - - - 50 15 35 - - 50 Example 8 90 10 - - - 35 15 50 - - 49 Example 9 90 10 - - - - 85 - - 15 48 Example 10 - 100 - - - - 100 - - - 55 Example 11 - 100 - - - 70 30 - - - 50 Example 12 - 100 - - - - 80 20 - - 48 Example 13 90 10 - - - 70 15 15 - - 50 Example 14 50 50 - - - 35 50 15 - 50 Comparative Example 1 100 - - - - 55 15 30 - - 50 Comparative Example 2 100 - - - - 70 15 15 - - 50 Comparative Example 3 100 - - - - 55 20 - - 25 51 Comparative Example 4 100 - - - - 50 15 35 - - 50 Comparative Example 5 100 - - - - - 80 20 - 48 Comparative Example 6 100 - - - - - 100 - - - 55 Comparative Example 7 100 - - - - 70 30 - - - 48 Comparative Example 8 70 - 30 - - 50 15 35 - 50 Comparative Example 9 70 - - 30 - 50 15 35 - 48 Comparative Example 10 80 - - 20 - 55 15 30 - 50 Comparative Example 11 70 - - - 30 50 15 35 - 50 Comparative Example 12 50 - - - 50 35 15 50 - 50

Evaluation 1. Evaluation of film formation

The thickness of the film made of the polymer according to Examples and Comparative Examples was measured three times each with a thin film thickness meter (TESA's μ-hite), and the average values are shown in Table 1 above.

It can be seen that the film made of the polymer of Example can form a film having a thickness sufficient to be used as a flexible window cover film.

Evaluation 2: Yellowness

By measuring the yellowness of the film made of the polymer according to Examples and Comparative Examples, it is described in Table 2 below.

yellowness evaluation Example 1 4.7 O Example 2 4.5 O Example 3 4.4 O Example 4 3.5 O Example 5 3.0 O Example 6 3.6 O Example 7 3.1 O Example 8 4.0 O Example 13 3.0 O Example 14 3.6 O Comparative Example 1 2.7 O Comparative Example 2 2.5 O Comparative Example 3 4.6 O Comparative Example 4 2.6 O Comparative Example 5 1.7 O Comparative Example 6 1.7 O Comparative Example 7 2.4 O Comparative Example 8 16.6 X Comparative Example 9 6.3 X Comparative Example 10 5.4 X Comparative Example 11 5.6 X Comparative Example 12 5.2 X

As shown in Table 2, it can be confirmed that the film of the example including the structural unit derived from diamine according to one embodiment of the present invention can implement excellent yellowness applicable to a cover window of a display, a substrate material, etc. . On the other hand, the films of Comparative Examples 8 to 12 prepared from diamines (C1 to C3) that do not contain a biphenyl group and/or an asymmetric structure have significantly deteriorated yellowness compared to the films of Examples having the same monomer molar ratio and heat treatment temperature. can confirm that Accordingly, it was confirmed that the films of Comparative Examples 8 to 12 were unsuitable for application as a cover window of a display, a substrate material, and the like.

The optical properties and mechanical properties of the films of Examples and Comparative Examples having excellent yellowness were measured and listed in Table 3.

Evaluation 3. Optical and mechanical properties

TFMB diamine 1 TPC Permeability (%) Haze (%) modulus
(GPa) Example 1 50 50 35 89.2 0.8 8.0 Example 2 50 50 35 89.0 0.6 7.5 Example 3 70 30 50 89.6 0.8 7.8 Example 4 77 23 55 90.0 0.6 7.5 Example 5 80 20 55 89.7 0.3 7.6 Example 6 80 20 55 89.5 0.6 7.7 Example 7 90 10 50 90.3 0.5 7.4 Example 8 90 10 35 90.1 0.3 7.5 Example 13 90 10 70 89.0 0.8 7.2 Example 14 50 50 35 89.3 0.5 8.3 Comparative Example 1 100 - 55 90.5 0.3 6.9 Comparative Example 2 100 - 70 89.7 0.3 6.6 Comparative Example 3 100 - 55 90.3 0.3 5.8 Comparative Example 4 100 - 50 90.5 0.3 6.8 Comparative Example 5 100 - - 91.3 0.4 4.0 Comparative Example 6 100 - - 91.4 0.4 3.8 Comparative Example 7 100 - 70 90.1 0.6 5.9

Referring to Table 3, the films of the Examples include structural units derived from diamine according to one embodiment of the present invention, and thus have transmittance and haze equivalent to or superior to those of Comparative Examples 1 to 7, and significantly increased modulus It can be confirmed that it has

In summary, as the novel diamine according to one embodiment of the present invention has a biphenyl group structure, an asymmetric structure, and an amide bond, by using it as a monomer, a polyimide-based film with significantly improved mechanical properties while maintaining excellent optical properties can be manufactured.

As described above, the present invention has been described with specific details and limited examples, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above examples, and the field to which the present invention belongs Those skilled in the art can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and it will be said that not only the claims to be described later, but also all modifications equivalent or equivalent to these claims belong to the scope of the present invention. .

Claims (17)

a structural unit derived from diamine represented by Formula 1 below; and
A polymer comprising a structural unit derived from a dianhydride, a structural unit derived from an aromatic diacid dichloride, or a combination thereof:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently (C2-C20)alkyl, (C1-C20)alkoxy, halo(C1-C20)alkyl, (C1-C20)alkylcarbonyl, (C1-C20)alkoxycarbonyl, ( C6-C20)arylcarbonyl, tri(C1-C20)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;
R ₃ is (C1-C20)alkyl, (C1-C20)alkoxy, halo(C1-C20)alkyl, (C1-C20)alkylcarbonyl, (C1-C20)alkoxycarbonyl, (C6-C20)arylcarbo yl, tri(C1-C20)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;
R ^a is hydrogen, (C1-C20)alkyl or (C6-C20)aryl;
a and b are each independently an integer of 1 to 4;
c is an integer from 0 to 4;
When a, b, and c are integers of 2 or more, each of R ₁ , R ₂ and R ₃ may be the same as or different from each other;
p is an integer from 1 to 3; According to claim 1,
The diamine represented by Formula 1 is a polymer represented by Formula 2 or Formula 3 below:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
R ₁ and R ₂ are each independently (C2-C7)alkyl, (C1-C7)alkoxy, halo(C1-C7)alkyl, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, (C6-C12)arylcarbonyl, tri(C1-C7)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;
R ₃ and R ₄ are each independently (C1-C7)alkyl, (C1-C7)alkoxy, halo(C1-C7)alkyl, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, tri(C1-C7)alkylsilyl, carboxyl, hydroxy, amino, nitro, cyano or halogen;
R ^a and R ^b are each independently hydrogen, (C1-C7)alkyl or (C6-C12)aryl;
a and b are each independently an integer of 1 to 3;
c and d are each independently an integer from 0 to 3;
Where a, b, c, and d are integers greater than or equal to 2, each R ₁ , R ₂ , R ₃ and R ₄ may be the same as or different from each other. According to claim 1,
The diamine represented by Formula 1 is a polymer represented by Formula 4 or Formula 5 below:
[Formula 4]

[Formula 5]

In Formulas 4 and 5,
R ₃ and R ₄ are each independently (C1-C7)alkyl, (C1-C7)alkoxy, halo(C1-C7)alkyl, carboxyl, hydroxy, amino or halogen;
R ₁₁ and R ₁₂ are each independently (C2-C7)alkyl, halo(C1-C7)alkyl or halogen;
n and m are each independently an integer of 1 to 5;
x, y, c and d are each independently an integer from 0 to 2;
When x, y, c, and d are 2, each R ₁₁ , R ₁₂ , R ₃ and R ₄ may be the same as or different from each other. According to claim 1,
The diamine represented by Formula 1 is a polymer represented by Formula 6 or Formula 7 below:
[Formula 6]

[Formula 7]

In Formulas 6 and 7,
R ₃ and R ₄ are each independently (C1-C5)alkyl, (C1-C5)alkoxy, halo(C1-C5)alkyl, carboxyl, hydroxy, amino or halogen;
R ₁₁ and R ₁₂ are each independently (C2-C5)alkyl, halo(C1-C5)alkyl or halogen;
x, y and d are each independently 0 or 1;
c is an integer from 0 to 2, and when x, y, c and d are 2, each R ₁₁ , R ₁₂ , R ₃ and R ₄ may be the same as or different from each other. According to claim 4,
The diamine represented by Formula 1 is a polymer selected from the following.

According to claim 1,
The polymer further comprises a structural unit derived from an aromatic diamine including 2,2-bis (trifluoromethyl) benzidine. According to claim 1,
wherein the dianhydride comprises an aromatic dianhydride, an cycloaliphatic dianhydride, or a combination thereof. According to claim 1,
The dianhydride is a polymer comprising a fluorine-based aromatic dianhydride and an alicyclic dianhydride. According to claim 1,
The aromatic diacid dichloride is terephthaloyl dichloride, isophthaloyl dichloride, 1,1'-biphenyl-4,4'-dicarbonyl dichloride, 1,4-naphthalenedicarboxylic dichloride, 2 ,6-naphthalenedicarboxylic dichloride and 1,5-naphthalenedicarboxylic dichloride, 4,4'-oxybis(benzoylchloride), or combinations thereof. A composition for forming a film comprising the polymer of any one of claims 1 to 9. A film prepared from the composition for forming a film of claim 10. According to claim 11,
Wherein the film comprises polyimide, polyamide, or a combination thereof. According to claim 12,
The film is a film having a thickness of 1 to 500 um. According to claim 13,
The film has a YI of 10 or less according to ASTM E313, a haze of 2.0% or less according to ASTM D1003, and a total light transmittance of 80% or more according to ASTM D1003. According to claim 13,
The film has a modulus of 5 GPa or more according to ASTM D882. A laminate comprising the film of claim 12 . An optoelectronic device comprising the film of claim 12 .