KR20160098833A - Polyamic acid, And Polyimide Resin And Polyimide Film - Google Patents

Abstract

The present invention relates to a polyamic acid, a polyimide resin as an imidization product thereof, and a polyimide film. The polyamic acid is a polymerizate of dianhydride with diamine and is any one of: (i) the polymerizate containing 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane dianhydride (HFBDA) as diamine; (ii) the polymerizate containing trans(equatorial) 4-amino-(1,1-bicyclohexyl)4-amine (T-BCA) as diamine; and (iii) the polymerizate containing 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane dianhydride (HFBDA) as dianhydride and trans(equatorial) 4-amino-(1,1-bicyclohexyl)4-amine (T-BCA) as diamine.

Description

Polyamic Acid, Polyimide Resin and Polyimide Film < RTI ID = 0.0 >

The present invention relates to polyamic acid, a polyimide resin prepared therefrom, and a colorless transparent polyimide film.

In general, a polyimide (PI) film is a film made of a polyimide resin, and a polyimide resin is produced by solution polymerization of an aromatic dianhydride and an aromatic diamine or aromatic diisocyanate to prepare a polyamic acid derivative, Refers to a high heat-resistant resin produced by imidization. Examples of the aromatic dianhydride used for producing the polyimide resin include pyromellitic dianhydride (PMDA) or biphenyltetracarboxylic acid dianhydride (BPDA), and the aromatic diamines include oxydianiline (ODA), p (P-PDA), m-phenylenediamine (m-PDA), methylene dianiline (MDA), and bisaminophenylhexafluoropropane (HFDA).

Polyimide resin is an insoluble and non-fusible ultra-high temperature resistant resin. It has excellent heat resistant oxidizing property, heat resistance property, radiation resistance property, low temperature property, chemical resistance and so on. It is a high heat resistant material such as automobile material, , An insulating film, a semiconductor, and an electrode protective film of a TFT-LCD. Recently, a display material such as an optical fiber or a liquid crystal alignment film and a conductive filler are contained in a film or coated on the surface to be used as a transparent electrode film.

However, since the polyimide film is colored in brown or yellow owing to its high aromatic ring density, it has a low transmittance in the visible light region and exhibits a yellowish color, so that the polyimide film has a low light transmittance or a large birefringence, have. In order to solve this problem, polymerization and purification of monomers and solvents with high purity have been attempted, but the improvement of the transmittance has not been significant.

U.S. Patent No. 5,053,480 discloses a method of using an aliphatic cyclic dianhydride component instead of an aromatic dianhydride. In comparison with the purification method, there is an improvement in transparency and color in the case of a solution phase or a film, And thus the high transmittance was not satisfied and the thermal and mechanical properties were deteriorated. Particularly, in the case of a polyimide film improved in yellow color, the value of Tg (glass transition temperature) is lowered and it is difficult to use in a field requiring a high temperature of 300 캜 or more.

On the other hand, U.S. Patent Nos. 4595548, 4603061, 4645824, 4895972, 5218083, 5093453, 5218077, 5367046, 5338826. 5986036 and 6232428 and Korean Patent Laid-Open Publication No. 2003-0009437 disclose monomers having a backbone structure connected to a linking group such as -O-, -SO ₂ -, or CH ₂ - and the like at an m-position other than the p-position There has been reported a novel structure of polyimide having improved transparency and color transparency as far as the thermal property is not significantly deteriorated by using aromatic dianhydride dianhydride and aromatic diamine monomer having a substituent such as -CF ₃ , Mechanical properties, yellowing degree and visible light transmittance are not enough to be used as a substrate for a semiconductor insulating film, a TFT-LCD insulating film, an electrode protecting film, and a flexible display.

Accordingly, it is an object of the present invention to provide a polyimide film that is colorless and transparent, has a relatively low birefringence, and is excellent in heat resistance and mechanical properties.

In order to solve the above problems, a first preferred embodiment of the present invention is a polymerization reaction product of a dianhydride and a diamine, wherein (i) 2,2-bis (4- (4- Aminophenoxy) phenyl) hexafluoropropane dianhydride (HFBDA); (Ii) a trans (equatorial) 4-amino- (1,1-bicyclohexyl) 4-amine (T-BCA) represented by the following formula 2 as a diamine; Or (iii) 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropanediamine hydrate (HFBDA) represented by the following formula (1) as a dianhydride and Including trans (equatorial) 4-amino- (1,1 bicyclohexyl) 4-amine (T-BCA); The polyamic acid is a polyamic acid.

≪ Formula 1 >

(2)

When the compound represented by the formula (1) is included as a dianhydride, its content is 10 to 100 mol% based on the total molar amount of the dianhydride. When the compound represented by the formula (2) is included as a diamine, Can be from 10 to 100 mole%.

The polyamic acid according to the first embodiment includes a compound represented by Formula 1 as a dianhydride, and the diamine includes bistrifluoromethylbenzidine (TFDB), oxydianiline (ODA), p-phenylenediamine (p-phenylenediamine), m-phenylenediamine (mPDA), p-methylene dianiline (pMDA), m-methylene dianiline (mMDA), cyclohexanediamine (13CHD, 14CHD), bisaminohydroxyphenylhexafluoropropane DBAP), bisaminophenoxybenzene (133APB, 134APB, 144APB), bisaminophenylhexafluoropropane (33-6F, 44-6F), bisaminophenyl sulfone (4DDS, 3DDS), bisaminophenoxyphenylhexafluoro (4BDAF), bisaminophenoxyphenyl propane (6HMDA), and bisaminophenoxy diphenyl sulfone (DBSDA).

(2) as the diamine, and the dianhydride includes a compound represented by the formula (2) as the diamine, wherein the dianhydride is selected from the group consisting of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanediamine hydride (6FDA), cyclobutane tetracarboxylic (CBDA), biphenyl tetracarboxylic dianhydride (BPDA), bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTA ), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA), pyromellitic acid Dianhydride (1,2,4,5-benzene tetracarboxylic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biscarboxyphenyldimethylsilanediamine hydride (SiDA), oxy Diphthalic dianhydride ODPA), bisdicarboxyphenoxy diphenylsulfide dianhydride (B DSDA), sulfonyl diphthalic anhydride (SO ₂ DPA), and isopropylidene phenoxy bisphthalic anhydride 6HDBA).

The second and third preferred embodiments of the present invention are respectively a polyimide resin which is an imide of a polyamic acid of the first embodiment and a polyimide film prepared by imidizing the polyamic acid.

In particular, the polyimide film according to the third embodiment may have a yellowness of 5 or less on the basis of a film thickness of 10 to 50 탆, an average light transmittance of 88% or more as measured at 550 nm, a transverse elictric (TM) The birefringence (? N) defined by the transverse magnetic field may be 0.01 or less.

Furthermore, a fourth preferred embodiment of the present invention is an image display device including the polyimide film of the third embodiment.

The polyimide resin and the film according to the present invention are colorless transparent and have a low birefringence after film formation, and thus can be usefully used as substrates for displays or electronic materials.

The present invention is a polymerization reaction of a dianhydride and a diamine,

(I) comprising 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropanediamine hydride (HFBDA) represented by the following formula (1) as dianhydride;

(Ii) a trans (equatorial) 4-amino- (1,1-bicyclohexyl) 4-amine (T-BCA) represented by the following formula 2 as a diamine; or

(Iii) 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropanediamine hydrate (HFBDA) represented by the following formula 1 as a dianhydride and Trans (equiv.) 4-amino- (1,1 bicyclohexyl) 4-amine (T-BCA);

The polyamic acid is a polyamic acid.

≪ Formula 1 >

(2)

In the present invention, the 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropanediamine hydride (HFBDA) represented by the chemical formula 1 is linked with the -O- group, -CF ₃ - substituents, which can impart flexibility and excellent mechanical properties while improving transparency and color transparency.

Also, the trans (equatorial) 4-amino- (1,1 bicyclohexyl) -4-amine, T-BCA represented by the above formula (2) (Cis-trans) and trans-type (trans) depending on the position of the trans-isomer. In the present invention, the trans (equatorial) 4-amino- 1,1-bicyclohexyl) -4-amine is used, the molecular weight can be easily increased. As a result, the film can be easily formed. However, since the compound has a short length and has an alicyclic structure, have.

In the present invention, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane dianhydride (HFBDA) represented by the above formula (1) is contained as a dianhydride, (1,1-bicyclohexyl) 4-amine (T-BCA) represented by the formula (2) is contained as a diamine when the content thereof is in the range of 10 to 100 mol% Can be from 10 to 100 mole%. If the HFBDA is less than 10 mol% of the total molar amount of the dianhydride, the mechanical properties (elongation at break) can not be improved. In the latter case, if T-BCA is less than 10 mol% And an improvement in transmittance may not be achieved.

In the present invention, the HFBDA and T-BCA may be independently included as a dianhydride or as a diamine, but they may be used at the same time, and when used at the same time, their color and birefringence characteristics may be improved and heat resistance may be enhanced . However, when used at the same time, the glass transition temperature may possibly be lowered to some extent.

On the other hand, when the polyamic acid of the present invention contains HFBDA as the dianhydride, the diamine may be selected from the group consisting of bistrifluoromethylbenzidine (TFDB), oxydianiline (ODA), p-phenylenediamine (pPDA) The reaction product of the diamine (mPDA), p-methylene dianiline (pMDA), m-methylene dianiline (mMDA), cyclohexanediamine (13CHD, 14CHD), bisaminohydroxyphenylhexafluoropropane (DBOH), bisaminophenoxybenzene (133APB, 134APB, 144APB), bisaminophenylhexafluoropropane (33-6F, 44-6F), bisaminophenyl sulfone (4DDS, 3DDS), bisaminophenoxyphenylhexafluoropropane (4BDAF), bisamino (6HMDA) and bisaminophenoxy diphenyl sulfone (DBSDA), and when the diamine contains T-BCA, the dianhydride may be at least one selected from the group consisting of 2,2-bis , 4-dicarboxyphenyl) hexafluoropropanediamine hydride (6FDA), cyclobutane tetracarboxylic dianhydride (CBDA), biphenyl tetracarboxylic dianhydride (BPDA), bicyclo [2.2.2] oct-7-ene-2,3,5,6 -Tetracarboxylic dianhydride (BTA), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic (TDA), pyromellitic acid dianhydride (1,2,4,5-benzene tetracarboxylic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biscarboxyphenyl (SiDA), oxydiphthalic dianhydride ODPA), bisdicarboxyphenoxy diphenylsulfide dianhydride (BDSDA), sulfonyldiphthalic anhydride (SO ₂ DPA), and isopropylidene And phenoxy bisphthalic anhydride 6HDBA).

The solvent (polymerization solvent) for the polymerization reaction of the dianhydride and the diamine is not particularly limited as long as it is a solvent dissolving the polyamic acid. As the known reaction solvent, there may be used, for example, m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) One or more polar solvents are used. In addition, a low boiling point solution such as tetrahydrofuran (THF), chloroform or a low-absorbency solvent such as? -Butyrolactone may be used. In addition, a low boiling point solution such as tetrahydrofuran (THF), chloroform or a low-absorbency solvent such as? -Butyrolactone may be used.

Although the content of the solvent is not particularly limited, the content of the solvent for the polymerization (first solvent) in the polyamic acid solution is preferably 50 to 95% by weight, more preferably, And more preferably 70 to 90% by weight.

According to the present invention, the polyamic acid obtained by polymerizing the above monomers can be appropriately selected and imidized by a known imidization method, and examples thereof include a thermal imidation method, a chemical imidation method, a thermal imidation method, The chemical imidation method can be used in combination.

In the chemical imidation method, a dehydrating agent represented by an acid anhydride such as acetic anhydride and the like and a imidation catalyst represented by tertiary amines such as isoquinoline, p-picoline, and pyridine are added to polyamic acid, The method is a method in which polyamic acid is gradually heated in a temperature range of 40 to 300 캜 and heated for 1 to 8 hours. In addition, the thermal imidization method may be used in combination with the chemical imidization method, and the heating conditions may vary depending on the type of the polyamic acid solution, the thickness of the film, and the like.

In the present invention, a composite imidation method in which a thermal imidation method and a chemical imidization method are used together can be applied as an example of producing polyamic acid. More specifically, a dehydrating agent and an imidation catalyst are added to a polyamic acid solution, cast on a support, and heated at 80 to 200 ° C, preferably 100 to 180 ° C to activate a dehydrating agent and an imidation catalyst, And then heated at 200 to 400 ° C for 5 to 400 seconds to obtain a polyimide film.

In the present invention, a polyimide film may also be produced as follows. Namely, after the obtained polyamic acid solution is imidized, the imidized solution is put into a second solvent, followed by precipitation, filtration and drying to obtain a solid content of the polyimide resin, and the solid content of the obtained polyimide resin is added to the first solvent Or may be obtained through a film-forming process using a dissolved polyimide solution.

The first solvent may be the same solvent as the solvent used in the polyamic acid solution polymerization. The second solvent may be one having a lower polarity than that of the first solvent in order to obtain a solid content of the polyamic acid resin, Alcohols, ethers, and ketones. At this time, the content of the second solvent is not particularly limited, but is preferably 5 to 20 times by weight of the polyamic acid solution.

The film applied to the support is gelled on the support by dry air and heat treatment. The gelation temperature of the coated film is preferably from 100 to 250 ° C, and a glass plate, an aluminum foil, a circulating stainless belt, a stainless steel drum, or the like can be used as a support. The treatment time required for the gelation varies depending on the temperature, the type of the support, the amount of the applied polyamic acid solution, and the mixing conditions of the catalyst, and is not limited to a certain time but is preferably in the range of 5 minutes to 30 minutes have.

The gelled film is separated from the support and is heat treated to complete drying and imidization. The temperature during the heat treatment is preferably from 100 to 500 ° C., and the treatment time is preferably from 1 minute to 30 minutes. It is preferable that the heat-treated film is subjected to heat treatment under a certain tension to remove residual stress inside the film, and more stable thermal characteristics can be obtained by eliminating thermal history and residual stress. In particular, when the final heat treatment is not performed, the residual stress to shrink in the film reduces the thermal expansion, so that the value of the thermal expansion coefficient may be significantly lowered. In this case, since the tension and temperature conditions are correlated with each other, the tension condition may vary depending on the temperature, but the temperature is preferably 300 to 500 ° C, the heat treatment time is preferably 1 minute to 3 hours, The volatile content is 5% or less, preferably 3% or less.

The thickness of the polyimide film thus obtained is not particularly limited, but is preferably in the range of 10 to 250 탆, more preferably 10 to 100 탆.

The polyimide film according to the present invention may have a yellowness value of 5 or less based on a film thickness of 10 to 50 탆, an average light transmittance measured at 550 nm of 88% or more, a transverse magnetic (TE) Is not more than 0.01, and can be used as a display substrate or an electronic material material. Accordingly, the present invention can provide an image display device including a polyimide film exhibiting the above-described characteristics.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for the purpose of illustrating the present invention more specifically, and the present invention is not limited thereto.

Example  One

Into a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a condenser was charged 341.514 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen, and 28.821 g (0.09 mol) of TFDB Lt; / RTI > 56.558 g (0.09 mol) of HFBDA was added thereto, followed by reaction for 18 hours to obtain a polyamic acid solution having a solid content of 20 wt% and a viscosity of 134 poise.

After the reaction was completed, the obtained solution was applied to a stainless steel plate, cast, and dried by hot air at 80 ° C for 30 minutes, at 150 ° C for 30 minutes, at 250 ° C for 30 minutes, at 300 ° C for 30 minutes by hot air, And a polyimide film having a thickness of 30 占 퐉 was prepared.

Example  2

In a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a condenser, 307.478 g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen, and 23.56 g (0.12 mol ). After maintaining the temperature of the reactor at 80 캜, 53.31 g (0.12 mol) of 6FDA was added thereto and reacted for 1 hour and then cooled to 25 캜. And reacted for 18 hours to obtain a polyamic acid solution having a solid content of 20% by weight and a viscosity of 256 poise.

Then, a polyimide film was produced in the same manner as in Example 1 above.

< Measurement example >

(1) Measurement of transmittance: The transmittance was measured three times at 550 nm using a UV spectrometer (Kotikaminolta CM-3700d). The average values are shown in Table 1.

(2) Viscosity: The Brookfield viscometer (RVDV-II + P) was measured twice at 50 rpm using a 6 scandal at 25 ° C and the average value was measured.

(3) Yellowness (Y.I.) measurement: Yellowness was measured according to ASTM E313 standard using a UV spectrometer (Konita Minolta, CM-3700d).

(4) Birefringence measurement: The average value was measured three times in TE (Transeverse Elictric) mode and TM (Transverse magnetic) mode at 532 nm using a birefringence analyzer (Prism Coupler, Sairon SPA4000) Mode) was reflected as a birefringence value.

division ingredient Mole ratio Film thickness
(탆) 550 nm transmittance
(%) Y.I. Prism Coupler TE
(transverse electric)
mode TM
(transverse magnetic)
mode Birefringence Example 1 TFDB / HFBDA 100: 100 30 88.65 3.86 1.5953 1.5898 0.0055 Example 2 T-BCA / 6FDA 100: 100 25 88.25 4.5 1.5507 1.549 0.0017

From the results of Table 1, it can be seen that the embodiment according to the present invention has excellent birefringence and excellent transparency and yellowing property for use as an optical material.

Claims (9)

A polymerization reaction product of dianhydride and diamine,
(I) comprising 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropanediamine hydride (HFBDA) represented by the following formula (1) as dianhydride;
(Ii) a trans (equatorial) 4-amino- (1,1-bicyclohexyl) 4-amine (T-BCA) represented by the following formula 2 as a diamine; or
(Iii) 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropanediamine hydrate (HFBDA) represented by the following formula 1 as a dianhydride and Trans (equiv.) 4-amino- (1,1 bicyclohexyl) 4-amine (T-BCA); &Lt; / RTI > polyamic acid.
&Lt; Formula 1 >

(2)

[2] The method of claim 1, wherein the compound represented by Formula 1 is contained in an amount of 10 to 100 mol% based on the total molar amount of dianhydride,
Wherein the compound represented by the formula (2) is contained as a diamine in an amount of 10 to 100 mol% based on the total amount of the diamine.
The polyamic acid according to claim 1, wherein the polyamic acid comprises a compound represented by the formula (1) as a dianhydride,
The diamine may be selected from the group consisting of bistrifluoromethylbenzidine (TFDB), oxydianiline (ODA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p- (33DA), aniline (mMDA), cyclohexanediamine (13CHD, 14CHD), bisaminohydroxyphenylhexafluoropropane (DBOH), bisaminophenoxybenzene (133APB, 134APB, 144APB), bisaminophenylhexafluoropropane 6F and 44-6F), bisaminophenyl sulfone (4DDS, 3DDS), bisaminophenoxyphenylhexafluoropropane (4BDAF), bisaminophenoxyphenylpropane (6HMDA) and bisaminophenoxy diphenyl sulfone (DBSDA) Wherein the polyamic acid is at least one selected from the group consisting of polylactic acid,
The polyamic acid according to claim 1, wherein the polyamic acid comprises a compound represented by the formula (2) as a diamine,
The dianhydride may be selected from the group consisting of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanediamine hydride (6FDA), cyclobutane tetracarboxylic dianhydride (CBDA), biphenyltetracarboxylic dianhydride (BPDA), bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTA), 4- (2,5-dioxotetrahydrofuran- 3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA), pyromellitic acid dianhydride (1,2,4,5-benzenetetracar (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biscarboxyphenyldimethylsilanediamine hydride (SiDA), oxydiphthalic dianhydride ODPA), bisdicarboxyphenoxy diphenyl (BDSDA), sulfonyldiphthalic anhydride (SO ₂ DPA), and isopropylidene are phenoxy Bisphthalic anhydride &lt; RTI ID = 0.0 &gt; 6HDBA). &Lt; / RTI &gt;
A polyimide resin which is an imide of a polyamic acid according to any one of claims 1 to 4.
A polyimide film produced by imidizing a polyamic acid according to any one of claims 1 to 4.
The polyimide film according to claim 6, wherein the polyimide film has a yellowness value of 5 or less and a mean light transmittance of 88% or more measured at 550 nm based on a film thickness of 10 to 50 탆.
7. The polyimide film according to claim 6, wherein the polyimide film has a birefringence (? N) of 0.01 or less, which is defined as TE (transverse elictric) - TM.
An image display device comprising the polyimide film of claim 6.