KR101421405B1 - A compound having trifluorovinyl ether group, copolymer comprising the same, preparation method thereof and optical films or display substrate using the same - Google Patents

Abstract

The present invention relates to a compound containing a trifluorovinyl ether group, a polyimide copolymer containing the same, a method for producing the same, and an optical film or a substrate for a display using the same, wherein the trifluorovinyl ether group The polyimide copolymer is remarkably improved in chemical resistance while maintaining the optical properties due to the characteristic of the cross-linking structure of the aromatic polyimide. Therefore, the polyimide copolymer can be effectively used for various optical films and display substrates.

Description

TECHNICAL FIELD [0001] The present invention relates to a compound containing a trifluorovinyl ether group, a polyimide copolymer containing the same, a method for producing the same, and an optical film or display substrate using the same, films or display substrate using the same}

TECHNICAL FIELD The present invention relates to a compound containing a trifluorovinyl ether group, a polyimide copolymer containing the same, a method of producing the same, and an optical film or a display substrate using the same.

Generally, a polyimide (PI) resin is a polyimide (PI) resin, which is imidized by using a polyamic acid obtained by polycondensation polymerization of an aromatic dianhydride and an aromatic diisocyanate or a diisocianate as a precursor, Resin. In general, pyromellitic anhydride (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) is used as an aromatic dianhydride component in the production of a polyimide resin. As the aromatic diamine component, Oxidianiline (ODA), or p-phenylenediamine (p-PDA).

Examples of the processing method of the polyimide resin include a thermal imidization method by heat treatment from polyamic acid (PAA) which is a precursor, a chemical imidization method using a solvent which is easy to form a hydrate such as pyridine, and a method using isocyanate. Among various methods, a thermal imidization method through a simple heat treatment process is widely used without using an additional solvent or isocyanate, and film casting is mainly used for the process characteristic.

(2) a high usable temperature; (3) a long-term usable temperature of about 260 ° C; and a short-term usable temperature of about 480 ° C .; a polyimide resin having a high heat- (4) radiation resistance, (5) excellent low temperature characteristics, and (6) excellent chemical resistance. Due to such physical properties, the polyimide resin is used in a wide range of fields such as heat-resistant high-temperature materials such as automobile materials, air materials and spacecraft materials, and electronic materials such as insulating coatings, insulating films, semiconductors, and electrode protective films of TFT- In recent years, display materials such as an optical fiber and a liquid crystal alignment film and a transparent electrode film containing a conductive filler or coated on the surface are also used. .

The aromatic polyimide resin has an advantage of having excellent heat resistance, but has a high surface tension due to high aromatic ring density and is colored in brown or yellow, and has low transmittance in the visible light region, making it difficult to use it as an optical material there was.

In recent years, in order to obtain a transparent polyimide which solves the problem of the conventional brown color, an aromatic dianhydride having a substituent such as a trifluoromethyl group and an aromatic diamine monomer are used to improve the transparency of color, And a method of producing a transparent polyimide by changing the manufacturing process have been developed (Patent Documents 1 to 5). However, the polyimide obtained by the above method has insufficient mechanical and chemical characteristics for use in a protective film, an insulating film, or the like for use in the production of a display substrate.

Therefore, there is a great interest in the development of a polyimide-based resin which is improved in chemical resistance and the like while maintaining optical transparency and mechanical properties.

Accordingly, the present inventors have succeeded in introducing a trifluorovinyl ether group into a conventional aromatic polyimide basic skeleton structure, thereby improving heat resistance and chemical resistance while maintaining transparency and mechanical properties owing to the characteristics of the crosslinked structure of the aromatic polyimide. Optical films and substrates for displays, and completed the present invention.

KR 2009-0053567 KR 2009-0021591 KR 2010-0023451 KR 2010-0010740 JP 2007-0022776

 Polymers (Korea), Vol. 34, No. 5, pp. 391-397, 2010  Polymers for Advanced Technology, Vol. 20, No. 1, 2009  Journal of Florine Chemistry, Vol. 130, No. 3, pp. 354-360

An object of the present invention is to provide a polyimide copolymer.

Another object of the present invention is to provide a process for producing the polyimide copolymer.

It is still another object of the present invention to provide an optical film comprising the polyimide copolymer.

Another object of the present invention is to provide a display substrate comprising the polyimide copolymer.

It is another object of the present invention to provide a compound comprising a trifluorovinyl ether group.

Another object of the present invention is to provide a process for producing a compound containing the trifluorovinyl ether group.

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

[Chemical Formula 1]

In Formula 1,

이고, 여기서 A는 직접결합(direct bond) 또는 산소이고;R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;

또는

이고, 여기서 A는 직접결합 또는 산소이고, X, Y 및 Z는 독립적으로 수소 또는 C_{1 - 4} 의 알킬이고, a, b 및 c는 독립적으로 1 내지 3의 정수이고;R ² is

or

, Wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _{1 -} alkyl of _4, a, b and c are independently an integer from 1 to 3;

이고, 여기서 B는 직접결합, 산소, S(=O)₂, C(CF₃)₂ 및

로 이루어진 군으로부터 선택되고, V 및 W는 독립적으로 H, C_{1 - 4} 의 알킬, C_{1 - 4} 의 트리플루오로알킬 또는 페닐이고, d 및 e는 독립적으로 1 내지 3의 정수이고;R ³ And R ⁴ are independently selected from the group consisting of C _{4 - 10} cycloalkanes, C _{1 - 4} alkyl C _{4 - 10} cycloalkanes, or

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;

이고, 여기서 B는 직접결합, 산소, S(=O)₂, C(CF₃)₂ 및

로 이루어진 군으로부터 선택되고, V 및 W는 독립적으로 H, C_{1 - 4} 의 알킬, C_{1 - 4} 의 트리플루오로알킬 또는 페닐이고, d 및 e는 독립적으로 1 내지 3의 정수이고;R ⁵ is

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;

and m and n are an integer of 10 to 1,000.

The present invention also relates to a process for producing a compound represented by the formula (1)

Reacting a compound containing a trifluorovinyl ether group represented by the formula (4), a dianhydride represented by the formula (2) and a diamine represented by the formula (3) to prepare a polyamic acid represented by the formula (5) (step 1); And

And a step (2) of preparing a polyimide copolymer represented by the general formula (1) through a heat treatment process of the polyamic acid represented by the general formula (5) prepared in the step (1) (step 2) .

[Reaction Scheme 1]

In the above Reaction Scheme 1,

이고, 여기서 A는 직접결합 또는 산소이고;R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;

또는

이고, 여기서 A는 직접결합 또는 산소이고, X, Y 및 Z는 독립적으로 수소 또는 C_1-4 의 알킬이고, a, b 및 c는 독립적으로 1 내지 3의 정수이고;R ² is

or

, Wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _1-4 alkyl, a, b and c are independently integers from 1 to 3;

이고, 여기서 B는 직접결합, 산소, S(=O)₂, C(CF₃)₂ 및

로 이루어진 군으로부터 선택되고, V 및 W는 독립적으로 H, C_{1 - 4} 의 알킬, C_{1 - 4} 의 트리플루오로알킬 또는 페닐이고, d 및 e는 독립적으로 1 내지 3의 정수이고;R ³ And R ⁴ are independently selected from the group consisting of C _{4 - 10} cycloalkanes, C _{1 - 4} alkyl C _{4 - 10} cycloalkanes, or

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;

이고, 여기서 B는 직접결합, 산소, S(=O)₂, C(CF₃)₂ 및

로 이루어진 군으로부터 선택되고, V 및 W는 독립적으로 H, C_{1 - 4} 의 알킬, C_{1 - 4} 의 트리플루오로알킬 또는 페닐이고, d 및 e는 독립적으로 1 내지 3의 정수이고;R ⁵ is

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;

and m and n are an integer of 10 to 1,000.

Further, the present invention provides an optical film comprising the polyimide copolymer.

The present invention also provides a display substrate comprising the polyimide copolymer.

Further, the present invention provides a compound comprising a trifluorovinyl ether group represented by the following formula (4).

[Chemical Formula 4]

In Formula 4,

이고, 여기서 A는 직접결합 또는 산소이고;R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;

또는

이고, 여기서 A는 직접결합 또는 산소이고, X, Y 및 Z는 독립적으로 수소 또는 C_1-4 의 알킬이고, a, b 및 c는 독립적으로 1 내지 3의 정수이다.
R ² is

or

Wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _1-4 alkyl and a, b and c are independently integers of 1 to 3.

The present invention also relates to a process for producing a compound represented by the formula

Reacting a compound represented by the formula (6) with a compound represented by the formula (7) to prepare a compound represented by the formula (8) (step 1); And

And reducing the compound represented by the formula (8) prepared in the step (1) to prepare a compound having the trifluorovinyl ether group represented by the formula (4).

[Reaction Scheme 2]

In the above Reaction Scheme 2,

이고, 여기서 A는 직접결합 또는 산소이고;R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;

또는

이고, 여기서 A는 직접결합 또는 산소이고, X, Y 및 Z는 독립적으로 수소 또는 C_{1 - 4} 의 알킬이고, a, b 및 c는 독립적으로 1 내지 3의 정수이다.
R ² is

or

It is an alkyl of _4, a, b and c are independently an integer from 1 to _3, wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _1.

The polyimide copolymer containing the trifluorovinyl ether group according to the present invention is remarkably improved in chemical resistance while maintaining the optical properties owing to the characteristic of the crosslinked structure of the aromatic polyimide. Therefore, it is useful for various optical films and display substrates Can be used.

1 is an FT-IR spectrum of a polyimide copolymer (PI) of Formula 1a and a polyamic acid (PAA) of Formula 5a according to Example 1 of the present invention.
2 is a ¹ H-NMR spectrum of the compound of Formula 8a according to Step 1 of Example 2 of the present invention.
3 is an EI-Mass spectrum of the compound of Formula 8a according to Step 1 of Example 2 of the present invention.
4 is a ¹ H-NMR spectrum of the compound of Formula 4a according to Step 2 of Example 2 of the present invention.
5 is an EI-Mass spectrum of the compound of Formula 4a according to Step 2 of Example 2 of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides a polyimide copolymer represented by the following formula (1).

In Formula 1,

이고, 여기서 A는 직접결합 또는 산소이고;R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;

또는

이고, 여기서 A는 직접결합 또는 산소이고, X, Y 및 Z는 독립적으로 수소 또는 C_{1 - 4} 의 알킬이고, a, b 및 c는 독립적으로 1 내지 3의 정수이고;R ² is

or

, Wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _{1 -} alkyl of _4, a, b and c are independently an integer from 1 to 3;

이고, 여기서 B는 직접결합, 산소, S(=O)₂, C(CF₃)₂ 및

로 이루어진 군으로부터 선택되고, V 및 W는 독립적으로 H, C_{1 - 4} 의 알킬, C_{1 - 4} 의 트리플루오로알킬 또는 페닐이고, d 및 e는 독립적으로 1 내지 3의 정수이고;R ³ And R ⁴ are independently selected from the group consisting of C _{4 - 10} cycloalkanes, C _{1 - 4} alkyl C _{4 - 10} cycloalkanes, or

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;

이고, 여기서 B는 직접결합, 산소, S(=O)₂, C(CF₃)₂ 및

로 이루어진 군으로부터 선택되고, V 및 W는 독립적으로 H, C_{1 - 4} 의 알킬, C_{1 - 4} 의 트리플루오로알킬 또는 페닐이고, d 및 e는 독립적으로 1 내지 3의 정수이고;R ⁵ is

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;

and m and n are an integer of 10 to 1,000.

Preferably,

,

또는

이고;The R ¹ silver

,

or

ego;

,

,

,

또는

이고;R ² is

,

,

,

or

ego;

,

,

,

,

또는

이고;R ³ And R < ⁴ > are independently

,

,

,

,

or

ego;

,

,

또는

이다.
R ⁵ is

,

,

or

to be.

More preferably,

이고;Wherein R < ^{1 &}

ego;

이고;R ² is

ego;

이고;R ³ And R < ⁴ &

ego;

이다.
R ⁵ is

to be.

Also, preferably, when m and n are represented by molar ratios of the repeating units, (n / m + n) is 0.01 to 0.5. If n / (m + n) is less than 0.01, the chemical resistance improving effect can not be obtained. If n / (m + n) is more than 0.5, the flexibility is lowered and the mechanical strength is lowered.

Further, the present invention relates to a process for producing a polyamic acid represented by the formula (5) by reacting a compound containing a trifluorovinyl ether group represented by the formula (4), a dianhydride represented by the formula (2) and a diamine represented by the formula Step 1); And

And a step (2) of preparing a polyimide copolymer represented by the general formula (1) through a heat treatment process of the polyamic acid represented by the general formula (5) prepared in the step (1) (step 2) .

[Reaction Scheme 1]

In the above Reaction Scheme 1,

이고, 여기서 A는 직접결합 또는 산소이고;R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;

또는

이고, 여기서 A는 직접결합 또는 산소이고, X, Y 및 Z는 독립적으로 수소 또는 C_{1 - 4} 의 알킬이고, a, b 및 c는 독립적으로 1 내지 3의 정수이고;R ² is

or

, Wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _{1 -} alkyl of _4, a, b and c are independently an integer from 1 to 3;

이고, 여기서 B는 직접결합, 산소, S(=O)₂, C(CF₃)₂ 및

로 이루어진 군으로부터 선택되고, V 및 W는 독립적으로 H, C_{1 - 4} 의 알킬, C_{1 - 4} 의 트리플루오로알킬 또는 페닐이고, d 및 e는 독립적으로 1 내지 3의 정수이고;R ³ And R ⁴ are independently selected from the group consisting of C _{4 - 10} cycloalkanes, C _{1 - 4} alkyl C _{4 - 10} cycloalkanes, or

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;

이고, 여기서 B는 직접결합, 산소, S(=O)₂, C(CF₃)₂ 및

로 이루어진 군으로부터 선택되고, V 및 W는 독립적으로 H, C_{1 - 4} 의 알킬, C_{1 - 4} 의 트리플루오로알킬 또는 페닐이고, d 및 e는 독립적으로 1 내지 3의 정수이고;R ⁵ is

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;

and m and n are an integer of 10 to 1,000.

Hereinafter, the method for producing the polyimide copolymer according to the present invention will be described in detail for each step.

In the process for producing a polyimide copolymer according to the present invention, the step 1 is a step of reacting a compound containing a trifluorovinyl ether group represented by the formula (4), a dianhydride represented by the formula (2) and a diamine represented by the formula To prepare a polyamic acid represented by the general formula (5). More specifically, the compound having a trifluorovinyl ether group represented by the general formula (4) and the diamine represented by the general formula (3) are dissolved in a solvent, The dianhydride is gradually added and then polymerized to prepare the polyamic acid represented by the general formula (5).

At this time, the reaction may be carried out in a molar ratio of 1: 1 of dianhydride represented by Formula 2 and diamine represented by Formula 3 according to a conventional 1: 1 solution polymerization method of polyimide.

Examples of the solvent for the polymerization reaction in Step 1 include m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide , Diethyl acetate, tetrahydrofuran (THF), a low-boiling solution such as chloroform, or a low-absorbency solvent such as? -Butyrolactone may be used, and preferably dimethylacetamide (DMAc) can be used.

The content of the solvent is not particularly limited, but it may be in the range of 50-95 wt.%, Preferably 70-90 wt.%, In the total reaction solution in order to obtain the molecular weight and viscosity of a suitable polyamic acid solution.

Further, the reaction conditions are not particularly limited, but may be carried out in the range of -20 to 80 ° C, preferably 0 to 30 ° C for 10 to 24 hours.

The polyamic acid prepared by the above-mentioned method usually has a solid content of 5 to 35% by weight, preferably 15 to 25% by weight, a preferred number average molecular weight (Mn) of 10,000 to 1,000,000 and a viscosity of 0.20 to 0.8 dl / g. < / RTI >

Also, in the method for producing a polyimide copolymer according to the present invention, the step 2 is a step of preparing a polyimide copolymer represented by the formula (1) through a heat treatment process of the polyamic acid represented by the formula (5) More specifically, the polyamic acid represented by the general formula (5) is subjected to film casting using a film applicator to produce a polyimide copolymer represented by the general formula (1).

The method for producing a polyimide film according to the present invention is a casting method in which a polymerized polyamic acid is cast on a support and imidized to obtain a polyamide copolymer in the form of a film, , 1 hour at 120 占 폚, 1 hour at 180 占 폚 and 1 hour at 300 占 폚.

Further, the thickness of the obtained polyimide film is not particularly limited, but is preferably 10-250 占 퐉, more preferably 25-150 占 퐉.

Further, the present invention provides an optical film comprising the polyimide copolymer.

The optical film comprising the polyimide copolymer of the present invention can be obtained by preparing a polyimide copolymer under appropriate molding conditions. For example, the polyimide copolymer of the present invention can be mixed with other components, melt-kneaded, granulated or pulverized, and then the film can be produced by press molding, extrusion molding, inflation molding or solution casting have.

The thickness of the optical film can be suitably set in accordance with the purpose of use, particularly, depending on birefringence and wavelength dependency of the optical component, and is usually 10-200 占 퐉, preferably 20-100 占 퐉. If the optical film is too thin, ease of handling may deteriorate. If the optical film is too thick, it may be difficult to handle with rolls and the length per roll may be short.

The present invention also provides a display substrate comprising the polyimide copolymer.

The substrate for display comprising the polyimide copolymer of the present invention can be obtained by preparing a polyimide copolymer under appropriate molding conditions. For example, the polyimide copolymer of the present invention can be mixed with other components, melt-extruded, and molded by a general molding process such as solution casting, press molding, etc., A solution casting method capable of producing a display substrate having excellent surface characteristics can be used.

The substrate for display may contain an antioxidant, an ultraviolet absorber, other polymer resin, a surfactant, a polymer electrolyte, a conductive adhesive, an inorganic filler, a pigment, a dye, an antistatic agent, an anti-blocking agent, a lubricant, A substrate for a display element, or the like.

The present invention also provides a compound comprising a trifluorovinyl ether group represented by the following general formula (4).

In Formula 4,

이고, 여기서 A는 직접결합 또는 산소이고;R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;

또는

이고, 여기서 A는 직접결합 또는 산소이고, X, Y 및 Z는 독립적으로 수소 또는 C_1-4 의 알킬이고, a, b 및 c는 독립적으로 1 내지 3의 정수이다.
R ² is

or

Wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _1-4 alkyl and a, b and c are independently integers of 1 to 3.

Preferably,

,

또는

이고;Wherein R < ^{1 &}

,

or

ego;

,

,

,

또는

이다.
R ² is

,

,

,

or

to be.

More preferably,

이고;Wherein R < ^{1 &}

ego;

이다.
R ² is

to be.

The compound having the trifluorovinyl ether group represented by the formula (4) forms a perfluorocyclobutane group in the polymerization of the polyimide copolymer represented by the formula (1) according to the present invention, and the perfluorocyclobutane group Since it has a low surface energy, it can exhibit insolubility to an organic solvent while maintaining mechanical properties such as heat resistance and transparency and optical properties. Particularly, the perfluorocyclobutane group bonded in the para form in the polyimide copolymer according to the present invention exhibits good physical properties and does not dissolve well in organic solvents. Therefore, the conventional mechanical and optical properties But also serves as a core monomer for preparing polyimide copolymers with greatly improved chemical resistance.

Further, the present invention relates to a process for the preparation of

Reacting a compound represented by the formula (6) with a compound represented by the formula (7) to prepare a compound represented by the formula (8) (step 1); And

And reducing the compound represented by the formula (8) prepared in the step (1) to prepare a compound containing the trifluorovinyl ether group represented by the formula (4) (step 2). Lt; RTI ID = 0.0 > 1, < / RTI >

[Reaction Scheme 2]

In the above Reaction Scheme 2,

이고, 여기서 A는 직접결합 또는 산소이고;R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;

또는

이고, 여기서 A는 직접결합 또는 산소이고, X, Y 및 Z는 독립적으로 수소 또는 C_{1 - 4} 의 알킬이고, a, b 및 c는 독립적으로 1 내지 3의 정수이다
R ² is

or

, Wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _{1 -} alkyl of _4, a, b and c are independently an integer of 1 to 3

Hereinafter, the method for preparing the compound having the trifluorovinyl ether group represented by the formula (4) according to the present invention will be described in detail in each step.

In the process for producing a compound having a trifluorovinyl ether group represented by the formula (4) according to the present invention, the step 1 of the above reaction scheme 2 may be carried out by reacting a compound represented by the formula (6) with a compound represented by the formula (7) More specifically, the compound represented by the formula (6) and the compound represented by the formula (7) are reacted in the presence of tetrakis (triphenylphosphine) palladium (0) .

Examples of the solvent for the reaction of Step 1 include ethers such as dimethoxyethane, tetrahydrofuran and dioxane, hydrocarbons such as cyclohexane, toluene and xylene, ethanol, 1-propanol, 2-propanol, -Butanol, and the like. Of these, toluene can be preferably used.

In the reaction of Step 1, a palladium catalyst such as palladium (II) chloride, palladium (II) acetate or tetrakis (triphenylphosphine) palladium (O) may be used, and preferably tetrakis Triphenylphosphine) palladium (0), wherein the palladium catalyst is used in a low proportion of 0.001 to 1.0 mol%, preferably 0.005 to 0.5 mol%, based on the amount of the compound represented by the general formula (7) .

Further, the reaction conditions are not particularly limited, but may be carried out in the range of 50 to 120 ° C, preferably at 70 to 110 ° C for 10 to 24 hours.

Further, in the method for producing a compound having a trifluorovinyl ether group represented by the formula (4) according to the present invention, the step 2 of Scheme 2 may be carried out by reducing the compound represented by the formula (8) Is a step of preparing a compound represented by the general formula (4) by reducing a dinitro group to a diamine by using a strong reducing agent such as tin chloride, etc., to prepare a compound represented by the general formula (8).

Examples of the solvent for the reduction reaction in the step 2 include a mixture of an aqueous solution and an organic solvent such as tetrahydrofuran (THF), acetonitrile, methanol, ethanol, isopropyl alcohol, A 1: 1 mixture of water and tetrahydrofuran (THF) can be used.

The reduction reaction is preferably carried out in the presence of a strong reducing agent such as a tin chloride catalyst until the starting material disappeared at 70-110 캜. An aqueous solution of sodium hydrogencarbonate is added until the pH is 8 to produce a precipitate, The precipitate may be extracted and used.

Reference is made to a method for producing a compound represented by the formula (6) used as a reaction material in a process for producing a compound containing a trifluorovinyl ether group represented by the formula (4) according to the present invention.

As shown in Scheme 3 below,

A step of preparing a compound represented by the formula (10) from the compound represented by the formula (9) (step 1); And

The compound represented by the formula (6) can be prepared by preparing the compound represented by the formula (6) from the compound represented by the formula (10) prepared in the step 1 (step 2) (Production Example 1 and Production Example 2) .

[Reaction Scheme 3]

In Scheme 3,

이고, 여기서 A는 직접결합 또는 산소이다.
R ¹ is phenyl or

, Wherein A is a direct bond or oxygen.

The compound represented by the formula (9) was dissolved in concentrated sulfuric acid and then reacted with N-bromosuccinimide to obtain a brominated compound represented by the formula (10), and the obtained compound represented by the formula (10) ) Diborane to give the compound of formula 6.

Referring to the experimental results for evaluating the chemical resistance of a polyimide copolymer film containing a trifluorovinyl ether group according to the present invention, a polyimide copolymer film without a trifluorovinyl ether group used for comparison (DMF), N-methylpyrrolidone (NMP) and dimethylformamide (DMF) except for chloroform (CHCl ₃ ), but it was found that the trifluorovinyl ether group Was not dissolved in all of the above four solvents. This indicates that the chemical resistance of the polyimide film is improved due to the nature of the crosslinked structure of the polyimide copolymer containing the trifluorovinyl ether group.

Further, with reference to the experimental results for evaluating the optical properties of the polyimide copolymer film containing the trifluorovinyl ether group according to the present invention, the polyimide copolymer containing no trifluorovinyl ether group The optical transparency of the film and the polyimide copolymer film containing the trifluorovinyl ether group according to the present invention showed 88.37% and 86.72%, respectively, and haze was 0.5% and 1.5%, respectively, . This indicates that the optical properties of the polyimide film did not deteriorate due to the nature of the crosslinked structure of the polyimide copolymer containing the trifluorovinyl ether group.

As described above, the polyimide copolymer containing the trifluorovinyl ether group according to the present invention has remarkably improved chemical resistance while maintaining the optical properties owing to the characteristic of the crosslinked structure of the aromatic polyimide. Therefore, Can be usefully used for a substrate.

Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.

≪ Preparation Example 1 & Compound formula  10a (1- Bromo -3,5- Dinitrobenzene )

(10 g, 0.06 mol) was dissolved in 60 mL of concentrated sulfuric acid, and N-bromosuccinimide (15 g, 0.083 mol) was added thereto while maintaining the temperature at 80 ° C. Was added dropwise 9 times over 10 minutes, the temperature was raised to 95 占 폚, and the reaction was carried out for 24 hours. After completion of the reaction, the reaction solution was poured into ice water, and the resulting precipitate was filtered, washed several times with distilled water, and recrystallized from methanol to obtain the target compound of Formula 10a.

_{^{1 H-NMR (CDCl 3)}} : δ9.00 (s, 1H), 8.71 (s, 2H)

< Manufacturing example  2 > The compound of formula (6a) (1- Dinitrophenylboronic acid , Pinacol  Ester)

(25.93 g, 104.9 mmol), bis (pinacolato) diborane (31.97 g, 125.9 mmol) prepared in Preparation Example 1, potassium acetate Dichloropalladium (II) (1.71 g, 2.10 mmol) was added to a flask in a glove box and 1,4-di (triphenylphosphino) (100 mL) was added thereto, followed by stirring at 85 占 폚 for 24 hours. After completion of the reaction, the reaction solution was extracted with ethyl acetate, washed with brine, dried over MgSO ₄ , and the solvent was removed under reduced pressure, followed by recrystallization from hexane to obtain the target compound of Formula 6a .

_{^{1 H-NMR (CDCl 3)}} : δ9.06 (t, 1H), 8.88 (d, 2H), 1.35 (s, 12H)

&Lt; Example 1 > Preparation of polyimide copolymer film of formula (Ia)

Step 1: Polyamic acid  Produce

(4'- (1,2,2-trifluorovinyloxy) biphenyl-3,5-diamine) (0.19 g, 0.68 mmol) prepared in Example 2 below was added to a 250 mL three- ) And the compound of formula 3a (2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl (TFDB)) (1.94 g, 6.08 mmol) were dissolved in 17.17 g of dimethylacetylamide (DMAc) (2, 2'-bis (3,4-dicarboxyphenyl) hexafluoropropane) (6FDA) (3.00 g, 6.75 mmol) was slowly added thereto at a temperature of 5 ° C or lower, The reaction was carried out for 12 hours while keeping the temperature at room temperature. Through the above 1: 1 solution polymerization process, a polyamic acid of formula (5a) having a solid content of 23% by weight was prepared.

^{1 H-NMR (PAA, DMSO} -d 6): δ7.36 (m, 2H), 7.57 (s, 1H), 7.72 (m, 2H), 7.84 (m, 8H), 7.94 (m, 4H), 8.12 ( d , 2H), 8.26 ( d , 4H), 10.96 ( d , 4H)

Step 2: Preparation of polyimide copolymer film of formula (Ia)

The polyamic acid of Chemical Formula 5a prepared in Step 1 was heated at 60 ° C for 1 hour, 120 ° C for 1 hour, 180 ° C for 1 hour, and 300 ° C using a film applicator (CK Trading Co Ltd., model name: CKAF- For 1 hour to prepare a 100 m thick polyimide copolymer film of formula (Ia).

< Example  2 > The compound of formula (4a) (4 &apos; - (1,2,2- Trifluorovinyloxy ) Biphenyl-3,5- Diamine )

Step 1: Preparation of the compound of formula (8a)

(3,5-dinitrophenylboronic acid) (1.06 g, 3.6 mmol) prepared in Preparation Example 2 was added to a 100 ml round bottom flask equipped with a stirrer, a nitrogen inlet, a temperature controller and a reflux condenser, (0.76 g, 3.0 mmol), tetrakis (triphenylphosphine) palladium (0) (Pd (0) (pph ₃ ) ₄ ) (0.11 g, 0.01 mmol), sodium carbonate (8.4 mL, 2M) and ethanol (4.2 mL) were added. Toluene (21 ml) was added as a solvent under nitrogen, Lt; / RTI &gt; After 24 hours, it was added to 100 ml of water and extracted using methylene chloride, washed with brine, then, dried over MgSO ₄ and the solvent removed under reduced pressure. This was followed by flash column chromatography using hexane / ethyl acetate 20/1 (v / v%) as the eluent to give a white powder of the compound of formula 8a (l, 3-dinitro- , 2-trifluorovinyloxy) benzene) in 74% yield.

The synthesis of the compound of formula (8a) prepared by the above-mentioned method was confirmed by ¹ H-NMR and EI-Mass, which are shown in FIGS. 1 and 2, respectively.

_{^{1 H-NMR (CDCl 3)}} : δ7.30 (d, 2H, J = 8.85Hz), 7.71 (d, 2H, J = 8.25Hz), 8.74 (d, 2H, J = 2.07Hz), 9.02 (t , 1H, J = 2.07 Hz)

m / z: 340.0307

Step 2: Preparation of compound of formula (4a)

To a 100 ml round-bottomed flask equipped with a stirrer, a nitrogen inlet, a temperature controller and a reflux condenser was added the compound of the formula 8a (1,3-dinitro-5- (1,2,2-tri (0.49 g, 1.45 mmol) and tin chloride (SnCl ₂ ) (3.06 g, 16.16 mmol) were added to the reaction mixture and 10 mL of tetrahydrofuran (THF) and water (H ₂ O) Lt; RTI ID = 0.0 &gt; 85 C &lt; / RTI &gt; until the starting material disappeared. After completion of the reaction, the reaction solution was cooled to room temperature, and then, in a water bath, NaHCO ₃ Aqueous solution was added. After the reaction solution was stirred for 1 hour, ethyl acetate was added thereto, and the precipitate was filtered. The filtrate was extracted with ethyl acetate, washed with brine, dried over MgSO ₄ , and then evaporated to remove the solvent. Thereafter, the reaction mixture was separated by flash column chromatography using 30/1 (v / v%) of methylene chloride / ethyl acetate as an eluent to obtain a pale yellow powder of the compound of Formula 4a (4 '- (1,2,2-tri Fluorovinyloxy) biphenyl-3,5-diamine) in 78% yield.

The synthesis of the compound of Formula 4a prepared by the above method was confirmed by ¹ H-NMR and EI-Mass, which are shown in FIGS. 3 and 4, respectively.

_{^{1 H-NMR (CDCl 3)}} : δ3.65 (br, 4H), 6.04 (t, 1H, J = 1.98Hz), 6.28 (d, 1H, J = 2.01Hz), 7.12 (d, 2H, J = 8.19 Hz), 7.51 ( d , 2H, J = 8.88 Hz)

m / z: 280.0823

&Lt; Comparative Example 1 & gt; Preparation of a polyimide copolymer film of the formula (1b) in which a trifluorovinyl ether group was not introduced

Step 1: Trifluoro  5b in which the vinyl ether group is not introduced Polyamic acid  Produce

(2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl) (TFDB) (1.94 g, 6.08 mmol) was added to a 250 mL three-necked flask in dimethylacetylamide (DMAc ) And the compound of formula 2a (2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane) (6FDA) (3.00 g, 6.75 mmol) was slowly added at 5 ° C or lower Thereafter, the reaction was carried out for 12 hours while maintaining the reaction temperature at room temperature. The polyamic acid of formula (5b) having a solid content of 23% by weight was prepared through the above 1: 1 solution polymerization.

Step 2: Trifluoro  Preparation of polyimide copolymer film of formula (1b) in which vinyl ether groups are not introduced

The polyamic acid of Chemical Formula 5b prepared in Step 1 was heated at 60 ° C for 1 hour, at 120 ° C for 1 hour, at 180 ° C for 1 hour, at 300 ° C using a film applicator (CK Trading Co Ltd., model name: CKAF-1003) For 1 hour to prepare a 100 m thick polyimide copolymer film of formula (Ib).

&Lt; Experimental Example 1 >

In order to evaluate the chemical resistance of the polyimide copolymer film produced in Example 1 of the present invention, the following experiment was conducted.

Specifically, the polyimide copolymer film prepared in Example 1 and the polyimide copolymer film prepared in Comparative Example 1 were mixed with dimethylacetamide (DMAc), chloroform (CHCl ₃ ), N-methylpyrrolidone (NMP ) And dimethylformamide (DMF), the excess solvent was wiped off, and after 24 hours, the chemical resistance was measured using an optical microscope (CAMSCOPE, magnification x 2400). The results are shown in Table 1.

division
Organic solvent Measuring time 24 hours Example 1


DMAc × CHCl ₃ × NMP × DMF × Comparative Example 1


DMAc ○ CHCl ₃ × NMP ○ DMF ○ &Amp; cir &amp;: dissolved, X: not dissolved

As shown in Table 1, the polyimide copolymer film prepared in Example 1 was not dissolved in all four solvents. On the other hand, the polyimide copolymer film prepared in Comparative Example 1 was easily dissolved in three solvents except chloroform (CHCl ₃ ). This indicates that the polyimide copolymer according to the Example is remarkably improved in chemical resistance due to the introduction of the trifluorovinyl ether group.

Accordingly, the polyimide copolymer containing the trifluorovinyl ether group according to the present invention has remarkably improved chemical resistance while maintaining the optical properties owing to the characteristic of the crosslinked structure of the aromatic polyimide. Therefore, Can be usefully used.

&Lt; Experimental Example 2 >

In order to evaluate the optical properties of the polyimide copolymer film prepared in Example 1 of the present invention, the following experiment was conducted.

Specifically, the polyimide copolymer film prepared in Example 1 and the polyimide copolymer film prepared in Comparative Example 1 were measured for transmittance and light transmittance at a wavelength of 550 nm using an UV spectrometer (model: 8453, manufactured by Agilent) Haze (Gardner, model: 4725) was measured for the analysis of turbidity and the results are shown in Table 2.

division Optical transparency (%) (550 nm) Haze (%) Example 1 86.72 1.5 Comparative Example 1 88.37 0.6

As shown in Table 2, the optical transparency of the polyimide copolymer film prepared in Example 1 was 86.72%, which was almost the same as the optical transparency of 88.37% of the polyimide copolymer film prepared in Comparative Example 1. In addition, the haze of the polyimide copolymer film prepared in Example 1 was 1.5%, which was not significantly different from that of the polyimide copolymer film prepared in Comparative Example 1, and remained low. This indicates that the introduction of the trifluorovinyl ether group did not lower the optical properties of the polyimide copolymer according to the examples.

Accordingly, the polyimide copolymer containing the trifluorovinyl ether group according to the present invention has remarkably improved chemical resistance while maintaining the optical properties owing to the characteristic of the crosslinked structure of the aromatic polyimide. Therefore, Can be usefully used.

Claims (10)

A polyimide copolymer represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

(In the formula 1,
R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;
R ² is

or

, Wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _{1 -} alkyl of _4, a, b and c are independently an integer from 1 to 3;
R ³ And R ⁴ are independently selected from the group consisting of C _{4 - 10} cycloalkanes, C _{1 - 4} alkyl C _{4 - 10} cycloalkanes, or

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;
R ⁵ is

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;
and m and n are integers from 10 to 1,000.
The method according to claim 1,
The R ¹ silver

,

or

ego;
R ² is

,

,

,

or

ego;
R ³ And R &lt; ⁴ &gt; are independently

,

,

,

,

or

ego;
R ⁵ is

,

,

or

&Lt; / RTI &gt; polyimide copolymer.
The method according to claim 1,
The R ¹ silver

ego;
R ² is

ego;
R ³ And R &lt; ⁴ &

ego;
R ⁵ is

&Lt; / RTI &gt; polyimide copolymer.
The method according to claim 1,
(M / n) is 0.01 to 0.5 when m and n are expressed as a molar ratio of the corresponding repeating unit.
As shown in Scheme 1 below,
Reacting a compound containing a trifluorovinyl ether group represented by the formula (4), a dianhydride represented by the formula (2) and a diamine represented by the formula (3) to prepare a polyamic acid represented by the formula (5) (step 1); And
A step of preparing a polyimide copolymer represented by the general formula (1) by a heat treatment process of the polyamic acid represented by the general formula (5) prepared in the step (1) (step 2) Way.
[Reaction Scheme 1]

(In the above Reaction Scheme 1,
R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;
R ² is

or

, Wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _{1 -} alkyl of _4, a, b and c are independently an integer from 1 to 3;
R ³ And R ⁴ are independently selected from the group consisting of C _{4 - 10} cycloalkanes, C _{1 - 4} alkyl C _{4 - 10} cycloalkanes, or

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;
R ⁵ is

, Wherein B is a direct bond, _{oxygen, S (= O) 2,} C (CF 3) 2 and

Selected from the group consisting of and, V and W are independently selected from H, C _{1 - 4} alkyl, C _{1 -} alkyl or phenyl trifluoroacetate of _4, d and e are independently an integer from 1 to 3;
and m and n are integers from 10 to 1,000.
6. The method of claim 5,
Wherein m and n are expressed as a molar ratio of the repeating unit, and (n / m + n) is 0.01 to 0.5.
An optical film comprising the polyimide copolymer of claim 1.
A substrate for a display comprising the polyimide copolymer of claim 1.
A compound comprising a trifluorovinyl ether group represented by the following formula (4): &lt; EMI ID =
[Chemical Formula 4]

(In the formula 4,
R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;
R ² is

or

Is an alkyl of _4, a, b and c are independently an integer from 1 to _3), wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _1.
As shown in Reaction Scheme 2 below,
Reacting a compound represented by the formula (6) with a compound represented by the formula (7) to prepare a compound represented by the formula (8) (step 1); And
A step of reducing a compound represented by the formula (8) prepared in the step (1) to prepare a compound having a trifluorovinyl ether group represented by the formula (4) (step 2); and reacting the trifluorovinyl Ether group. &Lt; / RTI &gt;
[Reaction Scheme 2]

(In the above Reaction Scheme 2,
R ¹ is phenyl or

, Wherein A is a direct bond or oxygen;
R ² is

or

Is an alkyl of _4, a, b and c are independently an integer from 1 to _3), wherein A is a direct bond or oxygen, X, Y and Z are independently hydrogen or C _1.

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