KR20230087015A - Novel diamine compound, preparation method thereof, and composition comprising the same - Google Patents

Abstract

상기 화학식 1에서, A 고리 내지 D고리, R₁ 내지 R₆, a 내지 f 및 p의 정의는 명세서에 기재한 바와 같다.It relates to a diamine compound represented by Formula 1 below, a method for preparing the same, and a composition comprising the same. Specifically, the diamine compound represented by Formula 1 below can be used very usefully as a monomer for producing a colorless and transparent polyimide film having improved mechanical strength.
[Formula 1]

In Formula 1, ring A to ring D, R ₁ to R ₆ , definitions of a to f and p are as described in the specification.

Description

Novel diamine compound, preparation method thereof, and composition comprising the same {Novel diamine compound, preparation method thereof, and composition comprising the same}

The present disclosure relates to novel diamine compounds, methods for their preparation, and compositions comprising them. More specifically, it relates to a diamine compound which is a monomer usefully used in the production of a polyimide-based film, a method for preparing the same, and a composition including the same.

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 existing displays, with polyimide-based films. 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 films 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 provides a novel diamine compound, which is a monomer for providing a polyimide-based film capable of realizing excellent optical and mechanical properties at the same time, and a method for preparing the same.

In addition, another embodiment provides a composition for forming a polyimide-based polymer containing the novel diamine compound.

One embodiment provides a diamine compound represented by Formula 1 below.

[Formula 1]

(In Formula 1 above,

Rings A to D are each independently a (C6-C20) aromatic ring;

R ₁ and R ₂ are each independently (C1-C10)alkyl, halo(C1-C10)alkyl, (C1-C10)alkoxy, (C1-C10)alkylcarbonyl, (C1-C10)alkoxycarbonyl, ( C6-C20)arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano or helogen;

R ₃ to R ₆ are each independently (C1-C10)alkyl, halo(C1-C10)alkyl, (C1-C10)alkoxy, (C1-C10)alkylcarbonyl, (C1-C10)alkoxycarbonyl, ( C6-C20)arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano, hydroxy or helogen;

R ^a is (C1-C10)alkyl;

R ^b to R ^e are each independently hydrogen, (C1-C10)alkyl or (C6-C20)aryl;

a to f are each independently an integer of 0 to 4;

p is 0 or 1;

When a to f are integers greater than or equal to 2, each R ₁ , R ₂ , R ₃ , R _{4 ,} R ₅ and R ₆ are the same as or different from each other.)

The diamine compound represented by Chemical Formula 1 may be represented by Chemical Formula 2 or 3 below.

[Formula 2]

[Formula 3]

(In Chemical Formulas 2 and 3,

R ₁ and R ₂ are each independently (C1-C7)alkyl, halo(C1-C7)alkyl, (C1-C7)alkoxy, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano or helogen;

R ₃ to R ₆ are each independently (C1-C7)alkyl, halo(C1-C7)alkyl, (C1-C7)alkoxy, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano, hydroxy or helogen;

R ^a is (C1-C7)alkyl;

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

a to f are each independently an integer of 0 to 3;

When a to f are integers greater than or equal to 2, each R ₁ , R ₂ , R ₃ , R _{4 ,} R ₅ and R ₆ are the same as or different from each other.)

The diamine compound represented by Formula 1 may be represented by Formula 4 or 5 below.

[Formula 4]

[Formula 5]

(In Chemical Formulas 4 and 5,

R ₁ to R ₄ and R ₁₁ and R ₁₂ are each independently ( C1-C7)alkyl, halo(C1-C7)alkyl, (C1-C7)alkoxy or halogen;

a to d and x and y are each independently 0 or 1;

n and m are each independently an integer from 1 to 5.)

The diamine compound represented by Formula 1 may be represented by Formula 6 or 7 below.

[Formula 6]

[Formula 7]

(In Chemical Formulas 6 and 7,

R ₁ to R _4- are each independently (C1-C3)alkyl, (C1-C3)alkoxy, halo(C1-C3)alkyl or halogen;

a to d are each independently 0 or 1.)

The diamine compound represented by Chemical Formula 1 may be selected from the following structures.

In addition, another embodiment provides a method for preparing a diamine compound, including the step of preparing a diamine compound represented by the following formula (1) by reducing a compound represented by the following formula (A).

[Formula 1]

[Formula A]

(In Formula 1 and A,

Ring A to ring D, R ₁ to R ₆ , definitions of a to f and p are as described above.)

The reduction reaction may be performed under a reduction catalyst selected from Zn, Cu, Ag, Au, Cd, Hg, Fe, K ₄ [Fe(CN) ₆ ], NaBH ₄ or a combination thereof, and the reduction catalyst is It may further include a cocatalyst selected from NH ₄ Cl, H ₂ CO ₃ , H ₃ PO ₄ , HCl, CH ₃ COOH, or a combination thereof.

The compound represented by Formula A may be prepared by reacting a compound represented by Formula A-1 with compounds represented by Formulas B-1 and B-2 below.

[Formula A]

[Formula A-1]

[Formula B-1]

[Formula B-2]

(In the above formulas A, A-1, B-1 and B-2

X ₁ and X ₂ are each independently halogen;

Ring A to ring D, R ₁ to R ₆ , definitions of a to f and p are as described above.)

In addition, another embodiment provides a composition for forming a polyimide-based polymer including the diamine compound represented by Formula 1 above.

A polyimide-based film prepared using the novel diamine compound according to one embodiment can simultaneously implement excellent optical and mechanical properties.

Specifically, the novel diamine compound according to one embodiment has a structure having a unit capable of improving mechanical properties and a unit capable of reducing the charge transfer complex (CTC) effect, and is a polyimide-based film. Mechanical properties can be more effectively improved without deterioration of yellowness and transparency.

In addition, the diamine compound according to one embodiment has excellent solution handling properties and can improve manufacturing processability.

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

Unless defined otherwise herein, 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. The terms used in the description herein are merely to effectively describe specific embodiments and are not intended to limit the 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 herein, 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. can Here, "polyamic acid" may be used as a meaning including polyamic acid or polyamic acid amide, and "polyimide" may be used as a meaning including polyimide or polyamideimide.

As used herein, the term "polyimide precursor" has the same meaning as "polyamic acid" and may refer to a polymer including a structural unit having an amic acid moiety.

As used herein, the term "polyimide precursor solution" may have the same meaning as "polyamic acid solution", and may mean a solution containing polyamic acid or a mixture of polyamic acid and polyimide.

As used herein, the term "polyimide film" is a molded body of polyimide derived from a polyimide precursor solution, and may have the same meaning as polyimide, and includes a polyimide film or a polyamideimide film. can be used

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 "perhaloalkyl" may mean that all hydrogen atoms in the alkyl are substituted with 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 , and "hydroxy" may mean -OH.

In order to apply the polyimide film to a display device, it is necessary to improve the inherent yellowness characteristic of the polyimide film, secure colorless and transparent performance, and simultaneously improve mechanical properties. However, when a rigid compound is used to improve mechanical properties or a polymer having an amide structure is produced as a film, optical properties such as yellowness, haze and transmittance are deteriorated even though mechanical properties are improved. There are limits. In addition, the handling of the solution is lowered, so the process difficulty is increased, and there may be limitations in obtaining a film using the resin. Accordingly, there is a need for a novel diamine compound capable of imparting excellent mechanical and optical properties to the polyimide film at the same time and having excellent solution handling properties.

The novel diamine compound according to one embodiment may include a plurality of aromatic rings to improve mechanical strength of the film. At the same time, since π-conjugation is reduced by having a plurality of amide bonds, the charge transfer complex (CTC) effect can be reduced. Accordingly, the novel diamine compound can provide a polyimide-based film with remarkably improved mechanical properties without deterioration of optical properties.

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 novel diamine compound, the aromatic ring may include at least one benzene and at least one biphenyl, the aromatic rings may be linked to each other by an amide group, and specifically, the novel diamine compound It can be represented by Formula 1 below.

[Formula 1]

(In Formula 1 above,

Rings A to D are each independently a (C6-C20) aromatic ring;

R ₁ and R ₂ are each independently (C1-C10)alkyl, halo(C1-C10)alkyl, (C1-C10)alkoxy, (C1-C10)alkylcarbonyl, (C1-C10)alkoxycarbonyl, ( C6-C20)arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano or helogen;

R ₃ to R ₆ are each independently (C1-C10)alkyl, halo(C1-C10)alkyl, (C1-C10)alkoxy, (C1-C10)alkylcarbonyl, (C1-C10)alkoxycarbonyl, ( C6-C20)arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano, hydroxy or helogen;

R ^a is (C1-C10)alkyl;

R ^b to R ^e are each independently hydrogen, (C1-C10)alkyl or (C6-C20)aryl;

a to f are each independently an integer of 0 to 4;

p is 0 or 1;

When a to f are integers greater than or equal to 2, each R ₁ , R ₂ , R ₃ , R _{4 ,} R ₅ and R ₆ may be the same as or different from each other.)

As the diamine compound represented by Formula 1 has the above-described structural characteristics, for example, a biphenyl group structure and a plurality of amide bonds, it is used as a monomer while maintaining excellent optical properties such as yellowness, haze, and transmittance. Films with significantly improved mechanical properties can be produced.

The A to D rings may be, for example, benzene or naphthalene, and specifically, the diamine compound may be represented by Formula 2 or 3 below.

[Formula 2]

[Formula 3]

(In Chemical Formulas 2 and 3,

R ₁ and R ₂ are each independently (C1-C7)alkyl, halo(C1-C7)alkyl, (C1-C7)alkoxy, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano or helogen;

R ₃ to R ₆ are each independently (C1-C7)alkyl, halo(C1-C7)alkyl, (C1-C7)alkoxy, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano, hydroxy or helogen;

R ^a is (C1-C7)alkyl;

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

a to f are each independently an integer of 0 to 3;

When a to f are integers greater than or equal to 2, each R ₁ , R ₂ , R ₃ , R _{4 ,} R ₅ and R ₆ may be the same as or different from each other.)

For example, in Formulas 1 to 3, at least one of R ₅ and R ₆ may be halo(C1-C7)alkyl, and for example, at least one of R- ₅ is halo(C1-C7)alkyl, and At least one of R ₆ may be halo(C1-C7)alkyl. Accordingly, it is possible to more effectively improve the deterioration of the optical properties of the film. Specifically, the halo (C1-C7) alkyl may be perfluoro (C1-C7) alkyl, and more specifically -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , C ₅ It may be F ₁₁ , but is not limited thereto.

For example, in Formulas 1 to 3, R ₁ to R ₆ may be the same as or 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 each other may be the same, for example, R ₅ and R ₆ may be the same as each other, for example, R ₁ and R ₂ and R ₃ and R ₄ may be the same as or different from each other, for example, R ₁ and R ₂ , R ₅ and R ₆ may be the same as or different from each other, for example, R ₃ and R ₄ and R ₅ and R ₆ 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 0 to 2, for example, 0 or 1, and for example, a and b may be the same as each other.

For example, in Chemical Formulas 1 to 3, c and d may each independently be 0 to 2, for example, 0 or 1, and, for example, c and d may be the same.

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

For example, in Chemical Formulas 1 to 3, a and b may be 0 or 1, c and d may be 0 or 1, and e and f may be 1 or 2, but are not limited thereto.

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

[Formula 4]

[Formula 5]

(In Chemical Formulas 4 and 5,

R ₁ to R ₄ and R ₁₁ and R ₁₂ are each independently (C1-C7)alkyl, halo(C1-C7)alkyl, (C1-C7)alkoxy or halogen;

a to d and x and y are each independently 0 or 1;

n and m are each independently an integer from 1 to 5.)

For example, in Chemical Formulas 4 and 5, a and b may be the same as each other, and c and d may be the same as each other.

In Chemical Formulas 4 and 5, R ₁ and R ₂ may be the same as each other, and R ₃ and R ₄ may be the same as each other.

In Chemical Formulas 4 and 5, R ₁₁ and R ₁₂ may be the same as or different from each other, and R ₁₁ and R ₁₂ may each independently be (C1-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.

Also, x and y may be the same as or different from each other, and for example, x and y may be 0, but are not limited thereto.

More specifically, the perfluoroalkyl group may be substituted at the ortho position of the biphenyl group. Without wishing to be bound by any particular theory, substitution of the perfluoroalkyl group at the ortho position of the biphenyl group may induce a torsion structure of the two aryl groups in the biphenyl group, and packing within the polyimide structure or between chains due to the steric hindrance effect. Density and CTC effects can be reduced. Accordingly, the optical properties of the polyimide film, for example, yellowness and haze, can be further improved.

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

[Formula 6]

[Formula 7]

In Formulas 6 and 7,

(R ₁ to R _4- are each independently (C1-C3)alkyl, (C1-C3)alkoxy, halo(C1-C3)alkyl or halogen;

a to d are each independently 0 or 1.)

In Chemical Formulas 6 and 7, a and b may be the same as each other, c and d may be the same as each other, R ₁ and R ₂ may be the same as each other, R ₃ and R ₄ may be the same as each other, R ₁ and R ₂ , R ₃ and R ₄ may be the same as or different from each other.

Specifically, the diamine compound represented by Chemical Formula 1 may be, for example, one selected from the following, but is not limited thereto.

In addition, another embodiment provides a method for preparing the diamine compound represented by Formula 1 above.

For example, the method for preparing the diamine compound represented by Chemical Formula 1 may include preparing a diamine compound represented by Chemical Formula 1 by reducing a compound represented by Chemical Formula A below.

[Formula 1]

[Formula A]

(In Formula 1 and A,

Ring A to ring D, R ₁ to R ₆ , definitions of a to f and p are as described above.)

For example, the reduction reaction may be performed under a reduction catalyst selected from Zn, Cu, Ag, Au, Cd, Hg, Fe, K ₄ [Fe(CN) ₆ ], NaBH ₄ or a combination thereof. In addition, the reduction catalyst may further include a cocatalyst selected from NH ₄ Cl, H ₂ CO ₃ , H ₃ PO ₄ , HCl, CH ₃ COOH, or a combination thereof, specifically Fe and NH ₄ Cl. can be used together.

In addition, the reduction reaction may be performed at 40 to 80 °C for 1 to 30 hours, specifically, at 50 to 70 °C for 10 to 30 hours.

For example, the compound represented by Formula A may be prepared by reacting a compound represented by Formula A-1 with compounds represented by Formulas B-1 and B-2 below.

[Formula A]

[Formula A-1]

[Formula B-1]

[Formula B-2]

(In the above formulas A, A-1, B-1 and B-2

X ₁ and X ₂ are each independently halogen;

Ring A to ring D, R ₁ to R ₆ , definitions of a to f and p are as described above.)

For example, the reaction may be performed at 20 to 40 °C for 1 to 30 hours, specifically at 20 to 30 °C for 1 to 24 hours.

In addition, another embodiment provides a composition for forming a polyimide-based polymer including the diamine compound represented by Formula 1 above.

Specifically, a polyimide precursor (ie, polyamic acid or polyamic acid ester) may be synthesized by reacting a diamine compound represented by Formula 1 with a dianhydride, and polyimide may be synthesized through imidation of the polyimide precursor. .

That is, the diamine compound represented by Formula 1 described above may be applied as a monomer for synthesizing a polyimide-based polymer. In this case, the polyimide-based polymer means a polyimide and a polyimide precursor (ie, polyamic acid or polyamic acid ester).

In addition, another embodiment provides a polyimide precursor prepared by using the diamine compound represented by Chemical Formula 1 as a monomer.

The polyimide precursor may include a structural unit derived from the diamine compound of Chemical Formula 1 and a structural unit derived from a dianhydride. More specifically, the polyimide precursor is obtained by reacting the terminal amino group (-NH ₂ ) of the diamine compound represented by Formula 1 with the terminal anhydride group (-OC-O-CO-) of the amino group and the anhydride group. may include a repeating unit in which bonds between carbon atoms of

As the diamine compound represented by Formula 1 has the above-described structural characteristics, for example, a biphenyl group structure and a plurality of amide bonds, it is applied as a monomer to maintain excellent optical properties while maintaining mechanical properties, for example, modulus. Significantly improved polyimide films can be produced.

The polyimide precursor may further include a structural unit derived from a known diamine compound in addition to the structural unit derived from the diamine compound represented by Chemical Formula 1.

The known diamine compound 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)benzoxa One selected from sol (6-Amino-2- (4-aminophenyl) benzoxazole) and 5-amino-2- (4-aminophenyl) benzoxazole (5-Amino-2- (4-aminophenyl) benzoxazole) or Two or more may be used, but is not limited thereto. Specifically, the diamine compound may be a fluorine-based aromatic diamine compound into which a fluorine substituent is introduced, and may be, for example, one selected from TFMB, 6FAPB, 6FODA, or a combination thereof, and more specifically, TFMB may be used.

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

Specifically, when the diamine compound of Formula 1 and the above-mentioned known diamine are used together, the diamine of Formula 1 and the known diamine may be used in a molar ratio of 1:1 to 1:100, specifically 1:1 to 1:100. 80 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 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, and more specifically, may be 6FDA. 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 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 may be used, for example, a combination of 6FDA and CBDA can be used.

In addition, when preparing the polyimide precursor described above, diamine; The equivalent ratio of the dianhydride and the diamine is not particularly limited, but the equivalent ratio of all diamines and the dianhydride may be 1:0.9 to 1.1, specifically 1:0.9 to 1:1. In addition, in the polyimide precursor described above, the equivalence ratio of all structural units derived from diamine and structural units derived from dianhydride may be 1:0.9 to 1.1, specifically 1:0.9 to 1:1. there is. As the above range is satisfied, physical properties of the film including film forming properties may be further improved.

In addition, the polyimide precursor may further include a structural unit derived from an aromatic diacid dichloride. The aromatic diacid dichloride forms an amide structure in the polymer chain, and can further improve mechanical properties including modulus 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.

When the polyimide precursor further includes a structural unit derived from an aromatic diacid dichloride, the content of the structural unit derived from the aromatic diacid dichloride is not particularly limited, but, for example, a structure derived from an entire diamine compound It may be included in 50 moles or less, and may be included in 50 moles or more with respect to 100 moles of the unit. Even if the structural unit derived from the aromatic diacid dichloride is included in an amount of 50 moles or more with respect to 100 moles of the structural unit derived from the entire diamine compound, as it is combined with the diamine represented by Formula 1, the mechanical properties are maintained while maintaining excellent optical properties. can be further improved. For example, the structural unit derived from the aromatic diacid dichloride may be used in an amount of 50 moles or more, or 55 moles or more, more specifically, 55 moles to 80 moles, based on 100 moles of the structural units derived from the entire diamine compound. , but is not limited thereto. When the structural unit derived from aromatic diacid dichloride is used within the above range, mechanical properties of the polyimide film can be further improved.

In addition, another embodiment provides a polyimide prepared from the polyimide precursor.

In addition, another embodiment provides a composition for forming a polyimide film including the polyimide precursor and/or the polyimide.

Specifically, the composition for forming the polyimide film may include a polyimide precursor including a structural unit derived from the diamine compound represented by Chemical Formula 1, polyimide, or a mixture thereof; And it may be one containing an organic solvent.

As the composition includes the above-described polyimide precursor and/or polyimide, it is possible to provide a polyimide film having significantly improved mechanical properties. In particular, the composition may provide a polyimide film having significantly improved modulus value while maintaining colorless and transparent properties.

For example, the organic solvent included in the composition is gamma-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl ketones such as -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, but is not limited thereto.

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-dimethylacetamide (DMAc), N,N-diethylformamide (DEF), N,N-diethylacetamide (DEAc), N-ethylpyrrolidone (NEP), N,N-dimethylpropionamide (DMPA), N,N-di ethylpropionamide (DEPA) or a combination thereof.

The composition for forming the polyimide film 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. . Here, the solid content may mean a polymer, and may specifically mean a polyimide precursor and/or polyimide.

For example, the composition for forming a polyimide film may have a viscosity of 10,000 cps or more, for example, 15,000 cps or more, and for example, 100,000 cps or less, for example, 50,000 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 producing a composition for forming a polyimide film will be described in detail.

A method for preparing a composition for forming a polyimide film according to an embodiment includes (A) preparing a polyimide precursor solution (polyamic acid solution) by dissolving a diamine compound in an organic solvent and then reacting with dianhydride; and (B) preparing a composition for forming a polyimide 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, polymerization conditions are not particularly limited, but the polymerization reaction is carried out under an inert gas atmosphere. It is more preferred to carry out, for example, it can be carried out while refluxing nitrogen or argon gas in the reactor. In addition, the reaction temperature may be carried out at 10 ° C to 50 ° C or 20 ° C to 40 ° C, and the reaction time may be carried out for 10 hours to 40 hours, or 15 hours to 30 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 after preparing a polyamide oligomer having an amine terminal by reacting diamine and aromatic diacid dichloride, the polyamide oligomer and additional It may be prepared by reacting a diamine compound and a dianhydride, but is not necessarily limited thereto. When a polyamide 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.

For example, in the case of preparing an amine-terminated polyamide oligomer, the step (A) may include (i) reacting diamine with an aromatic diacid dichloride; (ii) purifying and drying the obtained polyamide oligomer; (iii) preparing a polyimide precursor solution by reacting the purified oligomer, the diamine compound, and the dianhydride; may include. In this case, the amine-terminated polyamide oligomer may be prepared by adding the diamine compound in a molar ratio of 1.01 to 2 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, the step (B) may further include obtaining a polyimide resin by imidizing the polyimide precursor prepared in the step (A). 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, the step of precipitating and purifying the polyimide precursor in a solvent to obtain a solid content (polyimide powder) may be further included, and the solid content is adjusted by dissolving the polyimide precursor in an organic solvent to form a polyimide film. A composition for formation can be obtained.

The molecular weight of the polyimide is not particularly limited, but may be, for example, 50,000 to 1,000,000 g/mol, specifically 50,000 to 800,000 g/mol, and more specifically 50,000 to 500,000 g/mol.

In the case where chemical imidization is not performed as described above, the composition for forming the polyimide film may not further include any one or two or more selected from an imidation catalyst and a dehydrating agent.

In addition, another embodiment provides a polyimide film prepared using the composition for forming a polyimide film. Here, the polyimide film may be used as a meaning including a polyimide film or a polyamideimide film.

Since the polyimide film includes a structural unit derived from the diamine compound of Chemical Formula 1, it may have low yellowness and excellent transparency, as well as high modulus and excellent mechanical strength.

For example, the polyimide film has a thickness of 1 to 500 um, such as 10 to 500 um, such as 20 to 500 um, such as 30 to 300 um, such as 40 to 100 um can

For example, the polyimide film may have a modulus of 6 GPa or more, 7 GPa or more, or 7.2 GPa or more according to ASTM D882.

For example, the polyimide film may have a YI of 20 or less, or 15 or less, or 10 or less according to ASTM E313, a haze of 5.0 or less, or 4.0 or less, or 2.0 or less according to ASTM D1003, and a total ray of light according to ASTM D1003. The transmittance may be 80% or more, or 85% or more, or 87% or more.

That is, the polyimide film may maintain colorless and transparent properties even in a thickness range of 40 to 100 um and realize excellent mechanical strength. Accordingly, by including a structural unit derived from the diamine compound represented by Formula 1, the polyimide film is a device substrate, a display cover substrate, an optical film, an IC (integrated circuit) package, an electrodeposited film, a multilayer FRC ( It can be applied to various fields such as flexible printed circuit), tape, touch panel, and protective film for optical disks.

Hereinafter, the manufacturing method of the polyimide film described above will be described in detail.

The polyimide film may be prepared through chemical curing or thermal curing, and may further include stretching.

The chemical curing may be performed through chemical imidation of the polyimide precursor. Specifically, preparing a polyimide resin by chemical imidization of the above-described polyimide precursor solution; and applying a resin composition (a composition for forming a polyimide film) containing the polyimide resin and forming a film.

Since the chemical 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 the above-described composition for forming a polyimide film to a substrate. For example, glass, stainless steel, or film may be used as the substrate, and application may be performed by die coater, air knife, reverse roll, spray, blade, casting, gravure, spin coating, etc., but is not limited thereto.

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 may be performed through thermal imidization of the above-described polyimide precursor. Specifically, it may be performed by applying a composition for forming a polyimide film including a polyimide precursor or a mixture of a polyimide precursor and polyimide to a substrate, followed by thermal curing.

The thermal curing 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, before the thermal curing step, a drying step may be additionally performed 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, a polyimide film may be prepared by further mixing one or two or more additives selected from a flame retardant, an adhesion enhancer, an inorganic particle, an antioxidant, an ultraviolet inhibitor, and a plasticizer in the polyimide precursor solution.

In addition, the polyimide film may be provided as a multilayer structure having two or more layers.

Specifically, the multi-layer structure 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 another embodiment, various types of molded articles may be manufactured using the polyimide 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, the polyimide film can be used as a window cover film for a flexible display panel. A window cover including the above-described polyimide film not only has excellent optical properties and excellent visibility, but also has high modulus and excellent mechanical strength, so it can be used as an alternative material for tempered glass.

Hereinafter, the above-described implementation examples will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of rights.

Physical properties of the examples were measured as follows.

<Weight Average Molecular Weight>

Measurements were made by dissolving the film in DMAc eluent containing 0.05M LiCl. For GPC, Waters GPC system, Waters 1515 isocratic HPLC Pump, and Waters 2414 Refractive Index detector were used, and Olexis, Polypore, and mixed D columns were connected to the column, and polymethyl methacrylate (PMMA STD) was used as a standard material. Analysis was performed at 35 °C and a flow rate of 1 mL/min.

<Modulus>

In accordance with the ASTM D882 standard, a polyamideimide film having a length of 50 mm and a width of 10 mm was measured using Instron's UTM 3365 under conditions of pulling at 50 mm/min at 25 °C. The thickness of the film was measured and the value was input into the instrument. The modulus unit is GPa.

[Example 1] Preparation of Diamine Compound 1

Preparation of Compound 1-A

15 g of 4-[(4-nitrobenzoyl)amino]benzoic acid (4-[(4-nitrobenzoyl)amino]benzoic acid, compound 1-0) was dissolved in 300 ml of dichloromethane (DCM) in a nitrogen environment. and then cooled to 0°C. After slowly adding 17 g of oxalyl chloride to the solution, 0.1 ml of dimethylformamide (DMF) was added, followed by stirring at room temperature (25° C.) for 6 hours. Thereafter, the solvent was removed by distillation under reduced pressure to obtain 16 g of 4-[(4-nitrobenzoyl)amino]benzoyl chloride (4-[(4-nitrobenzoyl)amino]benzoyl chloride, Compound 1-A).

Preparation of Compound 1-B

Then, in a separate reactor, 7.55 g of 2,2'-Bis (trifluoromethyl) benzidine (TFMB) was dissolved in 150 ml of tetrahydrofuran (THF) and triethyl 7.95 g of amine (Triethyl amine, TEA) was added at room temperature. After dissolving 16 g of Compound 1-A obtained above in 50 ml of THF, the mixture was stirred at room temperature for 24 hours. Thereafter, 300 ml of ethyl acetate and 300 ml of distilled water were added to separate the layers, and the aqueous layer was removed. After washing the organic layer once with 300 ml of distilled water, the organic layer was dried over magnesium sulfate and the solid was filtered. The organic layer was concentrated under reduced pressure until a solid was precipitated, and 300 ml of hexane was added and stirred for 1 hour, and the resulting solid was filtered and dried to obtain 16.3 g of Compound 1-B.

¹ H-NMR (DMSO-d ₆ , 500 MHz, ppm): 10.80 (s, 2H), 10.53 (s, 2H), 8.34 (m, 6H), 8.18 (m, 4H), 8.08 (m, 2H), 8.01 (m, 4H), 7.93 (m, 4H), 7.34 (m, 2H).

Preparation of diamine compound 1

16.0 g of the compound 1-B prepared above was dissolved in 160 ml of tetrahydrofuran (THF), 80 ml of methanol (MeOH), and 80 ml of distilled water, and 11.0 g of Fe powder and 10.5 g of ammonium chloride (NH ₄ Cl) were dissolved at room temperature. g was added. The temperature was raised to 60 °C and stirred for 24 hours. After filtering the solid material present in the reaction solution using a Celite pad and 400 ml of ethyl acetate, the layers were separated by adding 400 ml of distilled water, and the aqueous layer was removed. Thereafter, the organic layer was washed once with 300 ml of distilled water, dried over magnesium sulfate, and the solid was filtered. The organic layer was concentrated under reduced pressure until a solid was precipitated, and 300 ml of DCM and 300 ml of Hexane were sequentially added thereto, and the resulting solid was filtered and dried to obtain 13.1 g of diamine compound 1.

¹ H-NMR (DMSO-d ₆ , 500 MHz, ppm): 10.46 (s, 2H), 10.00 (s, 2H), 8.31 (s, 2H), 8.07 (d, 2H), 7.94 (m, 8H), 7.71 (d, 4H), 7.32 (d, 2H), 6.57 (d, 4H), 5.77 (s, 4H).

[Example 2] Preparation of diamine compound 2

Preparation of compound 2-A

In a nitrogen environment, 10.0 g of 3-Methyl-4-amino benzoic acid was dissolved in 90 ml of THF and then cooled to 0 °C. 7.9 g of pyridine was added to the solution at room temperature. After dissolving 12.9 g of 4-nitrobenzoyl chloride in 35 ml of THF, the mixture was stirred at room temperature for 2 hours. Then, after adding 100 ml of distilled water, the THF solvent was distilled off. The resulting solid was filtered and washed with plenty of water to obtain 3-methyl 4-[(4-nitrobenzoyl)amino]benzoic acid (compound 2-A) 15.5 got g.

¹ H-NMR (DMSO-d ₆ , 500 MHz, ppm): 10.33 (s, 1H), 8.38 (d, 2H), 8.21 (d, 2H), 7.87 (s, 1H), 7.81 (d, 1H), 7.56 (d, 1H), 2.32 (s, 3H).

Preparation of diamine compound 2

Diamine compound 2 was prepared in the same manner as in Example 1, except that Compound 2-A was used instead of Compound 1-0.

¹ H-NMR (DMSO-d ₆ , 500 MHz, ppm): 10.56 (s, 2H), 9.47 (s, 2H), 8.36 (d, 2H), 8.12 (t, 2H), 7.90 (s, 2H), 7.84 (t, 2H), 7.75 (d, 4H), 7.63 (d, 2H), 7.37 (d, 2H), 6.62 (d, 4H), 5.75 (s, 4H), 2.35 (s, 6H).

[Example 3] Preparation of diamine compound 3

In Example 2, 2-trifluoromethyl-4-nitrobenzoyl chloride was used instead of 4-nitrobenzoyl chloride, and 3-methyl-4-amino Diamine compound 3 was prepared in the same manner except that 4-aminobenzoic acid was used instead of benzoic acid (3-Methyl-4-aminobenzoic acid).

¹ H-NMR (DMSO-d ₆ , 500 MHz, ppm): 10.49 (s, 2H), 10.47 (s, 2H), 8.30 (d, 2H), 8.06 (d, 2H), 7.96 (m, 4H), 7.81 (m, 4H), 7.35 (m, 4H), 6.92 (d, 2H). , 6.78 (d, 2H), 5.92 (s, 4H).

[Example 4] Preparation of diamine compound 4

Diamine was prepared in the same manner as in Example 3, except that 3-nitrobenzoyl chloride was used instead of 2-trifluoromethyl-4-nitrobenzoyl chloride. Compound 4 was prepared. ¹ H-NMR (DMSO-d ₆ , 500 MHz, ppm): 10.54 (s, 2H), 10.38 (s, 2H), 8.36 (s, 2H), 8.12 (d, 2H), 8.00 (m, 8H), 7.39 (d, 2H), 7.19 (d, 2H), 7.12 (d, 4H), 6.78 (d, 2H), 5.36 (s, 4H).

[Example 5] Preparation of diamine compound 5

Preparation of compound 5-A

In a nitrogen environment, 15.0 g of 2,2-bis(trifluoromethyl)benzidine (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 5-A (20.6 g) as a yellow solid.

Preparation of compound 5-B

15.0 g of ammonium chloride (NH ₄ Cl) and 15.7 g of Fe powder were added to 20.6 g of the compound 5-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 (EA) and distilled water, the solvent was removed by purification under reduced pressure, and compound 5-B (10.8 g, 53%) was obtained through column purification.

^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 of Compound 5-C

In a nitrogen environment, 8.5 g of the compound 5-B prepared above, 40 ml of THF, and 6.31 ml of TEA were added and then cooled to 0 °C. Then, after preparing a solution in which 7.39 g of 4-Nitrobenzoyl chloride was dissolved in another 40 ml of THF, it was slowly added dropwise to the compound 5-B solution in a nitrogen environment. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, washed with EA and distilled water to remove impurities, and the solvent was removed by distillation under reduced pressure to obtain Compound 5-C (13.0 g) as a yellow solid.

Preparation of diamine compound 5

7.54 g of NH ₄ Cl and 7.88 g of Fe powder were added to 13.0 g of the compound 5-C prepared above, and 150 ml of THF, 75 ml of MeOH, and 75 ml of H ₂ O were added. The mixture was strongly stirred and reacted at 60 ℃ for 20 hours, then residual Fe powder was removed through filtration with a Celite pad, extraction was performed using EA and water, the solvent was removed by purification under reduced pressure, and diamine was solidified using Ether/DCM. Compound 5 (11.2 g, 95%) was obtained.

^1H -NMR (DMSO-d ₆ , 500MHz, ppm): 10.50 (s, 1H), 10.15 (s, 1H), 10.04 (s, 1H), 8.34 (dd, 2H, J=8.0, 1.5 Hz), 8.10 (d, 1H, J=9.5 Hz), 8.07 (d, 1H, J=9.0 Hz), 7.99 (d, 2H, J=8.5 Hz), 7.95 (d, 2H, J=9.0 Hz), 7.36 ( d, 2H, J=8.5 Hz), 7.32 (d, 2H, J=8.5 Hz), 6.62 (m, 4H), 5.84 (s, NH2), 5.82 (s, _NH2 ).

[Example 6] Preparation of diamine compound 6

In Example 3, 3-methyl-4-nitrobenzoyl chloride was used instead of 2-trifluoromethyl-4-nitrobenzoyl chloride. Diamine compound 6 was prepared in the same manner except for the above.

¹ H-NMR (DMSO-d ₆ , 500 MHz, ppm): 10.50 (s, 2H), 10.04 (s, 2H), 8.36 (s, 2H), 8.11 (d, 2H), 7.97 (m, 8H), 7.65 (m, 4H), 7.37 (d, 2H), 6.66 (d, 2H), 5.58 (s, 4H), 2.13 (s, 6H).

<Experimental Example> Production of polyimide film

[Experimental Example 1]

Preparation of composition for forming polyimide film

After putting N,N-dimethylacetamide (DMAc) and 2,2'-bis(trifluoromethyl)-benzidine (TFMB) in a reactor under a nitrogen atmosphere and stirring them sufficiently, terephthaloyldichloride (TPC) was added and 6 The mixture was dissolved and reacted by stirring for a period of time. 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 compound 1 prepared in Example 1 were put in a reactor under a nitrogen atmosphere to make 100 moles of aromatic diamine (TFMB: diamine compound 1 = 80: 20 mole ratio). . Thereafter, cyclobutanetetracarboxylic dianhydride (CBDA) and 4,4'-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA) were sequentially added to have a molar ratio as shown in Table 1 below, A polyamic acid solution (polyimide precursor solution) was prepared by dissolving and reacting at 40 ° C. for 12 hours while stirring. At this time, the amount of each monomer is 80:20 and 55:15:30 based on the molar ratio of TFMB: diamine compound 1: TPC: 6FDA: CBDA to 100 of diamine raw material and 100 of other raw materials, as shown in the composition ratio of Table 1 below. And, the solid content was adjusted to 10% by weight, and the temperature of the reactor was maintained at 40 ° C.

Subsequently, pyridine and acetic anhydride were added to the polyamic acid solution in an amount of 2.5 times the total dianhydride, respectively, and stirred at 60 ° C. for 12 hours to obtain a composition containing a polyamideimide resin (film-forming composition 1) was manufactured. The weight average molecular weight of the polyamideimide resin was 270,000 g/mol.

Manufacture of polyimide film

Solution casting of the composition for film formation of Experimental Example 1 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, followed by cooling at room temperature. Thereafter, the film formed on the glass substrate was separated from the substrate to obtain a polyimide film of Experimental Example 1 having a thickness of about 50 μm.

[Experimental Examples 2 to 5]

A polyimide film was obtained in the same manner as in Experimental Example 1, except that the type and amount of the monomers were changed as shown in Table 1 below. The physical properties of the prepared samples were measured and listed in Table 2 below.

[Comparative Experimental Examples 1 and 2]

A polyimide film was obtained in the same manner as in Experimental Example 1, except that the type and amount of the monomers were changed as shown in Table 1 below. The physical properties of the prepared samples were measured and listed in Table 2 below.

composition ratio (molar ratio) thickness
(μm) TFMB Diamine Compound (Example) TPC 6FDA CBDA One 2 3 4 Experimental Example 1 80 20 - - 55 15 30 50 Experimental Example 2 70 30 - - 50 15 35 51 Experimental Example 3 70 - 30 - 50 15 35 51 Experimental Example 4 70 - 30 - 50 15 35 54 Experimental Example 5 70 - - - 30 50 15 35 49 Comparative Experimental Example 1 100 - - - - 55 15 30 50 Comparative Experimental Example 2 100 - - - - 50 15 35 50

Evaluation 1. Evaluation of film formation

The thickness of the film according to the Experimental Example and Comparative Experimental Example 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 diamine compound of Example can form a film having a thickness sufficient to be used as a flexible window cover film.

Evaluation 2. Modulus

The modulus of the film according to the Experimental Example and the Comparative Experimental Example was measured and shown in Table 2 below.

modulus Experimental Example 1 7.9 Experimental Example 2 8.2 Experimental Example 3 8.4 Comparative Experimental Example 1 7.1 Comparative Experimental Example 2 6.8

Referring to Table 1, the polyimide films according to Experimental Examples 1 to 3 contain structural units derived from the diamine compound represented by Chemical Formula 1, and thus have a higher modulus than the polyimide films of Comparative Examples 1 and 2. can confirm that

That is, a polyimide film having high modulus and mechanical properties while maintaining excellent optical properties can be prepared from the diamine compound represented by Formula 1.

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 (10)

A diamine compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
Rings A to D are each independently a (C6-C20) aromatic ring;
R ₁ and R ₂ are each independently (C1-C10)alkyl, halo(C1-C10)alkyl, (C1-C10)alkoxy, (C1-C10)alkylcarbonyl, (C1-C10)alkoxycarbonyl, ( C6-C20)arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano or helogen;
R ₃ to R ₆ are each independently (C1-C10)alkyl, halo(C1-C10)alkyl, (C1-C10)alkoxy, (C1-C10)alkylcarbonyl, (C1-C10)alkoxycarbonyl, ( C6-C20)arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano, hydroxy or helogen;
R ^a is (C1-C10)alkyl;
R ^b to R ^e are each independently hydrogen, (C1-C10)alkyl or (C6-C20)aryl;
a to f are each independently an integer of 0 to 4;
p is 0 or 1;
When a to f are integers greater than or equal to 2, each R ₁ , R ₂ , R ₃ , R _{4 ,} R ₅ and R ₆ are the same as or different from each other. According to claim 1,
The diamine compound represented by Formula 1 is a diamine compound represented by Formula 2 or 3 below:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
R ₁ and R ₂ are each independently (C1-C7)alkyl, halo(C1-C7)alkyl, (C1-C7)alkoxy, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano or helogen;
R ₃ to R ₆ are each independently (C1-C7)alkyl, halo(C1-C7)alkyl, (C1-C7)alkoxy, (C1-C7)alkylcarbonyl, (C1-C7)alkoxycarbonyl, ( C6-C12) arylcarbonyl, -SiR ^a R ^b R ^c , -NR ^d R ^e , -COOH, nitro, cyano, hydroxy or helogen;
R ^a is (C1-C7)alkyl;
R ^b to R ^e are each independently hydrogen, (C1-C7)alkyl or (C6-C12)aryl;
a to f are each independently an integer of 0 to 3;
When a to f are integers greater than or equal to 2, each R ₁ , R ₂ , R ₃ , R _{4 ,} R ₅ and R ₆ are the same as or different from each other. According to claim 1,
The diamine compound represented by Formula 1 is a diamine compound represented by Formula 4 or 5 below:
[Formula 4]

[Formula 5]

In Formulas 4 and 5,
R ₁ to R ₄ and R ₁₁ and R ₁₂ are each independently (C1-C7)alkyl, halo(C1-C7)alkyl, (C1-C7)alkoxy or halogen;
a to d and x and y are each independently 0 or 1;
n and m are each independently an integer of 1 to 5; According to claim 1,
The diamine compound represented by Formula 1 is a diamine compound represented by Formula 6 or 7 below:
[Formula 6]

[Formula 7]

In Formulas 6 and 7,
R ₁ to R _4- are each independently (C1-C3)alkyl, (C1-C3)alkoxy, halo(C1-C3)alkyl or halogen;
a to d are each independently 0 or 1. According to claim 1,
The diamine compound represented by Formula 1 is a diamine compound selected from the following structure:

A method for preparing a diamine compound comprising the step of preparing a diamine compound represented by the following formula (1) by reducing a compound represented by the following formula (A):
[Formula 1]

[Formula A]

In Formula 1 and A,
The definitions of ring A to ring D, R ₁ to R ₆ , a to f and p are the same as defined in Formula 1 of claim 1. According to claim 6,
The reduction reaction is performed under a reduction catalyst selected from Zn, Cu, Ag, Au, Cd, Hg, Fe, K ₄ [Fe(CN) ₆ ], NaBH ₄ or a combination thereof, a method for producing a diamine compound . According to claim 7,
The reduction catalyst is NH ₄ Cl, H ₂ CO ₃ , H ₃ PO ₄ , HCl, CH ₃ COOH, or a method for producing a diamine compound that further comprises a cocatalyst selected from a combination thereof. According to claim 6,
The compound represented by Formula A is prepared by reacting a compound represented by Formula A-1 with a compound represented by Formulas B-1 and B-2, Method for producing a diamine compound:
[Formula A]

[Formula A-1]

[Formula B-1]

[Formula B-2]

In the above formulas A, A-1, B-1 and B-2
X ₁ and X ₂ are each independently halogen;
The definitions of ring A to ring D, R ₁ to R ₆ , a to f and p are the same as defined in Formula 1 of claim 1. A composition for forming a polyimide-based polymer comprising the diamine compound of any one of claims 1 to 5.