WO2015111982A1

WO2015111982A1 - Polyimide and film using same

Info

Publication number: WO2015111982A1
Application number: PCT/KR2015/000812
Authority: WO
Inventors: 박효준; 정학기; 하창식; 쿠마르 타파쉬프라딥; 정영식
Original assignee: 코오롱인더스트리 주식회사
Priority date: 2014-01-27
Filing date: 2015-01-26
Publication date: 2015-07-30

Abstract

The present invention relates to a polyimide and to a film using same, and, more specifically, disclosed are: a polyimide which exhibits a low dielectric constant while maintaining the outstanding physical properties of the polyimide unchanged, and which is useful as a material for optical communication such as an optical waveguide or electronic material such as a protective material or an insulating material in a liquid crystal display element or semiconductor.

Description

Polyimide and Film Using the Same

The present invention relates to a polyimide and a film using the same, and more particularly, to a polyimide having excellent thermal stability and low dielectric constant and excellent light transmittance while maintaining excellent physical properties of the polyimide, and a polyimide film comprising the same. It is about.

In general, polyimides have high mechanical strength, heat resistance, insulation, solvent resistance, and the like, and thus are widely used as electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display devices and semiconductors. In recent years, optical communication materials such as optical waveguide materials and use as substrates for mobile phones are also expected.

In recent years, the development of this field is remarkable, and increasingly high characteristics are also required for the material used correspondingly. In other words, polyimide that is not only excellent in heat resistance and solvent resistance but also has a large number of performances depending on the application such as transparency is desired.

Since the wholly aromatic polyimide obtained by the polycondensation reaction of the aromatic tetracarboxylic dianhydride and aromatic diamine which is conventionally used generally has a dark amber color, there exists a problem in the use which requires high transparency. In addition, since the wholly aromatic polyimide has a high dielectric constant, there is a limit to being used as an electronic material requiring transparency and low dielectric constant.

As one method of realizing transparency, a polyimide precursor is obtained by polycondensation reaction of an alicyclic tetracarboxylic dianhydride and an aromatic diamine, and imidation of the precursor results in relatively little coloring and a high transparency polyimide. What is obtained is known (Japanese Patent Laid-Open No. 2-24294, Japanese Patent Laid-Open No. 58-208322).

In addition, recently, polyimide prepared using 1,2,3,4-cyclopentatetracarboxylic dianhydride (hereinafter abbreviated as CPDA) as a monomer is referred to as organic electroluminescence (hereinafter referred to as organic EL). Flagship) Use as a gas barrier film of an element is examined (Japanese Patent Laid-Open No. 2006-232960).

However, the polyimide produced by such a method has not only room for improvement in terms of low degree of polymerization and heat resistance, but also not necessarily sufficient optical properties.

The main object of the present invention is to provide a polyimide and a polyimide film comprising the same, which exhibits excellent thermal stability and low dielectric constant while maintaining excellent physical properties of the polyimide, while having excellent light transmittance.

In order to achieve the above object, one embodiment of the present invention is a polyimide obtained by imidizing a polyamic acid polymerized diamine and acid dianhydride, the acid dianhydride includes a compound represented by the following formula (1) It provides a polyimide characterized in that.

In a preferred embodiment of the invention, the diamine is p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 1,3-bis (4,4 ' -Aminophenoxy) benzene, 4,4'-diamino-1,5-phenoxypentane, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylpropane , Bis (3,5-diethyl-4-aminophenyl) methane, diaminodiphenylsulfone, diaminobenzophenone, diaminonaphthalene, 1,4-bis (4-aminophenoxy) benzene, 1,4- Bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 1,3-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) di Phenylsulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-trifluoromethyl-4,4'-diaminobiphenyl and mixtures thereof Being aromatic dia .; 1,4-diaminocyclohexane, 1,4-cyclohexanebis (methylamine), 4,4'-diaminodicyclohexylmethane (MCA), 4,4'-methylene bis (2-methyl cyclohexylamine Alicyclic diamines selected from the group consisting of (MMCA) and mixtures thereof; And ethylenediamine (EN), 1,3-diaminopropane (13DAP), tetramethylenediamine, 1,6-hexamethylenediamine (16DAH), 1,12-diaminododecane (112DAD) and mixtures thereof It may be characterized in that at least one member selected from the group consisting of aliphatic diamine selected from the group.

In a preferred embodiment of the invention, the diamine is 1,6-hexamethylenediamine (16DAH), 1,12-diaminododecane (112DAD), 4,4'-diaminodicyclohexylmethane (MCA) and It may be characterized by at least one member selected from the group consisting of 4,4'-methylene bis (2-methyl cyclohexylamine) (MMCA).

In a preferred embodiment of the invention, the acid dianhydride is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4- (2,5-dioxotetrahydro Furan-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA), pyromellitic dianhydride (1,2,4,5-benzene Tetracarboxylic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), biscarboxyphenyl Dimethyl silane dianhydride (SiDA), bis dicarboxyphenoxy diphenyl sulfide dianhydride (BDSDA), sulfonyl diphthalic hydride (SO ₂ DPA), cyclobutane tetracarboxylic dianhydride (CBDA), Isopropylideneifenoxy bis phthalic hydride (6HBDA), non Cyclo [2.2.2] -7-octene-2,3,5,6-tetracarboxylic dianhydride (BTA), cyclopentane tetracarboxylic dianhydride (CPDA), cyclohexane tetracarboxylic dian It may be characterized in that it further comprises one or more selected from the group consisting of hydride (CHDA) and bicyclohexane tetracarboxylic dianhydride (HBPDA).

Another embodiment of the present invention provides a polyimide film comprising the polyimide.

In another preferred embodiment of the present invention, the polyimide film may have a transmittance of 80% or more at 550 nm based on a film thickness of 10 to 100 μm, and a dielectric constant of 1 GHz to 3.3 or less.

The present invention exhibits low dielectric constant while maintaining excellent physical properties of polyimide, and includes polyimides useful as optical communication materials such as optical waveguides, electronic materials such as protective materials and insulating materials in liquid crystal display devices and semiconductors, and the like. A polyimide film can be provided.

1 is a FTIR spectrum graph of the polyimide film prepared in Examples 1 to 4.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated.

The present invention provides a polyimide obtained by imidizing a polyamic acid polymerized with diamine and an acid dianhydride, wherein the acid dianhydride includes a compound represented by the following Chemical Formula 1, and the polyimide comprises the polyimide. It relates to a polyimide film.

In general, aliphatic polyimides have low molecular weight, bipolarity, and intermolecular or intramolecular charge transfer properties in comparison to aromatic polyimides, so they have high solubility in organic solvents, high transparency, and low dielectric constant. It is attracting much attention as an optoelectronic and interlayer insulating material.

Accordingly, in the present invention, piperazine-disuccinic anhydride (acid dianhydride represented by Chemical Formula 1) containing nitrogen is used as an acid dianhydride to prepare aliphatic polyimide having high transparency and low dielectric constant. Used.

Acid dianhydride represented by the formula (1) according to the present invention contains one or more nitrogen atoms in the molecule, thereby causing the interaction of the intramolecular or intermolecular chain due to the isolated electron pair of the nitrogen atom, thereby using the intrinsic polyimide It can greatly improve the solubility and electrical properties of the polyimide while maintaining the excellent properties of.

Acid dianhydride according to the present invention can be prepared by a very simple organic synthesis method such as Michael addition reaction and hydrolysis reaction.

Specifically, the method for preparing an acid dianhydride according to the present invention reacts the compound represented by the formula (2) with piperazine to produce the compound represented by the formula (3), and hydrolyzes the compound represented by the formula (3) in the presence of a base catalyst To produce a compound represented by Formula 4, and then a dehydrating agent was added to prepare an acid dianhydride represented by Formula 1 below.

Summarizing the preparation method of the acid dianhydride according to the present invention described above, it is shown in Scheme 1.

Scheme 1

First, as shown in Scheme 1, the compound represented by the formula (3) is produced by the Michael addition reaction of the compound represented by the formula (2) (dimethyl fumalate) and piperazine. At this time, the compound represented by the formula (2) in the Michael addition reaction (dimethyl fumarate) is Michael acceptor (acceptor), piperazine is Michael donor (donor).

The Michael addition reaction is preferably performed for 4 to 16 hours at 20 ~ 140 ℃ in terms of reaction efficiency.

In preparing the compound represented by Chemical Formula 3, the compound represented by Chemical Formula 2 and piperazine may be preferably used in a yield ratio of 1: 0.45 to 1: 0.55.

In this case, the compound represented by Chemical Formula 2 may be prepared by various known methods. Preferably, fumaric acid is added to methanol, refluxed by adding an acid catalyst such as sulfuric acid, and neutralized with a neutralizing agent such as sodium carbonate. It can manufacture.

On the other hand, in the present invention, it is preferable to use the reaction material itself as a solvent as the reaction mode, but other reaction solvents may be used. In this case, the reaction solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof may include 1,4-dioxane, toluene, N-Methyl-2-pyrrolidone (NMP), and dimethylacetamide (DMAc).

The compound represented by Formula 3 thus produced generates a compound represented by Formula 4 by hydrolysis in the presence of a base catalyst. In this case, the hydrolysis reaction may be performed at 40 to 120 ° C. for 1 to 6 hours, sufficient reaction may occur to reduce unreacted materials, prevent evaporation of the solvent and catalyst, and may be preferable in terms of cost and efficiency. have.

The base catalyst used in the hydrolysis reaction may be at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide and magnesium hydroxide, preferably potassium hydroxide in terms of price and ease of handling, Sodium hydroxide and the like.

The base catalyst may be used in an amount of 5 to 10 moles with respect to 1 mole of the compound represented by Chemical Formula 3, and the amount of hydrochloric acid precipitated by using an appropriate amount of base catalyst in the progress of the hydrolysis reaction may be appropriately adjusted within this range. It may be advantageous in terms of efficiency and productivity.

Thus produced compound represented by the formula (4) is a dehydrating agent (dehydrating agent) is added to the compound represented by the formula (4), the aliphatic acid dianhydride represented by the formula (1) by the dehydration ring closure reaction. At this time, the dehydration ring-closure reaction is performed for 4 to 28 hours at 40 ~ 100 ℃, to prevent the evaporation of the catalyst and the solvent to improve the yield and the reaction time is appropriate while inducing a sufficient reaction time to improve the yield May be preferred.

The dehydrating agent may be at least one selected from the group consisting of tertiary amines such as acetic anhydride, pyridine, isoquinoline, triethylamine and the like, and in terms of efficiency, it is preferable to use acetic anhydride and / or pyridine.

In addition, the content of the dehydrating agent may be 2 or more moles, preferably 2 to 10 moles with respect to 1 mole of the compound represented by the formula (4). This range of use may lead to sufficient reaction to improve the yield and may be advantageous in terms of cost.

After the reaction described above, the resultant compound is filtered by a conventional method and then dried to prepare an acid dianhydride represented by the formula (1).

The acid dianhydride represented by the general formula (1) of the present invention described above may be prepared into a polyimide by preparing a polyamic acid by diamine and a polycondensation reaction, followed by dehydration ring closure using heat or a catalyst. At this time, the equivalent ratio of the diamine: acid dianhydride is preferably 1: 1.

The said diamine is not specifically limited, Various diamines conventionally used for polyimide synthesis can be used. Specific examples thereof include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 1,3-bis (4,4'-aminophenoxy) benzene, 4 , 4'-diamino-1,5-phenoxypentane, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy- 4,4'-diaminobiphenyl, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylpropane, bis (3,5-di Ethyl-4-aminophenyl) methane, diaminodiphenylsulfone, diaminobenzophenone, diaminonaphthalene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene , 9,10-bis (4-aminophenyl) anthracene, 1,3-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,2-bis Aromatic diamines such as [4- (4-aminophenoxy) phenyl] propane and 2,2'-trifluoromethyl-4,4'-diaminobiphenyl; 1,4-diaminocyclohexane, 1,4-cyclohexanebis (methylamine), 4,4'-diaminodicyclohexylmethane (MCA), 4,4'-methylene bis (2-methyl cyclohexylamine Alicyclic diamines such as) (MMCA); Aliphatic diamines such as ethylenediamine (EN), 1,3-diaminopropane (13DAP), tetramethylenediamine, 1,6-hexamethylenediamine (16DAH), 1,12-diaminododecane (112DAD), and the like. Can be. Moreover, these diamine can also be used individually or in mixture of 2 or more types.

In particular, in terms of optical and electrical properties, the diamine of the present invention may be 1,6-hexamethylenediamine (also referred to as 1,6-diaminohexane, 16DAH), 1,12-diaminododecane (1,12-diaminododecane, 112DAD), 4,4'-diaminodicyclohexylmethane (also referred to as 4,4'-methylene bis (cyclohexylamine), MCA) and 4,4'-methylene bis (2-methyl cyclohexylamine) (4, It may be one or more selected from the group consisting of 4'-methylene bis (2-methyl cyclohexylamine, MMCA).

The present invention also provides a 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) within a range that does not inhibit polyimide physical properties other than the acid dianhydride represented by the formula (1). , 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA), pyromellitic dian Hydrides (1,2,4,5-benzene tetracarboxylic dianhydride, PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA), oxy Diphthalic dianhydride (ODPA), biscarboxyphenyl dimethyl silane dianhydride (SiDA), bis dicarboxyphenoxy diphenyl sulfide dianhydride (BDSDA), sulfonyl diphthalic hydride (SO ₂ DPA), cyclo Butane tetracarboxylic dianhydride (CBDA), isof Filidenephenoxy bis phthalic anhydride (6HBDA), bicyclo [2.2.2] -7-octene-2,3,5,6-tetracarboxylic dianhydride (BTA), cyclopentane tetracarbide It further comprises at least one acid dianhydride selected from the group consisting of cyclic dianhydride (CPDA), cyclohexane tetracarboxylic dianhydride (CHDA) and bicyclohexane tetracarboxylic dianhydride (HBPDA). can do.

In particular, the present invention, in terms of improving optical properties and dielectric constant, preferably 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) containing fluorine which can increase free volume. ), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2- of aliphatic or cycloaliphatic family which can lower the polarization anisotropy in the molecule Dicarboxylic dianhydride (TDA), cyclobutane tetracarboxylic dianhydride (CBDA), cyclopentane tetracarboxylic dianhydride (CPDA), bicyclo [2.2.2] -7-octen-2 Acid dianhydrides such as, 3,5,6-tetracarboxylic dianhydride (BTA), cyclohexane tetracarboxylic dianhydride (CHDA), bicyclohexane tetracarboxylic dianhydride (HBPDA) And may include pyromellitic as described above Acid dianhydrides (1,2,4,5-benzene tetracarboxylic dianhydride, PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA) Aromatic acid dianhydrides such as these can also be added and used within the range of not impairing the target optical properties.

At this time, the content of the acid dianhydride additionally included may be expected to improve the heat resistance in a range of 80 mol% or less, preferably 10 to 50 mol% relative to the total moles of acid dianhydride does not inhibit the optical properties and dielectric constant. .

The method for obtaining the polyamic acid of the present invention is not particularly limited, and the acid dianhydride represented by the general formula (1) and the diamine may be reacted and polymerized by a known production method, but the acid dianhydride represented by the general formula (1) in an organic solvent. The method of mixing and reacting with diamine is simple.

At this time, specific examples of the organic solvent used include m-cresol, N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), and N. -Methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoramide, gamma -butyrolactone, etc. are mentioned. These solvents may be used alone or in combination of two or more thereof. Moreover, even if it is a solvent which does not melt a polyamic acid, you may add to and use the said solvent within the range from which a uniform solution is obtained.

The reaction temperature of solution polymerization can select arbitrary temperature of -20-150 degreeC, Preferably -5-100 degreeC. Moreover, the molecular weight of a polyamic acid can be controlled by changing the molar ratio of the acid dianhydride represented by General formula (1) used for reaction, and diamine, and similar to a normal polycondensation reaction, the polya produced as this molar ratio approaches 1, The molecular weight of the acid is increased.

On the other hand, the method of dehydrating and ringing a polyamic acid in order to obtain a polyimide from a polyamic acid is not specifically limited, but similarly to the conventional polyamic acid, the method of ring closure by heating or chemically ringing using a well-known dehydration ring closure catalyst is employ | adopted. can do. The heating method can be stepped up step by step from 80 ℃ to 300 ℃.

The method of chemically ring closing can be performed in presence of organic bases, such as a pyridine and a triethylamine, and acetic anhydride, etc., and the temperature at this time can select arbitrary temperature of -20-200 degreeC. In this reaction, the polymerization solution of polyamic acid can be used as it is or diluted. Moreover, you may perform polyamic acid collect | recovered from the polymerization solution of polyamic acid, and this is melt | dissolved in the suitable organic solvent. As an organic solvent at this time, the polymerization solvent of the polyamic acid mentioned above is mentioned.

The polyimide (containing) solution thus obtained may be used as it is, or a solvent such as methanol or ethanol may be added to precipitate the polymer, which is isolated and re-dissolved as a powder or in a suitable solvent for use. Can be. The solvent for re-dissolution is not particularly limited as long as it dissolves the obtained polymer. For example, m-cresol, 2-pyrrolidone, NMP, N-ethyl-2-pyrrolidone, and N-vinyl-2-pyrroli DON, DMAc, DMF (dimethylformamide), (gamma) -butyrolactone, etc. are mentioned.

In addition, the polyimide film of the present invention can be obtained by casting polyamic acid on a support and dehydrating and closing the ring in the same manner as described above. Here, the rate of change (dehydration closure rate) from polyamic acid to polyimide is defined as the imidization rate, but the imidation rate of the polyimide of the present invention is not limited to 100%, and optionally 1 to 100%. You can select the value of.

In the present invention, by applying the heat treatment step once more to the polyimide film dehydrated and closed as described above, the thermal hysteresis and residual stress remaining in the film can be solved to obtain stable thermal stability and to have an excellent coefficient of thermal expansion. The residual volatile content of the film after heat treatment is 5% or less, and preferably 3% or less.

Although the thickness of the polyimide film manufactured in this way is not specifically limited, It is preferable that it is the range of 10-250 micrometers, More preferably, it is 10-100 micrometers.

As described above, a polyimide and a polyimide film can be prepared by imidating a polyamic acid obtained by reacting with a diamine and an acid dianhydride, and the polyimide film thus prepared is N-methyl-2- High solubility in organic solvents such as pyrrolidone (N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl phthalate (DMP) and dimethylsulfoxide (DMSO) As seen, the transmittance at 550 nm based on the film thickness of 10 to 100 μm is 80% or more, and the dielectric constant of 1 GHz is 3.3 or less.

As described above, the polyimide film according to the present invention exhibits a low dielectric constant and is colorless and transparent, which is useful for use as an optical communication material such as an optical material such as an electronic material such as a protective material or an insulating material in a liquid crystal display device or a semiconductor. .

Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following examples are only one preferred embodiment of the present invention and the present invention is not limited to the following examples.

<제조예 1><Manufacture example 1>

1-1: Synthesis of Compound Represented by Chemical Formula 2

Mix 14.5 g (125 mmol) of fumaric acid with 200 ml of methanol, add 5 ml of concentrated sulfuric acid, It was refluxed at 100 ° C. for 1 hour. The reflux was cooled in a cooling bath and neutralized with 200 g of 10% sodium carbonate to produce a white precipitate. The resulting precipitate was filtered, washed with water and dried in a vacuum oven at 50 ° C. for 12 hours to obtain 16.6 g of the compound represented by Formula 2 (yield 92%). The method for preparing the compound represented by Formula 2 is reported by Carr G. et al. , and Andersen RJ, J. Nat. Prod . 2010, 73, 422).

As a result of measuring the melting point (Buchi, M-560) of the compound represented by Chemical Formula 2, the melting point (Mp) of the compound prepared by the method reported by Carr G. et al. Confirm the same.

1-2: Synthesis of Compound Represented by Chemical Formula 3

14.4 g (0.1 mol) of the compound represented by Formula 2 obtained in Example 1-1 and 4.3 g (0.05 mol) of piperazine were added to 100 ml of 1,4-dioxane, followed by reflux for 16 hours, and the reflux. Cooling produced a precipitate. After filtering and concentrating the resulting precipitate was repeated for 12 hours in a vacuum oven to give 15.3g of a compound represented by the formula (3) of a colorless solid (yield 82%).

The obtained compound represented by the formula (3) measured the melting point (Buchi, M-560), and also NMR ( ¹ H and ¹³ C) (JEOL, JNM-LA400) and IR (AVATAR, 360 FT-IR) Analyzed using.

Melting Point: 158 ℃ (EtOAc)

¹ H NMR (400 MHz, CDCl ₃ ): δ 2.38-2.50 (m, 4H, Het-CH ₂ CH ₂ ), 2.54-2.70 (m, 6H, β-CH ₂ , Het-CH ₂ CH ₂ ), 2.81 (dd, J = 16.0 and 9.2 Hz, 2H, β-CH ₂ ), 3.64 (s, 6H, 2CH ₃ ), 3.68 (dd, 2H, overlapped signals, α-CH), 3.70 (s, 6H, 2OCH ₃ ) (FIG. 4);

¹³ C NMR (100 MHz, CDCl ₃ ): δ 171.7 and 170.9 (ester C), 63.4 (α- C H), 51.8 (O C H ₃ ), 51.5 (O C H ₃ ), 49.9 (Het- C H ₂ C H ₂ ), 34.0 (β- C H ₂ ); Anal. Calcd. for C ₁₆ H ₂₆ N ₂ O ₈ ; C: 51.33, H: 7.00, N: 7.48%. Found: C: 51.19, H: 7.09, N: 7.53%;

IR (KBr, cm ^-1 ): 1734 for νC = O

1-3: Synthesis of Compound Represented by Chemical Formula 4

11.2 g (0.03 mol) of the compound represented by Chemical Formula 3 obtained in Example 1-2 were added to a 500 ml round bottom flask, and then 120 ml (0.24 mol) of 2-normal potassium hydroxide and 120 ml of methanol were mixed. The mixture was dissolved by heating to 60 ° C. and then further heated at the same temperature for 3 hours. Concentrated hydrochloric acid was added to the mixture to adjust the pH to 3.8, followed by stirring at room temperature for 30 minutes to form a precipitate. The resulting precipitate was filtered off and washed with water. The washed precipitate was dried in a vacuum oven for 24 hours, and recrystallized in 2,000 ml of a mixture of water and methanol in a 1: 1 ratio to obtain 8.7 g of a compound represented by Formula 4 (yield 92%). The obtained compound represented by the formula (4) is not soluble in a general organic solvent and water mixed with the compound represented by the formula (4) in heavy water (D ₂ O) in which solid potassium hydroxide is dissolved in order to make an NMR sample for NMR analysis Used.

For the compound represented by Formula 3, the melting point (Buchi, M-560), NMR ( ¹ H and ¹³ C) (JEOL, JNM-LA400) and IR (AVATAR, 360 FT-IR) using Analyzed.

Melting Point: 218-219 ℃ (H ₂ O + MeOH)

¹ H NMR (400 MHz, D ₂ O / KOH): δ 2.46-2.54 (bd, 4H, Het-CH ₂ CH ₂ ), 2.56-3.40 (bm, 6H, β-CH ₂ , Het-CH ₂ CH ₂ ), 3.44-3.54 (bm, 2H, β-CH ₂ ), 4.80 (dd, 2H, overlapped signals, α-CH);

¹³ C NMR (100 MHz, D ₂ O / KOH): δ 178.8 ( C OOH), 67.7 (α- C H), 49.1 (Het- C H ₂ C H ₂ ), 37.4 (β- C H ₂ ); Anal. Calcd. for C ₁₂ H ₁₈ N ₂ O ₈ ; C: 45.28, H: 5.70, N: 8.80%. Found: C: 45.16, H: 5.79, N: 8.83%;

IR (KBr, cm ⁻¹ ): 1723 for νC═O.

1-4: Synthesis of Aliphatic Anhydride Compound of Formula 1

5.4 g (17 mmol) of a compound represented by Formula 4, 3.18 g (35.7 mmol) of pyridine and 3.6 g (35.7 mmol) of acetic anhydride obtained in Examples 1-3 were added to a 50 ml flask equipped with a condenser and a magnetic stirrer. The reaction was carried out at 60 ℃ for 24 hours. After the reaction was completed, the reaction was cooled and filtered. The filtered filtrate was washed with 200 ml of acetic anhydride and 200 ml of purified diethyl ether, dried at 40 ° C. in an oven in a vacuum, and then recrystallized from 100 ml of acetic anhydride. 2.9 g were obtained (yield 60%).

For the compound represented by Formula 1, the melting point (Buchi, M-560) was measured, NMR ( ¹ H and ¹³ C) (JEOL, JNM-LA400) and IR (AVATAR, 360 FT-IR) It was analyzed using.

Melting Point: 156 ℃ (decompose)

¹ H NMR (400 MHz, d6-DMSO): δ 2.39 (bd, J = 6.8 Hz, 4H, Het-CH ₂ CH ₂ ), 2.76 (bd, J = 6.8 Hz, 4H, Het-CH ₂ CH ₂ ) , 3.04 (d, J = 8.4 Hz, 4H, β-CH ₂ ), 4.21 (t, J = 16.4 Hz, 2H, α-CH);

¹³ C NMR (100 MHz, d6-DMSO): δ 171.6 (COOCO), 170.6 (COOCO), 63.6 (α-CH), 48.9 (Het-CH ₂ CH ₂ ), 31.9 (β-CH ₂ ); Anal. Calcd. for C ₁₂ H ₁₄ N ₂ O ₆ ; C: 51.06, H: 5.00, N: 9.93%. Found: C: 49.93, H: 5.10, N: 9.96%;

IR (KBr, cm ⁻¹ ): 1860, 1781 (νC═O), 1210, 1127 (COC).

<실시예 1 내지 4> <Examples 1 to 4>

In a 30 ml three-necked flask equipped with a mechanical stirrer, acid dianhydride (2.0 mmol) obtained in Preparation Example 1 and 4 mL of m-cresol were added thereto, and the mixture was stirred until the acid dianhydride was completely dissolved while slowly flowing nitrogen gas. Each diamine (2.0 mmol) and 2 ml of m-cresol described in Table 1 were further added thereto, and the flask was heated to 60 ° C. and stirred for 2 days. A portion of the polycondensation solution containing polyamic acid was cast on a glass plate, and the glass plate was heated under vacuum for 3 hours at 80 ° C., 1 hour at 200 ° C. and 1 hour at 250 ° C. to obtain a polyimide film. After curing, the film was removed from the glass plate by immersing the glass plate in hot water to remove the flexible and support-free polyimide film to prepare a polyimide film having a thickness of 15 μm.

The obtained polyimide films were able to identify characteristic 1771-1775 cm ^-1 absorption bands appearing in the imide through FTIR (AVATAR 360 FT-IR) (FIG. 1). This is due to the asymmetric stretching of the carbonyl group, and 1691-1697 cm ^-1 is due to the symmetric stretching of the carbonyl group. Due to the absence of the aromatic ring, the nonconjugated structure of the imide carbonyl group is the It can be confirmed that it causes the change of absorption.

Table 1

	Example 1	Example 2	Example 3	Example 4
Diamine Type	1,6-hexamethylene diamine (16DAH)	1,12-diaminododecane (112DAD)	4,4'-diaminodicyclohexylmethane (MCA)	4,4'-methylene bis (2-methylcyclohexylamine) (MMCA)

<실시예 5 내지 21> <Examples 5 to 21>

In a 30 ml three-necked flask equipped with a mechanical stirrer, the first acid dianhydride and m-cresol 4 mL obtained in Preparation Example 1 were added, and the mixture was stirred until the first acid dianhydride was completely dissolved while slowly flowing nitrogen gas. The second acid dianhydride shown in Table 2 was further added thereto and dissolved completely. Thereafter, 4,4'-methylene bis (cyclohexylamine) (MCA) (100 mmol) and 2 ml of m-cresol were added as diamine, and the flask was heated to 60 ° C and stirred for 2 days. A portion of the polycondensation solution containing polyamic acid was cast on a glass plate, and the glass plate was heated under vacuum for 3 hours at 80 ° C., 1 hour at 200 ° C. and 1 hour at 250 ° C. to obtain a polyimide film. After curing, the film was removed from the glass plate by immersing the glass plate in hot water to remove the flexible and support-free polyimide film to prepare a polyimide film having a thickness of 15 μm.

TABLE 2

	Primary acid dianhydride content (mmol)	Second kind of dianhydride	Second acid dianhydride content (mmol)
Example 5	90	6FDA	10
Example 6	70	6FDA	30
Example 7	50	6FDA	50
Example 8	90	CBDA	10
Example 9	70	CBDA	30
Example 10	50	CBDA	50
Example 11	90	CHDA	10
Example 12	70	CHDA	30
Example 13	50	CHDA	50
Example 14	90	BTA	10
Example 15	70	BTA	30
Example 16	50	BTA	50
Example 17	90	HBPDA	10
Example 18	70	HBPDA	30
Example 19	50	HBPDA	50
Example 20	90	PMDA	10
Example 21	90	BPDA	10

<비교예 1>Comparative Example 1

A polyimide film was prepared in the same manner as in Example 1, but a polyimide film (thickness 15 μm) was prepared using pyromellitic dianhydride (PMDA) as an acid dianhydride.

<비교예 2>Comparative Example 2

A polyimide film was prepared in the same manner as in Example 1, except that pyromellitic dianhydride (PMDA) and diamine were used as an acid dianhydride (4,4'-oxydianiline, ODA). ) And N, N-dimethyl acetamide as a solvent to prepare a polyimide film (thickness 15㎛).

<물성평가><Property Evaluation>

Using the polyimide films prepared in Examples and Comparative Examples, the molecular weight, optical properties, electrical properties and thermal properties were measured by the following method, and the results are shown in Table 3.

(1) Measurement of molecular weight and molecular weight distribution

Polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) (Waters: Waters707). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of 4000 ppm, and 100 µl was injected into GPC. The mobile phase of GPC used tetrahydrofuran and was introduced at a flow rate of 1.0 mL / min, and the analysis was performed at 35 ° C. The column connected four Waters HR-05,1,2,4E in series. The detector was measured at 35 ° C using RI and PAD Detecter. In addition, molecular weight distribution (PDI) was calculated by dividing the measured weight average molecular weight (Mw) by the number average molecular weight (Mn).

(2) Light transmittance measurement

The transmittance at 550 nm was measured using a UV spectrometer (Konita Minolta, CM-3700d).

(3) permittivity measurement

It was measured using Agilent's E4980A precision LCR meter and gold plated sputtered with 2 probe method. The frequency of 1Mhz, A is 2mm x 2mm, the film thickness is different for each point and calculated by measuring the thickness of each point through the alpha step, the bottom plate was measured the capacitance of the middle film through the ITO coating surface. Using the measured value and the capacitance, the dielectric constant was calculated through Equation 1 below.

[Equation 1]

K = (C × d) / (A × ε _o )

In 1, K is the dielectric constant, C is the capacitance, d is the film thickness, A is the specimen (film) area (2 × 2 mm), and ε _o is the dielectric constant of vacuum (8.85 × 10 ⁻¹²⁾ Fm ^-1 ).

(4) Glass transition temperature (Tg) measurement

The second value was calculated as glass transition temperature (Tg) by performing a 2nd run from 50 ° C to 300 ° C at a heating rate of 10 ° C / min using a Perkin Elmer DSC7 device.

TABLE 3

	Number average molecular weight (× 10 ⁴ g / mol, Mn)	PDI	Dielectric constant (ε)	Light transmittance (%, 550nm)	Tg (℃)
Example 1	2.19	1.6	2.67	83	186
Example 2	2.23	1.8	2.14	86	192
Example 3	3.2	2.3	3.30	84	220
Example 4	2.9	2.3	2.87	85	225
Example 5	3.3	2.1	2.98	84	230
Example 6	6.2	2.4	3.05	84	235
Example 7	10.3	2.3	3.13	85	247
Example 8	4.9	2.4	2.94	84	231
Example 9	9.3	2.0	3.02	84	238
Example 10	12.8	1.9	3.08	84	255
Example 11	4.1	2.7	2.90	84	235
Example 12	8.6	2.4	2.94	85	241
Example 13	11.4	2.6	2.98	85	262
Example 14	3.0	2.5	3.02	84	225
Example 15	2.8	2.4	3.16	83	239
Example 16	3.1	2.2	3.30	83	246
Example 17	4.2	2.0	2.91	84	223
Example 18	10.1	2.3	2.99	84	239
Example 19	13.6	2.1	3.07	84	245
Example 20	5.6	2.5	3.29	82	250
Example 21	4.9	2.4	3.26	82	247
Comparative Example 1	4.2	2.2	3.8	74	287
Comparative Example 2	25.7	1.9	4.0	68	Not measurable

As shown in Table 3, it was confirmed that the films of Examples 1 to 21 exhibited a low dielectric constant and a high transmittance compared with the films of Comparative Examples 1 and 2.

On the other hand, in the case of the film prepared by adding a certain molar ratio of acid dianhydride (second acid dianhydride) to the acid dianhydride (first acid dianhydride) of Preparation Example 1, as in Examples 5 to 21. Compared with 4, the glass transition temperature was increased to a certain level while maintaining the same transmittance and permittivity.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims

A polyimide obtained by imidating a polyamic acid polymerized with diamine and an acid dianhydride, wherein the acid dianhydride comprises a compound represented by the following general formula (1).

<Formula 1>
The method of claim 1, wherein the diamine is p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 1,3-bis (4,4'-aminophenoxy Benzene, 4,4'-diamino-1,5-phenoxypentane, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3 '-Dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylpropane, bis ( 3,5-diethyl-4-aminophenyl) methane, diaminodiphenylsulfone, diaminobenzophenone, diaminonaphthalene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4 -Aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 1,3-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, Aromatic diamine selected from the group consisting of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-trifluoromethyl-4,4'-diaminobiphenyl and mixtures thereof ; 1,4-diaminocyclohexane, 1,4-cyclohexanebis (methylamine), 4,4'-diaminodicyclohexylmethane (MCA), 4,4'-methylene bis (2-methyl cyclohexylamine Alicyclic diamines selected from the group consisting of (MMCA) and mixtures thereof; And ethylenediamine (EN), 1,3-diaminopropane (13DAP), tetramethylenediamine, 1,6-hexamethylenediamine (16DAH), 1,12-diaminododecane (112DAD) and mixtures thereof Polyimide, characterized in that at least one selected from the group consisting of aliphatic diamine selected from the group.
The method of claim 1, wherein the diamine is 1,6-hexamethylenediamine (16DAH), 1,12-diaminododecane (112DAD), 4,4'-diaminodicyclohexylmethane (MCA) and 4,4 '-Methylene bis (2-methyl cyclohexylamine) (MMCA) polyimide, characterized in that at least one member selected from the group consisting of.
The acid dianhydride according to claim 1, wherein the acid dianhydride is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4- (2,5-dioxotetrahydrofuran-3 -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA), pyromellitic dianhydride (1,2,4,5-benzene tetracarboxyl Ric dianhydride, PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), biscarboxyphenyl dimethyl silane dian Hydride (SiDA), bis dicarboxyphenoxy diphenyl sulfide dianhydride (BDSDA), sulfonyl diphthalic hydride (SO 2 DPA), cyclobutane tetracarboxylic dianhydride (CBDA), isopropylidene Inepoxy bis phthalic anhydride (6HBDA), bicyclo [2.2.2] -7-jade -2,3,5,6-tetracarboxylic dianhydride (BTA), cyclopentane tetracarboxylic dianhydride (CPDA), cyclohexane tetracarboxylic dianhydride (CHDA) and bicyclohexane tetra Carboxylic dianhydride (HBPDA) polyimide, characterized in that it further comprises one or more selected from the group consisting of.
The polyimide film containing the polyimide of any one of Claims 1-4.
The polyimide film of claim 5, wherein the polyimide film has a transmittance of 80% or more at 550 nm based on a film thickness of 10 to 100 μm, and a dielectric constant of 1 GHz is 3.3 or less.