TW200815500A - Resin composition for phase difference film, color filter substrate for liquid crystal display device, liquid crystal display device, process for producing color filter substrate for liquid crystal display device having phase difference film - Google Patents

Abstract

Disclosed is a resin composition for a phase difference film which does not need aligning and stretching steps and forms a phase difference film with high transparency and high birefringence by coating it on a substrate. The composition comprises a polyamide precursor obtained by reacting at least one tetracarboxylic acid dianhydride and at least one diamine and an organic solvent, at least anyone of the above at least one tetracarboxylic acid dianhydride and the above at least one diamine being an acyclic compound. The composition is useful for a liquid crystal display device, has optically negative uniaxial anisotropy and an optic axis vertical or nearly vertical to the film surface, and is used for forming a phase difference film which has a birefringence Δn of 0.01 to 0.3 in the thickness direction.

Description

[Technical Field] The present invention relates to a resin composition for a retardation film, a liquid crystal substrate, a liquid crystal display device, and a method for producing a color filter substrate with a retardation film. [Prior Art] At present, liquid crystal display devices are used in a wide variety of applications such as notebook PCs, portable information terminals, and digital cameras, using lightweight, thin, and versatile features. In the liquid crystal display device or the development of the monitor, the viewing angle of the liquid crystal display device requiring the viewing angle is compared with the self-luminous cathode device or the plasma display device, and the reason for the narrowness is generally two polarized lights. The difference in hysteresis of the liquid crystal layer due to the difference in the structure of the film sandwiching the liquid crystal layer affects the transmission direction, and since the hysteresis becomes large, the amount of light leakage in the incident state of the linearly polarized light increases, resulting in a decrease in contrast. Therefore, in order to suppress the contrast reduction in the oblique direction, a retardation film using hysteresis is effective. At present, in a twisted crystal display device, a viewing angle is increased by adhering a phase retardation film formed of a disk-shaped liquid crystal. On the other hand, there is a new VA (Vertical Alignment) method, an IPS (In-Plane Switching) method, etc., which develops a viewing angle, and a retardation film which is stretched by two axes at a wider viewing angle even for the VA method. . However, these films are indispensable for the alignment or stretching step, so that the liquid crystal display device has a low power consumption and the like, and the desktop monitor has a large screen size. : The line tube (CRT) shows the intensity of the light traveling in the direction of the liquid crystal display device. That is, it is not easy and complicated to use the production system because the oblique is elliptically polarized, and the liquid crystal layer can compensate for the liquid crystal layer. 200815500 For this problem, there is a proposal to expand the viewing angle of the liquid crystal display device by providing a polyimine retardation film having an optically negative one-axis anisotropy and an optical axis perpendicular or substantially perpendicular to the film surface. (Patent Document 1) The polyimine exhibits a function of a retardation film, and has an aromatic ring or an aromatic heterocyclic ring in the main chain direction of the polymer, so that the main chain is in a direction perpendicular to the main chain. The refractive index in the direction is increased, the large birefringence is exhibited as a molecule, and since the molecular chain is easily aligned in parallel with the substrate, a refractive index difference is generated between the film thickness direction and the direction parallel to the film surface (as a film). Birefringence). However, the polyimine retardation film is strong in light absorption due to the aromatic molecular structure, and it cannot be said that the transparency is sufficient. When used in a retardation film, the white display of the liquid crystal display device is provided. Yellow tone, the image shows a problem with the quality. In order to improve the transparency of the polyimine, it is proposed to introduce an acid component or a diamine component having a non-aromatic group such as an alicyclic group in the polyimide resin, thereby preventing intramolecular conjugate and charge shifting. Object formation (Patent Documents 2 to 4). In addition, there is a proposal to improve the transparency and reduce the birefringence and stress birefringence of the alignment, and the polyimine resin which is characterized by high transparency and low birefringence is used as an optical element (Patent Documents 5 to 7). . On the other hand, as a polyimide pigment material suitable for a retardation film, a polyimide material having high transparency and high birefringence is required. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 9-73 No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] The present invention provides a resin composition for a retardation film which can form a retardation film having high transparency and high birefringence by coating a substrate without an alignment and stretching step, and has the phase A color filter substrate having a poor film, a wide viewing angle, a high contrast liquid crystal display device, and a filter for a liquid crystal display device with a retardation film. In order to solve the above problems, the present invention is constituted by the following. 1 . A resin composition for forming a retardation film for forming a liquid crystal display device having an optically negative one-axis anisotropy, an optical axis being substantially perpendicular to a film surface, and a birefringence Δη of a thickness direction of 0.01 to 〜1. a retardation film of 0.3, wherein the resin composition comprises a polyimine precursor obtained by reacting at least one type of tetracarboxylic dianhydride with at least one type of diamine, and an organic solvent, wherein the at least one of vi At least one of the tetracarboxylic dianhydride and at least one of the above-described diamines is an alicyclic compound. 2. The composition of item 1, wherein the diamine of the alicyclic compound is the following formula (1)

(wherein R1 represents a monovalent organic group or a hydrogen atom) represents a trans-1,4-diaminocyclohexane compound. 3. The composition of item 2, wherein the tetracarboxylic dianhydride is the following formula (2) 200815500

(wherein R (wherein, 3 and 3, 4 represented by t and r3 each independently represent a monovalent organic group or a hydrogen atom) ^ d,4,4'-biphenyltetracarboxylic dianhydride compound 4. The composition according to item 3, wherein the polyimine precursor has at least a constituent unit represented by the following formula (3).

ΝΗ— (3) (wherein R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a monovalent organic group or a hydrogen atom). 5. The composition according to item 1, wherein the tetracarboxylic dianhydride of the alicyclic compound is 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 6. The composition of item 5, wherein the diamine is an aromatic diamine having a rigid molecular structure. 7. The composition according to item 6, wherein the aromatic diamine having a rigid molecular structure is at least one selected from the group consisting of p-phenylenediamine and 4,4,-diaminobenzimidamide. 8. A resin composition comprising the following formula (i) R1

(wherein R1 represents a monovalent organic group or a hydrogen atom). The diamine component of the trans-1,4-diaminocyclohexane compound represented by the following formula (2) 200815500

(wherein R2 and R3 each independently represent a monovalent organic group or a hydrogen atom), and the tetracarboxylic dianhydride component of the 3,3',4,4'-biphenyltetracarboxylic dianhydride compound represented by The polyphthalic acid compound and the organic solvent obtained by the reaction are formed into a phase difference film which is formed on a liquid crystal display device and has an optically negative one-axis anisotropy and an optical axis which is substantially perpendicular to the film surface. 9. The composition according to Item 8, wherein the polyamic acid compound has at least a constituent unit represented by the following formula (3): 0 II II c

(wherein R1, R2, R3, R4 and R5 each independently represent a monovalent organic group or a hydrogen atom). 10. The composition according to item 9, wherein the above R1 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; and r2, r3, r4 and r5 are hydrogen atoms. The composition of the ninth aspect, wherein the poly-proline compound further contains at least one structural unit selected from the group consisting of structural units represented by the following general formulae (4) to (8). - 200815500

(4) (5) (6)

(In the formulae (4), (5), (6), (7) and (8), Ri, R2, r3, 4 and r5 each independently represent a monovalent organic group or a hydrogen atom). 1 2 The composition of item 10, wherein in the formulas (4), (5), (6), (7) and (8), the above R1 hydrogen atom or a linear chain having a carbon number of 1 to 4 a branched or branched alkyl group, R 2 , R 3 ' R 4 and R 5 are a hydrogen atom. The composition of the item (1) or (2), wherein the total content of the structural unit represented by the formula (3), (4), (5), (6) (7) or (8) is constituted. The total structural unit of the above polyamic acid is 5 〇 mol% or more. The resin composition according to any one of items 1 to 3, wherein the polyfluorene-10-200815500 imine precursor or one or all of the amine terminal groups of the polylysine is by @ = The valine acid of the carboxylic anhydride forms a reaction and is blocked. The composition according to item 14, wherein the dicarboxylic anhydride is at least one dicarboxylic anhydride selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, and nadic anhydride (n a d i c a n h y d r i d e ). The composition according to any one of items 1 to 5, which is used for producing a resin composition for forming a phase difference film. A color filter substrate for a liquid crystal display device, which is a color filter substrate for a liquid crystal display device in which a plurality of red, blue, and green color pixels are arranged in a single order on a transparent substrate. A retardation film formed of a resin composition for a retardation film according to any one of items 1 to 5 above. The color filter substrate of item 17, wherein the retardation film comprises a general formula (8) containing 50 mol% or more

(wherein, R1, R2 and R3 each independently represent a monovalent organic group or a hydrogen atom) each of the structural unit polyimine. 19. The color filter substrate according to item 18, wherein the R1 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R2 and R3 are hydrogen atoms. The color filter substrate for a liquid crystal display device according to any one of the items 17 to 19, which is formed by coating a phase difference film formed of a resin composition for a retardation film. A liquid crystal display device using a color filter substrate for a liquid crystal display device according to any one of items 7 to 20, wherein the display mode of the liquid crystal display device -11 - 200815500 When no voltage is applied, the liquid crystal molecules are aligned in a direction perpendicular to the cell surface of the liquid crystal, and when a voltage is applied, the liquid crystal molecules are in a liquid crystal display mode in which the liquid crystal cell faces are aligned substantially in parallel. A method for producing a color filter substrate for a liquid crystal display device with a retardation film, comprising the resin composition for a retardation film according to any one of items 1 to 5, which is coated on a transparent substrate. The side faces of the pixels of the color filter substrates of the red, blue, and green color pixels arranged in the second element are heat-treated. According to the resin composition for a retardation film of the present invention, a retardation film for a liquid crystal display device can be easily formed, and the phase difference film can be used to obtain a viewing angle characteristic and a contrast of the liquid crystal display device. Further improve. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The resin composition for a retardation film of the present invention is used for forming a liquid crystal display device having an optically negative one-axis anisotropy, an optical axis slightly perpendicular to a film surface, and a birefringence Δη in a thickness direction. a retardation film of 0.01 to 0.3, wherein the resin composition for a retardation film comprises a polyimide precursor obtained by reacting a tetracarboxylic dianhydride with a diamine, and an organic solvent, wherein the tetracarboxylic dianhydride and the second At least one of the amines is an alicyclic compound. The polyamidiamine precursor used in the present invention may be poly-proline, polyphthalate, poly-proline partial ester, polydecyl phthalate, polyamidomate, polyisodecimide. Any of the structures that can be heated or chemically converted into polyimine. In order to obtain a polyimine precursor, the diamine of the alicyclic compound to be used is preferably a trans-i,4-diaminocyclohexane compound represented by the following formula (1). -12- 200815500 ί Η2ΝΗ^^ΝΗ2 (1) (wherein R1 represents a monovalent organic group or a hydrogen atom). Here, R1 is preferably an organic group or a hydrogen atom having 1 to 30 carbon atoms, more preferably a carbon such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl. A linear or branched alkyl group or a hydrogen atom of 1 to 4 is used. Among these, trans-1,4-amino-cyclohexanyl, trans-1,4-diamino-2-methylcyclohexan, trans-1,4·2 are preferred. Amino-2,5-dimethylcyclohexane, particularly preferably trans-l,4-diamino/cyclohexan. In the 1,4-diaminocyclohexane compound, the stereo configuration of the amine group at the 1,4 position exists in the trans configuration of the trans form and the cis-configuration of the cis form. Usually, a trans-1,4-diaminocyclohexane compound is obtained by hydrogenating a p-phenylenediamine compound of a precursor, but the product of the reaction is a mixture of a trans form and a cis form (for example, Special Gong Zhao 51 - 4 8198). As the suitable trans-1,4-diaminocyclohexane compound usable in the present invention, the above hydrogenated compound is isolated and purified by a well-known method such as distillation or recrystallization. The content of the cis isomer is not particularly limited as long as it does not impair the effects of the present invention. It is generally recommended to refine the content of the cis form to 50% by weight or less, preferably 30% by weight or less, more preferably 10% by weight. By setting the content of the cis isomer within the above range, it is possible to suppress a decrease in the alignment of the polyimine molecular chain due to the curved structure of the cis isomer, and to obtain practically sufficient birefringence. The trans-1,4-diaminocyclohexane compound is an effective method for improving transparency by repeating refining by recrystallization using a solvent such as n-hexane to reduce the coloring component. In the trans-1,4-diaminocyclohexane compound, other diamine compounds can be used within the range of not impairing the effect of the present invention -13-200815500. In this case, the ratio of use of the trans-indole, 4-diaminocyclohexane compound is preferably 5 % by mole or more, more preferably 70 % by mole or more, based on the entire diamine. 90% or more. When the proportion of the trans-1,4-diaminocyclohexane compound used is less than 50 mol%, the characteristics of the object of the present invention are not obtained. Examples of the diamine which can be used in combination with the trans-1,4-diaminocyclohexane compound include 2,2'-bis(trifluoromethyl)benzidine, p-phenylenediamine, and m-benzene. Diamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diamino () durene, 4,4'-diamine Diphenylmethane, 4,4'-diaminodiphenylethane, 4,4,-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenyl hydrazine, 3,3'-diaminodiphenyl fluorene, 4,4'-diaminobenzophenone, 3,3,-diaminobenzophenone, 4,4 '-Diaminobenzimidamide, benzidine, 3,3,-dihydroxybenzidine, 3,3'.dimethoxybenzidine, o-toluidine, m-toluidine, 14-bis (4 -aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3 bis(3-aminophenoxy)benzene, 4,4'-bis (4- Aminophenoxy)biphenyl, bis(4-(3-aminophenoxy)phenyl)anthracene, bis(4-(4-aminophenoxy)phenyl)anthracene, 2,2- Bis(4-(4-aminophenoxy)(/yl)phenyl)propane, 2,2-bis(4-(4-aminophenoxy)benzene An aromatic diamine such as hexafluoropropane or 2,2-bis(4-aminophenyl)hexafluoropropane; 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, and hexa Methylenediamine, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methylene-decyldimethylenediamine, tricyclo[6.2.1.02'7] -undecene dimethyldiamine, 4,4'-methylenebis(cyclohexylamino), 2,5-original bismuth bis(methylamino), 2,6-original slab An aliphatic or alicyclic diamine such as an amine group or a 2,7-orthobornane bis(methylamino) group. Further, when a nonoxyldiamine is used as a part of a diamine, an inorganic substrate or the like is used. The adhesiveness may be good. The usual amount of the oxane diamine is preferably from 1 to 20% by mole based on the total of the -14 to 200815500 diamine. As a specific example of the oxanediamine, a double (3) is exemplified. -Aminopropyl)tetramethyl dioxin. As the tetracarboxylic dianhydride which reacts with the diamine of the alicyclic compound, 3,3',4,4'-biphenyltetracarboxylic acid Anhydride, 2,3,3,,4,-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, Tetra-anhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 3,3,4,4,-diphenylphosphonium tetracarboxylic dianhydride, 4,4,-oxydiphthalic acid dianhydride 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3,,4,4'-paired triphenyltetracarboxylic dianhydride, 3,3',4,4'-biased three An aromatic tetracarboxylic dianhydride such as phenyltetracarboxylic dianhydride or 4,4'-(2,2-hexafluoroisopropylidene)di/decanoic acid dianhydride; 1,2,3,4-butyl Alkane tetracarboxylic dianhydride, 1,3-dimethyl-anthracene, 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4·cyclopentane tetracarboxylic dianhydride, 2 , 3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4,-dicyclohexane tetracarboxylic dianhydride 1,2,4,5-Orbornane tetracarboxylic dianhydride, 5-(2,5-di-oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylate Acid dianhydride, l53, 3a, 455, 9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furyl)-naphthoquinone [l,2-c]furan-l53-di Ketone, l,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-di-oxy-3-furanylnaphthalene [丨, 2 _ c ] furan-oxime, 3 _dione, I 丨, 3,3, 4,5,91^-hexahydro-5,8-dimethyl-5-(tetrahydrogen) - 2,5-di-oxy-3-furanyl)-naphtho[l,2-c]furan-1,3·dione, bicyclo[2·2.2]-octyl-7-ene_2,3 An aliphatic or alicyclic tetrahydro acid dianhydride such as 5,6-tetraresidic acid dianhydride, bicyclo[2·2·2]octane-2, 3:5,6-tetracarboxylic dianhydride or the like. Among the tetraphthalic acid dianhydrides, it is preferred to use a substituted or unsubstituted 3,3,4,4,4-diphenyltetracarboxylic dianhydride represented by the following formula (2). More preferably, 3' 3 ', 4, 4 '-biphenyltetracarboxylic dianhydride is used. -15 - 200815500

(wherein R and R3 each represent a monovalent organic group or a hydrogen atom, and each may be the same or different). Further, in the formula (2), preferred examples of R2 and R3 include hydrogen, an alkyl group having 1 to 3 carbon atoms, a halogenated compound having 3 carbon atoms, a phenyl group, or a substituted phenyl group. Etc., especially good for hydrogen. Along with the 3,3 ',4,4 '-biphenyltetracarboxylic dianhydride compound, other tetracarboxylic dianhydrides may also be used. In this case, the ratio of use of the 3,3,4,4,-biphenyltetracarboxylic dianhydride compound is preferably 5 〇 mol% or more of the entire tetracarboxylic dianhydride, more preferably 70 More than 90% of the ear is more than 90% of the total. When the ratio of use of the 3,3,4,4,-biphenyl tetraresic acid monoanhydride compound is less than 5 〇 mol%, the characteristics of the object of the present invention are not obtained. a trans-1,4-diaminocyclohexane compound represented by the following formula (1) and a substituted or unsubstituted 3,3',4,4 represented by the following formula (2) The polyimine precursor obtained by reacting the biphenyltetracarboxylic dianhydride compound preferably has the structural unit represented by the following formula (3). Further, the structural unit represented by the general formula (3) may contain structural units which are not represented by the general formulae (4) to (8). These structural units can be converted into the same structural unit represented by the general formula (8) by heating or chemical acid imidization reaction.

A monovalent organic group or a hydrogen atom, wherein R1, R2, R3, R4 and R5 each represent the same or different. -16- 200815500,

Ο

(4) (5)

η (6)

(7) (8) (In the formulae (3) to (8), R1, R3, ^ and r5 each represent an valence organic group or a hydrogen atom, and each may be the same or different). Further, preferred examples of 'reverse 1 and ... and R3 in the formulas (3) to (8) are as described in the descriptions of the above formulas (1) and (2), and are preferable as R4 and R5. Examples thereof include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a phenyl group, or a substituted phenyl group. The structural units shown in /α, ~(8) are all in the polyimine precursor, formula (3) (

d. / Above 'Better 7 〇 Moile% or more of the structural unit ratio is preferably 5 0 Mo Qi M -17- 200815500 The ratio of the structural unit shown in the general formula (3) ~ (8) is less than 5 0 Mo With the ear %, the characteristics of the object of the present invention are not obtained. As described above, after the imidization by heating or the like, "the structural unit represented by the general formula (8) is formed by heating, etc., so in the polyimine after the ruthenium imidization, the general formula ( 8) The ratio of the structural unit shown to all structural units is preferably 50% by mole or more, more preferably 70% by mole or more. The present invention also provides a resin composition comprising a diamine component containing the trans-1,4-diaminocyclohexane compound represented by the above formula (i), and containing the above formula ( 2) The polyphthalic acid compound obtained by reacting the tetracarboxylic dianhydride component of the 3,3',4,4'-biphenyltetracarboxylic dianhydride compound and the organic solvent are used for formation. In a liquid crystal display device, a phase difference film having an optically negative one-axis anisotropy and an optical axis which is substantially perpendicular to a film surface. In this case, it is preferred that the polyproline compound has at least a constituent unit represented by the above formula (3). The birefringence Δη in the thickness direction of the phase difference film formed is preferably from 0.01 to 0.3. Further, the trans-1,4-diaminocyclohexane compound represented by the formula (1) and the 3,3',4,4'-biphenyl group represented by the above formula (2) The carboxylic acid dianhydride compound can be used as it is in the description of U and a preferred compound containing each other, etc., and the above-described description of the ruthenium phthalimide precursor is carried out by a reaction of a tetracarboxylic dianhydride with a diamine by a well-known method. Come to get. Further, the polyglycolate is, for example, described in JP-A-H08-92496, after the tetracarboxylic dianhydride is esterified with an organic substance having an alcoholic hydroxyl group to form a tetracarboxylic acid diester. As a method of reacting with a diamine, the tetracarboxylic dianhydride is esterified with an organic substance having an alcoholic hydroxyl group to form a tetracarboxylic acid diester, and after reacting with the carbodiimide, The method of amine reaction is obtained. a poly-proline partial ester, which is an organic substance having a glycidyl group or an isocyanate group, for example, a carboxyl group of a poly-proline which is obtained by reacting a tetracarboxylic dianhydride with a diamine, -18-200815500 A method for reacting an acetal compound with a carboxyl group of a polyamidic acid obtained by reacting a tetracarboxylic dianhydride with a diamine, as described in JP-A-2000-2 1 22 1 6 And got it. The polyalkylene phthalate is exemplified by a decylating agent as described in JP-A-H06-63 070, JP-A-200-72768, JP-A No. 2 005 - 1 460, 73 After the diamine is converted into a bis-decylated diamine, it is obtained by a method of reacting with a tetracarboxylic dianhydride. In order to obtain a polyimine precursor, as the tetra-f'carboxylic acid dianhydride used as the alicyclic compound, 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferably used. The 1,2,3,4-cyclobutanetetracarboxylic dianhydride can be obtained by a well-known method (for example, JP-A No. 2-61956, JP-A-3-137125, J. Polym. Sci.: Part A) : Polymer Chemistry, 38 巻, 108 pages (2000)) to synthesize. 1,2,3,4-cyclobutanetetracarboxylic dianhydride can also be used together with other tetracarboxylic dianhydrides. In this case, the ratio of use of 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferably more than 50% by mole of the total tetracarboxylic dianhydride, more preferably 70 moles. More than %, especially good 90% or more. When the use of 1,2,3,4-cyclobutanetetracarboxylic dianhydride I / ratio is less than 50% by mole, the characteristics of the object of the present invention are not obtained. Examples of the tetracarboxylic dianhydride which can be used together with 1,2,3,4-cyclobutanetetracarboxylic dianhydride include 3,3',4,4'-biphenyltetracarboxylic dianhydride. 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic anhydride, 3,4,9, 10-茈tetracarboxylic dianhydride, 3,3,,4,4,-diphenylphosphonium tetracarboxylic dianhydride, 4,4,-oxydiphthalic acid dianhydride, 1,2,5,6-naphthalene Tetracarboxylic dianhydride, 3,3',4,4'-paired triphenyltetracarboxylic dianhydride, 3,3',4,4,-biased triphenyltetracarboxylic dianhydride, 4,4 An aromatic tetracarboxylic dianhydride such as '-(2,2-hexafluoroisopropylidene) dicarboxylic acid dianhydride; 1,2,3,4-butane tetracarboxylic dianhydride, 1,3_2 Methyl-l,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- -19- 200815500 cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxyl ring Amyl phthalic acid dianhydride; i, 2,4,5-cyclohexane tetracarboxylic dianhydride, ^. ', succinyl-dicyclohexane tetracarboxylic dianhydride ~ ^ must ^ original borneol tetracarboxylic dianhydride, 5 · ( 2 5 5 - di-oxytetrahydrofuranyl) -3 - methyl - 3 · ring -1,2-diphthalic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5.(tetrahydro-2,5-di-oxy-3-furanyl)-naphthalene And [l,2-c]furan-l,3-dione, 1,3,3&,4,5,913-hexahydro-5-methyl-5-(tetrahydro-2,5-di-oxyl -3-furanyl)-naphtho[l,2-c]furan-1,3-dione, 1,3,3&,4,5,91--hexahydro-5,8-dimethyl- 5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[l,2_c]furan-1,3-dione, bicyclo[2·2·2]-oct-7- Aliphatic and alicyclic tetracarboxylic acid II of olefin-2,3:5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic dianhydride anhydride. As the diamine which reacts with the tetracarboxylic dianhydride of the alicyclic compound, from the viewpoint of obtaining a retardation film having a high birefringence, it is preferred to use an aromatic diamine having a rigid molecular structure. Here, the aromatic diamine having a rigid molecular structure means a structure having a small change in a configuration (stereo-coordination) due to thermal motion of a molecule and a small change in position of two amine groups constituting a diamine. Aromatic diamine. Preferably, it is: (1) having any one selected from the group consisting of a benzene ring, an aromatic hetero ring, or a condensed ring thereof, and the two amine groups are opposite to each other, and the CN bond of one of the amine groups is preferably An aromatic diamine having a substantially parallel or substantially parallel structure with respect to the other CN bond of the amine group, and (2) having a group consisting of a benzene ring, an aromatic hetero ring, or a condensed ring thereof Two or more structural units are selected, and the structures are directly or via a guanamine bond. The two amine groups are opposite, and the CN bond of one amine group and the other amine group are CN bonds. Aromatic diamines that are substantially in the same straight line or in a substantially parallel configuration. Examples of the aromatic diamine having a rigid molecular structure include compounds represented by the following formulas (9) to (1). -20- 200815500

(wherein R6, R7, R8, R9 and R1 each represent -H, -ch3, -OH, -CF3, _S03H, -COOH, _CONH2, -F, -Cl, _Br, _Cf3 and - 〇CH3 Any of the groups selected by the ethnic group may each be the same or different). Specific examples of the aromatic diamine having a rigid molecular structure include 4,4'-diaminobenzimidamide, benzidine, 3,3'-dimethylbenzidine, and 3,3,-di Hydroxybenzidine, 3,3'-dimethoxybenzidine, 2,2'dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, p-phenylenediamine, 2-5- Diaminotoluene, 3,6-diaminoducyclen, m-phenylenediamine, 2,4-diaminotoluene, 2.4-diaminoxylene. Among them, 4,4'-diaminobenzimidamide, p-phenylenediamine, 2,2,-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine are preferably used. Particularly preferred is 4,4'-diaminobenzimidamide and p-phenylenediamine. A phase difference film containing a polyimine obtained by reacting such a diamine with 1,2,3,4-cyclobutanetetracarboxylic dianhydride has high transparency and high birefringence. It can be preferably used. These diamines may be used alone or in combination of two or more. Further, together with the aromatic diamine having a rigid molecular structure, other diamines may be used. In this case, the ratio of use of the aromatic diamine having a rigid molecular structure is preferably 50% by mole or more of the entire diamine, more preferably 70% by mole or more, and particularly preferably 90% by mole or more. . When the ratio of use of the aromatic diamine-21 - 200815500 having a rigid molecular structure is less than 50 mol%, the object of the present invention cannot be obtained as an aromatic diamine having a rigid molecular structure. As the other diamine used, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 3, can be used. 4'-Diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-double (3-Aminophenoxy)benzene, 4,45.bis(4-aminophenoxy), biphenyl, bis(4-(3-aminophenoxy)phenyl), bis ( 4-(4-Aminophenoxy)phenyl)anthracene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-amine) An aromatic diamine such as phenoxy)phenyl)hexafluoropropane or 2,2-bis(4-aminophenyl)hexafluoropropane. Further, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, trans-1,4-diaminocyclohexane, cis-1 may also be used. 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methylenedecyldimethylenediamine, tricyclo[6· 2·1·02,7]-undecenedimethyldiamine, 4,4′-i 1 i methyl bis(cyclohexylamino), 2,5-oriborane bis(methylamino), Aliphatic and alicyclic diamines such as 2,6-oriborane bis(methylamino), 2,7-oriborane bis(methylamino). Further, when a nonoxyldiamine is used as a part of the diamine, the adhesion to an inorganic substrate or the like can be improved. The usual amount of the siloxane diamine is preferably from 1 to 20 mol% of the total diamine. Specific examples of the decanediol diamine include bis(3-aminopropyl)tetramethyldioxane. The reaction of the tetracarboxylic dianhydride with the diamine can be carried out by mixing in a polar organic solvent. At this time, the polymerization degree of the obtained poly-proline is -22-200815500 by the mixing ratio of the tetracarboxylic dianhydride and the diamine. The ratio of the tetracarboxylic dianhydride to the diamine used for the synthesis reaction of the poly-proline, and the acid anhydride group of the tetracarboxylic dianhydride is preferably 0. 2 for the amine group contained in one equivalent of the diamine. The ratio of ~2 equivalents is more preferably 0. 8~1 · 2 equivalents. Similarly to the usual polycondensation reaction, the closer the molar ratio of the tetracarboxylic dianhydride to the diamine is 1, the greater the degree of polymerization of the resulting polymer. When the degree of polymerization is too small, the strength of the polyimide film is insufficient, and if the degree of polymerization is too large, workability at the time of formation of the polyimide film is deteriorated. Therefore, in terms of the degree of polymerization of polylysine, the relative viscosity (also referred to as iisp/C) is preferably 0.05 f to 5.0 dl/g (in N-methylpyrrolidone at a temperature of 30 ° C, The concentration is 〇5g/dl, and more preferably 〇. 1~2.0 d 1 / g. Further, in order to improve the heat resistance and the processability, in order to block a part or all of the amine group or the residue at the terminal of the polyglycolic acid molecule, a dihydric anhydride, a monoamine compound, a monoisocyanate compound or the like may be added to the reaction. In the department. Examples of the dicarboxylic acid anhydride include maleic anhydride, phthalic anhydride, 4-methyl phthalic anhydride, 4-tributyl phthalic anhydride, itaconic anhydride, and nadic anhydride. Further, examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, and n-hexylamine. Further, as a monoisocyanate compound, for example, phenyl isocyanate or naphthyl isocyanate may, for example, be mentioned. It is particularly preferred that some or all of the amine terminal groups are blocked by reaction with the valine acid of the di-resin anhydride, which is preferably selected from maleic anhydride, phthalic anhydride, succinic anhydride and nadic anhydride. At least one dicarboxylic anhydride. The synthesis reaction of polylysine is carried out in an organic solvent, preferably at -20 Torr to 2 〇 ° C, more preferably at a temperature of 〇 1 to 150 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyaminic acid, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamidine. Amine, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, 1,3 -dimethyl-2-mi-23-200815500 oxazolinedione, six An aprotic polar solvent such as methylphosphonamide. Further, the amount of the organic solvent to be used is preferably such that the concentration of the solid content of the tetracarboxylic dianhydride and the diamine is from 1 to 30% by weight based on the total amount of the reaction solution. In the above organic solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like of a weak solvent of polyproline may be used insofar as the polyamic acid formed is not precipitated. Specific examples of the weak solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, and 3- Methyl-3-methoxybutanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate , methyl-3-methoxypropionate, 3-methyl-3-methoxybutyl acetate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, two Ethyl ether, tetrahydrofuran, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, Ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol single Methyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, dichloro (; methane, 1,2-dichloroethane, 1,4-dichlorobutane, three Ethyl chloride, chlorobenzene, o-dichlorobenzene, hexane, Alkane, octane, benzene, toluene, xylene. The resin composition for a retardation film can be produced by uniformly mixing a polyimine imide or a solution thereof with an organic solvent by a usual method. When the resin composition is prepared, the temperature is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 6 ° C. The organic solvent may be exemplified by those used in the synthesis reaction of polylysine. Further, the weak solvent exemplified as the polypyridic acid in the synthesis reaction may be appropriately selected and used. The solid content concentration in the resin composition is considered in terms of viscosity, volatility, and the like. -24- 200815500 is selected, but preferably in the range of 1 to 10% by weight. That is, the resin composition is applied to the surface of the substrate to form a coating film as a retardation film, and if the solid content concentration is less than 1% by weight The film thickness of the coating film is too small, and a good retardation film cannot be obtained. When the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and a good retardation film cannot be obtained, and the resin composition is not obtained. Increased viscosity The coating property is deteriorated. In the resin composition, 3-aminopropyltrimethoxydecane and 3-(2-aminoethyl)aminepropyltriamide may be contained from the viewpoint of improving adhesion to the surface of the substrate. Oxydecane, N-phenyl-3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 2-(3,4- Functional decane-containing compound and/or bisphenol epoxy resin such as epoxycyclohexyl)ethyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, 3-aminopropyltriethoxydecane, etc. , bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, alkyl phenol novolak type epoxy resin, polyglycol type epoxy resin, cyclic aliphatic ring Oxygen resin, cresol novolak type epoxy resin, glycidyl amine type epoxy resin, naphthalene type epoxy resin, urethane modified, epoxy resin, rubber modified epoxy resin, epoxy modified An epoxy group-containing compound such as an epoxy resin such as a polyoxyalkylene oxide. Further, from the viewpoint of improving the film thickness uniformity or surface smoothness of the coating film, a nonionic surfactant such as polyoxyethylene lauryl ether or polyethylene oxide dilaurate or a fluorine-based interface activity may be contained. A surfactant such as a surfactant, a decane-based surfactant, or an acrylic copolymer-based surfactant. The content of such additives is such that it does not adversely affect the effects of the present invention, and is usually 20% by weight or less, preferably 10% by weight or less, based on the total composition. The resin composition is applied onto a substrate by a dipping method, a roll coating method, a spin coating method, a die coating method-25-200815500 method, a wire rod method, or the like, and then air drying, vacuum drying, an oven, or a hot plate is used. The coating film is formed by heat drying or the like. The heating conditions vary depending on the resin, solvent, and coating amount used, but are usually heated at 50 to 400 ° C for 1 to 300 minutes. The substrate to be coated may be a substrate for a liquid crystal display device, that is, a color filter substrate or a TFT substrate itself. Further, once the resin composition is applied onto the base film, it may be adhered to the liquid crystal display substrate via the adhesive layer. These are formed on the substrate surface on the opposite side to the liquid crystal layer. Further, it may be formed on the side in contact with the liquid/crystal layer of the substrate for a liquid crystal display device. For example, a side of a pixel on a color filter substrate for a liquid crystal display device having a second element %, / a red, blue, or green color pixel arranged on a transparent substrate may be formed on the transparent substrate in a manner of covering pixels. The above resin composition was applied. Here, the cover pixel is formed on the liquid crystal layer side of the pixel, and the phase difference film formed by the pixel and the resin composition may be directly or in contact with each other. For example, when the overcoat layer is formed to planarize the color filter substrate, the retardation film formed of the resin composition may be formed on the liquid crystal layer side of the overcoat layer or on the substrate side of the overcoat layer. Further, a color difference film formed by the resin composition may be formed into a color filter for a liquid crystal display device in which red, blue, and green color pixels of a secondary element are formed on a substrate. Further, in the resin composition, a coloring component such as a pigment or a dye is used, and a varnish for each color pixel used as a color filter is used, and a phase difference compensation function can be imparted to each color pixel itself. In the case of pixels, in the pixels of red, green, and blue, the hysteresis 値R is adjusted so that the phase difference R/λ is substantially the same for the dominant wavelength λ, which causes the phase difference of each color. The retardation film for a liquid crystal display device of the present invention can be formed by applying a resin composition on a substrate -26-200815500 and heat-treating the film. The retardation film has a phase difference. It has the function of correcting the birefringence which occurs when the light passes through the liquid crystal layer in the liquid crystal display device. The molecular chain of the polyamidene resin is easily aligned with the substrate surface, so the film thickness is In the direction parallel to the film surface, a refractive index difference (birefringence of the film) occurs. Further, since the molecular alignment in the film plane is random, there is no refraction in a direction parallel to the film surface. In the retardation film of the present invention, when the X-axis and the y-axis are obtained in the in-plane direction of the film, and the z-axis is obtained in the direction perpendicular to the film surface, the polyimide film containing the polyimide-based resin is obtained. # . The refractive index of each direction of the film is nX-ny>nz, which is a phase difference film (negative C plate) having an optically negative one-axis anisotropy and an optical axis perpendicular to the film surface. The optically negative one-axis anisotropy means that for the refractive indices of two axes that are equal to each other, the refractive index of the remaining one axis is small, and the optical axis is roughly perpendicular to the film surface, nx = ny > Specifically, the birefringence Δ n (= nx-nz) in the thickness direction of the OSnx-ny $ 0.005, ny > nzo retardation film is preferably 0.01 to 〇·3, more preferably 0.0 3 or more. It is more than 0.0 5 or more. If the birefringence is less than 0.01 μm, it is required to compensate the phase difference of the liquid crystal. The film thickness of the dislocation film may become too large, and the formation of the film may become difficult. The film thickness of the retardation film is preferably 0.5 to 20 μm. The retardation film of the present invention is generally effective for a liquid crystal display device, but due to the optical axis and The phase difference film surface is slightly vertical. Therefore, in the liquid crystal display device, it is particularly preferable that the liquid crystal molecules are aligned in a direction perpendicular to the liquid crystal cell surface when there is no applied voltage (vertical alignment), and liquid crystal molecules and liquid crystal are applied when a voltage is applied. The cell surface is displayed in a substantially parallel direction as a display mode, specifically a vertical alignment of MVΑ (multi-domain vertical alignment) mode, PVA (patterned vertical alignment) mode, CPA (continuous flame-like alignment) -27-200815500 mode, etc. In the liquid crystal display device of the mode. As described above, since the optical axis of the retardation film of the present invention is in a substantially vertical direction with respect to the substrate surface of the two substrates sandwiched with the liquid crystal, there is no phase difference compensation effect when viewed perpendicularly to the screen. In the case of the vertical alignment mode, when no voltage is applied, the phase difference of the liquid crystal layer in the vertical direction is also almost zero, so that phase difference compensation is not required. That is, when no voltage is applied, a good black display can be obtained even if the phase difference is not compensated. However, in the oblique direction, even if no voltage is applied, the liquid crystal layer has a phase difference. Therefore, if the phase difference is not compensated for, light leakage occurs, and a good black display is not obtained, which causes a decrease in contrast. However, in the vertical alignment mode of the present invention, the contrast in the oblique direction is improved, and the remarkable effect of expanding the viewing angle is displayed. [Examples] <Measurement of Relative Viscosity (qsp/C) of Polyimine Precursor> Solution of Polyimine Precursor Dissolved at a Concentration of 0.5 g/dl and Dilute in N-Methylpyrrolidone It was measured at 30 °C using a Uber-Look-type viscometer. % <Measurement method of optical axis> Measurement was carried out using "OPTIPRO" manufactured by SHINTECH. On the glass substrate, the polyimine precursor solution was applied by a spin coater so that the thickness of the finish was 2·0 μm, and then dried at 120 ° C for 20 minutes, at 240 ° C for 30 minutes or at The heat treatment was carried out at 270 ° C for 40 minutes to obtain a polyimide film. The refractive index anisotropy in the direction parallel to the film surface of the polyimide film and the refractive index anisotropy perpendicular to the film surface were measured. -28- 200815500 <Measurement method of birefringence> The measurement was performed using "Prism Coupler-20 1 0," manufactured by METRIC ON Co., Ltd. on a glass substrate by a spin coater so that the thickness of the finish was 2 · 0 μηη After coating the polyimide precursor solution, it was dried at 120 ° C for 20 minutes, and heat-treated at 24 ° for 30 minutes or at 270 ° C for 40 minutes to obtain a polyimide film. The refractive index nl (= nx) in the direction parallel to the film surface of the imide resin film and the refractive index n2 (= nz) in the film thickness direction, and the difference in refractive index, the birefringence is calculated by the following formula. The system uses 63 2.8 nm / HeNe laser light. Δη = nl-n2 <Measurement method of coloring of film> The measurement was carried out using a "MCPD-2000" microspectrophotometer manufactured by Otsuka Electronics Co., Ltd. On the glass substrate, the polyimine precursor solution was applied by a spin coater so that the thickness of the finish was 2·0 μηη, and then dried at 120 ° C for 20 minutes, at 240 ° C for 30 minutes or at The heat treatment was carried out at 270 ° C for 40 minutes to obtain a poly-/imine film. In the color system (CIE1931 standard color system), the color coordinates (X, y) of the standard c light source = (〇.3100, 0.3162) and the color coordinates of the light after transmission of the polyimide film (Xl, The difference of yl) (Αχ, Ay). Here, xl-x, Δ y = y 1-y. When △ χ and △ y are both large, the white display has a yellow hue, indicating a lower grade. Preferably, Δ X and Δ y are both 0.05 5 or less, and more preferably 0.0 3 3 or less. Synthesis Example (Synthesis of 1,2,3,4-Cyclobutanetetracarboxylic dianhydride) In a 2 liter internal irradiation type glass reaction flask equipped with a PYREX (registered trademark) glass water-cooled lamp tube 2 5 5 g (2·60 mol) of Malay-29-200815500 anhydride and 1,445 g of ethyl acetate were placed, and the flask was replaced with nitrogen, and then stirred and dissolved at room temperature. Then, while stirring, the reaction solution was cooled to 5 ° C, and irradiation of a 400 W high-pressure mercury lamp was started, and irradiation with light for 96 hours was continued. During the irradiation, the temperature of the reaction solution was maintained at 3 to 5 °C. After the reaction was completed, the crystals and the filtrate were separated by filtration. After the crude crystals were washed with ethyl acetate, they were dried in a vacuum dryer at 40 t for 10 hours to obtain crystals of 194 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride. Example 1 Under dry nitrogen flow, 10.96 g (0.096 mol) of trans-l,4-diamine p-cyclohexane and 0.99 g (0.004 mol) of bis(3-aminopropyl)tetramethyl were obtained. Dioxane was dissolved in 1 77.28 g of N-methyl-2-pyrrolidone. Then, 2 8.25 g (0.096 mol) of 3,3,4,4'-biphenyltetracarboxylic dianhydride and 40.00 g of N-methyl-2-pyrrolidone were added and stirred at 60 ° C for 3 hours. . Further, after adding 1.18 g (0.008 mol) of phthalic anhydride, the mixture was stirred at 60 ° C for 3 hours to obtain a transparent viscous polyamine solution A (polymer concentration: 16% by weight). The viscosity of solution A measured at 25 °C was 803 mPa.s. The relative viscosity is 0.70 dl/g. On the glass substrate, the polyaminic acid solution was applied by a spin coater so that the thickness of the finish was 2·0 μm, and then dried at 120 ° C for 20 minutes, followed by heat treatment to obtain a polyimide film. . When the heat treatment was carried out for 30 minutes at 240, the direction of the polyimine resin film parallel to the film surface showed no refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured. The result ιιχ > nz showed a negative one-axis property. Namely, the obtained polyimine resin S film system has an optically negative one-axis anisotropy, and the optical axis is large @ perpendicular to the film surface. The refractive index of the polyimide film in the direction parallel to the film surface is η1 = 1·683, the refractive index in the film thickness direction is 1x2 = 1.592, and the birefringence system is ^11 = 0.091. Further, the color coordinate system of the transmitted light (0.3108, 0.3172), Δχ = 0.0008, Δ -30 - 200815500 y = 0· 00 1 0, and Δ x and Δ y are all 0.003 or less, and a phase difference film having no coloration is obtained. Further, in the heat treatment at 70 ° C for 40 minutes, the direction in which the polyimide film of the polyimide film is parallel to the film surface has no refractive index anisotropy, that is, nX = ny . The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, nx > nz showed a negative one-axis property. Namely, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide film of the polyimide film in the direction parallel to the film surface is niMjA 5, η2 = 1.571, so the birefringence Δ n = 0.174, according to the color coordinates of the transmitted light (0.31 16, f 0.3179), / ^=0.0016, Δy = 〇.〇〇17, Z\x, and Ay are all 0.003 or less, and a retardation film which is not colored is obtained. Example 2 Under a dry nitrogen stream, 10.96 g (0.096 mol) of trans-1,4-diaminocyclohexane and hydrazine·99 g (0.004 mol) of bis(3-aminopropyl)tetramethyl Dioxane was dissolved in 1 73.2 8 g of N-methyl-2-pyrrolidone. Then, 25.3 0 g (0.086 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2.18 g (0.010 mol) of pyromellitic anhydride and 4 0 · 0 g of N- were added. Methyl-2-pyrrolidone was stirred at 60 ° C for 3 hours. Further, after adding 1.18 g (0.008 mol) of phthalic anhydride, the mixture was stirred at 60 ° C for 3 hours to obtain a transparent viscous polyamine solution B (polymer concentration: 16% by weight). The viscosity of solution B measured at 25 ° C was 690 mPa*s. The relative viscosity system was 6767 dl/g. The same procedure as in Example 1 was carried out, and the polyimide film which was heat-treated at 270 ° C for 40 minutes was parallel to the film surface, and had no refractive index anisotropy. , nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, nx > nz showed a negative one-axis property. Namely, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. -31 - 200815500 The index of refraction of the polyimide-based resin film in a direction parallel to the film surface η1 = 1·6 9 8. The refractive index in the film thickness direction is η2 = 1·5 8 6. The birefringence system Δnw Ju , color coordinate system of transmitted light (0.3 1 1丨, Q > 3174) △ χ = (Κ(10)i iy = (eight) i2 , △ X, △ y white system 0 · 0 0 3 or less, to obtain a phase difference film without coloration. Example 3 Under a dry nitrogen stream, 1 〇.96 g (〇.〇96 mol) trans-L4-diaminocyclohexyl and 〇·99 g (0.004 mol) bis (3-aminopropyl) Tetramethyldioxane was dissolved in 17.61 g of N-methyl-2-pyrrolidone. Then, 2 8 · 25 g (〇·〇9 6 / mol) 3,3 ' , 4,4 '-biphenyltetracarboxylic dianhydride and 4 〇. 〇〇N_methyl-2 _pyrrolidone' was stirred at 60 ° C for 5 hours to obtain a transparent viscous polyamine solution c (Polymer concentration: 1% by weight). The viscosity of the solution C measured at 2 ° C was 5.2 2 2 m P a • s. The relative viscosity was 0.81 dl/g. The same procedure as in Example 1 was carried out, 240 ° C. The 30-minute heat-treated polyimine resin film is flat with the film surface The refractive index of the direction is η 1 = 1 . 7 〇6, the refractive index in the film thickness direction is η2 = 1.592, and the birefringence system Δ η = 0.11 4 , the color coordinate system of transmitted light (0.3109, 0.3171) ), 0.0009, ΔyW.OOOg, Z\x, and Ay are all 0.003 or less, and a phase difference film having no coloration is obtained. Further, when it is subjected to heat treatment for 40 minutes at 27 Å, the film surface of the polyimide film is formed. In the parallel direction, there is no refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface is measured, and as a result, nx > nz shows a negative one-axis property. The quinone imine resin film has optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide film of the polyimide film in the direction parallel to the film surface is nl = 1.735, n2 = 1.572, Therefore, the birefringence /^11 = 0.163, according to the color coordinates of the transmitted light (0.3116, 0.3180), Δχ^Ο.ΟΟΙό, Ay^O.0018, Λχ, △ y are all below 0 · 0 0 3, which is not colored. Phase difference film. -32- 200815500 Example 4 Under a dry nitrogen stream, 1 1 · 4 2 g (0 · 1 (10) mol Trans-1,4-diaminocyclohexane is dissolved in 174.42 g of N-methyl-2-pyrrolidone. Then, 29 42 g (0.100 mol) of 3,3',4,4'- is added. Biphenyltetracarboxylic dianhydride and 4 g of 1-methyl-2-pyrrolidone were stirred at 60 ° C for 5 hours. After cooling at room temperature, 8 5 . 7 g of N-methyl-2-pyrrolidone was added to give a transparent viscous poly phthalic acid solution D (polymer concentration: 12% by weight). The viscosity of solution D measured at 25 ° C was 5.8 7 8 mPa • s. The relative viscosity is 1.68 dl/g. In the same manner as in Example 1, the direction in which the polyimide film which was heat-treated at 270 ° C for 40 minutes was parallel to the film surface, and had no refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, nx > η ζ showed a negative one-axis property. Namely, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide film of the polyimide film in the direction parallel to the film surface is nl = l.745, and the refractive index in the film thickness direction is η 2 = 1 · 5 7 1, and the birefringence system Δ n = 〇.丨7 4, the color coordinate system of transmitted light (0.3120, 0.3187), △ χ = 0·0020, △ "〇. 〇〇 25, △ X, △ y are all below 〇 · 〇〇 3, to obtain a phase difference film without coloration Example 5 Under a dry nitrogen stream, 42.42 g (0.100 mol) of trans-l,4-diaminocyclohexane was dissolved in 1 76.3 g of N-methyl-2-pyrrolidone. Add 29.78 g (0.096 mol) of 4,4'-oxydiphthalic acid dianhydride and 40.00 g of N-methyl-2-pyrrolidone, and stir at 60 ° C for 5 hours. After cooling to room temperature, add 8 5.8 3 g of N-methyl-2-pyrrolidone to obtain a transparent viscous poly-proline solution E (polymer concentration of 12% by weight). The viscosity of solution E measured at 2 ° C was 1,1 3 9 m P a · s. The relative viscosity is 96.96 dl/g. The same procedure as in Example 1 was carried out, and the film of the poly-A-33-200815500 amine resin heat-treated at 270 ° C for 40 minutes was parallel to the film surface. The direction system has no refractive index anisotropy, Nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, nx > η ζ showed a negative one-axis property. That is, the obtained polyimine resin film had an optically negative one-axis difference. The directionality, the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide film in the direction parallel to the film surface is nl = l.631, and the refractive index in the film thickness direction is η2 = 1·616. The birefringence system Δ η = 0·015, the color coordinate system of transmitted light (0.3122, 0.3190), AxW.0022, AyM.0028, Δx, Δ y are all below 0.003, and a phase difference film having no coloration is obtained. 'Example 6 Under a dry nitrogen stream, 1 0 · 38 g (0.09 6 mol) of p-phenylenediamine and 0.9 9 g (0.004 mol) of bis(3-aminopropyl)tetramethyldioxane The alkane was dissolved in 1 24.79 g of N-methyl-2-pyrrolidone. Then, 18.83 g (0.096 mol) of 1,2,3,4-cyclobutane.tetracarboxylic dianhydride and 40.00 g of N-A were added. The base-2-pyrrolidone was stirred at 60 ° C for 3 hours. Further, 1.18 g (0.008 mol) of phthalic anhydride was added, and the mixture was stirred at 60 ° C for 3 hours to obtain a transparent viscous polyaminic acid solution F ( The compound concentration i 6 wt%). The viscosity of the solution F measured at 25 ° C was 3 84 mPa·s. The relative viscosity (; 0.56 dl / g 〇 was produced in the same manner as in Example 1, and 2 4 0 ° C 3 0 The refractive index of the film of the polyimine resin film which has been heat treated for a minute is in the direction of the film surface η 1 = 1 · 62 The refractive index of the film thickness direction is η2 = 1.5 86, and the birefringence system △!! = 0 · 03 5. Further, the color coordinate system of the transmitted light (0.3 1 09, 0.3 1 73), Δ χ = 0.0009, Δ y = 0.00 1 1, Δ X and Δ y are all 0.005 or less, and a phase-difference film having a small coloration is obtained. Further, in the heat treatment at 270 ° C for 40 minutes, the direction in which the polyimide film of the polyimide film was parallel to the film surface had no refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, nx > nz showed a negative one-axis property. That is, -34-, the obtained optical axis is parallel to 0.045, Δ y = 0. The film is exemplified by benzoanilide to 1: D ketone. The dianhydride and the hydride are obtained by the measurement of °c and the amine resin nx = ny > nz » The optically imine, the color of the film X, △ y 200815500 to the polyimine resin film has The optically negative axis is roughly perpendicular to the film surface. The refractive index of the polyimide film in the direction of the film is nl = 1.631 and n2 = 1.586, so it is based only on the color coordinates of the transmitted light (0.3127, 0.3197), △ • 003 5, Δ X, Δ y are 0 · 0 0 5 Following, a small dry nitrogen stream was obtained to make 21.82 g (0.096 mol) of 4,4'- and 0.99 g (0.004 mol) bis(3-aminopropyl)tetramethyl [2.41 g γ-butane] ester. Next, add 72.41 g of hydrazine - then 'add 18.83 g (0.096 mol) 1,2,3,4-ring 40.00 g Ν-methyl-2-pyrrolidone, add 1.18 g at 60 °c (0· 008 mol) phthalic anhydride, transparent viscous polyglycine solution G at 60 ° C (polymer concentration of 16 疋 solution G viscosity system 1, 〇 80 m P a · s. Relative adhesion I In the same manner as in Example 1, the heat-treated film at 240 ° C for 30 minutes had a refractive index in a direction parallel to the film surface. The refractive index in the direction perpendicular to the film surface showed a negative one-axis property in the opposite direction. The negative axis of the polyimine tree negative axis' optical axis is the refractive index of the film surface in the direction parallel to the film surface of the large resin film, the refractive index of the direction is n2 = l.604, the birefringence system △ n = coordinate system (0.3115, 0.3180), △ χ ^ ο. οου, Ay are all 0 · 0 0 3 or less 'obtained the phase difference of the uncolored, thin directionality, and the film surface is E refraction Δ η χ = 0.0027 > Colored phase diaminobenzylidenedioxane dissolved in methyl-2-pyrrolidine tetracarboxylic acid for 3 hours, stirred for another 3 hours by weight). 2 5 : 〇.71 dl / g over the poly-Asian unidirectionality, sex, the result nx lipid film ties: slightly vertical. The polymerization system η 1 = 1. 6 6 9 0.065 , transmission = 0.0018, Δ film. Further, the 270-35-200815500 °C 40-minute heat-treated polyimide film has a direction parallel to the film surface and has no refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, nx > nz showed a negative one-axis property. Namely, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide film in the direction parallel to the film surface is η1 = 1·688, η2=1·601, and birefringence /^11 = 0.087, according to the color coordinates of the transmitted light (0.3142, 0.3212), = 0.0042, = 0 · 0 0 5 0 '△ x, △ y are all 〇. 〇〇5 or less, a phase difference film of a small color is obtained, and Example 8 is dried under a nitrogen stream to make 2 0 · 38 g (〇. 〇9 6 mol) 2,2 '-dimethylbiphenyl moon female and 0.99 g (0.004 旲 ear) bis(3-aminopropyl) tetramethyl oxalate dissolved in 177.28 g N - Methyl-2-indole is slightly more than B-butanone. Then, 18.83 g (0.096 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 40.00 g of N-methyl-2-pyrrolidone were added and stirred at 60 ° C for 3 hours. Furthermore, after adding []1 · 1 8 g (0 · 0 0 mol) of phthalic anhydride, the mixture was stirred at 60 ° C for 3 hours to obtain a transparent viscous poly-proline solution η (concentration of poly-hybrid 16% by weight). The viscosity of the solution measured at 25 °C is 1.05 5 mPa • s. The relative viscosity is 0.78 dl/g. In the same manner as in Example 1, the refractive index of the polyimide film which was heat-treated at 240 ° C for 30 minutes in the direction parallel to the film surface was nl = 1.625, and the refractive index in the film thickness direction was η2 = 1· 587, birefringence Δη = 0·038, the color coordinate system of the transmitted light (0.3114, 0.3180), ΔxW.OOM, Δy = 〇.〇〇18, Ax, Ay are all below 0.003, and the phase without coloration is obtained. Poor film. Further, 27 (r 4 min heat-treated polyimine resin film has a direction parallel to the film surface, and has no refractive index anisotropy, nx = ny. Measured in a direction perpendicular to the film surface - 36 - 200815500 rate is different, and the result is nx > nz, showing a negative one-axis property. That is, the obtained poly-fee resin film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide film in the direction parallel to the film surface is 111 = 1.625, 112 = 1.586, so the birefringence is eight 11:=〇.039, according to the color coordinate of the transmission (0.3134, 0.3210), ^1 = 0.0034, Δγο. 〇〇48, Αχ, △ y are all Ο. Ο Ο 5 or less, a small colored phase difference film is obtained. Example 9 Under a dry nitrogen flow, 3 0.74 g (0.096 mol) 2 is obtained. 2,-bis(tri-f-f:'-yl)benzidine and 0.99 g (0.004 mol) bis(3-aminopropyl)tetramethyldioxane gluten solution in 2 3 1 · 6 9 g Ν · methyl - 2 - hydrazide quinone ketone 1. Then, add 1 8 · 8 3 g (0.096 mol) 1,2.3,4-cyclobutane tetracarboxylic dianhydride and 40.00 g Ν - A Base-2-pyrrolidone, stirred at 60 ° C for 3 hours. Further, 8 g (0.00 8 mol) of phthalic anhydride was added and stirred at 60 ° C for 3 hours to obtain a transparent viscous polyamine. Acid solution 1 (polymer concentration: 16% by weight). The viscosity of solution I measured by 25 t was 27 5 mPa_s, and the relative viscosity was 58.58 dl/g. It was produced in the same manner as in Example 1, and was dried at 240 ° C for 30 minutes. The refractive index of the heat-treated polyfluorene-imide resin film in a direction parallel to the film surface is nl = 1.5 60, the refractive index in the film thickness direction 丨± η2 = 1·540, and the birefringence system Δ η = 0·020 The color coordinate system of the transmitted light (0.3103, 0.3164), ΔxrO.OOOS, ^7 = 0.0002, △ ", all are 0.003 or less, and a phase difference film having no coloration is obtained. Also, at 27 〇. 〇 is performed for 40 minutes. In the heat treatment, the direction in which the polyimide film is parallel to the film surface has no refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface is measured, and as a result, η X > η z, showing a negative one-axis property. That is, the obtained polyimide film has optically negative one-axis anisotropy, optical axis The film surface is slightly vertical. The refractive index of the polyimide film is flat with the film surface -37-200815500. The refractive index is η1 = 1·5 5 9 and η2 = 1·541, so the birefringence is 0.018. According to the color coordinates of the transmitted light (〇·31〇8, 0.3171), △ x = 0.0〇〇8, Δ y = 0.0 0 0 9, △ X, △ y are all 〇. 〇〇3 or less, and no coloration is obtained. Phase difference film. Example 1 Under a dry nitrogen stream, 1 9.2 2 g (0 · 0 6 mol) of 4,4,-diaminodiphenyl ether and 0.99 g (0.004 mol) of bis(3-aminopropyl) Tetramethyl oxalate was dissolved in 171.2 1 g of N-methyl-2-pyrrolidone. Then, 18.83 g (0.096 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 40.00 g of N-methyl-2-pyrrolidone were added, and the mixture was stirred at 60 ° C for 3 hours. Further, after adding 1.18 g (0.008 mol) of citric anhydride, the mixture was stirred at 60 ° C for 3 hours to obtain a transparent viscous polyaminic acid solution j (polymer concentration: 16% by weight). The viscosity of solution J measured at 25 ° C is 25 8 mPa • s. The relative viscosity is 0.56 dl/g. In the same manner as in Example 1, the polyimide film which had been heat-treated at 240 °C for 30 minutes was parallel to the film surface, and had no refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, nx U > nz showed a negative one-axis property. Namely, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide film in the direction parallel to the film surface is η 1 = 1 . 6 2 0 , the refractive index in the film thickness direction is η2 = 1.608, the birefringence system Δ η = 0.013, transmitted light The color coordinate system (〇·3111, 〇.3178), 0011, Δγ = 〇.0016, ΔX, Δ y are all 0.003 or less, and a retardation film which is not colored is obtained. Further, when the heat treatment was carried out at 270 ° C for 40 minutes, the direction in which the polyimide film of the polyimide film was parallel to the film surface was not refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, η X > η z showed a negative one-axis property. -38- 200815500 That is, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide film of the polyimide film in the direction parallel to the film surface is η1 = 1·622, η2 = 1.607, so the birefringence VIII = 0.015, according to the color coordinates of the transmitted light (0.3127, 0.3197), ^)^0.0027 , Δ y = 0 · 0 0 3 5, Δ X, Δ y are all 0.02 5 or less, and a phase-difference film having a small coloration is obtained. Example 1 1 Under a dry nitrogen stream, 1 0 · 8 1 g (0·100 mol) of p-phenylenediamine was dissolved in f) 132·41 g of N-methyl-2-pyrrolidone. Then, 19.61 g (0.100 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 40.00 g of N-methyl-2-indolebiolone were added, and stirred at 60 °C. After hours, a transparent viscous polyamine solution κ (polymer concentration 15% by weight) was obtained. The viscosity of the solution measured at 25 ° C was 9,257 mPa.s. The relative viscosity is 1.36 dl/g. In the same manner as in Example 1, the polyimine resin film heat-treated at 240 ° C for 30 minutes had no refractive index anisotropy in a direction parallel to the film surface, and nx = ny 〇 was measured in a direction perpendicular to the film surface. The refractive index is different in directivity, and as a result, nx U > nz ' shows a negative one-axis property. Namely, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide film in the direction parallel to the film surface is η1 = 1·635, the refractive index in the film thickness direction is ιχ2 = 1.584, and the birefringence system Δ η = 0 · 05 1 . Further, the color coordinate system (0.3116, 0.3182) of the transmitted light, /^ = 0.0016, ^7 = 0.0020, and Δ X and Δ y were all 0.003 or less, and a retardation film having no coloration was obtained. Example 1 2 Under a dry nitrogen stream, 2 2 · 7 3 g (0.1 mol) of 4,4,-diaminobenzilide was dissolved in 11.1 g of γ-butyrolactone. Next, 71.14 g of N-methyl-39-200815500-based 2-pyrrolidone was added. Then, 19.61 g (0.100 mol) of 12,3,4-cyclobutanetetracarboxylic dianhydride and 40.00 g of N-methyl-2-pyrrolidone were added and stirred at 60 ° C for 4 hours to obtain a transparent viscous layer. Polylysine solution L (polymer concentration i 6 wt%). The viscosity of the solution L measured at 25 ° C is 3 1.400 mPa·s. The relative viscosity is 1.81 dl/g. In the same manner as in Example 1, the polyimide film which had been heat-treated at 240 °C for 30 minutes was parallel to the film surface, and had no refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, η χ > η ζ showed a negative one-axis property. Namely, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the film of the 3 曰 film of the 醯 fefee tree is in the direction of the film surface η1 = 1·685 'The refractive index in the film thickness direction η2 = 1.5 98, the birefringence system △ ^ = 0.087, the transmission first The color coordinate system (0.3131, 0.3204), 〇〇31, =, ΔX, and Δy are all 0.005 or less, and a phase-difference film having a small coloration is obtained. Comparative Example 1 Under a dry nitrogen stream, 11.92 g (0.048 mol) of 3,3,-diaminodiphenylphosphonium, 5.19 g (0.048 mmol) of p-phenylenediamine and hydrazine·99 g (〇〇〇4) Mole) bis(3-aminopropyl)tetramethyldioxane was dissolved in 209 5 5 g of Ν-methyl-2-pyrrolidone. Then, 28.25 g (0.096 mol) of 3,3,4,4,_biphenyltetracarboxylic dianhydride and 40.00 g of hydrazine-methyl-2-pyrrolidone were added at 6 Torr: stirring for 3 hours. . Further, after adding 1.18 g (0.008 mol) of phthalic anhydride, the mixture was stirred for 6 hours at 6 , to obtain a transparent viscous polyamic acid solution M (polymer concentration of 16 湏 (湏 疋 161 之 黏 系94 GmPa.s. Relative viscosity: G64 dl/g. Manufactured in the same manner as in Example i, the 27-generation 4 〇 minute heat-treated polyimide resin film was parallel to the film surface (4) without (four) rate directionality, - 40- 200815500 nx = ny 〇 Measure the refractive index anisotropy in the direction perpendicular to the film surface, and as a result, η χ > η z, showing a negative one-axis property. That is, the obtained polyimide film has optical properties. Negative one-axis anisotropy, the optical axis is slightly perpendicular to the film surface. The refractive index of the polyimide film is parallel to the film surface η1 = 1.754, and the refractive index in the film thickness direction is η2 = 1· The birefringence system Δ η = 0.091, the color coordinate system of the transmitted light (0.3170, 0.3272), 0070, ΔytO.〇11〇, △ x, Z\y are larger than 0.005, which is a yellow colored retardation film. Comparative Example 2 ^ 10.38 g (0,096 mol) of p-phenylenediamine and 0.99 under a stream of dry nitrogen (0.004 mol) bis(3-aminopropyl)tetramethyldioxane was dissolved in 1 74.23 g of N-methyl-2-pyrrolidone. Then, 28.25 g (0.096 mol) of 3,3 was added. 4,4,-biphenyltetracarboxylic dianhydride and 40.00 g of N-methyl-2-pyrrolidone were stirred at 60 ° C for 3 hours. Further, after adding 1.18 g (0.008 mol) of phthalic anhydride After stirring at 60 ° C for 3 hours, a transparent viscous polyaminic acid solution N (polymer concentration of 16% by weight) was obtained. The viscosity of the solution N measured at 25 ° C was 664 mPa·s. The relative viscosity was 0.66 dl / g. J was produced in the same manner as in Example 1. The polyimine resin film heat-treated at 240 ° C for 30 minutes had no refractive index anisotropy in the direction parallel to the film surface, and nx = ny. The measurement was perpendicular to the film surface. The refractive index of the direction is different, and the result is nx > nz, which shows a negative one-axis property. That is, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is for the film surface system. Slightly vertical. The refractive index of the polyimide film in the direction parallel to the film surface is nl = 1.8 d, and the refractive index in the film thickness direction is η2 = 1·621. △ η = 0·189, the color coordinate system of transmitted light (0.3195, 0.3327), △ χΜ. 〇〇 95, / ^ 7 = 0.0165, △ X, Ay are larger than 0.005, is the phase difference of yellow coloring In addition, when heat treatment is carried out for -40 minutes at -41 - 200815500 270 °C, the polyimide resin is thin nl = 1.831, n2 is 1.616, so birefringence, according to coordinates (0.3206, 0.3339), Αχ^Ο.οΐοβ Aysoom is larger than 0.005 and is a yellow-colored phase difference film. Comparative Example 3 Under a dry nitrogen stream, 2 1 · 8 2 g (〇·〇9 6 mol) 4,4,-nonanilide and 0.99 g (0.004 mol) bis(3-aminopropyl)tetramethyl Solution to 137.14 g of γ-butyrolactone. Next, 97·14 g of N-, ketone was added. Then, add 28.25 g (0.096 mol) of 3,3,4,4,-acid dianhydride and 40.00 g of N-methyl-2-pyrrolidone at 6 (rC stir, add force 1.18 g After (0.00 8 mol) phthalic anhydride, a transparent viscous polyaminic acid solution 0 was obtained at 60 ° C (the viscosity of the solution measured at a polymer concentration of 16 ° C was 5,8 7 8 mPa·s. The viscosity 〇 was produced in the same manner as in Example 1. The heat-treated amine resin film at 240 ° C for 30 minutes was parallel to the film surface and had no refractive index ηX = ny. The refractive index in the direction perpendicular to the film surface was measured. Nz, showing a negative one-axis property. That is, the obtained polyimine tree has an optically negative one-axis anisotropy, and the optical axis is in a direction parallel to the film surface of the film of the bismuth imide resin film. Refractive index>, refractive index in the film thickness direction is n2 = l.610, birefringence system Δ n = color coordinate system of light (0.3260, 0.3450), ΔχΜ.ΟΙόΟ' Δ yx, Ay are larger than 0.005. When the phase difference of yellow coloring is 270 ° C for 40 minutes, the polyimide resin is thin nl = 1.838, n2 = 1.609, so the birefringence is based on The color Δ X and Δ y of the refractive index transmitted light are all diamino benzomethoxane dissolved methyl-2-pyrene mixed with biphenylene tetracarboxylate for 3 hours. Stirring for 3 hours by weight.) 25 : l. 〇 3dl / g over the 醯 醯 directionality, sex, the result nx lipid film ties: slightly vertical. Polymer η 1 = 1 · 8 2 6 〇. 2 1 6, transmission = 0.0288, Δ film. Further, in the refractive index of the film, the color-42-200815500 coordinates (0.3255, 0.3437), Λχ0.0155, Δy = 0.027 5, and Δχ and Ay are both larger than 0.005, and are yellow-colored phase difference films. Example 4 Under a dry nitrogen stream, 8 g of p-phenylenediamine was dissolved in 92.92 g of N-mercapto-2-pyrrolidone. Then, 22.42 g (〇) was added. 1〇〇Moel) 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 4 〇·〇〇克 N _methyl-2 _pyrrolidone' were stirred at 60 ° C for 4 hours to obtain transparency Viscous poly-proline solution p (polymer concentration 20% by weight). 25. (: The viscosity of the measured solution P is 550 mPa·s "" Relative viscosity system 3. 3 0 d 1 / g Same as in the first embodiment Direction produced, 2 4 0 ° c 3 0 minutes heat treated Juxi imine resin film of the film surface is not parallel to the lines with anisotropic refractive index, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, η χ > η ζ showed a negative one-axis property. Namely, the obtained polyimide film has an optically negative one-axis anisotropy, and the optical axis is substantially perpendicular to the film surface. The refractive index of the polyimide-based resin film in a direction parallel to the film surface is n丨=丨·6 〇〇, the refractive index in the film thickness direction is n2 = 1.5 9 8, and the birefringence system Δ n = 0.002, transmission\ The color coordinate system (0.3111, 0.3173), ΛπΟ.0011, Δywjon, ΔX, and Δy are all 0.003 or less, and are retardation films which are not colored, but the birefringence system is insufficient. Comparative Example 5 Under a dry nitrogen stream, 22.73 g (0.100 mol) of 4,4,-diaminobenzidine was dissolved in 90.29 g of γ-butyrolactone. Next, 5 〇. 29 g of N-methyl-2-indolepyrrolidine was added. Then, 22.42 g (〇1〇〇莫耳)丨, 2,4,5-cyclohexanetetracarboxylic dianhydride and 40.00 g of Νmethyl-2-pyrrolidone were added at 6 (Γ( : Stirring for 4 hours, obtaining a transparent viscous polyaminic acid solution q (polymer concentration: 2 〇 weight. /.) -43- 200815500 The viscosity of the solution measured at 25 ° C is 209 mPa·s. Relative viscosity system 〇 .24 dl / g 〇 was produced in the same manner as in Example 1. The direction of the parallel direction of the film surface of the polyimide film which was heat-treated at 270 ° C for 30 minutes was not refractive index anisotropy, nx = ny. The refractive index anisotropy in the direction perpendicular to the film surface was measured, and as a result, nx > nz showed a negative one-axis property. That is, the obtained polyimine resin film had optically negative one-axis anisotropy, light. The axis is substantially perpendicular to the film surface. The refractive index of the polyimide film in the direction parallel to the film surface is nl = 1.63 8 , and the refractive index in the film thickness direction is η2 = 1·63 2 , and the birefringence system △ η = 〇·006, transmission: . The color coordinate system of light (0.3114, 0.3178), △xW.0014, AyW.〇〇16, △ x, △ y are all 〇. 〇〇3 or less No coloration of the retardation film, the birefringence is not sufficient, but Example 13 The following shows the method of manufacturing a color filter with a retardation film. <Preparation of black matrix> In a solvent of γ-butyrolactone (3825 g), pyromellitic anhydride (149.6 g), di V / benzophenone tetracarboxylic dianhydride (22 5.5 g), 3, 3,-Diaminodiphenylphosphonium (69.5 g), 4,4'-diaminodiphenyl ether (2 10.2 g), bis(3-aminopropyl)tetramethyldioxane (1 7 · 4 g) After reacting at 60 ° C for 3 hours, maleic anhydride (2 · 25 g) was added, and then reacted at 60 ° C for 1 hour to obtain a polyaminic acid solution (polymer concentration of 15 weight) %) using a homomixer, at 730 rpm for 30 minutes, 7.3 grams of carbon black (MA-77 made by Mitsubishi Chemical), 44.8 grams of polyglycine with a polymer concentration of 15% by weight Solution, 35 g of N-methyl-2-pyrrolidone, 1 2 · 9 g of 3-methyl-3-methoxyacetate together with 1 g of glass beads, as a dispersion treatment, filtered to remove -44- 200815500 Glass beads, a pigment dispersion having a pigment concentration of 14% by weight was obtained. The primary particle size of the carbon black used was 23 nm. At this time, the weight ratio of the carbon black/polyamido acid compound was 52/48. To 57.2 g of the pigment dispersion, 36.4 g of N-methyl-2-pyrrolidone and 6.4 g of 3-methoxy-3-methyl-butyl acetate were added and mixed to prepare a black paste. After the paste was applied onto an alkali-free glass substrate, it was prebaked at 130 ° C to form a black colored film. Next, a positive resist was applied and dried by heating at 90 ° C to form a photoresist film. It is exposed through a reticle using an ultraviolet exposure machine. After exposure and light, it was immersed in an alkali developing solution, and at the same time, development of a resist and etching of a polyamic acid black colored film were performed to form an opening. After etching, the unnecessary photoresist layer is stripped by ethylene glycol monomethyl acetate, and the etched polyphthalic acid black colored film is heated to 290 ° C for thermal hardening to form a polyimide resin black. matrix. <Preparation of pixels> In γ-butyrolactone, pyromellitic anhydride (0.49 molar equivalent), benzophenone tetracarboxylic dianhydride (0.50 molar equivalent), and 4,4'- Diaminodiphenyl ether (0.75 mole equivalent), 3,3'-diaminodiphenyl hydrazine (〇.20 mole equivalent), bis-(3-aminopropyl)tetramethyldioxime The alkane (0.05 molar equivalent) was reacted with maleic anhydride (0.02 mole equivalent) to give a polyaminic acid solution (polymer concentration 20% by weight). 200 g of this polylysine solution was taken out, and 136 g of γ-butyrolactone and 64 g of ethylene glycol butyl ether were added thereto to obtain a polyphosphoric acid solution for a pixel having a polymer concentration of 1% by weight. Using a homomixer, 4 grams of Pigment Red 177 (blush), 40 grams of gamma-butyrolactone, 6 grams of ethylene glycol butyl ether, and 1 gram of glass beads at 70 rpm for 30 minutes After the dispersion treatment, the glass beads were removed by filtration to obtain a pigment dispersion having a pigment concentration of 8% by weight. -45- 200815500 Into 30 g of the pigment dispersion liquid was added and mixed with 3 g of the above-mentioned polymer concentration of 10% by weight of a polyglycine solution to obtain a red color paste. On the substrate on which the resin black matrix was formed, a red paste was applied and pre-baked to form a polyphthalamide red colored film. Using a photoresist, red pixels were formed by the same means as described above, and heated to 290 ° C for thermal hardening. Using a homomixer, 3.6 g of Pigment Green 7 (cyanine green), 0.4 g of Pigment Yellow 83 (benzidine yellow), 32 g of γ-butyrolactone, 4 g of ethylene glycol butyl at 700 O rpm for 30 minutes The base ether was mixed with 120 g of glass beads, and after dispersion treatment, the glass beads were removed by filtration through f to obtain a pigment dispersion having a pigment concentration of 10% by weight. To 32 g of the pigment dispersion liquid, 30 g of a polyphosphonic acid solution of the above-mentioned polymer having a concentration of 10% by weight of the above polymer was added and mixed to obtain a green color paste. In the same manner as in the case of using a red paste, a green color paste was used to form a green color, and it was heated to 290 ° C to be thermally cured. Using a homomixer, 60 g of the above polymer concentration of 1 〇% by weight of the poly-proline solution, 2.8 g of Pigment Blue-1 5 (cyanine blue) at 7 rpm for 30 minutes ), 30 g of N-methyl-2-pyrrolidone, 10 g of ethylene glycol butyl ether and ν / 150 g glass beads, after dispersion treatment, the glass beads are removed by filtration to obtain blue Colored paste. The blue color paste was used to form a blue pixel by the same procedure as described above, and it was heated to 290 ° C to be thermally hardened. This was done to make a color filter. Next, 187.5 g of the polyamic acid solution A (polymer concentration: 16% by weight) prepared in Example 1 was added with 0.25 g of a surfactant "Disparlon" LC95 1 (manufactured by Nanben Chemical Co., Ltd.), and 218.3 g of N-methyl- 2-Pyrrolidone, 94.0 g of 3-methoxy-3-methyl-1-butanol' was prepared to prepare a solution of -46-200815500 having a polymer concentration of 6% by weight. The surface of the color filter substrate on which the pixel is formed is coated by a slit die coating method, dried at 1 20 ° C for 1 minute, and then heat treated at 270 ° C for 40 minutes. And a polyimide film having a film thickness of 1.2 μm was formed on the color filter. The birefringent film of the polyimine film has Δ η = 0.174; therefore, by the above method, a phase difference of optically negative refractive index anisotropy with a hysteresis 値 of 209 nm and an optical axis perpendicular to the film can be obtained. Thin film color filter. Example 1 4 A polyimine film was formed on a color filter in the same manner as in Example 13 except that the polyamic acid solution F (polymer concentration of 16 (% by weight)) produced in Example 6 was used. The polyimide film has a film thickness of 4.4 μm and a birefringence system Δ η = 0.045; therefore, a retardation 値 is 198 nm, and an optical negative refractive index is perpendicular to the film. Film color filter. Example 1 5 For 20 0.0 g of the polylysine solution K (polymer concentration 15% by weight) prepared in Example 11, 0.25 g of a surfactant "Dispar Ion" LC 951 (Nanben) was added. 205.8 g of N-methyl-2-pyrrolidone and 94.0 g of 3-methoxy-3-kut-methyl-1-butanol were prepared to prepare a coating solution having a polymer concentration of 6 wt%. In the same manner as in Example 13, the surface on which the pixel on the color filter substrate was formed was applied by a slit die coating method, and dried at 1 20 ° C for 1 minute, at 2 40 °. C was subjected to a heat treatment for 30 minutes, and a polyimide film having a film thickness of 4.0 μm was formed on the color filter. Department birefringence △ η = 0 · 051; thus, the color filter can be obtained as the hysteresis Zhi 204nm, having an optical axis perpendicular to a negative form of a film with anisotropic refractive index of the retardation film of Example 16. <Production and Evaluation of Color Liquid Crystal Display Element> -47-200815500 A transparent electrode made of indium oxide was formed on the phase difference film-attached color filter produced in Example 13. On the other hand, a substrate on which a TFT element, a pixel electrode, a reflector, or the like is formed on an alkali-free glass is prepared as a counter substrate. Then, on the transparent electrode of each substrate, a strip-like protrusion formed of polyimine was formed by a lithography method, and then a vertical alignment film was provided. The protrusion has a trapezoidal cross section and a height of about 1. 5 μm. However, when the color filter substrate is bonded to the TFT substrate, the position of the strip-like projections is fixed such that the strip-shaped projections and the opposing strip-like projections are alternately arranged. After coating the ends of the two substrates with a sealant and bonding them, < The n-type liquid crystal is sealed between the unit cells and sealed, and the polarizing plate is disposed so as to cross the Nicols before and after the unit cell. In this way, a test liquid crystal display (sample A) of the simulation ΜV Α (multi-domain vertical alignment) method was produced. The electrode spacing of the unit cell is about 5 μm by the bead spacer. Further, a test liquid crystal display element (sample B) was produced as a comparative product, and the difference was that the polyimide film retardation film was not provided. The transmission angle of 5 volts (on) and 0 volts (off) is applied in the azimuth angle of the 90° direction of the strip direction of the protrusion and the polar angle of 70° in the normal direction of the unit cell surface. The light intensity ratio (comparative), for the comparison of sample B, is 8.3, and the product A is 18. The contrast effect of the polyimine retardation film is observed. Further, in Sample A, a good white display without yellow tone was obtained. [Example 1] A color filter having a retardation film produced in Example 14 was used in the same manner as in Example 16 to prepare a test liquid crystal display device (Sample C). The transmitted light intensity ratio (comparative) of sample C was 18.8, and the contrast effect of the polyimine retardation film was observed. Also, a good white display without yellow tone is obtained. [Example 1] A color filter having a retardation film produced in Example 15 was used in the same manner as in Example-48-200815500 Example 16 to prepare a test liquid crystal display device (Sample D). The transmitted light intensity ratio (contrast) of sample D was 18.8, and the contrast effect of the polyimine retardation film was observed. Also, a good white display without yellow tone is obtained. Comparative Example 6 A polyimide film was formed on a color filter in the same manner as in Example 13 except that the polyaminic acid solution 0 (polymer concentration: 16% by weight) produced in Comparative Example 3 was used. The film thickness of the polyimide film is 〇·9μηι, birefringence Δ n = 0.229, so the hysteresis 値 is 20 6 nm, and the phase difference of the optically negative f, the refractive index anisotropy perpendicular to the film is obtained. Thin film color filter. (1) Using the prepared color filter having a retardation film, the same procedure as in Example 16 was carried out to prepare a test liquid crystal display (sample E). The transmitted light intensity ratio (comparative) of sample E was 15 . However, the white display has a yellow hue and the image shows a poor quality. Table 1 shows the results of Examples 1 to 12 and Comparative Examples 1 to 5. As described in Table 1, it was confirmed that Examples 1 to 2 were less colored, and a retardation film having good birefringence was obtained. Further, in Table 1, each abbreviation symbol indicates the following C / compound. BPDA : 3,3',4,4'-biphenyltetracarboxylic dianhydride CBDA : 1,2,3,4-cyclobutane tetracarboxylic dianhydride H-PMDA: 1,2,4,5- Cyclohexane tetracarboxylic acid dianhydride ODPA : 4,4'-oxydicarboxylic acid dianhydride PMDA : pyromellitic anhydride PA : phthalic anhydride DABA: 4,4'-diaminobenzimidamide t-DACH: anti Formula -1,4-diaminocyclohexane-49- 200815500 DDE: 4,4'-diaminodiphenyl ether DDS: 3,3'-diaminodiphenylfluorene PDA: p-phenylenediamine

SiDA ··bis-(3-aminopropyl)tetramethyldioxanane m-TB-HG: 2,2,-dimethylbenzidine TFMB: 2,2'-bis(trifluoromethyl) linkage苯胺-50- 200815500 [I嗽] Coloring >>< 0.0010 0.0017 0.0012 0.0009 0.0018 0.0025 0.0028 0.0011 0.0035 0.0018 0.0050 0.0018 0.0048 0.0002 0.0009 X <1 0.0008 0.0016 0.0011 0.0009 0.0016 0.0020 1 1 0.0022 1_ 0.0009 °·0027 ; 0.0015 0.0042 0.0014 1 0.0034 l ! 0.0003 0·_ Birefringence a < 0.091 0.174 0.112 0.114 0.163 0.174 0.015 0.035 0.045 0.065 0.087 0.038 0.039 0.020 0.018 Hardening temperature 240〇C 270〇C 270〇C 240〇C 270〇C 270〇 C 270〇C 240〇C 270〇C 240〇C 270〇C 240〇C 270〇C 240〇C 270〇C End Sealant (Molar%) PA(8) PA(8) 1 1 1 PA( 8) PA(8) PA(8) PA(8) Diamine (mol%) t-DACH(96) SiDA(4) t-DACH(96) SiDA(4) 1 _ . t-DACH(96) SiDA(4) t-DACH(lOO) t-DACH(lOO) PDA(96) SiDA(4) DABA(96) | SiDA(4) —__________________1 m-TB-HG(96) SiDA(4) 1 TFMB( 96) SiDA(4) acid dianhydride (% by mole) BPDA(96) BPDA(86) PMDA(10) BPDA(96) BPDA(IOO ODPA (96) CBDA (96) CBDA (96) CBDA (96) 丨 | 1 CBDA (96) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 •Ις丨200815500 0.0016 0.0035 0.0020 0.0042 0.0110 0.0165 0.0177 ” 0.0288 1 0.0275 0.0011 0.0016 0.0011 0.0027 0.0016 0.0031 0.0070 0.0095 0.0106 0.0160 0.0155 I | 0.0011 1_ '0.0014 0.013 0.015 0.051 0.087 ; 0.091 0.189 0.215 0.216 0.229 0.002 0.006 240〇C 270〇 C 240〇C 240〇C 270〇C 240〇C 270〇C 240〇C 270〇C 240〇C 240〇C PA(8) 1 1 PA(8) 1 1 PA(8) PA(8) 1 1 DDE(96) SiDA(4) PDA(IOO) DABA(IOO) 孑 inch inch w Q q 〇y Q Ph ^ PDA(96) SiDA(4) DABA(96) SiDA(4) PDA(IOO) DABA(IOO) CBDA (96) CBDA (IOO) CBDA (IOO) BPDA (96) BPDA (96) BPDA (96) H-PMDA (IOO) H-PMDA (IOO) Example 10 Example 11 Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 丨 (Νς丨200815500 [A brief description of the figure Μ. y \ \ν [Component symbol description Μ . j\ \\

Claims (1)

200815500 X. Patent Application Range 1. A resin composition for forming a phase difference film for forming a liquid crystal display device having an optically negative one-axis anisotropy, an optical axis being substantially perpendicular to a film surface, and a thickness direction a retardation film having a birefringence Δη of 0.01 to 0.3, wherein the resin composition comprises a polyimide precursor obtained by reacting at least one type of tetracarboxylic dianhydride with at least one type of diamine, and an organic solvent. At least one of the at least one of the tetracarboxylic dianhydride and the at least one of the diamines is an alicyclic compound. 2. The composition of claim 1, wherein the diamine of the alicyclic compound is represented by the following formula (1) (wherein R1 represents a monovalent organic group or a hydrogen atom) represents a trans-1,4-diaminocyclohexane compound. 3. The composition of claim 2, wherein the tetracarboxylic dianhydride is the following formula (2) The 3,3',4,4'-biphenyltetracarboxylic dianhydride compound represented by the formula (H2 and R3 each independently represent a monovalent organic group or a hydrogen atom). 4. The composition of claim 3, wherein the polyimine precursor has at least a constituent unit represented by the following formula (3), -54- 200815500 (wherein R1, R2, R3, R4 and R5 each independently represent a monovalent organic group or a hydrogen atom). 5. The composition of claim 1, wherein the tetracarboxylic dianhydride of the alicyclic compound is 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 6. The composition of claim 5, wherein the diamine is an aromatic diamine having a rigid molecular structure. 7. The composition of claim 6, wherein the aromatic diamine having a rigid molecular structure is at least one selected from the group consisting of p-phenylenediamine and 4,4'-diaminobenzimidamide. 8. A resin composition comprising R1 having the following general formula (1) (wherein R1 represents a monovalent organic group or a hydrogen atom) represents a diamine component containing a trans-1,4-diaminocyclohexane compound, and is represented by the following formula (2) 0 〇 II II (wherein R2 and R3 each independently represent a monovalent organic group or a hydrogen atom), and the tetracarboxylic dianhydride component of the 3,3',4,4,-biphenyltetracarboxylic dianhydride compound The polyglycolic acid compound and the organic solvent obtained by the reaction are used in a liquid crystal display device, a phase difference film having an optically negative one-axis anisotropy, and an optical axis which is substantially perpendicular to the film surface, in the form of -55-200815500. 9. The composition of claim 8, wherein the polyamic acid compound has at least a constituent unit represented by the following formula (3). (wherein R1, R2, R3, R4 and R5 each independently represent a monovalent organic group or a hydrogen atom). 10. The composition of claim 9, wherein the R1 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R2, R3, R4 and R5 are a hydrogen atom. The composition of claim 9 or claim 1, wherein the polyproline compound further contains at least a group selected from the group consisting of structural units represented by the following general formulae (4) to (8); 1 structural unit, -56 - 200815500 (In the formulae (4), (5), (6), (7) and (8), R1, R2, R3, R4 and R5 each independently represent a monovalent organic group or a hydrogen atom). (' I2. The composition of claim 10, wherein in the formulas (4), (5), (6), (7) and (8), the above-mentioned Ri hydrogen atom or carbon number! ~ 4 a linear or branched alkyl group 'R2, R3, R4 and R5 are a hydrogen atom. 1 3. A composition according to claim 11 or 12, wherein the formula (3), (4) The total content of the structural unit represented by (5) '(6), (7) or (8) is 50% by mole or more of all the structural units constituting the above polyamic acid. The resin composition according to any one of items 1 to 3, wherein the polyethylenimine precursor or one of the amine terminal groups of the polylysine is a part or all of a guanamine with a dicarboxylic anhydride The acid forming reaction is capped. The composition of claim 14 wherein the above dicarboxylic anhydride is selected from maleic anhydride, phthalic anhydride, succinic anhydride, and nadic anhydride. A composition according to any one of claims 1 to 5, which is used for producing a resin composition for forming a retardation film. A color filter substrate for a display device, which is a color filter substrate for a liquid crystal display device having red, blue, and green color pixels arranged in a second order on a transparent substrate, wherein a color filter substrate is formed as described in the patent application. The retardation film formed by the resin composition for a retardation film according to any one of the first to fifth aspects of the present invention, wherein the retardation film comprises a The following general formula (8) 50 O r1 of 50 mol% or more (wherein, R1, R2 and R3 each independently represent a monovalent organic group or a hydrogen atom) structural unit polyimine. The color filter substrate according to claim 18, wherein the R1 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R2 and R3 are hydrogen atoms. The color filter substrate for a liquid crystal display device according to any one of claims 17 to 19, which is formed by coating a pixel with a retardation film formed of a resin composition for a retardation film. A liquid crystal display device using a color filter substrate for a liquid crystal display device according to any one of claims 17 to 20, wherein the display mode of the liquid crystal display device is no applied voltage At this time, the liquid crystal molecules are aligned in a direction perpendicular to the cell surface of the liquid crystal, and when a voltage is applied, the liquid crystal molecules are in a liquid crystal display mode in which the liquid crystal cell faces are aligned substantially in a direction parallel to each other. 2-2. A method for producing a color filter substrate for a liquid crystal display device with a retardation film, which comprises a resin for a phase-58-200815500 dislocation film according to any one of claims 1 to 15. The composition is applied to a side of the side of the transparent substrate on which the pixels of the color filter substrates of the red, blue, and green pixels of the second-order array are arranged, and heat-treated. -59 - 200815500 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 八 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: