KR20230081486A - Polyimide resin, manufacturing method thereof, and polyimide film and display device comprising the same - Google Patents

Abstract

상기 화학식 1에 대해서는 전술한 내용을 참조한다.The present invention relates to a polyimide resin having excellent optical and mechanical properties and having a structure represented by Formula 1 below:
[Formula 1]

For Formula 1, refer to the above description.

Description

Polyimide resin, manufacturing method thereof, and polyimide film and display device including the same

The present invention relates to a polyimide resin, a manufacturing method thereof, and a polyimide film and display device including the same.

In general, polyimide (PI) resin is prepared by solution polymerization of aromatic dianhydride and aromatic diamine or aromatic diisocyanate to produce a polyamic acid derivative, followed by an imidation process in which ring closure and dehydration is performed at a high temperature. It refers to a high heat-resistant resin manufactured through

These polyimide resins are insoluble and insoluble ultra-high heat-resistant resins, and have excellent properties such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. And it is widely used in electronic materials such as insulating coatings, insulating films, semiconductors, and electrode protective films of LCDs.

However, since polyimide resins are colored brown or yellow due to the high density of aromatic rings, they have low transmittance in the visible ray region, making it difficult to use them in fields requiring transparency. In order to solve this problem, a method of polymerization by purifying the monomer and solvent to high purity was attempted, but the transmittance was not significantly improved. In addition, U.S. Patent No. 5,053,480 describes a method of using alicyclic dianhydride instead of aromatic dianhydride, but transparency and color are improved, but transmittance is not satisfactorily high, and furthermore, thermal and mechanical properties are poor. There was a problem with deterioration. As such, conventional polyimide resins are still limited in their use in fields requiring transparency.

In order to solve this problem, a method of introducing a fluorine-based substituent into polyimide has been devised. However, when the fluorine-based substituent is introduced into the polyimide, the mechanical strength of the polyimide deteriorates.

Therefore, it is required to develop a technology for manufacturing a transparent plastic substrate having excellent mechanical properties while exhibiting high transparency such as a glass substrate so as to be applicable as a display material.

Therefore, the problem to be solved by the present invention is to provide a polyimide resin having improved mechanical properties while maintaining excellent optical properties.

Another problem to be solved by the present invention is to provide a method for producing a polyimide resin having improved mechanical properties while maintaining excellent optical properties.

Another problem to be solved by the present invention is to provide a composition for forming a polyimide resin having improved mechanical properties while maintaining excellent optical properties.

Another problem to be solved by the present invention is to provide a polyimide film including a polyimide resin having improved mechanical properties while maintaining excellent optical properties, and a display device including the polyimide film.

In order to solve the above problems, according to an aspect of the present invention, polyimide resins of the following embodiments are provided.

In the first embodiment,

It relates to a polyimide resin comprising the structure of Formula 1 below:

[Formula 1]

In Formula 1,

X includes a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group, and the alicyclic organic group is a monocyclic alicyclic organic group; two or more condensed polycyclic alicyclic organic groups bonded to each other; Or a C ₁ to C ₁₀ cycloalkylene group in which two or more alicyclic rings are single bonded, substituted or unsubstituted, -O-, -S-, -CH(OH)-, -Si(CH ₃ ) ₂ -, - (CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , or a combination of two or more of them linked by a functional group,

Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by a functional group that is a combination of the above,

Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group;

n and m are each an integer of 1 or greater.

The second embodiment, in the first embodiment,

X in Formula 1 may be a substituted or unsubstituted C ₄ to C ₃₀ cycloalkanetetrayl group.

In the third embodiment, in the first embodiment or the second embodiment,

X in Formula 1 may be selected from the group consisting of the following formula:

,

,

, 및

.

,

,

, and

.

In the fourth embodiment, in any one of the first to third embodiments,

X in Chemical Formula 1 may further include a substituted or unsubstituted C ₆ to C ₃₀ tetravalent aromatic organic group, and the tetravalent aromatic organic group may exist alone; Two or more are bonded to each other to form a condensed ring; Or two or more aromatic rings are single bonds, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a combination of two or more of these It may be linked by a phosphorus functional group.

In the fifth embodiment, in the fourth embodiment,

The tetravalent aromatic organic group may be a substituted or unsubstituted C ₆ to C ₃₀ arentetrayl group connected by -C(C _n F _2n+1 ) ₂ - (here, 1≤n≤10).

In the sixth embodiment, in the fourth embodiment or the fifth embodiment,

일 수 있다.The tetravalent aromatic organic group

can be

In the seventh embodiment, in any one of the first to sixth embodiments,

Y in Formula 1 may include two or more C ₆ to C ₃₀ aromatic rings substituted with -CF ₃ ,

The aromatic ring is a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -( CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a combination of two or more of them may be linked by a functional group.

In the eighth embodiment, in any one of the first to seventh embodiments,

Y of Formula 1 may be selected from the group consisting of the following formula:

,

, 및

.

,

, and

.

In the ninth embodiment, in any one of the first to eighth embodiments,

Z in Chemical Formula 1 may be a trivalent group derived from unsubstituted benzene.

In the tenth embodiment, in any one of the first to ninth embodiments,

Z in Formula 1 may be a trivalent unsubstituted phenyl group.

In the eleventh embodiment, in any one of the first to tenth embodiments,

The polyimide resin may have a structure represented by Chemical Formula 2 below:

[Formula 2]

In Formula 2,

n and m are each an integer of 1 or greater.

In the twelfth embodiment, in any one of the first to eleventh embodiments,

The polyimide resin may have a structure represented by Chemical Formula 3 below:

[Formula 3]

In Formula 3,

n, m, and l are each an integer of 1 or greater.

In the thirteenth embodiment, in any one of the first to twelfth embodiments,

The polyimide resin may have a structure represented by Chemical Formula 4 below:

[Formula 4]

In Formula 4,

Each of n, m, l, and o is an integer of 1 or greater.

In order to solve the above problems, according to an aspect of the present invention, a method for producing a polyimide resin of the following embodiments is provided.

The fourteenth embodiment,

generating a second diamine compound having a structure of Formula 7 by reacting a compound of Formula 5 with a first diamine compound having a structure of Formula 6;

Generating a polyamic acid by reacting the second diamine compound and a dianhydride compound having a structure represented by Chemical Formula 8; and

It relates to a method for producing a polyimide resin comprising the step of imidizing the polyamic acid:

[Formula 5]

In Formula 5,

Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group.

[Formula 6]

In Formula 6,

Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by the functional group which is a combination of the above.

[Formula 7]

In Formula 7,

Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by a functional group that is a combination of the above,

Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group;

i is an integer greater than or equal to 1;

[Formula 8]

In Formula 8,

X includes a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group, and the alicyclic organic group is a monocyclic alicyclic organic group; two or more condensed polycyclic alicyclic organic groups bonded to each other; Or a C ₁ to C ₁₀ cycloalkylene group in which two or more alicyclic rings are single bonded, substituted or unsubstituted, -O-, -S-, -CH(OH)-, -Si(CH ₃ ) ₂ -, - (CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , or a combination of two or more of these functional groups.

The fifteenth embodiment is the fourteenth embodiment,

X may further include a substituted or unsubstituted C ₆ to C ₃₀ tetravalent aromatic organic group, and the tetravalent aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or two or more aromatic rings are single bonds, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a combination of two or more of these It may be linked by a phosphorus functional group.

In the 16th embodiment, in the 14th embodiment or the 15th embodiment,

The compound of Chemical Formula 5 may include trimellitic anhydride chloride.

In the 17th embodiment, in any one of the 14th to 16th embodiments,

The first diamine compound is 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (2,2'-bis(trifluoromethyl)-[1,1 '-biphenyl] -4,4'-diamine) may be included.

In the eighteenth embodiment, in any one of the fourteenth to seventeenth embodiments,

The second diamine compound may have a structure represented by Formula 9 below:

[Formula 9]

In Formula 9,

i is an integer greater than or equal to 1;

In the 19th embodiment, in any one of the 14th to 18th embodiments,

The dianhydride compound may include 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

In the 20th embodiment, in any one of the 15th to 19th embodiments,

The dianhydride compound may further include 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride.

In the 21st embodiment, in any one of the 14th to 20th embodiments,

The step of generating the polyamic acid may be further reacting the first diamine compound having the structure of Chemical Formula 6 in addition to the second diamine compound and the dianhydride compound.

In order to solve the above problems, according to an aspect of the present invention, a composition for forming a polyimide resin of the following embodiment is provided.

The 22nd embodiment,

A composition for forming a polyimide resin comprising a compound of Formula 5 below, a first diamine compound having a structure of Formula 6 below, and a dianhydride compound having a structure of Formula 8 below:

[Formula 5]

In Formula 5,

Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group.

[Formula 6]

In Formula 6,

Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by the functional group which is a combination of the above.

[Formula 8]

In Formula 8,

X includes a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group, and the alicyclic organic group is a monocyclic alicyclic organic group; two or more condensed polycyclic alicyclic organic groups bonded to each other; Or a C ₁ to C ₁₀ cycloalkylene group in which two or more alicyclic rings are single bonded, substituted or unsubstituted, -O-, -S-, -CH(OH)-, -Si(CH ₃ ) ₂ -, - (CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , or a combination of two or more of these functional groups.

The 23rd embodiment is the 22nd embodiment,

X may further include a substituted or unsubstituted C ₆ to C ₃₀ tetravalent aromatic organic group, and the tetravalent aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or two or more aromatic rings are single bonds, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a combination of two or more of these It may be linked by a phosphorus functional group.

In the twenty-fourth embodiment, in the twenty-second embodiment or the twenty-third embodiment,

The compound of Chemical Formula 5 may include trimellitic anhydride chloride.

In the 25th embodiment, in any one of the 22nd to 24th embodiments,

The first diamine compound is 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (2,2'-bis(trifluoromethyl)-[1,1 '-biphenyl] -4,4'-diamine) may be included.

In the twenty-sixth embodiment, in any one of the twenty-second to twenty-fifth embodiments,

The dianhydride compound may include 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

In the 27th embodiment, in any one of the 23rd to 26th embodiments,

The dianhydride compound may further include 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride.

In order to solve the above problems, according to an aspect of the present invention, a polyimide film of the following embodiment is provided.

The 28th embodiment,

It relates to a polyimide film comprising the polyimide resin according to any one of the first to thirteenth embodiments.

In order to solve the above problems, according to an aspect of the present invention, a display device of the following embodiment is provided.

The 29th embodiment,

It relates to a display device including the polyimide film according to the twenty-eighth embodiment.

The 30th embodiment is the 29th embodiment,

The display device may be a flexible display device.

The polyimide resin according to one embodiment of the present invention has high light transmittance, low yellowness, and excellent mechanical strength.

The method for producing a polyimide resin according to an embodiment of the present invention can produce a polyimide resin having high light transmittance, low yellowness and excellent mechanical strength.

The composition for forming a polyimide resin according to an embodiment of the present invention can prepare a polyimide resin having high light transmittance, low yellowness and excellent mechanical strength.

A polyimide film comprising a polyimide resin according to an embodiment of the present invention has low yellowness and excellent mechanical strength, so it can be used as a film, varnish, molding part, etc. in the display and semiconductor industries, and can be used as a foldable, roller It can be used as a film material that can implement flexible displays such as blue.

The following drawings attached to this specification illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the contents of the above-described invention, so the present invention is limited to those described in the drawings. It should not be construed as limiting.
1 is a diagram showing light transmittance of polyimide films prepared in Examples 1 to 3 and Comparative Example 1;
2 is a diagram showing yellowness (YI) and haze values of polyimide films prepared in Examples 1 to 3 and Comparative Example 1;
3 is a diagram showing Young's modulus of the polyimide films prepared in Examples 1 to 3 and Comparative Example 1;
4 is a diagram showing the tensile strength of the polyimide films prepared in Examples 1 to 3 and Comparative Example 1.

Hereinafter, preferred embodiments of the present invention will be described in detail. Prior to this, the terms or words used in this specification and claims should not be construed as being limited to the usual or dictionary meaning, and the inventor appropriately uses the concept of the term in order to explain his/her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

Therefore, since the embodiments described in this specification are only one of the most preferred embodiments of the present invention and do not represent all of the technical spirit of the present invention, various equivalents and modifications that can replace them at the time of this application are It should be understood that there may be

A polyimide resin according to an aspect of the present invention includes a structure represented by Formula 1 below:

[Formula 1]

In Formula 1,

X includes a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group, and the alicyclic organic group is a monocyclic alicyclic organic group; two or more condensed polycyclic alicyclic organic groups bonded to each other; Or a C ₁ to C ₁₀ cycloalkylene group in which two or more alicyclic rings are single bonded, substituted or unsubstituted, -O-, -S-, -CH(OH)-, -Si(CH ₃ ) ₂ -, - (CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , or a combination of two or more of them linked by a functional group,

Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by a functional group that is a combination of the above,

Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group;

n and m are each an integer of 1 or greater.

The polyimide resin according to one embodiment of the present invention includes an amide group and an imide group.

The polyimide resin according to one embodiment of the present invention includes an amide group, and the amide group is capable of hydrogen bonding, so that a hydrogen bond can be formed between the finally prepared polyimide, thereby improving the mechanical strength of the polyimide film. can

The “alicyclic organic group” refers to a substituted or unsubstituted C ₃ to C ₃₀ cycloalkanetetrayl group, and specifically, it may be a substituted or unsubstituted C ₄ to C ₁₅ cycloalkanetetrayl group.

At this time, the "substitution" means, unless otherwise specified, that one or more hydrogen atoms of a functional group in a specific formula is a halogen atom (F, Br, Cl or I), a hydroxyl group, an amino group {NH ₂ , NH(R) or N(R`)(R``), where R, R`, and R`` are the same or different from each other, and are each independently a C ₁ to C ₁₀ alkyl group}, an amidino group, a hydrazine group, a hydra It means that it is substituted with one or more substituents selected from the group consisting of an existing group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic organic group, and a substituted or unsubstituted heterocyclic group, wherein the substituents are connected to each other to form a ring can also form.

Here, "alkyl group" means a C ₁ to C ₃₀ alkyl group, and "heterocyclic group" means a heteroatom selected from the group consisting of O, S, N, P, Si, and combinations thereof in one ring. A substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group containing three, or a substituted or unsubstituted C ₄ to C ₁₅ cycloalkyl group.

In the polyimide resin according to one embodiment of the present invention, since part X of Chemical Formula 1 includes an alicyclic organic group, mechanical strength may be improved due to excellent rigidity.

In one embodiment of the present invention, the X may not contain a double bond. When the X does not include a double bond, it may be easy to prepare a polyimide film having excellent optical properties by reducing a charge transfer effect.

In one embodiment of the present invention, X in Formula 1 may be a substituted or unsubstituted C ₄ to C ₃₀ cycloalkanetetrayl group or a substituted or unsubstituted C ₄ to C ₁₅ cycloalkanetetrayl group.

In one embodiment of the present invention, X in Formula 1 may be selected from the group consisting of the following formula:

,

,

, 및

.

,

,

, and

.

In one embodiment of the present invention, X in Formula 1 may be a cyclobutanetetrayl group.

In one embodiment of the present invention, the X may include a substituted or unsubstituted C ₆ to C ₃₀ tetravalent aromatic organic group in addition to a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group. The tetravalent aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or two or more aromatic rings are single bonds, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a combination of two or more of these can be linked by phosphorus functional groups.

The “tetravalent aromatic organic group” refers to a substituted or unsubstituted C ₆ to C ₃₀ arentetrayl group, and specifically, it may be a substituted or unsubstituted C ₆ to C ₁₆ arentetrayl group such as a phenylene group.

At this time, the "substitution" means, unless otherwise specified, that one or more hydrogen atoms of a functional group in a specific formula is a halogen atom (F, Br, Cl or I), a hydroxyl group, a nitro group, a cyano group, an amino group {NH ₂ , NH(R) or N(R`)(R``), where R, R`, and R`` are the same or different from each other, and are each independently a C ₁ to C ₁₀ alkyl group}, an amidino group , Hydrazine group, hydrazone group, carboxyl group, ester group, ketone group, substituted or unsubstituted alkyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, substituted or an unsubstituted alkynyl group, and one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, and the substituents may be linked to each other to form a ring.

Here, "ester group" means a C ₂ to C ₃₀ ester group, specifically means a C ₂ to C ₁₈ ester group, and "alkyl group" refers to the above description. The term "alicyclic organic group" means a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkenyl group, or a substituted or unsubstituted C ₃ to C ₃₀ cycloalkynyl group. and, specifically, a substituted or unsubstituted C ₃ to C ₁₅ cycloalkyl group, a substituted or unsubstituted C ₃ to C ₁₅ cycloalkenyl group, or a substituted or unsubstituted C ₃ to C ₁₅ cycloalkynyl group.

"Aryl group" means a C ₆ to C ₃₀ aryl group, specifically means a C ₆ to C ₁₈ aryl group, and "alkenyl group" means a C ₂ to C ₃₀ alkenyl group containing at least one carbon-carbon double bond. group, specifically means a C ₂ to C ₁₈ alkenyl group, and “alkynyl group” refers to a C ₂ to C ₃₀ alkynyl group containing at least one carbon-carbon triple bond, specifically a C ₂ to C ₁₈ Means an alkynyl group, and "heterocyclic group" is a substituted or unsubstituted C containing 1 to 3 heteroatoms selected from the group consisting of O, S, N, P, Si, and combinations thereof in one ring. ₃ to C ₃₀ cycloalkyl group, substituted or unsubstituted C ₃ to C ₃₀ cycloalkenyl group, substituted or unsubstituted C ₃ to C ₃₀ cycloalkynyl group, or substituted or unsubstituted C ₆ to C ₃₀ hetero Means an aryl group, specifically, a substituted or unsubstituted C ₃ to C ₁₅ containing 1 to 3 heteroatoms selected from the group consisting of O, S, N, P, Si, and combinations thereof in one ring. A cycloalkyl group, a substituted or unsubstituted C ₃ to C ₁₅ cycloalkenyl group, a substituted or unsubstituted C ₃ to C ₁₅ cycloalkynyl group, or a substituted or unsubstituted C ₆ to C ₁₅ heteroaryl group. .

In one embodiment of the present invention, the tetravalent aromatic organic group has two or more aromatic rings having a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -C(=O )NH-, -S(=0) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1 ≤q≤10), -C(C _n H _2n+1 ) ₂ - (where 1≤n≤10), -C(C _n F _2n+1 ) ₂ - (where 1≤n≤10), -( CH ₂ ) _p -C(C _n H _2n+1 ) ₂ -(CH ₂ ) _q - (where 1≤n≤10, 1≤p≤10, and 1≤q≤10), or -(CH ₂ ) _p -C(C _n F _2n+1 ) ₂ -(CH ₂ ) _q - (Where 1≤n≤10, 1≤p≤10, and 1≤q≤10), or two or more functional groups linked thereto can

In one embodiment of the present invention, the tetravalent aromatic organic group may be one in which X in Formula 1 is substituted with -F or -CF ₃ so that a fluorine-based substituent can be introduced. When X in Chemical Formula 1 includes an aromatic organic group into which a fluorine-based substituent is introduced, it may be easy to prepare a polyimide resin having excellent optical properties by reducing the charge transfer effect of polyimide.

In one embodiment of the present invention, the tetravalent aromatic organic group may be one in which two or more aromatic rings are connected by -C(C _n F _2n+1 ) ₂ - (here, 1≤n≤10).

In one embodiment of the present invention, the tetravalent aromatic organic group is a substituted or unsubstituted C ₆ to C ₃₀ arentetrayl group linked by -C(C _n F _2n+1 ) ₂ - (wherein 1≤n≤10); or a substituted or unsubstituted C ₆ to C ₁₆ arentetrayl group.

일 수 있다.In one embodiment of the present invention, the tetravalent aromatic organic group

can be

In one embodiment of the present invention, when part X of Chemical Formula 1 includes an aromatic organic group into which a fluorine-based substituent is introduced, a polyimide resin having excellent optical properties is prepared by reducing the charge transfer effect of polyimide. can do.

In the polyimide resin according to an embodiment of the present invention, Y in Formula 1 is substituted with -F or -CF ₃ so that a fluorine-based substituent can be introduced.

In the polyimide resin according to an embodiment of the present invention, a fluorine-based substituent is introduced to reduce the charge transfer effect of the polyimide, thereby producing a polyimide resin having excellent optical properties.

The “divalent aromatic organic group” refers to a substituted or unsubstituted C ₆ to C ₃₀ arylene group, and specifically, it may be a substituted or unsubstituted C ₆ to C ₁₆ arylene group such as a phenylene group.

At this time, the "substitution" means, unless otherwise specified, that one or more hydrogen atoms of a functional group in a specific formula is a halogen atom (F, Br, Cl or I), a hydroxyl group, a nitro group, a cyano group, an amino group {NH ₂ , NH(R) or N(R`)(R``), where R, R`, and R`` are the same or different from each other, and are each independently a C ₁ to C ₁₀ alkyl group}, an amidino group , Hydrazine group, hydrazone group, carboxyl group, ester group, ketone group, substituted or unsubstituted alkyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, substituted or an unsubstituted alkynyl group, and one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, and the substituents may be linked to each other to form a ring.

Here, "ester group" means a C ₂ to C ₃₀ ester group, specifically means a C ₂ to C ₁₈ ester group, and "alkyl group" refers to the above description. The term "alicyclic organic group" means a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkenyl group, or a substituted or unsubstituted C ₃ to C ₃₀ cycloalkynyl group. and, specifically, a substituted or unsubstituted C ₃ to C ₁₅ cycloalkyl group, a substituted or unsubstituted C ₃ to C ₁₅ cycloalkenyl group, or a substituted or unsubstituted C ₃ to C ₁₅ cycloalkynyl group.

"Aryl group" means a C ₆ to C ₃₀ aryl group, specifically means a C ₆ to C ₁₈ aryl group, and "alkenyl group" means a C ₂ to C ₃₀ alkenyl group containing at least one carbon-carbon double bond. group, specifically means a C ₂ to C ₁₈ alkenyl group, and “alkynyl group” refers to a C ₂ to C ₃₀ alkynyl group containing at least one carbon-carbon triple bond, specifically a C ₂ to C ₁₈ Means an alkynyl group, and "heterocyclic group" is a substituted or unsubstituted C containing 1 to 3 heteroatoms selected from the group consisting of O, S, N, P, Si, and combinations thereof in one ring. ₃ to C ₃₀ cycloalkyl group, substituted or unsubstituted C ₃ to C ₃₀ cycloalkenyl group, substituted or unsubstituted C ₃ to C ₃₀ cycloalkynyl group, or substituted or unsubstituted C ₆ to C ₃₀ hetero Means an aryl group, specifically, a substituted or unsubstituted C ₃ to C ₁₅ containing 1 to 3 heteroatoms selected from the group consisting of O, S, N, P, Si, and combinations thereof in one ring. A cycloalkyl group, a substituted or unsubstituted C ₃ to C ₁₅ cycloalkenyl group, a substituted or unsubstituted C ₃ to C ₁₅ cycloalkynyl group, or a substituted or unsubstituted C ₆ to C ₁₅ heteroaryl group. .

In one embodiment of the present invention, Y in Formula 1 may include two or more C ₆ to C ₃₀ aromatic rings substituted with -CF ₃ ,

The aromatic ring is a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -( CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a combination of two or more of them may be linked by a functional group.

In one embodiment of the present invention, Y in Formula 1 may be selected from the group consisting of the following formula.

,

, 및

.

,

, and

.

일 수 있다.In one embodiment of the present invention, Y of Formula 1 is

can be

In the present invention, Z in Chemical Formula 1 is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group. For the "aromatic organic group", refer to the above description.

In one embodiment of the present invention, Z in Formula 1 may be a trivalent group derived from unsubstituted benzene. For example, Z in Chemical Formula 1 may be a trivalent unsubstituted phenyl group.

In one embodiment of the present invention, the polyimide resin may have a structure of Formula 2 below:

[Formula 2]

In Formula 2,

n and m are each an integer of 1 or greater.

In one embodiment of the present invention, the polyimide resin may have a structure of Formula 3 below:

[Formula 3]

In Formula 3,

n, m, and l are each an integer of 1 or greater.

In one embodiment of the present invention, the polyimide resin may have a structure of Formula 4 below:

[Formula 4]

In Formula 4,

Each of n, m, l, and o is an integer of 1 or greater.

The polyimide resin according to one embodiment of the present invention includes an alicyclic organic group not including a double bond, an amide group, and a fluorine-based substituent, so it may have excellent mechanical strength and optical properties.

In one embodiment of the present invention, the molar ratio of the amide group and the imide group of the polyimide resin is 0.1:1 to 0.5:1, or 0.5:1 to 1:1, or 1:1 to 1:0.5, or 1 :0.5 to 1:0.1. When the molar ratio of the amide group and the imide group in the polyimide resin satisfies the aforementioned range, it may be easy to simultaneously secure excellent mechanical properties and excellent optical properties.

The polyimide resin according to one embodiment of the present invention may be prepared by the following method, but is not limited thereto.

A method for producing a polyimide resin according to an embodiment of the present invention,

generating a second diamine compound having a structure of Formula 7 by reacting a compound of Formula 5 with a first diamine compound having a structure of Formula 6;

Generating a polyamic acid by reacting the second diamine compound and a dianhydride compound having a structure represented by Chemical Formula 8; and

Imidizing the polyamic acid:

[Formula 5]

In Formula 5,

Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group.

[Formula 6]

In Formula 6,

Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by the functional group which is a combination of the above.

[Formula 7]

In Formula 7,

Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by a functional group that is a combination of the above,

Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group;

i is an integer greater than or equal to 1;

[Formula 8]

In Formula 8,

X includes a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group, and the alicyclic organic group is a monocyclic alicyclic organic group; two or more condensed polycyclic alicyclic organic groups bonded to each other; Or a C ₁ to C ₁₀ cycloalkylene group in which two or more alicyclic rings are single bonded, substituted or unsubstituted, -O-, -S-, -CH(OH)-, -Si(CH ₃ ) ₂ -, - (CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , or a combination of two or more of these functional groups.

Hereinafter, a method for producing a polyimide resin according to an embodiment of the present invention will be mainly described.

First, a second diamine compound having the structure of Formula 7 is produced by reacting the compound of Formula 5 with the first diamine compound having the structure of Formula 6. The amine group of the first diamine compound may react with the acyl halide group and anhydride group of the compound of Formula 5, respectively, to generate a second diamine compound having a structure of Formula 7 below.

For Z in Formula 5, refer to the above description for Z in Formula 1.

In one embodiment of the present invention, the compound of Formula 5 may include trimellitic anhydride chloride.

For Y of Formula 6, refer to the above description of Y of Formula 1.

In one embodiment of the present invention, the first diamine compound having the structure of Formula 6 is 2,2'-bis (trifluoromethyl) - [1,1'-biphenyl] -4,4'-diamine ( 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine).

For Z in Formula 7, refer to the above description for Z in Formula 1.

For Y of Formula 7, refer to the above description of Y of Formula 1.

In one embodiment of the present invention, the second diamine compound having the structure of Chemical Formula 7 may have the following structure:

In the above formula,

For Y, refer to the above description of Y in Formula 1.

i is an integer greater than or equal to 1;

In one embodiment of the present invention, the second diamine compound may have a structure represented by Formula 9 below:

[Formula 9]

In Formula 9,

i is an integer greater than or equal to 1;

Next, a polyamic acid is produced by reacting the second diamine compound with the dianhydride compound having the structure of Chemical Formula 8. A polyamic acid including a polyimideamide repeating unit and a polyamic acid repeating unit may be generated by reacting the second diamine compound with the dianhydride compound.

For X of Chemical Formula 8, refer to the above description of X of Chemical Formula 1 above.

In one embodiment of the present invention, the dianhydride compound may include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1,2,3,4-cyclobutanetetracarboxylic dianhydride).

In one embodiment of the present invention, the dianhydride compound is 2,2-bis (3 ,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA), 4-(trifluoromethyl)pyromellitic dianhydride (4-TFPPMDA) , 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride (6FCDA), and the like, wherein the non-fluorinated aromatic dianhydride is pyromellitic acid dianhydride ( PMDA), 4,4'-oxydiphthalic anhydride (ODPA), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTDA), 3 ,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,3,3',4'-biphenyltetracarboxylic acid dianhydride (A-BPDA), 3,3 ',4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4-((2,5-dioxotedrahydrofuran-3-yl)-1,2,3,4-tetranaphthalene -1,2-dicarboxylic anhydride (DTDA), or two or more of them may be further included.

In one embodiment of the present invention, a dianhydride compound substituted with -F or -CF ₃ so that a fluorine-based substituent can be introduced into X in Formula 8 may further include a dianhydride compound. When X in Chemical Formula 8 includes an aromatic organic group into which a fluorine-based substituent is introduced, it may be easy to prepare a polyimide resin having excellent optical properties by reducing the charge transfer effect of polyimide. For example, as the dianhydride compound of Formula 8, in addition to 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride may be further included.

In one embodiment of the present invention, the step of generating the polyamic acid further reacts the first diamine compound having the structure of Formula 6 in addition to the second diamine compound and the dianhydride compound having the structure of Formula 8. can make it

In one embodiment of the present invention, the molar ratio of the first diamine compound and the second diamine compound is 1:1 to 1:0.5, or 1:0.5 to 1:0.1, or 0.1:1 to 0.5:1, or 0.5 :1 to 1:1. When the molar ratio of the first diamine compound and the second diamine compound satisfies the aforementioned range, it is easier to manufacture products in the form of films and coatings of desired shapes by effectively inducing and controlling chain entanglement between polymer chains. can do.

In one embodiment of the present invention, the molar ratio of the mixture of the first diamine compound and the second diamine compound and the dianhydride may be 1:1 to 1:0.8, or 0.8:1 to 1:1. When the reaction molar ratio of the mixture of the first diamine compound and the second diamine compound and the dianhydride compound satisfies the above-described range, entanglement between polymer chains is effectively induced and controlled to form films and coatings of a desired shape. It may be easier to manufacture a product in the form.

Then, the polyamic acid is imidized to finally obtain a polyimide resin.

The imidization method includes a thermal imidization method and a chemical imidization method. As the thermal imidization method, for example, there is a method of imidizing polyamic acid by applying heat to 250 to 500 ° C. At this time, a dehydration ring closure agent, a ring closure catalyst, or two or more of these may be added to the polyamic acid dissolved in an organic solvent in order to promote imidation. The dehydration ring-closing agent or ring-closing catalyst may be, for example, tertiary amines such as pyridine, triethylamine, tributylamine, and isoquinoline; or an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride;

As the chemical imidization method, for example, in the presence of a catalyst such as tributylamine, triethylamine, triphenyl phosphite, isoquinoline, pyridine, etc. (25 parts by weight or less of the total reactant) or p-toluenesulfonic acid, etc. There is a method of directly obtaining polyimide by heating the polyamic acid to 100 ° C. or higher, or 180 ° C. or higher in the presence of a dehydration catalyst (25 parts by weight or less of the total reactant). In addition, the polyamic acid is mixed with an acid anhydride such as acetic anhydride, propionic anhydride, benzoic anhydride, or a carbodiimide compound such as dicyclohexylcarbodiimide, and, if necessary, pyridine, isoquinoline, imidazole, There is a method of adding a ring closure catalyst such as triethylamine to cause ring closure at a relatively low temperature (room temperature to 100°C).

In one embodiment of the present invention, after imidization, the product may be obtained as a solid through precipitation and grinding in an excess of solvent.

In one embodiment of the present invention, the step of obtaining a high-purity polyimide resin solid content by adding the imidized polyimide resin to an excess of ethanol and stirring and filtering it may be further included. At this time, the step of adding the imidized polyimide resin to ethanol and stirring may be performed for 4 to 12 hours. The obtained high-purity polyimide resin may be dried at 60 to 100° C. for 12 to 48 hours.

A polyimide resin according to an aspect of the present invention may be prepared by the following composition for forming a polyimide resin.

A composition for forming a polyimide resin according to an aspect of the present invention includes the compound of Chemical Formula 5, the first diamine compound having the structure of Chemical Formula 6, and the dianhydride compound having the structure of Chemical Formula 8.

For the compound of Chemical Formula 5, the first diamine compound having a structure of Chemical Formula 6, and the dianhydride compound having a structure of Chemical Formula 8, the above description is referred to.

In one embodiment of the present invention, the molar ratio of the compound of Formula 5 and the dianhydride having the structure of Formula 8 is 1:1 to 1:0.5, or 1:0.5 to 1:0.1, or 0.1:1 to 0.5 :1, or from 0.5:1 to 1:1. When the molar ratio of the compound of Chemical Formula 5 and the dianhydride having the structure of Chemical Formula 8 satisfies the aforementioned range, it may be easier to simultaneously secure excellent mechanical properties and excellent optical properties.

In one embodiment of the present invention, the molar ratio of the mixture of the compound of Formula 5 and the dianhydride compound having the structure of Formula 8 and the first diamine compound having the structure of Formula 6 is 1:1 to 1:0.8, or 0.8:1 to 1:1. When the reaction molar ratio of the mixture of the compound of Formula 5 and the dianhydride compound having the structure of Formula 8 and the first diamine compound having the structure of Formula 6 satisfies the above range, excellent mechanical properties and excellent optical properties are obtained. It may be easier to simultaneously secure the properties.

In one embodiment of the present invention, X of the dianhydride compound having the structure of Chemical Formula 8 is a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group in addition to a substituted or unsubstituted C ₆ to C ₃₀ In the case of containing a tetravalent aromatic organic group, X is a substituted or unsubstituted C ₄ to C ₃₀ dianhydride containing a tetravalent alicyclic organic group and X is a substituted or unsubstituted C ₆ to C ₃₀ tetravalent The molar ratio of the dianhydride containing an aromatic organic group may be 1:1 to 1:0.5, or 1:0.5 to 1:0.1. In this case, it may be easier to secure excellent optical properties.

A polyimide film containing the polyimide resin described above may be manufactured.

The polyimide film according to one embodiment of the present invention may have improved mechanical properties as well as optical properties (transparency and yellowness) by including the polyimide resin according to one embodiment of the present invention.

In one embodiment of the present invention, the polyimide film may have a yellow index (YI) of 3.5 or less, or 2.0 or less, and a Young's modulus of 2.0 GPa or more. For example, the yellowness of the polyimide film may be the yellowness of a polyimide film having a thickness of 50 μm.

The polyimide film according to one embodiment of the present invention is obtained by precipitating and pulverizing the polyimide resin according to an embodiment of the present invention in an excess of water to obtain a solid content, and then performing a solvent exchange process and drying the obtained product to obtain a high purity film. It can be prepared by obtaining a polyimide resin solid content, dissolving it in a solvent, and coating and drying a polyimide resin solution formed on a substrate.

A polyimide film according to another embodiment of the present invention may be prepared by coating and drying the composition for forming a polyimide resin according to an embodiment of the present invention on a substrate.

As a method of coating the composition for forming the polyimide resin on the substrate, a conventional method known in the art may be used without limitation, and for example, spin coating, dip coating, solvent casting casting), slot die coating, spray coating, etc. may be used.

The drying may be performed, for example, at 50 to 200 °C for 10 to 120 minutes, but is not limited thereto.

The polyimide film according to one embodiment of the present invention can be used in various fields, and in particular, displays for organic electroluminescent devices (OLED) requiring high transparency and heat resistance, displays for liquid crystal devices, TFT substrates, flexible printed circuit boards, It can be used as a substrate and protective film for flexible displays such as flexible OLED surface lighting substrates and substrate materials for electronic paper.

Hereinafter, examples will be described in detail to aid understanding of the present invention. However, the embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the following examples. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example 1

As the first diamine compound, 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (2,2'-bis(trifluoromethyl)-[1,1' 0.8 mol of -biphenyl] -4,4'-diamine) (TFDB) and 0.4 mol of trimellitic anhydride chloride (TAC) as a compound of Formula 5 are reacted in a dimethylacetamide solvent to prepare A 2 diamine compound was obtained.

Then, 0.4 mol of the second diamine compound prepared above and 0.1 mol of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,2-bis (3 ,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) 0.5 mol, 2,2'-bis(trifluoromethyl)-[1,1 Polyamic acid was prepared by reacting 0.2 mol of `-biphenyl] -4,4`-diamine (2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine).

Then, acetic anhydride as a ring closure dehydration agent and pyridine as a ring closure catalyst were added to the prepared polyamic acid and stirred to imidize the polyamic acid through a chemical imidation method.

The imidized polyimide resin was precipitated and pulverized in an excess of water to obtain a solid content, and then a solvent exchange process was performed for 4 hours by putting the polyimide resin into an excess of ethanol. Thereafter, the product obtained through filtering was dried at 80° C. for 24 hours to obtain a high-purity polyimide resin solid content.

The solid content of the high-purity polyimide resin was dissolved in a solvent to form a polyimide resin solution. The solution was coated on a glass substrate by a casting method and dried to prepare a polyimide film.

Example 2

As the first diamine compound, 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (2,2'-bis(trifluoromethyl)-[1,1' -biphenyl] -4,4'-diamine) (TFDB) 0.6 mol and 0.3 mol of trimellitic anhydride chloride (TAC) as a compound of Formula 5 are reacted in a dimethylacetamide solvent to prepare A 2 diamine compound was obtained.

Then, 0.3 mol of the second diamine compound prepared above and 1,2,3,4-cyclobutanetetracarboxyl 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3, 3-Hexafluoropropane dianhydride (6FDA) 0.5 mol, 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (2,2'- Polyamic acid was prepared by reacting 0.4 mol of bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine).

Then, acetic anhydride as a ring closure dehydration agent and pyridine as a ring closure catalyst were added to the prepared polyamic acid and stirred to imidize the polyamic acid through a chemical imidation method.

The imidized polyimide resin was precipitated and pulverized in an excess of water to obtain a solid content, and then a solvent exchange process was performed for 4 hours by putting the polyimide resin into an excess of ethanol. Thereafter, the product obtained through filtering was dried at 80° C. for 24 hours to obtain a high-purity polyimide resin solid content.

The solid content of the high-purity polyimide resin was dissolved in a solvent to form a polyimide resin solution. The solution was coated on a glass substrate by a casting method and dried to prepare a polyimide film.

Example 3

As the first diamine compound, 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (2,2'-bis(trifluoromethyl)-[1,1' 0.4 mol of -biphenyl] -4,4'-diamine) (TFDB) and 0.2 mol of trimellitic anhydride chloride (TAC) as a compound of Formula 5 are reacted in a dimethylacetamide solvent to prepare A 2 diamine compound was obtained.

Then, 0.2 mol of the second diamine compound prepared above and 0.3 mol of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,2-bis (3 ,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) 0.5 mol, 2,2'-bis(trifluoromethyl)-[1,1 Polyamic acid was prepared by reacting 0.6 mol of `-biphenyl] -4,4`-diamine (2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine).

Then, acetic anhydride as a ring closure dehydration agent and pyridine as a ring closure catalyst were added to the prepared polyamic acid and stirred to imidize the polyamic acid through a chemical imidation method.

The imidized polyimide resin was precipitated and pulverized in an excess of water to obtain a solid content, and then a solvent exchange process was performed for 4 hours by putting the polyimide resin into an excess of ethanol. Thereafter, the product obtained through filtering was dried at 80° C. for 24 hours to obtain a high-purity polyimide resin solid content.

The solid content of the high-purity polyimide resin was dissolved in a solvent to form a polyimide resin solution. The solution was coated on a glass substrate by a casting method and dried to prepare a polyimide film.

Comparative Example 1

2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4 After reacting 1.0 mol of ,4'-diamine (TFDB) and 0.5 mol of trimellitic anhydride chloride (TAC) in a dimethylacetamide solvent, 2,2-bis (3,4 -Dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) was reacted with 0.5 mol to obtain a polyamic acid, and then imidized by the same method as in the above example. Thus, a polyimide resin was prepared.

A polyimide resin solution was formed by the same method as used in the above example, coated on a glass substrate by a casting method, and dried to prepare a polyimide film.

Evaluation Example 1: Measurement of light transmittance

The total light transmittance of the polyimide films prepared in Examples 1 to 3 and Comparative Example 1 was measured according to ASTM D1003 standard and is shown in FIG. 1 .

As can be seen in FIG. 1 , it was confirmed that the polyimide films prepared in Examples 1 to 3 showed superior light transmittance than the polyimide films prepared in Comparative Example 1.

Evaluation Example 2: Yellow index (YI) and haze measurement

The yellowness of the polyimide films prepared in Examples 1 to 3 and Comparative Example 1 was measured according to the ASTM-E313 standard and the haze was measured according to the ASTM D1003 standard, and is shown in FIG. 2 .

As can be seen in FIG. 2 , it was confirmed that the polyimide films prepared in Examples 1 to 3 showed better yellowness and Haze values than the polyimide films prepared in Comparative Example 1.

Evaluation Example 3: Young's modulus analysis

The Young's modulus of the polyimide films prepared in Examples 1 to 3 and Comparative Example 1 was measured according to ASTM D882 standards using Instron (Model 3345 Electromechanical system) by making samples with a width of 1 cm and a length of 5 cm. shown in Figure 3.

As can be seen in FIG. 3 , it was confirmed that the polyimide films prepared in Examples 1 to 3 had a higher level of elastic modulus, that is, mechanical strength, than the polyimide film prepared in Comparative Example 1.

Evaluation Example 4: Tensile strength measurement

The tensile strength of the polyimide films prepared in Examples 1 to 3 and Comparative Examples was measured according to the ASTM D882 standard using Instron (Model 3345 Electromechanical system) by preparing samples with a width of 1 cm and a length of 5 cm, and the results are shown in FIG. was

As can be seen in FIG. 4 , it was confirmed that the polyimide films prepared in Examples 1 to 3 had higher tensile strength than the polyimide film prepared in Comparative Example 1.

Claims (30)

A polyimide resin comprising the structure of Formula 1 below:
[Formula 1]

In Formula 1,
X includes a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group, and the alicyclic organic group is a monocyclic alicyclic organic group; two or more condensed polycyclic alicyclic organic groups bonded to each other; Or a C ₁ to C ₁₀ cycloalkylene group in which two or more alicyclic rings are single bonded, substituted or unsubstituted, -O-, -S-, -CH(OH)-, -Si(CH ₃ ) ₂ -, - (CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , or a combination of two or more of them linked by a functional group,
Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by a functional group that is a combination of the above,
Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group;
n and m are each an integer of 1 or greater. According to claim 1,
A polyimide resin in which X in Formula 1 is a substituted or unsubstituted C ₄ to C ₃₀ cycloalkanetetrayl group. According to claim 1,
A polyimide resin in which X in Formula 1 is selected from the group consisting of the following formula:

,

,

, and

. According to claim 1,
X in Formula 1 further comprises a substituted or unsubstituted C ₆ to C ₃₀ tetravalent aromatic organic group, and the tetravalent aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or two or more aromatic rings are single bonds, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a combination of two or more of these A polyimide resin linked by a phosphorus functional group. According to claim 4,
The polyimide resin wherein the tetravalent aromatic organic group is a substituted or unsubstituted C ₆ to C ₃₀ arentetrayl group connected by -C(C _n F _2n+1 ) ₂ - (here, 1≤n≤10). According to claim 4,
The tetravalent aromatic organic group

phosphorus polyimide resin. According to claim 1,
Y in Formula 1 includes two or more C ₆ to C ₃₀ aromatic rings substituted with -CF ₃ ,
The aromatic ring is a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -( CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a polyimide resin connected by a functional group that is a combination of two or more of them. According to claim 1,
A polyimide resin in which Y in Formula 1 is selected from the group consisting of the following formula:

,

, and

. According to claim 1,
A polyimide resin in which Z in Formula 1 is a trivalent group derived from unsubstituted benzene. According to claim 1,
A polyimide resin in which Z in Formula 1 is a trivalent unsubstituted phenyl group. According to claim 1,
A polyimide resin having a structure represented by the following formula (2):
[Formula 2]

In Formula 2,
n and m are each an integer of 1 or greater. According to claim 1,
A polyimide resin having a structure represented by the following formula (3):
[Formula 3]

In Formula 3,
n, m, and l are each an integer of 1 or greater. According to claim 1,
A polyimide resin having a structure represented by the following formula (4):
[Formula 4]

In Formula 4,
Each of n, m, l, and o is an integer of 1 or greater. generating a second diamine compound having a structure of Formula 7 by reacting a compound of Formula 5 with a first diamine compound having a structure of Formula 6;
Generating a polyamic acid by reacting the second diamine compound and a dianhydride compound having a structure represented by Chemical Formula 8; and
Method for producing a polyimide resin comprising the step of imidizing the polyamic acid:
[Formula 5]

In Formula 5,
Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group.
[Formula 6]

In Formula 6,
Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by the functional group which is a combination of the above.
[Formula 7]

In Formula 7,
Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by a functional group that is a combination of the above,
Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group;
i is an integer greater than or equal to 1;
[Formula 8]

In Formula 8,
X includes a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group, and the alicyclic organic group is a monocyclic alicyclic organic group; two or more condensed polycyclic alicyclic organic groups bonded to each other; Or a C ₁ to C ₁₀ cycloalkylene group in which two or more alicyclic rings are single bonded, substituted or unsubstituted, -O-, -S-, -CH(OH)-, -Si(CH ₃ ) ₂ -, - (CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , or a combination of two or more of these functional groups. According to claim 14,
X further comprises a substituted or unsubstituted C ₆ to C ₃₀ tetravalent aromatic organic group, and the tetravalent aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or two or more aromatic rings are single bonds, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a combination of two or more of these A method for producing a polyimide resin linked by a phosphorus functional group. According to claim 14,
A method for producing a polyimide resin in which the compound of Formula 5 includes trimellitic anhydride chloride. According to claim 14,
The first diamine compound is 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (2,2'-bis(trifluoromethyl)-[1,1 A method for producing a polyimide resin containing '-biphenyl] -4,4'-diamine). According to claim 14,
Method for producing a polyimide resin in which the second diamine compound has a structure represented by Chemical Formula 9:
[Formula 9]

In Formula 9,
i is an integer greater than or equal to 1; According to claim 14,
A method for producing a polyimide resin in which the dianhydride compound includes 1,2,3,4-cyclobutanetetracarboxylic dianhydride. According to claim 15,
Method for producing a polyimide resin wherein the dianhydride compound further comprises 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride . According to claim 14,
The method for producing a polyimide resin, wherein the step of generating the polyamic acid further reacts the first diamine compound having the structure of Chemical Formula 6 in addition to the second diamine compound and the dianhydride compound. A composition for forming a polyimide resin comprising a compound of Formula 5 below, a first diamine compound having a structure of Formula 6 below, and a dianhydride compound having a structure of Formula 8 below:
[Formula 5]

In Formula 5,
Z is a substituted or unsubstituted C ₆ to C ₄₀ trivalent aromatic organic group.
[Formula 6]

In Formula 6,
Y includes a C ₆ to C ₃₀ divalent aromatic organic group substituted with -F or -CF ₃ , and the aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or a single bond of two or more aromatic rings, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S -, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10 ), -(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or two of these It is linked by the functional group which is a combination of the above.
[Formula 8]

In Formula 8,
X includes a substituted or unsubstituted C ₄ to C ₃₀ tetravalent alicyclic organic group, and the alicyclic organic group is a monocyclic alicyclic organic group; two or more condensed polycyclic alicyclic organic groups bonded to each other; Or a C ₁ to C ₁₀ cycloalkylene group in which two or more alicyclic rings are single bonded, substituted or unsubstituted, -O-, -S-, -CH(OH)-, -Si(CH ₃ ) ₂ -, - (CH ₂ ) _p - (here, 1≤p≤10), -(CF ₂ ) _q - (here, 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , or a combination of two or more of these functional groups. The method of claim 22,
X further comprises a substituted or unsubstituted C ₆ to C ₃₀ tetravalent aromatic organic group, and the tetravalent aromatic organic group exists alone; Two or more are bonded to each other to form a condensed ring; Or two or more aromatic rings are single bonds, a fluorenylene group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₆ to C ₁₅ arylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a combination of two or more of these A composition for forming a polyimide resin linked by a phosphorus functional group. The method of claim 22,
A composition for forming a polyimide resin, wherein the compound of Formula 5 includes trimellitic anhydride chloride. The method of claim 22,
The first diamine compound is 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine (2,2'-bis(trifluoromethyl)-[1,1 A composition for forming a polyimide resin comprising '-biphenyl] -4,4'-diamine). The method of claim 22,
A composition for forming a polyimide resin, wherein the dianhydride compound includes 1,2,3,4-cyclobutanetetracarboxylic dianhydride. According to claim 23,
A composition for forming a polyimide resin in which the dianhydride compound further comprises 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride . A polyimide film comprising the polyimide resin according to any one of claims 1 to 13. A display device comprising the polyimide film according to claim 28 . According to claim 29,
The display device is a flexible display device.

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