KR20230047546A - Novel diamine compound, preparation method thereof, and composition comprising the same - Google Patents

Abstract

One embodiment of the present invention relates to a novel diamine compound, a preparation method thereof, and a composition comprising the same. Specifically, the novel diamine compound according to one embodiment of the present invention can be very useful as a monomer for producing a colorless and transparent polyimide film with improved mechanical strength. The novel diamine compound according to one embodiment is represented by chemical formula 1.

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 film, a method for preparing the same, and a composition including the same.

As a light and flexible material with high heat resistance, polyimide (PI) is being considered. Polyimide is a polymer material that is easy to synthesize and can be made into a thin film, as well as having excellent heat and chemical resistance, excellent mechanical properties and electrical properties. It is in the limelight as an electrical and electronic material such as adhesive and coating agent.

In particular, 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 required performance of polyimide for display devices is gradually increasing.

To this end, research is being conducted to improve mechanical properties by combining monomers with strong linearity and rigidity in colorless polyimide (CPI) or by introducing an amide group. However, the optical properties and mechanical properties of polyimide are in a trade-off relationship, and this attempt has a limit in that the optical properties deteriorate even if the mechanical properties of polyimide are improved. In addition, there is a problem of deteriorating solution handling of polyimide, 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 polyimide 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 film capable of realizing excellent optical and mechanical properties at the same time, and a method for preparing the same.

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

The diamine compound according to one embodiment of the present invention may be represented by Formula 1 below.

[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 compound represented by Formula 1 according to an embodiment 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.)

The compound represented by Formula 1 according to an embodiment 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.)

The compound represented by Formula 1 according to an embodiment 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.)

The diamine compound according to one embodiment may be selected from the following.

In addition, the method for preparing a diamine compound according to one embodiment of the present invention may include preparing a diamine compound represented by the following Chemical Formula 1 by reducing a compound represented by the following Chemical Formula A under a reduction catalyst.

[Formula 1]

[Formula A]

(In Formula 1 and A,

Y ₁ is nitro or amino;

The definitions of R ₁ to R ₃ , R ^a , a, b, c and p are the same as those in Formula 1 of claim 1.)

The reduction catalyst according to an embodiment may be selected from Zn, Cu, Ag, Au, Cd, Hg, Fe, K ₄ [Fe(CN) ₆ ], NaBH ₄ or a combination thereof.

The reduction catalyst according to an embodiment 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.

According to an embodiment, the compound represented by Formula A may be prepared by reacting Y ₂ of the compound represented by Formula A-1 and X of the compound represented by Formula A-2 below.

[Formula A]

[Formula A-1]

[Formula A-2]

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

X is halogen;

Y ₁ is nitro or amino;

또는

이고;Y ₂ is

or

ego;

The definitions of R ₁ to R ₃ , R ^a , a, b, c and p are the same as those in Formula 1 of claim 1.)

In addition, one embodiment of the present invention may provide a composition for forming a polyimide-based polymer containing the diamine compound.

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

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

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

That is, the diamine compound according to one embodiment of the present invention not only can provide a polyimide 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 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.

In addition, units used in this specification without special mention are based on weight, and as an example, the unit of % or ratio means weight% or weight ratio, and unless otherwise defined, weight% is any one component of the entire composition It means the weight percent occupied in the composition.

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. As such, it may be used as a meaning including polyimide or polyamideimide.

As used herein, the term "polyimide precursor solution" refers to a composition for preparing polyimide, and specifically, the polyimide precursor may have a meaning equivalent to "polyamic acid".

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.

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.

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. Accordingly, there is a need for a novel diamine compound capable of remarkably improving mechanical properties while maintaining excellent optical properties of the transparent polyimide film.

The novel diamine compound according to one embodiment of the present invention includes a plurality of aromatic rings to improve the mechanical strength of the film, and at the same time has an asymmetric structure, thereby improving crystallinity and electron transfer complex (Charge Transfer Complex, CTC). ) can reduce the effect. That is, the novel diamine compound according to one embodiment of the present invention can provide a polyimide 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,

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.)

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.

As the diamine compound according to one embodiment of the present invention has the above-described structural characteristics, for example, a biphenyl group structure, an asymmetric structure, and an amide bond, optical properties such as yellowness, haze, and transmittance are obtained by using the diamine compound as a monomer. It is possible to manufacture a polyimide film with remarkably improved mechanical properties while maintaining excellent properties.

In another embodiment of the present invention, p may be, for example, an integer of 1 or 2, and more specifically, the diamine compound 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 compound may be represented by Formula 4 or Formula 5 below.

[Formula 4]

[Formula 5]

(In Chemical Formulas 4 and 5,

c and d may be as described above, respectively,

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 polyimide film, for example, yellowness and haze, can be further improved.

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

[Formula 6]

[Formula 7]

(In Chemical Formulas 6 and 7,

x, y, c and d may each be as described above;

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, and when x, y, c and d are 2, each of 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 compound according to one embodiment of the present invention, for example, may be selected from the following, but is not limited thereto.

In addition, one embodiment of the present invention provides a method for preparing the diamine compound.

The method for preparing the diamine compound according to an embodiment of the present invention may include preparing a diamine compound represented by Formula 1 by reducing a compound represented by Formula A below using a reduction catalyst.

[Formula 1]

[Formula A]

(In Formula 1 and A,

Y ₁ is nitro or amino;

The definitions of R ₁ to R ₃ , R ^a , a, b, c and p are the same as those in Formula 1 of claim 1.)

The reduction catalyst according to an embodiment of the present invention may be 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.

The compound represented by Formula A according to an embodiment of the present invention may be prepared by reacting Y ₂ of a compound represented by Formula A-1 with X of a compound represented by Formula A-2 below.

[Formula A]

[Formula A-1]

[Formula A-2]

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

X is halogen;

Y ₁ is nitro or amino;

또는

이고;Y ₂ is

or

ego;

The definitions of R ₁ to R ₃ , R ^a , a, b, c and p are the same as those in Formula 1 of claim 1.)

The reaction according to an embodiment of the present invention may be performed at 20 to 40 °C for 1 to 10 hours, specifically at 20 to 30 °C for 1 to 5 hours.

In addition, one embodiment of the present invention provides a composition for forming a polyimide-based polymer containing the novel diamine compound.

Specifically, the diamine compound according to one embodiment may be reacted with a dianhydride compound to synthesize a polyimide precursor (ie, polyamic acid or polyamic acid ester), and polyimide may be synthesized through imidation of the polyimide precursor. there is.

That is, the diamine compound according to one embodiment 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, one embodiment of the present invention provides a polyimide precursor and/or polyimide prepared by using the novel diamine compound as a monomer.

Specifically, the polyimide precursor may include a structural unit derived from the diamine compound of Formula 1 and a structural unit derived from the dianhydride compound. In addition, the polyimide precursor may further include a structural unit derived from an aromatic diacid dichloride.

The polyimide precursor according to one embodiment of the present invention 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 Formula 1 above.

The known diamine compound is not particularly limited, but, for example, PDA (p-phenylenediamine), m-PDA (m-phenylenediamine), 4,4'-ODA (4,4'-oxydiamine) aniline), 3,4'-ODA (3,4'-oxydianiline), BAPP (2,2-bis (4- [4-aminophenoxy] -phenyl) propane), TPE-Q (1,4 -Bis (4-aminophenoxy) benzene), TPE-R (1,3-bis (4-aminophenoxy) benzene), BAPB (4,4'-bis (4-aminophenoxy) biphenyl), BAPS (2,2-bis(4-[4-aminophenoxy]phenyl)sulfone), m-BAPS(2,2-bis(4-[3-aminophenoxy]phenyl)sulfone), HAB(3, 3'-dihydroxy-4,4'-diaminobiphenyl), TB (3,3-dimethylbenzidine), m-TB (2,2-dimethylbenzidine), TFMB (2,2-bistrifluoro methylbenzidine), 6FAPB (1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene), 6FODA (2,2'-bis(trifluoromethyl)-4,4'-diamino diphenyl ether), APB (1,3-bis (3-aminophenoxy) benzene), 1,4-ND (1,4-naphthalenediamine), 1,5-ND (1,5-naphthalenediamine) ), DABA (4,4'-diaminobenzanilide), 6-amino-2- (4-aminophenyl) benzoxazole, and 5-amino-2- (4-aminophenyl) benzoxazole. Alternatively, a mixture of two or more may be used, but is not limited thereto. Specifically, the diamine compound may be a fluorine-based aromatic diamine compound having a fluorine substituent introduced therein, for example, TFMB (2,2-bistrifluoromethylbenzidine), 6FAPB (1,4-bis (4-amino -2-trifluoromethylphenoxy) benzene), 6FODA (2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether), or a combination thereof, More specifically, TFMB (2,2-bistrifluoromethylbenzidine) can 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 polyimide film can be further improved.

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

The dianhydride compound 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 aliphatic dianhydride, or a combination thereof. The aromatic dianhydride is, for example, BPAF (9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride), 6FDA (2,2'-bis- (3,4-dicarboxyphenyl) Hexafluoropropane dianhydride), BPDA (biphenyltetracarboxylic dianhydride), ODPA (oxydiphthalic dianhydride), SO ₂ DPA (sulfonyl diphthalic anhydride), 6HDBA (isopropylidene diphenoxy) bis(phthalic anhydride)), TDA(4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2- dicarboxylic dianhydride), PMDA (1,2,4,5-benzene tetracarboxylic dianhydride) and BTDA (benzophenone tetracarboxylic dianhydride), or a mixture of two or more It can be used, but is not limited thereto. Specifically, the aromatic dianhydride may be a fluorine-based aromatic dianhydride compound, for example, BPAF (9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride), 6FDA (2,2' -Bis-(3,4-dicarboxylphenyl)hexafluoropropane dianhydride) or mixtures thereof, more specifically 6FDA (2,2'-bis-(3,4-dicarboxylphenyl) hexafluoropropane dianhydride) can be used. By using the fluorine-based aromatic dianhydride, not only the optical properties of the polyimide film but also the mechanical strength, particularly the modulus, can be more effectively improved.

The aliphatic dianhydride compound is, for example, CBDA (1,2,3,4-cyclobutanetetracarboxylic dianhydride), DOCDA (5- (2,5-dioxotetrahydrofuryl) -3 -methylcyclohexene-1,2-dicarboxylic dianhydride), BTA (bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride), BODA (bicyclooctene-2,3,5,6-tetracarboxylic dianhydride), CPDA (1,2,3,4-cyclopentanetetracarboxylic dianhydride), CHDA (1,2, 4,5-cyclohexanetetracarboxylic dianhydride), TMDA (1,2,4-tricarboxy-3-methylcarboxycyclopentane dianhydride), TCDA (1,2,3,4-tetracarboxycyclo Pentane dianhydride) and any one or a mixture of two or more selected from the group consisting of derivatives thereof, but is not limited thereto. Specifically, the alicyclic dianhydride compound may be CBDA (1,2,3,4-cyclobutanetetracarboxylic dianhydride).

More specifically, the dianhydride compound according to one embodiment of the present invention may use a mixture of an aromatic dianhydride and an aliphatic cyclic dianhydride, for example, 6FDA (2,2'-bis-(3,4-dica) A mixture of boxylphenyl)hexafluoropropane dianhydride) and CBDA (1,2,3,4-cyclobutanetetracarboxylic dianhydride) can be used.

In addition, when preparing the polyimide precursor according to an embodiment of the present invention, the equivalent ratio of the mixture of the diamine compound and the aromatic diacid dianhydride and the aliphatic cyclic dianhydride is not particularly limited, but may be 1:0.9 to 1.1, specifically It may be 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.

In addition, the polyimide precursor according to one embodiment of the present invention 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), TPC (terephthaloyl dichloride), BPC (1,1'-biphenyl-4,4'-dicarbonyl dichloride), NPC (1,4-naphthalene dicarboxylic dichloride), NTC (2,6-naphthalene dicarboxylic dichloride), NEC (1,5-naphthalene dicarboxylic dichloride) One or a mixture of two or more selected from the group consisting of chloride (1,5-naphthalene dicarboxylic dichloride) and derivatives thereof may be used, but is not limited thereto.

Specifically, TPC (terephthaloyl dichloride) may be included as the aromatic diacid dichloride. When the content of terephthaloyl dichloride is 50 moles or more with respect to 100 moles of aromatic diamine, mechanical properties of the film such as modulus can be greatly improved. However, as the intermolecular density increases, a problem of deterioration of optical properties such as yellowness and haze may occur. However, it was found that the deterioration of the optical properties of the polyimide film can be improved by using the diamine compound of Chemical Formula 1 as a monomer according to an embodiment of the present invention, and excellent optical and mechanical properties as desired. It is possible to provide a film that simultaneously satisfies physical properties.

When the polyimide precursor according to one embodiment of the present invention further includes a structural unit derived from an aromatic diacid dichloride, the amount of the aromatic diacid dichloride is 40 mol or more, or 45 mol or more, or 50 mol or more, based on 100 mol of the diamine compound. Molar or more, more specifically, 50 to 100 moles may be used, but is not limited thereto. When the aromatic diacid dichloride in the above range is used, mechanical properties of the polyimide film can be further improved.

In addition, one embodiment of the present invention provides a composition containing the diamine compound represented by the formula (1).

Specifically, the composition according to one embodiment of the present invention may include a polyimide precursor and/or polyimide including a structural unit derived from the diamine compound of Chemical Formula 1; And it may be a composition for forming a polyimide film containing an organic solvent.

As the composition according to one embodiment of the present invention includes the above-described polyimide precursor and/or polyimide, it is possible to provide a polyimide film having significantly improved optical and mechanical properties. In particular, the composition according to one embodiment of the present invention can provide a polyimide film having high transparency and low yellowness value, and 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 composition for forming a polyimide film according to one embodiment of the present invention may have a solid content of 5 to 20% by weight, 10 to 20% by weight, or 10 to 15% by weight based on the total weight of the composition.

Specifically, the composition for forming a polyimide film according to one embodiment of the present invention may have a viscosity of 2,000 to 50,000 cps or 5,000 to 30,000 cps. When the above-described viscosity range is satisfied, the efficiency of defoaming is more excellent during processing of the polyimide film, and thus, a process advantage may be provided. Thus, a more uniform surface can be realized. At this time, the viscosity was measured using a Brookfield (RVDV-III) viscometer spindle (Spindle) No. 52 and stabilizing for 2 minutes at the time when the torque value reached 80% by placing the sample at room temperature (25 ℃). can mean value.

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

A method for preparing a composition for forming a polyimide 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 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, 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, when aromatic diacid dichloride is further added in step (A), after preparing the polyimide precursor solution, imidizing the polyimide precursor and obtaining polyamideimide powder; 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.

After imidization of the polyimide precursor, it is precipitated and purified in a solvent to obtain a solid content (polyamideimide powder), which is dissolved in an organic solvent to adjust the solid content to obtain a composition for forming a polyimide film.

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

The polyimide 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 polyimide film according to one embodiment of the present invention may have a thickness of 20 to 500 um, for example, 30 to 300 um, for example, 40 to 100 um.

The polyimide film according to one embodiment of the present invention may have a YI of 20 or less, or 15 or less, or 10 or less, or 7 or less according to ASTM E313.

The polyimide 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 polyimide 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 D1746.

The polyimide film according to one embodiment of the present invention may have a modulus of 5 GPa or more, 5.5 GPa or more, or 5.7 GPa or more, or 6 GPa or more, or 7 GPa or more according to ASTM D882.

The polyimide film according to one embodiment of the present invention has a YI of 20 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 D1746, and a modulus according to ASTM D882. may be greater than or equal to 5 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 polyimide film according to one embodiment of the present invention is prepared from a diamine compound 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 the diamine compound represented by Chemical Formula 1, and thus can provide a polyimide film excellent in optical properties, mechanical strength and flexibility. Therefore, the polyimide film according to one embodiment of the present invention is a substrate for devices, a cover substrate for display use, an optical film, an IC (integrated circuit) package, an electrodeposited film, a multi-layer flexible printed circuit (FRC), a tape, a touch panel, and an optical disk. It can be applied to various fields such as a protective film for

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

A method for manufacturing a polyimide film according to an embodiment of the present invention includes (a) a coating step of applying the composition for forming a polyimide film onto a substrate; and (b) a curing step of curing the composition for forming the polyimide film by drying and heating the composition.

Specifically, the step (a) is to apply the composition for forming a polyimide film to a substrate such as glass, and the coating method may be used without limitation as long as it is commonly used in the related field. Non-limiting examples thereof include knife coating, dip coating, roll coating, slot die coating, lip die coating, and slide coating. coating) and curtain coating, etc., and the same type or different types may be sequentially applied one or more times.

In addition, the substrate may be used without limitation as long as it is commonly used in the field, and non-limiting examples thereof include glass; stainless; or polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly(meth)acrylic acid alkyl ester, poly(meth)acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, plastic films such as polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride/vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene; etc. can be used, but is not limited thereto.

In the step (b) according to an embodiment of the present invention, the drying is to remove the solvent present in the composition for forming a polyimide film, 30 to 100 ℃, or 40 to 90 ℃, or 50 to 90 ℃ can be performed in The thermal curing according to one 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 carried out at 80 to 100 ° C for 1 minute to 2 hours, or above 100 to 200 ° C for 1 minute to 2 hours, or above 200 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 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 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 polyimide 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 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, it can be used as a window cover film for flexible displays and the like.

As the polyimide film according to one embodiment of the present invention includes a structural unit derived from the diamine compound represented by Chemical Formula 1, it can implement excellent optical properties such as high transparency and low yellowness and excellent modulus. Accordingly, the polyimide 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 polyimide 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 10 or less, X: Yellowness 10 or more

<Total light transmittance>

The total light transmittance (%) of the polyimide 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 polyimide film, the haze (%) value was measured using a spectrophotometer (Nippon Denshoku Co., COH-5500) according to ASTM D1003 standard.

<modulus>

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

<Weight Average Molecular Weight>

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

[Example 1] Preparation of Diamine Compound 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 compound 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 compound 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 ).

[Example 2] Preparation of diamine compound 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 compound 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, the solvent was removed by purification under reduced pressure, and diamine compound 2 (11.2 g, 68%) was obtained through column purification.

^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 ).

[Example 3] Preparation of diamine compound 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

In a nitrogen environment, 22.7 g of 4'-Nitro-2,2'-bis(trifluoromethyl)[1,1'-biphenyl]-4-amineHCl, 120 ml of tetrahydrofuran (THF), and 16.2 g of pyridine were added. . 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 compound 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 compound 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

[Example 4] Preparation of diamine compound 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 compound 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

[Example 5] Preparation of diamine compound 5

In Example 3, 4-nitro-2-trifluoromethylbenzoic acid was used instead of 4-nitro-2-fluorobenzoic acid. ), diamine compound 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 ).

[Example 6] Preparation of diamine compound 6

In Example 3, 4-nitro-2-methylbenzoic acid was used instead of 4-nitro-2-fluorobenzoic acid. Diamine compound 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 ).

[Example 7] Preparation of diamine compound 7

In Example 3, 4-nitro-2-methoxybenzoic acid was used instead of 4-nitro-2-fluorobenzoic acid. Diamine compound 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

[Example 8] Preparation of diamine compound 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

In a nitrogen environment, 11.7 g of 4'-Nitro-2,2'-bis(trifluoromethyl)[1,1'-biphenyl]-4-amineHCl, 60 ml of tetrahydrofuran (THF), and 8.4 g of pyridine were added. . 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 compound 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 compound 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

[Example 9] Preparation of diamine compound 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 compound 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

<Experimental Example> Production of polyimide film

[Experimental Example 1]

After filling 209.9 g of N,N-dimethylacetamide (DMAc) in a reactor under a nitrogen atmosphere, 16.28 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB) while maintaining the temperature of the reactor at 40 °C. And 0.50 g of the diamine compound 1 of Example 1 was sufficiently dissolved. After adding 1.51 g of cyclobutanetetracarboxylic dianhydride (CBDA) to 1 solution of the TFMB/diamine compound and sufficiently dissolving, 4,4'-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA) ) 3.41 g and 7.28 g of terephthaloyl dichloride (TPC) were added and stirred for 6 hours to dissolve and react to prepare a polyimide precursor solution. Subsequently, pyridine and acetic anhydride were added in an amount of 2.5 times the total amount of dianhydride to the polyamic acid resin composition, 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 composition 1 for forming a polyimide film having a solid content of 10.45% by weight.

Solution casting of the composition 1 for forming a polyimide film 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 obtain a thickness of 48 A polyimide film 1 of μm was obtained. The physical properties are listed in Tables 2 to 4 below.

[Experimental Example 2]

After filling 200 g of N,N-dimethylacetamide (DMAc) in a reactor under a nitrogen atmosphere, 10.34 g of TFMB and 14.18 g of diamine compound 1 were dissolved while maintaining the temperature of the reactor at 40 °C. 22.83 g of 6FDA and 22.83 g of CBDA were added to the TFMB/diamine compound 1 solution, and the mixture was dissolved and stirred at 60° C. for 12 hours. Composition 2 for forming a polyimide film was prepared by adding DMAc so that the solid content of the polyimide precursor solution prepared from the reaction was 10.45% by weight.

Solution casting of the composition 2 for forming a polyimide film 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 49 μm A phosphorus polyimide film 2 was obtained.

[Experimental Example 3]

Polyimide film 3 having a thickness of 46 μm was obtained in the same manner as in Experimental Example 1, except that the types and mole ratios of the monomers were changed as shown in Table 1 below.

[Comparative Example 1]

As shown in Table 1 below, polyimide film A having a thickness of 50 μm was prepared in the same manner as in Experimental Example 1, except that 100 moles of TFMB was used instead of the diamine compound having a molar ratio of TFMB: diamine compound of 1 = 98: 2 got

[Comparative Example 2]

As shown in Table 1 below, polyimide film B having a thickness of 48 μm was prepared in the same manner as in Experimental Example 2, except that 100 moles of TFMB was used instead of the diamine compound having a molar ratio of TFMB: diamine compound 1 = 50:50. got

[Comparative Example 3]

As shown in Table 1 below, in Experimental Example 3, except that 100 moles of TFMB was used instead of the diamine compound in the molar ratio of TFMB: diamine compound 2 = 70:30, polyimide film C having a thickness of 50 μm got

[Comparative Example 4]

As shown in Table 1 below, a polyimide film D having a thickness of 50 μm was obtained in the same manner except that the diamine compound of C1 was used instead of the diamine compound 1 in Experimental Example 2.

[Comparative Example 5]

As shown in Table 1 below, a polyimide film E having a thickness of 48 μm was obtained in the same manner except that the diamine compound of C2 was used instead of the diamine compound 2 in Experimental Example 3.

composition ratio (molar ratio) TFMB diamine compound 1 diamine compound 2 C1 C2 TPC 6FDA CBDA Experimental example 1 98 02 - - - 70 15 15 Experimental Example 2 50 50 - - - - 80 20 Experimental Example 3 70 - 30 - - 50 15 35 Comparative Example 1 100 - - - - 70 15 15 Comparative Example 2 100 - - - - - 80 20 Comparative Example 3 100 - - - - 50 15 35 Comparative Example 4 50 - - 50 - - 80 20 Comparative Example 5 70 - - - 30 50 15 35

Evaluation 1: Yellowness

The yellowness of the polyimide films of Experimental Examples 1 to 3 and Comparative Examples 1 to 5 was measured and shown in Table 2 below.

yellowness evaluation Experimental Example 1 2.1 O Experimental Example 2 4.1 O Experimental Example 3 6.6 O Comparative Example 1 2.5 O Comparative Example 2 1.7 O Comparative Example 3 6.8 O Comparative Example 4 16.8 X Comparative Example 5 10 X

As shown in Table 2, the polyimide films of Experimental Examples 1 to 3 including structural units derived from the novel diamine of the present invention can realize excellent yellowness applicable to cover windows and substrate materials of displays. You can check. On the other hand, the polyimide films of Comparative Examples 4 and 5 prepared from diamines (C1 and C2) not containing a biphenyl group and an asymmetric structure have yellowness compared to the films of Experimental Examples 2 and 3 having the same monomer molar ratio and heat treatment temperature. It can be seen that there is significant deterioration. Accordingly, it was confirmed that the polyimide films of Comparative Examples 4 and 5 were unsuitable for application as a cover window of a display, a substrate material, and the like.

Optical properties of the polyimide films of Experimental Examples 1 to 3 and Comparative Examples 1 to 3 having excellent yellowness were measured and listed in Table 3, and mechanical properties were measured and listed in Table 4.

Evaluation 2. Transmittance and Haze

Permeability (%) Haze (%) Experimental Example 1 90.6 0.2 Experimental Example 2 89.8 0.5 Experimental Example 3 89.1 0.8 Comparative Example 1 89.7 0.3 Comparative Example 2 91.3 0.4 Comparative Example 3 90.5 0.3

Referring to Table 3, it can be seen that the polyimide films of Experimental Examples 1 to 3 have transmittance and haze equal to or superior to those of Comparative Examples 1 to 3.

Evaluation 3. Modulus

Modulus (GPa) Modulus (GPa) △ Experimental Example 1 7.0 Comparative Example 1 6.6 +0.4 Experimental Example 2 5.9 Comparative Example 2 4.0 +1.9 Experimental Example 3 7.3 Comparative Example 3 6.8 +0.5

Referring to Table 4, it can be confirmed that the polyimide films of Experimental Examples 1 to 3 have significantly increased modulus compared to Comparative Examples 1 to 3 as they contain the novel diamine compound according to an embodiment of the present invention. there is.

In summary, as the novel diamine compound 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 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 (10)

A diamine compound represented by Formula 1 below:
[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 compound represented by Formula 1 is a diamine compound 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 compound represented by Formula 1 is a diamine compound 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 compound represented by Formula 1 is a diamine compound 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 compound is a diamine compound selected from the following:

A method for producing a diamine compound comprising the step of preparing a diamine compound represented by the following formula (1) by reducing a compound represented by formula A under a reduction catalyst.
[Formula 1]

[Formula A]

In Formula 1 and A,
Y ₁ is nitro or amino;
The definitions of R ₁ to R ₃ , R ^a , a, b, c and p are the same as defined in Chemical Formula 1 of claim 1. According to claim 6,
The reduction catalyst is 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 Y ₂ of a compound represented by Formula A-1 and X of a compound represented by Formula A-2 below, a method for producing a diamine compound.
[Formula A]

[Formula A-1]

[Formula A-2]

In the above formulas A, A-1 and A-2,
X is halogen;
Y ₁ is nitro or amino;
Y ₂ is

or

ego;
The definitions of R ₁ to R ₃ , R ^a , a, b, c and p are the same as defined in Chemical 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.