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    • 专利摘要:
    There is provided a polyimide optical member for optical use which is excellent in physical properties inherent to polyimide, that is, heat resistance, mechanical properties, electrical properties, thermal oxidation stability, chemical resistance, transparency and high refractive index. The invention is based on the premise that a specific diamine compound and a tetracarboxylic acid dianhydride are used, and a compound represented by the general formula (1) Wherein X represents a direct bond, -O-, -SO 2 -, or -C (CF 3 ) 2 , wherein A is a group represented by the general formula (2), (3) Display. In the general formula (2), R 1 and R 2 represent H, Cl, Br, CH 3 or CF 3 . In the general formula (3), A 1 represents -O-, -S-, -CO-, -CH 2 -, -SO 2 -, C (CH 3 ) 2 or -C (CF 3 ) 2 . In the general formula (4), A 2 represents a direct bond, -O-, -S-, -CO-, -SO 2 -, C (CH 3 ) 2 or -C (CF 3 ) 2 . Is an optical member made of polyimide having a repeating unit structure.
    公开号:KR20020044160A
    申请号:KR1020027004566
    申请日:2001-08-08
    公开日:2002-06-14
    发明作者:오노다카시；오카와유이치；타마이쇼지；사카타요시히로
    申请人:사토 아키오；미쯔이카가쿠 가부시기가이샤；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an optical member made of a polyimide resin,
    [2] Conventionally, various inorganic glasses have been used as optical lens materials. With the spread of the glasses, a glass lens for spectacle glasses having a high refractive index has been developed from the requirement of a lighter and thinner lens. However, since the glass lens is heavy and fragile, a lighter, more durable lens is required.
    [3] On the other hand, since the plastic optical member is light, durable, and easy to mold and can be mass-produced, the demand for various optical members is increasing. As the plastic optical member, a transparent resin such as a poly (methyl methacrylate) resin, a polystyrene resin, or a polycarbonate resin is used.
    [4] BACKGROUND ART Plastics optical materials are expected to be applied not only to spectacle lenses, but also to microlenses, coating materials of optical devices, matching materials for optical fibers, and core materials in the optical information communication field expected to be developed in the future, liquid crystal projectors and the like. At that time, there are many processes requiring heat resistance of 150 deg. C or higher at the time of processing. However, since transparency resins such as poly (methyl methacrylate) resin, polystyrene resin, and polycarbonate resin have a glass transition temperature (Tg) of 100 DEG C or less and deteriorate in heat resistance, Lt; / RTI >
    [5] Polyimide is conventionally known as a high heat-resistant engineering plastic. However, the conventional polyimide has good heat resistance and high refractive index, but is colored yellow or brown, and has a large birefringence. For example, polyimide shown in JP-A-8-504967 is used as an optical member, but its birefringence is 0.01 level at the minimum, so that it can not be a sufficiently small value. Also, according to page 300 of "PHOTOSENSITIVE POLYIMIDE-Fundamentals and Applications" (edited by KAZUYUKI HORIE and TAKASHI YAMASHITA, TECHNOMIC PUBLISHING COMP., 1995), a commercially available polyimide has a birefringence of 0.1 or more and a specific fluorinated polyimide level of 0.01 to be. Thus, although the heat resistance is greatly improved, there is a problem that the range of use as an optical lens such as a lens and a microlens is largely limited.
    [6] 2. Description of the Related Art In recent years, microlenses have been used in many optical devices for the purpose of increasing the utilization efficiency of light, and projection liquid crystal projection devices and the like are known.
    [7] 2. Description of the Related Art Conventionally, there are a direct type screen CRT, a projection type CRT projector, a projection type liquid crystal projection device, and the like, which are widely used in presentations and public waiting rooms. However, the use of a CRT among these is not good in image quality because the display is dark and the contrast is insufficient in a bright place. Further, in the projection-type liquid crystal projection apparatus, a bright light source is used to solve these problems, but a light shielding portion for shielding the light of the light source lamp, for example, between the pixels of each pixel for displaying an image and the TFT portion for operating the liquid crystal is provided. The light of the light source has not sufficiently been utilized because of the light loss of the light shielding portion.
    [8] Therefore, a microlens designed to effectively utilize the light cut by the light-shielding portion or the like for the purpose of increasing the utilization efficiency of light. This microlens is disposed corresponding to each pixel of the liquid crystal, thereby greatly improving the utilization efficiency of light. As the microlens, a lens part made of glass has already been used on the market. However, the following problems have been pointed out in using this glass microlens.
    [9] When manufacturing a microlens-added liquid crystal panel, as described in Japanese Patent Application Laid-Open No. 11-24059, in order to prevent gap defects and leveling defects between opposing substrates and to improve liquid crystal display quality, Needs to be. As a method of planarization, a method of coating a surface of a micro lens or a method of attaching a cover glass by an adhesive is performed. However, in the method of attaching the cover glass, reflection of light occurs on the surface of the cover glass and light loss occurs. Therefore, a method of coating is preferable.
    [10] In order to use the glass as a microlens, the coating must be made of a material having a lower refractive index than glass. The glass acts as a lens due to the difference in refractive index between the microlens of this glass and the coating material. Examples of the coating material include generally high transparency resins such as poly (methyl methacrylate) (PMMA), polystyrene (PS), polycarbonate (PC) and the like, and low refractive index overcoat materials. The glass for lenses usually has a refractive index of about 1.54 to 1.62. On the other hand, since the refractive index of the transparent resin is 1.49, the PS is 1.59, and the PC is 1.58, the refractive index difference from the glass is small, so that the performance as a lens can not be fully utilized. The low refractive index resin for overcoat has a problem that the glass transition temperature of the resin having a low heat resistance and a high transparency is 150 DEG C or lower so that it can not withstand the temperature exposed when the liquid crystal panel is assembled or adhered on the micro lens substrate .
    [11] On the other hand, it is also possible to use a resin as a lens by using a glass as a low refractive index material and a resin as a high refractive index material.
    [12] Various methods of using a resin microlens have been proposed. However, as disclosed in Japanese Patent Application Laid-Open No. 6-194502, a thermal deformation method is practically used. The thermal deformation method is a method in which a film of a thermoplastic photosensitive material is formed on a substrate and is patterned in accordance with the shape of a microlens and a pattern corresponding to the arrangement state of the microlenses and the film of the photosensitive material is thermally deformed, A refracting surface is formed by using a deformation temperature and a surface tension, and then this is solidified to manufacture a microlens.
    [13] In this method, since the heat distortion temperature of the lens itself is low, the use of a high-energy light flux can not be used for high-energy light because the lens itself is softened by the temperature rise of the lens. Further, in this method, it is difficult to manufacture microlenses which are preferable in terms of effective utilization of light and are connected to each other.
    [14] As a resin having high heat resistance, polyimide is known. As a colorless and high-transparency polyimide, JP-A-61-14173, JP-A-62-13436, JP-A-62-57421, Open No. 63-170420 and the like. The polyimide is generally colored in brown or yellow and is difficult to use as an optical material. However, as can be seen from the above patent publications, it is suggested that colorless transparency is improved by using a specific structure.
    [15] When polyimide has a high refractive index and the coloration is reduced, it is possible to use the polyimide as a lens for use in Japanese Patent Application Laid-Open Nos. 63-226359, 63-252159, 1-313058, -155868, 6-190942, and the like. However, they are all used for spectacle lenses or guide lenses and not for microlens applications. In addition, the microlens is significantly different from the spectacle lens and the guide lens in the size of the lens and the method of using it.
    [16] The polyimide in the above patent is a fluorine-containing polyimide and has a low resistance to an organic solvent. When polyimide is used as a microlens or the like, there is a problem in chemical resistance to various medicines used for medicines such as etching solution, plating solution, photoresist solution and the like.
    [17] As another optical member, there is an optical filter. As a method for forming a colored layer of a color filter used in a liquid crystal display element, a dyeing method, a pigment dispersion method, an electrodeposition method, a printing method, and the like are known. Of these, organic and inorganic pigments are used as coloring agents for the pigment dispersion method, and polyimide, PVA, acrylic, epoxy and the like are used as the resin. Among them, it is known that the polyimide resin has a high heat resistance and reliability and therefore is less discolored in the step of forming the transparent electrode and in the step of heating the alignment film, and is useful as a color filter (Japanese Patent Application Laid-Open No. 60-184202, -184203). However, the polyimide for an optical filter having excellent transparency may have a problem in solvent resistance like a microlens.
    [18] In addition, there is an intraocular lens as one of optical members. Intraocular lens, so-called guide lens implantation, has been performed as a method of visual recovery for patients who have undergone uncorrected vision after cataract extraction.
    [19] Natural light includes wavelengths in the ultraviolet, visible and infrared regions, and the large amount of ultraviolet light transmitted through the guide can cause damage to the retina. Since the lens in the eye absorbs the ultraviolet rays preferentially and protects the retina, there is a case where the transmission of ultraviolet rays is a big problem in the anhydrous state as described above. Therefore, it is desired that the guide lens absorbs ultraviolet rays in a wavelength range of 200 to 380 nm and is transparent to visible light in a wavelength range of 380 to 780 nm. In addition, since the guide lens puts a heavy burden on the heavy lens, it is required to have a large specific gravity as its material and a large refractive index so as to reduce the lens thickness.
    [20] SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide film which has inherent physical properties such as heat resistance, mechanical properties, sliding characteristics, low absorptivity, electrical properties, thermal oxidation stability, chemical resistance and radiation resistance, And an optical member having a high heat resistance such as a lens of polyimide which is remarkably improved. Another object of the present invention is to solve the problem that the refractive index difference from the coating material of the conventional glass microlens is small, and to solve the problem of heat resistance without deformation due to high energy light And to provide an excellent colorless transparent polyimide microlens.
    [21] (Disclosure of the Invention)
    [22] The inventors of the present invention have conducted intensive investigations in order to achieve the above object. As a result, it has been found that polyimides obtained from specific aromatic diamines and tetracarboxylic dianhydrides exhibit excellent transparency, low refractive index and high refractive index And can be used as an excellent optical member, thereby completing the present invention.
    [23] That is,
    [24] (a) An optical member obtained by using a polyimide resin containing a repeating structural unit represented by the general formula (1) as an essential component.
    [25] Wherein A represents a general formula (2), (3) or (4), X represents a direct bond, -O-, -SO 2 - or -C (CF 3 ) 2 - Display.
    [26] In the general formula (2), A 1 represents a direct bond, -O-, -S-, -SO 2 -, -CO-, -C (CH 3 ) 2 - or -C (CF 3 ) 2 - . In the general formula (2), R 1 and R 2 each represent H, Cl, Br, CH 3 or CF 3 .
    [27] In the general formula (3), R 3 , R 4 and R 5 each represent H, Cl, Br, CN, CH 3 or CF 3 .
    [28] In the general formula (4), A 2 represents a direct bond, -O-, -S-, -SO 2 -, -CO-, -C (CH 3 ) 2 - or -C (CF 3 ) 2 - . In the general formula (4), R 6 and R 7 represent H or CF 3 .
    [29] (b) a polyimide resin in which the terminal of the polyimide represented by the general formula (1) described in (a) is encapsulated by a structure represented by the following general formula (5) or (6) (A).
    [30] [In the formula (5), Ar 1 represents one species selected from the group of the formula (I), and Y represents one species selected from the group of the formula (II). In the general formula (6), Ar 2 represents one species selected from the group of the formula (III), and Z represents one species selected from the group of the (IV).
    [31] (c) a polyimide resin in which the terminal of the polyimide represented by the general formula (1) described in (a) is encapsulated by a structure capable of introducing a crosslinked structure represented by the following general formula (7) or (8) The optical member as described in (a), further comprising:
    [32] In the general formula (7), Ar 3 represents one kind selected from the group of the formula (V), and in the formula (V), R 8 to R 13 each represent H, F, CF 3, CH 3 , C 2 H 5 or a phenyl group, and they may be the same or different.
    [33] In the general formula (8), Ar 4 represents one species selected from the group of the formula (VI).
    [34] (d) The optical member according to any one of (a) to (c), wherein the optical member is a micro lens.
    [35] (e) The optical member according to (c), wherein the optical member is any one of an optical lens, an information lens, and a microlens.
    [36] (5) An optical member obtained by using a polyimide resin having a repeating structural unit represented by the general formula (9) as an essential component.
    [37] In the general formula (9), A represents a general formula (10), (11) or (12), and X represents a direct bond -O-, -SO 2 - or -C (CF 3 ) 2 - do.
    [38] In the general formula (10), A 1 represents a direct bond -O-, -S-, -SO 2 -, -CO-, -C (CH 3 ) 2 - or -C (CF 3 ) 2 -. In the general formula (10), R 1 and R 2 represent Cl, Br, CH 3 or CF 3 , respectively.
    [39] R 3 , R 4 and R 5 each represent H, Cl, Br, CN, CH 3 or CF 3 , and at least one of R 3 , R 4 and R 5 represents a group other than H Display.
    [40] In the general formula (12), A 2 represents a direct bond -O-, -S-, -SO 2 -, -CO-, -C (CH 3 ) 2 - or -C (CF 3 ) 2 -. In the general formula (12), R 6 and R 7 represent CF 3 .
    [41] (g) The optical member as described in (f), wherein the optical member is any one of an optical lens, a microlens, an information lens, or an optical filter.
    [42] (h) an optical lens obtained by using a polyimide resin having the structure described in (b) and / or (c) and at least one of R 3 , R 4 and R 5 being a group other than H, An optical member selected from the group of lenses or optical filters.
    [1] The present invention relates to optical members such as optical lenses, guide lenses, microlenses, and optical filters obtained using polyimide resins. The optical member such as a lens or a microlens using the polyimide of the present invention has excellent physical properties inherent to polyimide such as heat resistance, mechanical characteristics, electrical characteristics, thermal oxidation stability, chemical resistance and radiation resistance, And has transparency, low birefringence, and high refractive index required as optical members.
    [43] In the present invention, it has been found that the polyimide represented by the general formula (1) is suitable for optical members such as optical lenses, guide lenses, microlenses and optical filters.
    [44] The polyimide represented by the above general formula (1) is a polyimide represented by the general formulas (13), (14), (15)
    [45] [In the general formula (13), A 1 represents -O-, -S-, -SO 2 -, -CO-, -C (CH 3 ) 2 - or -C (CF 3 ) 2 -. In the general formula (13), R 1 and R 2 each represent H, Cl, Br, CH 3 or CF 3 . Preferably, at least one of R 1 and R 2 represents a group other than H.
    [46] In the general formula (14), R 3 , R 4 and R 5 each represent H, Cl, Br, CN, CH 3 or CF 3 . Preferably, at least one of R 3 , R 4 and R 5 represents a group other than H in the general formula (14).
    [47] In the general formula (15), A 2 represents a direct bond -O-, -S-, -SO 2 -, -CO-, -C (CH 3 ) 2 - or -C (CF 3 ) 2 -. In the general formula (15), R 6 and R 7 represent H or CF 3 , preferably CF 3 , and a diamine component represented by the general formula (16)
    [48] [Wherein X represents a direct bond -O-, -SO 2 -, or -C (CF 3 ) 2 -].
    [49] Is subjected to a dehydration condensation reaction in a solvent to obtain a tetracarboxylic dianhydride.
    [50] [Diamine]
    [51] The diamine component used for producing the polyimide resin of the present invention will be described.
    [52] Specific examples of the diamine represented by the general formula (13) are as follows.
    [53] (1-1) A 1 is a direct bond
    [54] 4, 4 ' - Diamino-2, 2 ' - dichlorobiphenyl,
    [55] 4, 4 ' - Diamino-2, 2 ' - dichlorobiphenyl,
    [56] 4, 4 ' - Diamino-2, 2 ' - dicyanobiphenyl,
    [57] 4, 4 ' - Diamino-2, 2 ' - dimethyl biphenyl,
    [58] 4, 4 ' - Diamino-3, 3 ' - dimethyl biphenyl,
    [59] 4, 4 ' - Diamino-2, 2 ' - ditrifluoromethylbiphenyl;
    [60] (1-2) A 1 is -O-;
    [61] 4, 4 '-diaminodiphenyl ether,
    [62] 3, 4 '-diaminodiphenyl ether,
    [63] 3, 3 '-diaminodiphenyl ether,
    [64] 4, 4 '-diamino-2-trifluoromethyldiphenyl ether,
    [65] 4, 4'-diamino-3-trifluoromethyldiphenyl ether,
    [66] 4, 4'-diamino-2, 2 ' - ditrifluoromethyl diphenyl ether,
    [67] 4, 4'-diamino-2,3 ' - ditrifluoromethyl diphenyl ether,
    [68] 4, 4'-diamino-3,3 ' - ditrifluoromethyl diphenyl ether,
    [69] 3, 4 '-diamino-5-trifluoromethyldiphenyl ether,
    [70] 3, 4 ' -diamino-2 ' - trifluoromethyldiphenyl ether,
    [71] 3, 4 ' -diamino-3 ' - trifluoromethyldiphenyl ether,
    [72] 3, 4 '-diamino-5, 2' - ditrifluoromethyl diphenyl ether,
    [73] 3, 4 '-diamino-5,3' - ditrifluoromethyl diphenyl ether,
    [74] 3, 3 ' -diamino-5 - trifluoromethyldiphenyl ether,
    [75] 3, 3 '-diamino-5, 5' - ditrifluoromethyl diphenyl ether,
    [76] 4, 4 ' -diamino-2 - methyl diphenyl ether,
    [77] 4, 4 ' -diamino-3 - methyl diphenyl ether,
    [78] 4, 4'-diamino-2, 2 ' - dimethyl diphenyl ether,
    [79] 4, 4'-diamino-2,3 ' - dimethyl diphenyl ether,
    [80] 4, 4'-diamino-3,3 ' - dimethyl diphenyl ether,
    [81] 3, 4 ' -diamino-5 - methyl diphenyl ether,
    [82] 3, 4 ' -diamino-2 ' - methyl diphenyl ether,
    [83] 3, 4 ' -diamino-3 ' - methyl diphenyl ether,
    [84] 3, 4 '-diamino-5, 2' - dimethyl diphenyl ether,
    [85] 3, 4 '-diamino-5,3' - dimethyl diphenyl ether,
    [86] 3, 3 ' -diamino-5 - methyl diphenyl ether,
    [87] 3, 3 '-diamino-5, 5' - dimethyl diphenyl ether,
    [88] 4, 4 ' -diamino-2 - bromodiphenyl ether,
    [89] 4, 4 ' -diamino-3 - bromodiphenyl ether,
    [90] 4, 4'-diamino-2, 2 ' - dibromodiphenyl ether,
    [91] 4, 4'-diamino-2,3 ' - dibromodiphenyl ether,
    [92] 4, 4'-diamino-3,3 ' - dibromodiphenyl ether,
    [93] 3, 4 ' -diamino-5 - bromodiphenyl ether,
    [94] 3, 4 ' -diamino-2 ' - bromodiphenyl ether,
    [95] 3, 4 ' -diamino-3 ' - bromodiphenyl ether,
    [96] 3, 4 '-diamino-5, 2' - dibromodiphenyl ether,
    [97] 3, 4 '-diamino-5,3' - dibromodiphenyl ether,
    [98] 3, 3 ' -diamino-5 - bromodiphenyl ether,
    [99] 3, 3 '-diamino-5, 5' - dibromodiphenyl ether,
    [100] 4, 4 ' -diamino-2 - chlorodiphenyl ether,
    [101] 4, 4 ' -diamino-3 - chlorodiphenyl ether,
    [102] 4, 4'-diamino-2, 2 ' - dichlorodiphenyl ether,
    [103] 4, 4'-diamino-2,3 ' - dichlorodiphenyl ether,
    [104] 4, 4'-diamino-3,3 ' - dichlorodiphenyl ether,
    [105] 3, 4 ' -diamino-5 - chlorodiphenyl ether,
    [106] 3, 4 ' -diamino-2 ' - chlorodiphenyl ether,
    [107] 3, 4 ' -diamino-3 ' - chlorodiphenyl ether,
    [108] 3, 4 '-diamino-5, 2' - dichlorodiphenyl ether,
    [109] 3, 4 '-diamino-5,3' - dichlorodiphenyl ether,
    [110] 3, 3 ' -diamino-5 - chlorodiphenyl ether,
    [111] 3, 3 '-diamino-5, 5' - dichlorodiphenyl ether;
    [112] (1-3) A 1 is -S-
    [113] 4, 4 '-diaminodiphenylsulfide,
    [114] 3, 4 '-diaminodiphenylsulfide,
    [115] 3, 3 '-diaminodiphenylsulfide,
    [116] 4, 4 ' -diamino-2 - trifluoromethyldiphenylsulfide, < RTI ID = 0.0 >
    [117] 4, 4 ' -diamino-3 - trifluoromethyldiphenylsulfide, < RTI ID = 0.0 >
    [118] 4, 4'-diamino-2, 2 ' - ditrifluoromethyl diphenyl sulfide,
    [119] 4, 4'-diamino-2,3 ' - ditrifluoromethyl diphenyl sulfide,
    [120] 4, 4'-diamino-3,3 ' - ditrifluoromethyl diphenyl sulfide,
    [121] 3, 4 ' -diamino-5 - trifluoromethyldiphenylsulfide, < RTI ID = 0.0 >
    [122] 3, 4 ' -diamino-2 ' - trifluoromethyldiphenylsulfide, < RTI ID = 0.0 >
    [123] 3, 4 ' -diamino-3 ' - trifluoromethyldiphenylsulfide, < RTI ID = 0.0 >
    [124] 3, 4 '-diamino-5, 2' - ditrifluoromethyl diphenyl sulfide,
    [125] 3, 4 '-diamino-5,3' - ditrifluoromethyl diphenyl sulfide,
    [126] 3, 3 ' -diamino-5 - trifluoromethyldiphenylsulfide, < RTI ID = 0.0 >
    [127] 3, 3 '-diamino-5, 5' - ditrifluoromethyl diphenyl sulfide,
    [128] 4, 4 ' -diamino-2 - methyl diphenyl sulfide,
    [129] 4, 4 ' -diamino-3 - methyl diphenyl sulfide,
    [130] 4, 4'-diamino-2, 2 ' - dimethyl diphenyl sulfide,
    [131] 4, 4'-diamino-2,3 ' - dimethyl diphenyl sulfide,
    [132] 4, 4'-diamino-3,3 ' - dimethyl diphenyl sulfide,
    [133] 3, 4 ' -diamino-5 - methyl diphenyl sulfide,
    [134] 3, 4 ' -diamino-2 ' - methyl diphenyl sulfide,
    [135] 3, 4 ' -diamino-3 ' - methyl diphenyl sulfide,
    [136] 3, 4 '-diamino-5, 2' - dimethyl diphenyl sulfide,
    [137] 3, 4 '-diamino-5,3' - dimethyl diphenyl sulfide,
    [138] 3, 3 ' -diamino-5 - methyl diphenyl sulfide,
    [139] 3, 3 '-diamino-5, 5' - dimethyl diphenyl sulfide,
    [140] 4, 4 ' -diamino-2 - bromodiphenylsulfide,
    [141] 4, 4 ' -diamino-3 - bromodiphenylsulfide,
    [142] 4, 4'-diamino-2, 2 ' - dibromodiphenylsulfide,
    [143] 4, 4'-diamino-2,3 ' - dibromodiphenylsulfide,
    [144] 4, 4'-diamino-3,3 ' - dibromodiphenylsulfide,
    [145] 3, 4 ' -diamino-5 - bromodiphenylsulfide,
    [146] 3, 4 ' -diamino-2 ' - bromodiphenylsulfide,
    [147] 3, 4 ' -diamino-3 ' - bromodiphenylsulfide,
    [148] 3, 4 '-diamino-5, 2' - dibromodiphenylsulfide,
    [149] 3, 4 '-diamino-5,3' - dibromodiphenylsulfide,
    [150] 3, 3 ' -diamino-5 - bromodiphenylsulfide,
    [151] 3, 3 '-diamino-5, 5' - dibromodiphenylsulfide,
    [152] 4, 4 ' -diamino-2 - chlorodiphenylsulfide,
    [153] 4, 4 ' -diamino-3 - chlorodiphenylsulfide,
    [154] 4, 4'-diamino-2, 2 ' - dichlorodiphenylsulfide,
    [155] 4, 4'-diamino-2,3 ' - dichlorodiphenylsulfide,
    [156] 4, 4'-diamino-3,3 ' - dichlorodiphenylsulfide,
    [157] 3, 4 ' -diamino-5 - chlorodiphenylsulfide,
    [158] 3, 4 ' -diamino-2 ' - chlorodiphenylsulfide,
    [159] 3, 4 ' -diamino-3 ' - chlorodiphenylsulfide,
    [160] 3, 4 '-diamino-5, 2' - dichlorodiphenylsulfide,
    [161] 3, 4 '-diamino-5,3' - dichlorodiphenylsulfide,
    [162] 3, 3 ' -diamino-5 - chlorodiphenylsulfide,
    [163] 3, 3 '-diamino-5, 5' - dichlorodiphenylsulfide,
    [164] (1-4) A 1 is -SO 2 -
    [165] 4, 4 '-diaminodiphenyl sulfone,
    [166] 3, 4 '-diaminodiphenyl sulfone,
    [167] 3, 3 '-diaminodiphenyl sulfone,
    [168] 4, 4 '- diamino-2-trifluoromethyldiphenyl sulfone,
    [169] 4, 4 '-diamino-3-trifluoromethyldiphenyl sulfone,
    [170] 4, 4'-diamino-2, 2 '-ditrifluoromethyldiphenyl sulfone,
    [171] 4, 4'-diamino-2,3 '-ditrifluoromethyldiphenyl sulfone,
    [172] 4, 4'-diamino-3,3'-ditrifluoromethyldiphenyl sulfone,
    [173] 3, 4 '-diamino-5-trifluoromethyldiphenyl sulfone,
    [174] 3, 4 ' -diamino-2 ' -trifluoromethyldiphenyl sulfone,
    [175] 3, 4 ' -diamino-3 ' -trifluoromethyldiphenyl sulfone,
    [176] 3, 4 '-diamino-5, 2' -ditrifluoromethyldiphenyl sulfone,
    [177] 3, 4 '-diamino-5, 3' -ditrifluoromethyldiphenylsulfone,
    [178] 3, 4 '-diamino-5-trifluoromethyldiphenyl sulfone,
    [179] 3, 3 '-diamino-5, 5' -ditrifluoromethyldiphenyl sulfone,
    [180] 4, 4 '-diamino-2-methyldiphenyl sulfone,
    [181] 4, 4'-diamino-3-methyldiphenyl sulfone,
    [182] 4, 4 '-diamino-2, 2' -dimethyldiphenyl sulfone,
    [183] 4, 4 '-diamino-2, 3' -dimethyldiphenyl sulfone,
    [184] 4, 4'-diamino-3,3'-dimethyldiphenyl sulfone,
    [185] 3, 4 '- diamino-5-methyldiphenyl sulfone,
    [186] 3, 4 ' -diamino-2 ' -methyldiphenyl sulfone,
    [187] 3, 4'-diamino-3'-methyldiphenyl sulfone,
    [188] 3, 4 '-diamino-5, 2' -dimethyldiphenyl sulfone,
    [189] 3, 4-diamino-5, 3 '-dimethyldiphenyl sulfone,
    [190] 3, 3 '-diamino-5-methyldiphenyl sulfone,
    [191] 3, 3 '-diamino-5, 5' -dimethyldiphenyl sulfone,
    [192] 4, 4 '-diamino-2-bromodiphenylsulfone,
    [193] 4, 4 '- diamino-3-bromodiphenylsulfone,
    [194] 4, 4'-diamino-2, 2 '-dibromodiphenylsulfone,
    [195] 4, 4'-diamino-2,3 '-dibromodiphenylsulfone,
    [196] 4, 4'-diamino-3,3'-dibromodiphenylsulfone,
    [197] 3, 4 '- diamino-5-bromodiphenylsulfone,
    [198] 3, 4 ' -diamino-2 ' -bromodiphenylsulfone,
    [199] 3, 4 ' -diamino-3 ' -bromodiphenylsulfone,
    [200] 3, 4 '-diamino-5, 2' -dibromodiphenylsulfone,
    [201] 3, 4 '-diamino-5, 3' -dibromodiphenylsulfone,
    [202] 3, 3 '-diamino-5-bromodiphenylsulfone,
    [203] 3, 3 '-diamino-5, 5' -dibromodiphenylsulfone,
    [204] 4, 4 '-diamino-2-chlorodiphenylsulfone,
    [205] 4, 4'-diamino-3-chlorodiphenylsulfone,
    [206] 4, 4 '-diamino-2, 2' -dichlorodiphenylsulfone,
    [207] 4, 4 '-diamino-2, 3' -dichlorodiphenylsulfone,
    [208] 4, 4'-diamino-3,3'-dichlorodiphenylsulfone,
    [209] 3, 4 '- diamino-5-chlorodiphenylsulfone,
    [210] 3, 4'-diamino-2'-chlorodiphenylsulfone,
    [211] 3, 4'-diamino-3'-chlorodiphenylsulfone,
    [212] 3, 4 '-diamino-5, 2' -dichlorodiphenylsulfone,
    [213] 3, 4'-diamino-5,3'-dichlorodiphenylsulfone,
    [214] 3, 3 '-diamino-5-chlorodiphenylsulfone,
    [215] 3, 3 '-diamino-5, 5' -dichlorodiphenylsulfone,
    [216] (1-5) Al is -CO-
    [217] 4, 4 '- diaminobenzophenone,
    [218] 3, 4 '- diaminobenzophenone,
    [219] 3, 3 ' - diaminobenzophenone,
    [220] 4, 4 '-diamino-2-trifluoromethylbenzophenone,
    [221] 4, 4'-diamino-3-trifluoromethylbenzophenone,
    [222] 4, 4'-diamino-2, 2 '-ditrifluoromethylbenzophenone,
    [223] 4, 4 ' -diamino-2, 3 ' -ditrifluoromethylbenzophenone,
    [224] 4, 4'-diamino-3,3'-ditrifluoromethylbenzophenone,
    [225] 3, 4 '-diamino-5-trifluoromethyldibenzophenone,
    [226] 3, 4 ' -diamino-2 ' -trifluoromethylbenzophenone,
    [227] 3, 4 ' -diamino-3 ' -trifluoromethylbenzophenone,
    [228] 3, 4'-diamino-5, 2 '-ditrifluoromethylbenzophenone,
    [229] 3, 4 '-diamino-5, 3' -ditrifluoromethylbenzophenone,
    [230] 3, 3 '-diamino-5-trifluoromethylbenzophenone,
    [231] 3, 3'-diamino-5, 5 '-ditrifluoromethylbenzophenone,
    [232] 4, 4 '-diamino-2-methylbenzophenone,
    [233] 4, 4'-diamino-3-methylbenzophenone,
    [234] 4, 4 '-diamino-2, 2' -dimethylbenzophenone,
    [235] 4, 4'-diamino-2, 3 '-dimethylbenzophenone,
    [236] 4, 4'-diamino-3,3'-dimethylbenzophenone,
    [237] 3, 4 '- diamino-5-methyldibenzophenone,
    [238] 3, 4 ' -diamino-2 ' -methylbenzophenone,
    [239] 3, 4 ' -diamino-3 ' -methylbenzophenone,
    [240] 3, 4'-diamino-5, 2 '-dimethylbenzophenone,
    [241] 3, 4'-diamino-5, 3 '-dimethylbenzophenone,
    [242] 3, 3 '-diamino-5-methylbenzophenone,
    [243] 3, 3 '-diamino-5, 5' -dimethylbenzophenone,
    [244] 4, 4'-diamino-2-bromobenzophenone,
    [245] 4, 4'-diamino-3-bromobenzophenone,
    [246] 4, 4'-diamino-2, 2 '-dibromobenzophenone,
    [247] 4, 4'-diamino-2,3 '-dibromobenzophenone,
    [248] 4, 4'-diamino-3, 3 '-dibromobenzophenone,
    [249] 3, 4 '- diamino-5-bromobenzophenone,
    [250] 3, 4 ' -diamino-2 ' -bromobenzophenone,
    [251] 3, 4 ' -diamino-3 ' -bromobenzophenone,
    [252] 3, 4 ' -diamino-5, 2 ' - dibromobenzophenone,
    [253] 3, 4'-diamino-5, 3 '-dibromobenzophenone,
    [254] 3, 3 ' - diamino-5-bromobenzophenone,
    [255] 3, 3 '-diamino-5, 5' -dibromobenzophenone,
    [256] 4, 4'-diamino-2-chlorobenzophenone,
    [257] 4, 4'-diamino-3-chlorobenzophenone,
    [258] 4, 4'-diamino-2, 2 '-dichlorobenzophenone,
    [259] 4, 4'-diamino-2, 3 '-dichlorobenzophenone,
    [260] 4, 4'-diamino-3, 3 '-dichlorobenzophenone,
    [261] 3, 4 '- diamino-5-chlorobenzophenone,
    [262] 3, 4 ' -diamino-2 ' -chlorobenzophenone,
    [263] 3, 4'-diamino-3'-chlorobenzophenone,
    [264] 3, 4'-diamino-5, 2 '-dichlorobenzophenone,
    [265] 3, 4'-diamino-5, 3 '-dichlorobenzophenone,
    [266] 3, 3 '-diamino-5-chlorobenzophenone,
    [267] 3, 3 ' -diamino-5,5 '-dichlorobenzophenone;
    [268] (1-6) A 1 is -CH 2 -
    [269] 4, 4'-diaminodiphenylmethane,
    [270] 3, 4 '- diaminodiphenylmethane,
    [271] 3, 3 '- diaminodiphenylmethane,
    [272] 4, 2 '- diaminodiphenylmethane,
    [273] (1-7) A 1 is -C (CH 3 ) 2 - or -C (CF 3 ) 2 -
    [274] 2, 2-bis (4-aminophenyl) propane,
    [275] 2, 2-bis (3-aminophenyl) propane,
    [276] 2- (3-aminophenyl) -2- (4-aminophenyl) propane,
    [277] 2, 2-bis (4-amino-2-trifluoromethylphenyl) propane,
    [278] 2, 2-bis (4-amino-3-trifluoromethylphenyl) propane,
    [279] 2- (4-aminophenyl) -2- (4'-amino-2'-trifluoromethylphenyl) propane,
    [280] 2- (4-aminophenyl) -2- (4'-amino-3'-trifluoromethylphenyl) propane,
    [281] 2, 2-bis (3-amino-5-trifluoromethylphenyl) propane,
    [282] 2- (3-amino-5-trifluoromethylphenyl) -2- (3'-aminophenyl) propane,
    [283] 2- (3-amino-5-trifluoromethylphenyl) -2- (4'-amino-2'-trifluoromethylphenyl) propane, 2- (4'-amino-3'-trifluoromethylphenyl) propane, 2- (3-aminophenyl) -2- Amino-3-trifluoromethylphenyl) propane, 2- (3-amino-5-trifluoromethylphenyl) -2- (4'- Bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-aminophenyl) Hexafluoropropane,
    [284] 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane,
    [285] 2,2-bis (4-amino-2-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane,
    [286] 2,2-bis (4-amino-3-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane,
    [287] 2- (4-aminophenyl) -2- (4'-amino-2'-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane,
    [288] 2- (4-aminophenyl) -2- (4'-amino-3'-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane,
    [289] 2,2-bis (3-amino-5-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane,
    [290] 2- (3-amino-5-trifluoromethylphenyl) -2- (3'-aminophenyl) -1,1,1,3,3,3-hexafluoropropane,
    [291] 2- (3-amino-5-trifluoromethylphenyl) -2- (4'-amino-2'-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane,
    [292] 2- (3-amino-5-trifluoromethylphenyl) -2- (4'-amino-3'-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane,
    [293] 2- (3-aminophenyl) -2- (4'-amino-2'-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2- ) -2- (4'-amino-3'-trifluoromethylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-amino-5-trifluoromethylphenyl) -2- (4'-amino-phenyl) -1,1,1,3,3,3-hexafluoropropane,
    [294] Specific examples of the diamine represented by the general formula (14) are as follows.
    [295] 1, 3-bis (3-aminophenoxy) benzene,
    [296] 1, 3-bis (4-aminophenoxy) benzene,
    [297] 1, 4-bis (3-aminophenoxy) benzene,
    [298] 1, 4-bis (4-aminophenoxy) benzene,
    [299] 2, 6-bis (3-aminophenoxy) benzonitrile,
    [300] 2, 6-bis (4-aminophenoxy) benzonitrile,
    [301] 1, 3-bis (3-aminophenoxy) -2-chlorobenzene,
    [302] 1, 3-bis (3-aminophenoxy) -5-chlorobenzene,
    [303] 1, 3-bis (4-aminophenoxy) -4-chlorobenzene,
    [304] 1, 3-bis (3-aminophenoxy) -2-bromobenzene,
    [305] 1, 3-bis (3-aminophenoxy) -5-bromobenzene,
    [306] 1, 3-bis (4-aminophenoxy) -4-bromobenzene,
    [307] 1, 3-bis (3-aminophenoxy) -4-trifluoromethylbenzene,
    [308] 1, 3-bis (4-aminophenoxy) -4-trifluoromethylbenzene,
    [309] 1, 3-bis (3-aminophenoxy) -5-trifluoromethylbenzene,
    [310] 1, 3-bis (4-aminophenoxy-5-trifluoromethylphenoxy) benzene,
    [311] 1, 3-bis (3-amino-5-trifluoromethylphenoxy) benzene,
    [312] 1, 3-bis (4-amino-2-trifluoromethylphenoxy) benzene,
    [313] 1, 4-bis (3-amino-5-trifluoromethylphenoxy) benzene,
    [314] 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene,
    [315] 1, 3-bis (3-amino-5-trifluoromethylphenoxy) -4-trifluoromethylbenzene,
    [316] 1, 3-bis (4-amino-2-trifluoromethylphenoxy) -4-trifluoromethylbenzene,
    [317] 1, 3-bis (3-amino-5-trifluoromethylphenoxy) -5-trifluoromethylbenzene,
    [318] 1, 3-bis (4-amino-2-trifluoromethylphenoxy) -5-trifluoromethylbenzene,
    [319] Specific examples of the diamine represented by the general formula (15) include the following.
    [320] 4, 4'-bis (3-aminophenoxy) biphenyl,
    [321] 4, 4'-bis (4-aminophenoxy) biphenyl,
    [322] Bis [4- (3-aminophenoxy) phenyl] sulfide,
    [323] Bis [4- (4-aminophenoxy) phenyl] sulfide,
    [324] Bis [4- (3-aminophenoxy) phenyl] sulfone,
    [325] Bis [4- (4-aminophenoxy) phenyl] sulfone,
    [326] Bis [4- (3-aminophenoxy) phenyl] ether,
    [327] Bis [4- (4-aminophenoxy) phenyl] ether,
    [328] Bis [4- (3-aminophenoxy) phenyl] ketone,
    [329] Bis [4- (4-aminophenoxy) phenyl] ketone,
    [330] 2,2-bis [4- (3-aminophenoxy) phenyl] propane,
    [331] 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
    [332] 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,
    [333] 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,
    [334] 4,4'-bis (3-amino-5-trifluoromethylphenoxy) biphenyl,
    [335] 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl,
    [336] Bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] sulfide,
    [337] Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] sulfide,
    [338] Bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] sulfone,
    [339] Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] sulfone,
    [340] Bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] ether,
    [341] Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] ether,
    [342] Bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] ketone,
    [343] Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] ketone,
    [344] Bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] propane,
    [345] Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] propane,
    [346] Bis [3- (3-amino-5-trifluoromethylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane.
    [347] Particularly preferred diamines include those represented by the general formula (13)
    [348] 4,4'-diamino-2,2'-ditrifluoromethylbiphenyl,
    [349] 4,4'-diaminodiphenyl ether,
    [350] 3,4'-diaminodiphenyl ether,
    [351] 3,3'-diaminodiphenyl ether,
    [352] 3,3'-diamino-5,5'-ditrifluoromethyl diphenyl ether,
    [353] 4,4'-diaminodiphenyl sulfone,
    [354] 3,4'-diaminodiphenyl sulfone,
    [355] 3,3'-diaminodiphenylsulfone,
    [356] 4,4'-diaminodiphenylsulfide,
    [357] 3,4'-diaminodiphenylsulfide,
    [358] 3,3'-diaminodiphenylsulfide,
    [359] 2,2-bis (4-aminophenoxy) -1,1,1,3,3,3-hexafluoropropane,
    [360] 2,2-bis (3-aminophenoxy) -1,1,1,3,3,3-hexafluoropropane,
    [361] 2- (3-Aminophenoxy) -2- (4-aminophenoxy) -1,1,1,3,3,3-hexafluoropropane.
    [362] [0064] The compound represented by the general formula (14)
    [363] 1, 3-bis (3-aminophenoxy) benzene,
    [364] 1, 3-bis (4-aminophenoxy) benzene,
    [365] 1, 4-bis (3-aminophenoxy) benzene,
    [366] 1, 4-bis (4-aminophenoxy) benzene,
    [367] 2, 6-bis (3-aminophenoxy) benzonitrile,
    [368] 2, 6-bis (4-aminophenoxy) benzonitrile,
    [369] 1, 3-bis (3-aminophenoxy) -2-chlorobenzene,
    [370] 1, 3-bis (3-aminophenoxy) -5-chlorobenzene,
    [371] 1, 3-bis (4-aminophenoxy) -4-chlorobenzene,
    [372] 1, 3-bis (3-aminophenoxy) -2-bromobenzene,
    [373] 1, 3-bis (3-aminophenoxy) -5-bromobenzene,
    [374] 1, 3-bis (4-aminophenoxy) -4-bromobenzene,
    [375] 1, 3-bis (3-aminophenoxy) -4-trifluoromethylbenzene,
    [376] 1, 3-bis (4-aminophenoxy) -4-trifluoromethylbenzene,
    [377] 1, 3-bis (3-aminophenoxy) -5-trifluoromethylbenzene,
    [378] 1, 3-bis (4-aminophenoxy) -5-trifluorotylphenoxy) benzene,
    [379] 1, 3-bis (3-amino-5-trifluorotylphenoxy) benzene,
    [380] 1, 3-bis (4-amino-2-trifluorotylphenoxy) benzene,
    [381] 1, 4-bis (3-amino-5-trifluorotylphenoxy) benzene,
    [382] 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene,
    [383] 1, 3-bis (3-amino-5-trifluoromethylphenoxy) -4-trifluoromethylbenzene,
    [384] 1, 3-bis (4-amino-2-trifluorothylphenoxy) -4-trifluoromethylbenzene,
    [385] 1,3-bis (3-amino-5-trifluorotylphenoxy) -5-trifluoromethylbenzene,
    [386] 1, 3-bis (4-amino-2-trifluorothylphenoxy) -5-trifluoromethylbenzene.
    [387] The compound represented by the general formula (15)
    [388] 4,4'-bis (3-aminophenoxy) biphenyl,
    [389] 4,4'-bis (4-aminophenoxy) biphenyl,
    [390] Bis [4- (3-aminophenoxy) phenyl] sulfide,
    [391] Bis [4- (4-aminophenoxy) phenyl] sulfide,
    [392] Bis [4- (3-aminophenoxy) phenyl] sulfone,
    [393] Bis [4- (4-aminophenoxy) phenyl] sulfone,
    [394] Bis [4- (3-aminophenoxy) phenyl] ether,
    [395] Bis [4- (4-aminophenoxy) phenyl] ether,
    [396] Bis [4- (3-aminophenoxy) phenyl] ketone,
    [397] Bis [4- (4-aminophenoxy) phenyl] ketone,
    [398] 2,2-bis [4- (3-aminophenoxy) phenyl] propane,
    [399] 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
    [400] Bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [ Phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) biphenyl, 4,4'-bis 4-amino-2-trifluoromethylphenoxy) biphenyl.
    [401] (Diamine which may be used in combination)
    [402] The polyimide of the present invention can be used by mixing one or more of the above diamines for the purpose of improving performance, modifying or reducing the cost, and further mixing the following diamines with the diamines of the general formulas (13), (14), ). ≪ / RTI >
    [403] The proportion of the total of the diamines of the general formulas (13), (14) and (15) is preferably 50 mol% or more, and more preferably 70 mol% or more.
    [404] Examples of the diamine to be used in combination include the following.
    [405] a) with one benzene ring
    [406] p - phenylenediamine,
    [407] m - phenylenediamine;
    [408] b) with two benzene rings
    [409] 1,1-di (3-aminophenyl) -1-phenylethane,
    [410] 1,1-di (4-aminophenyl) -1-phenylethane,
    [411] 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane;
    [412] c) with three benzene rings
    [413] 1,3-bis (3-aminobenzoyl) benzene,
    [414] 1,3-bis (4-aminobenzoyl) benzene,
    [415] 1,4-bis (4-aminobenzoyl) benzene,
    [416] 1,3-bis (3-amino-alpha, alpha -dimethylbenzyl) benzene,
    [417] 1,3-bis (4-amino- alpha, alpha -dimethylbenzyl) benzene,
    [418] 1,4-bis (3-amino-alpha, alpha -dimethylbenzyl) benzene,
    [419] 1,4-bis (4-amino- alpha, alpha -dimethylbenzyl) benzene,
    [420] 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene,
    [421] 1,3-bis (4-amino-alpha, alpha -ditrifluoromethylbenzyl) benzene,
    [422] 1,4-bis (3-amino-alpha, alpha -ditrifluoromethylbenzyl) benzene,
    [423] 1,4-bis (4-amino-alpha, alpha -ditrifluoromethylbenzyl) benzene,
    [424] 2,6-bis (3-aminophenoxy) pyridine,
    [425] 2,6-bis (3-aminophenoxy) benzonitrile,
    [426] 2,6-bis (4-aminophenoxy) benzonitrile;
    [427] d) with 4 benzene rings
    [428] 4,4'-bis (3-aminophenoxy) biphenyl,
    [429] 4,4'-bis (4-aminophenoxy) biphenyl,
    [430] Bis [4- (3-aminophenoxy) phenyl] ketone,
    [431] Bis [4- (4-aminophenoxy) phenyl] ketone,
    [432] Bis [4- (3-aminophenoxy) phenyl] sulfide,
    [433] Bis [4- (4-aminophenoxy) phenyl] sulfide,
    [434] Bis [4- (3-aminophenoxy) phenyl] sulfone,
    [435] Bis [4- (4-aminophenoxy) phenyl] sulfone,
    [436] Bis [4- (3-aminophenoxy) phenyl] ether,
    [437] Bis [4- (4-aminophenoxy) phenyl] ether,
    [438] 2,2-bis [4- (3-aminophenoxy) phenyl] propane,
    [439] 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
    [440] 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,
    [441] 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane;
    [442] d) with 5 benzene rings
    [443] 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene,
    [444] 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene,
    [445] 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene,
    [446] 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene,
    [447] 1,3-bis [4- (3-aminophenoxy) - , - dimethylbenzyl] benzene,
    [448] 1,3-bis [4- (4-aminophenoxy) - , - dimethylbenzyl] benzene,
    [449] 1,4-bis [4- (3-aminophenoxy) - , - dimethylbenzyl] benzene,
    [450] 1,4-bis [4- (4-aminophenoxy) - , - dimethylbenzyl] benzene;
    [451] e) with 6 benzene rings
    [452] 4,4'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether,
    [453] 4,4'-bis [4- (4-amino- alpha, alpha -dimethylbenzyl) phenoxy] benzophenone,
    [454] 4,4'-bis [4- (4-amino- alpha, alpha -dimethylbenzyl) phenoxy] diphenyl sulfone,
    [455] 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenyl sulfone;
    [456] f) having an aromatic substituent
    [457] 3,3'-diamino-4,4'-diphenoxybenzophenone,
    [458] 3,3'-diamino-4,4'-dibiphenoxybenzophenone,
    [459] 3,3'-diamino-4-phenoxybenzophenone,
    [460] 3,3'-diamino-4-biphenoxybenzophenone;
    [461] g) Spirobians with monocytes
    [462] 6,6'-bis (3-aminophenoxy) -3,3,3 ', 3' -tetramethyl-1,1'-spiroindane,
    [463] 6,6'-bis (4-aminophenoxy) -3,3,3 ', 3' -tetramethyl-1,1'-spiroindane;
    [464] , And as the aliphatic diamine
    [465] h) siloxane diamines
    [466] 1,3-bis (3-aminopropyl) tetramethyldisiloxane,
    [467] 1,3-bis (4-aminobutyl) tetramethyldisiloxane,
    [468] , - bis (3-aminopropyl) polydimethylsiloxane,
    [469] , - bis (3-aminobutyl) polydimethylsiloxane;
    [470] i) Ethylene glycol diamine
    [471] Bis (aminomethyl) ether,
    [472] Bis (2-aminomethyl) ether,
    [473] Bis (3-aminopropyl) ether,
    [474] Bis (2-aminoethoxy) ethyl] ether,
    [475] Bis [2- (2-aminoethoxy) ethyl] ether,
    [476] Bis [2- (3-aminopropoxy) ethyl] ether,
    [477] 1,2-bis (aminomethoxy) ethane,
    [478] 1,2-bis (2-aminoethoxy) ethane,
    [479] 1,2-bis [2- (aminomethoxy) ethoxyethane,
    [480] Bis [2- (2-aminoethoxy) ethoxy] ethane,
    [481] Ethylene glycol bis (3-aminopropyl) ether,
    [482] Diethylene glycol bis (3-aminopropyl) ether,
    [483] Triethylene glycol bis (3-aminopropyl) ether;
    [484] j) methylene diamine
    [485] Ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane,
    [486] 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane,
    [487] 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane,
    [488] 1,11-diamino undecane, 1,12-diaminododecane;
    [489] k) alicyclic diamines
    [490] 1,2-diaminocyclohexane,
    [491] 1,3-diaminocyclohexane,
    [492] 1,4-diaminocyclohexane,
    [493] 1,2-di (2-aminoethyl) cyclohexane,
    [494] 1,3-di (2-aminoethyl) cyclohexane,
    [495] 1,4-di (2-aminoethyl) cyclohexane,
    [496] Bis (4-aminocyclohexane) methane,
    [497] 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane,
    [498] 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane,
    [499] .
    [500] When the tetracarboxylic dianhydride represented by the formula (16) used for obtaining the polyimide of the present invention is specifically represented,
    [501] 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride,
    [502] Bis (3,4-dicarboxyphenyl) ether dianhydride,
    [503] Bis (3,4-dicarboxyphenyl) sulfone dianhydride,
    [504] 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane
    [505] There are four kinds of water.
    [506] The structure of the polyimide of the present invention is the polyimide of the general formula (1), but the specific substituent represented by the general formula (9) is particularly preferred because it has a high light transmittance and a high refractive index.
    [507] For the purpose of improving or modifying the performance of the polyimide of the present invention, copolymerization using one or more of the following tetracarboxylic dianhydrides may be carried out without any problem. In this case, the tetracarboxylic acid dianhydride represented by the formula (16) is preferably used in an amount of 50 mol% or more, more preferably 70 mol% or more, based on the total tetracarboxylic acid dianhydride.
    [508] The tetracarboxylic acid dianhydride which can be used in combination is pyromellitic dianhydride,
    [509] 3,3 ', 4,4'-benzophenonetracarboxylic acid dianhydride,
    [510] Bis (3,4-dicarboxyphenyl) sulfide dianhydride,
    [511] Bis (3,4-dicarboxyphenyl) methane dianhydride,
    [512] 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride,
    [513] 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride,
    [514] 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride,
    [515] 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride,
    [516] 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride,
    [517] 2,3,6,7-naphthalenetetracarboxylic acid dianhydride,
    [518] 1,4,5,8-naphthalenetetracarboxylic dianhydride,
    [519] Ethylene tetracarboxylic acid dianhydride,
    [520] Butane tetracarboxylic acid dianhydride,
    [521] Cyclopentane tetracarboxylic acid dianhydride,
    [522] 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride,
    [523] 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride,
    [524] 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
    [525] 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride,
    [526] Bis (2,3-dicarboxyphenyl) ether dianhydride,
    [527] Bis (2,3-dicarboxyphenyl) sulfide dianhydride,
    [528] Bis (2,3-dicarboxyphenyl) sulfone dianhydride,
    [529] 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride,
    [530] 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride,
    [531] 1,2,5,6-naphthalenetetracarboxylic acid dianhydride
    [532] to be.
    [533] When the amount of tetracarboxylic acid dianhydride to be used is less than 1 mole per 1 mole of diamine in producing the polyimide for optical member of the present invention, the terminal of the obtained polyimide remains as an amino group. Thus, the aromatic dicarboxylic acid anhydride represented by the general formula (5), which is used for the purpose of encapsulating the amino group at the terminal, is selected from the group consisting of phthalic anhydride, 4-phenylphthalic anhydride, 4-phenoxyphthalic anhydride, 4-phenylsulfinylphthalic anhydride, 4-phenylcarbamoylphthalic anhydride, 4- (2-phenylisopropyl) phthalic anhydride, 4- (1,1,1,3,3,3-hexafluoro-2-phenyliso Propyl) phthalic anhydride, 2,3-naphthalenedicarboxylic acid anhydride, and 1,8-naphthalenedicarboxylic anhydride.
    [534] And is most preferable in view of the properties and implementation of the polyimide of the present invention in which phthalic anhydride is obtained in the aromatic dicarboxylic acid anhydride.
    [535] In particular, in the present invention, encapsulating at least a part of the terminal amino group of the polyimide for an optical member with a dicarboxylic acid anhydride having a structure capable of introducing the crosslinking structure of the general formula (7) improves the chemical resistance of the polyimide It is particularly useful as an optical member.
    [536] <End of crosslinking period>
    [537] When the amount of the tetracarboxylic acid dianhydride to be used is less than 1 mole per 1 mole of diamine in the production of the polyimide for an optical lens of the present invention, the terminal of the obtained polyimide remains as an amino group. The crosslinkable group-containing dicarboxylic acid anhydride represented by the general formula (7), which is used for encapsulating the amino group at the terminal and for improving the chemical resistance, which is the greatest object of the present invention, is as follows.
    [538] Maleic anhydride, 2-methyl maleic anhydride, 2, 3-dimethyl maleic anhydride, 2-fluoromaleic anhydride, 2,3-difluoromaleic anhydride, 2-trifluoromethyl maleic anhydride, 2 , 2-ethyl maleic anhydride, 2,3-diethyl maleic anhydride, 2-phenyl maleic anhydride, 2,3-diphenyl maleic anhydride, 5-norbornene anhydride, Dicarboxylic acid anhydride,
    [539] Methyl-5-norbornene-2,3-dicarboxylic acid anhydride,
    [540] Dimethyl-5-norbornene-2,3-dicarboxylic acid anhydride,
    [541] Fluoro-5-norbornene-2,3-dicarboxylic acid anhydride,
    [542] Difluoro-5-norbornene-2,3-dicarboxylic acid anhydride,
    [543] 5-norbornene-2,3-dicarboxylic acid anhydride, trifluoromethyl-
    [544] Ditrifluoromethyl-5-norbornene-2,3-dicarboxylic acid anhydride,
    [545] Ethyl-5-norbornene-2,3-dicarboxylic acid anhydride,
    [546] Di-5-norbornene-2,3-dicarboxylic acid anhydride,
    [547] Phenyl-5-norbornene-2,3-dicarboxylic acid anhydride,
    [548] Diphenyl-5-norbornene-2,3-dicarboxylic acid anhydride,
    [549] Cis-1,2,3,4-tetrahydrophthalic anhydride,
    [550] 5-methyl-cis-1,2,3,4-tetrahydrophthalic anhydride,
    [551] 5,6-dimethyl-cis-1,2,3,4-tetrahydrophthalic anhydride,
    [552] 5-fluoro-cis-1,2,3,4-tetrahydrophthalic anhydride,
    [553] 5,6-difluoro-cis-1,2,3,4-tetrahydrophthalic anhydride,
    [554] 5-trifluoromethyl-cis-1,2,3,4-tetrahydrophthalic anhydride,
    [555] 5,6-ditrifluoromethyl-cis-1,2,3,4-tetrahydrophthalic anhydride,
    [556] 5-ethyl-cis-1,2,3,4-tetrahydrophthalic anhydride,
    [557] 5,6-diethyl-cis-1,2,3,4-tetrahydrophthalic anhydride,
    [558] 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride,
    [559] 5-phenyl-cis-1,2,3,4-tetrahydrophthalic anhydride,
    [560] 5,6-diphenyl-cis-1,2,3,4-tetrahydrophthalic anhydride, and 6-ethynylphthalic anhydride.
    [561] These crosslinking group-containing dicarboxylic acid anhydrides may be used singly or in combination of two or more.
    [562] Further, a crosslinking group-containing di (meth) acrylate wherein a part or all of the hydrogen atoms on the aromatic ring of the crosslinking group-containing dicarboxylic acid anhydride are substituted with a substituent selected from the group consisting of a fluoro group, a methyl group, a trifluoromethyl group, and a trifluoromethoxy group Carboxylic anhydride can be used. In addition, when a crosslinking point is formed by reacting an ethynyl group, a benzocyclobutene-4'-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrile group, May also be used as a substituent. The vinylene group, vinylidene group or ethylidene group which is a crosslinking point may be bonded to the backbone skeleton not as a substituent.
    [563] The amount of the aromatic dicarboxylic acid anhydride used is from 10 to 100 mol% of the remaining amino groups. Specifically, when the number of moles of diamine is A and the number of moles of tetracarboxylic dianhydride is B, the number of moles of amino groups remaining at the terminals is theoretically expressed by the formula (a). That is, when the number of moles of the aromatic dicarboxylic acid anhydride used is C, the range of C is expressed by the formula (b).
    [564] (A-B) x2 (a)
    [565] 10 {C [(A-B) 2]} 100 100 B
    [566] When the amount of the aromatic dicarboxylic acid anhydride to be used is less than 10 mol% of the remaining amino groups, sufficient end-capping can not be performed. When the amount of the aromatic dicarboxylic acid anhydride is more than 100 mol%, sufficient molecular weight can not be obtained. The amount thereof is preferably 20 to 100 mol%, more preferably 40 to 100 mol%.
    [567] When the amount of the diamine to be used is less than 1 mole per 1 mole of the tetracarboxylic dianhydride in the production of the polyimide for optical member of the present invention, the terminal of the obtained polyimide remains as the dicarboxylic acid anhydride. Thus, the aromatic monoamine represented by the general formula (6), which is used for the purpose of encapsulating the terminal dicarboxylic acid anhydride,
    [568] Aniline, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline,
    [569] 2-chloroaniline, 3-chloroaniline, 4-chloroaniline,
    [570] 2-bromoaniline, 3-bromoaniline, 4-bromoaniline,
    [571] 2-nitroaniline, 3-nitroaniline, 4-nitroaniline,
    [572] 2-cyanoaniline, 3-cyanoaniline, 4-cyanoaniline,
    [573] 2-methyl aniline, 3-methylaniline, 4-methylaniline,
    [574] Trifluoromethylaniline, 2-trifluoromethylaniline, 3-trifluoromethylaniline, 4-trifluoromethylaniline,
    [575] 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline,
    [576] 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl,
    [577] 2-aminodiphenyl ether, 3-aminodiphenyl ether, 4-aminodiphenyl ether,
    [578] 2-aminodiphenylsulfide, 3-aminodiphenylsulfide, 4-aminodiphenylsulfide,
    [579] 2-aminodiphenylsulfone, 3-aminodiphenylsulfone, 4-aminodiphenylsulfone,
    [580] 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone,
    [581] 1-aminonaphthalene, and 2-aminonaphthalene.
    [582] And is most preferable from the viewpoint of properties and implementation of the polyimide of the present invention in which aniline is obtained from the aromatic monoamine.
    [583] Particularly, in the present invention, when an amine having a structure capable of introducing the crosslinking structure of the general formula (8) for the purpose of encapsulating at least a part of the terminal dicarboxylic acid anhydride of the polyimide for an optical member is used, It is particularly useful as an optical member.
    [584] Examples of the amine having a structure capable of introducing the crosslinking structure of the general formula (8) include 4-vinyl aniline, 3-vinyl aniline, 4-ethynyl aniline and 3-ethynyl aniline.
    [585] The amount of the aromatic monoamine used is from 10 to 100 mol% of the residual terminal dicarboxylic acid anhydride. Specifically, when the number of moles of the diamine is A and the number of moles of the tetracarboxylic dianhydride is B, the number of moles of the dicarboxylic acid anhydride group remaining at the terminal is theoretically the formula (C). That is, when the number of moles of the aromatic monoamine to be used is D, the range of D is represented by the formula (d).
    [586] (B-A) x 2 (C)
    [587] 10 {D (B-A) x 2} x 100 100 (d)
    [588] If the amount of the aromatic monoamine to be used is less than 10 mol% of the residual terminal dicarboxylic acid anhydride, sufficient end-sealing can not be performed, and if it exceeds 100 mol%, molecules capable of drawing sufficient characteristics can not be obtained. The amount thereof is preferably 20 to 100 mol%, more preferably 40 to 100 mol%.
    [589] The specific polyimide of the present invention can be used for optical lenses, guide lenses, microlenses, optical filters and the like.
    [590] Further, in the present invention, it is more preferable to perform end sealing because the coloring of the obtained polyimide is suppressed by encapsulating the amino group or the carboxylic acid anhydride group at the molecular end with a dicarboxylic acid anhydride or an aromatic monoamine.
    [591] As the tetracarboxylic acid dianhydride, one or more of the compounds represented by the general formula (16) are used, and tetracarboxylic acid dianhydride may be used for a part thereof other than the general formula (16). The total amount of the tetracarboxylic acid dianhydride is 0.9 to 1.1 molar ratio per mol of the total amount of the diamine to be used. By changing the molar ratio, the molecular weight of the resulting polyamic acid or polyimide can be controlled. If the molar ratio is less than 0.9 or more than 1.1, a molecular weight sufficient to obtain sufficient characteristics can not be obtained. The molar ratio is preferably 0.92 to 1.08, more preferably 0.94 to 1.06, and most preferably 0.95 to 1.05.
    [592] A diamine represented by the general formula (13), (14) or (15) and other diamines partially added, a tetracarboxylic acid dianhydride represented by the general formula (16) and some additional tetracarboxylic acid dianhydrides, The method of adding the dicarboxylic acid anhydride represented by the general formula (5) and / or (7) or the aromatic monoamine represented by the general formula (6) or (8)
    [593] I) reacting a diamine with tetracarboxylic dianhydride and then adding a dicarboxylic acid anhydride or an aromatic monoamine to react;
    [594] Ii) adding a dicarboxylic acid anhydride to the diamine and reacting, then adding a tetracarboxylic acid dianhydride, and continuing the reaction further;
    [595] Iii) a method in which an aromatic monoamine is added to tetracarboxylic dianhydride and reacted, and then a diamine is added to continue the reaction;
    [596] Iv) a method of dividing the whole amount of the dicarboxylic anhydrides, adding one to the diamine first, then adding tetracarboxylic dianhydride, continuing further reaction, and then continuing the reaction by adding the other ;
    [597] V) a method of dividing the whole amount of the aromatic monoamine, adding one to the tetracarboxylic dianhydride first, then adding the diamine, continuing the reaction, and then continuing the reaction by adding the other one;
    [598] (Vi) a method of combining the above methods (i) to (v), and any of the addition methods may be employed.
    [599] The reaction for producing the polyimide of the present invention is usually carried out in a solvent. As the solvent,
    [600] m) As a solvent which is a phenolic solvent, o-chlorophenol, m-chlorophenol, p-chlorophenol,
    [601] O-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6- - xylenol, 3,5-xylenol;
    [602] N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide;
    [603] (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- Methoxyethoxy) ethyl] ether, 1,4-dioxane;
    [604] p) an amine-based solvent such as pyridine, quinoline, isoquinoline, -picoline, -picoline, -picoline, isophorone, pyrrolidine, 2,4-lutidine, 2,6- , Triethylamine, tripropylamine, tributylamine;
    [605] g) Other solvents such as dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, and anisole. These solvents may be used alone or in combination of two or more. In this reaction, it is not necessary to select a combination of solvents to be mutually dissolved at an arbitrary ratio, and it is not necessary to mix them so that they may be uneven.
    [606] In addition, there is no problem even if the solvent shown below coexists. Examples of the coexisting organic solvent include organic solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, Bromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, and p- Toluene.
    [607] There is no limitation on the concentration of the reaction (hereinafter referred to as polymerization concentration) in these solvents. In the present invention, the polymerization concentration in the solvent is preferably the total weight of the total diamine and total tetracarboxylic dianhydride used, based on the total weight of the total weight of the total solvent used and the total weight of the total diamine and total tetracarboxylic dianhydride used, Is defined as a value expressed as a percentage. The preferred polymerization concentration is 5 to 40%, more preferably 10 to 30%, and the most preferable polymerization concentration is 15 to 25%.
    [608] The reaction for producing the polyimide for an optical member of the present invention is preferably carried out in a solvent,
    [609] I) reacting the diamine and / or tetracarboxylic dianhydride at a temperature above the melting point of the dianhydride and / or tetracarboxylic dianhydride in the melt state;
    [610] Ii) a method in which the diamine and / or tetracarboxylic dianhydride is reacted in a vaporized state under reduced pressure or the like;
    [611] Iii) a method of activating the diamine and / or tetracarboxylic dianhydride by activating external energy such as light, ultrasonic waves and plasma may be performed.
    [612] The diamine of the formula (13), (14) or (15), the tetracarboxylic acid dianhydride of the formula (16) and optionally the dicarboxylic acid anhydride of the formula (5) and / , Or an aromatic monoamine of the general formula (6) and / or (8) to obtain the polyimide or polyamic acid of the present invention.
    [613] In producing a polyamide, first, a polyamic acid which is a polyimide precursor is prepared. The polyamic acid can be prepared by reacting the diamine of the formula (13), (14) or (15), the tetracarboxylic acid dianhydride of the formula (16) and the dicarboxylic acid anhydride of the formula (5) Is obtained by reacting an aromatic monoamine of formula (6). Particularly preferred solvents in this reaction include the nonprotonic amide solvent of the above n) and the ether solvent of the o). The reaction temperature, the reaction time and the reaction pressure are not particularly limited, and known conditions can be applied.
    [614] That is, the reaction temperature is preferably in the range of about -10 DEG C to 100 DEG C, more preferably in the range of about -50 DEG C to about -50 DEG C, and most preferably room temperature. The reaction time varies depending on the kind of the monomer to be used, the kind of the solvent, and the reaction temperature, but is preferably 1 to 48 hours. More preferably from about 2 hours to about 10 hours, and most preferably from 4 hours to 10 hours. Further, the reaction pressure is sufficient at normal pressure. The logarithmic viscosity of the obtained polyamic acid is in the range of 0.1 to 2.0 dl / g (measured in N, N-dimethylacetamide at a concentration of 0.5 g / dl at 35 캜). When the logarithmic viscosity is less than 0.1, the molecular weight is lowered, so that the mechanical properties remarkably deteriorate. When the logarithmic viscosity is more than 2.0, the melt viscosity is increased.
    [615] The polyimide of the present invention is obtained by subjecting a polyamic acid obtained by the above method to a dehydrating imidization reaction by a known method. The method can be categorized into a chemical imidation method and a thermal imidation method, and all dehydration imidation methods can be applied including a method in which both of them are used in combination.
    [616] In the chemical imidation method, dehydration is chemically performed by reacting the polyamic acid obtained by the above method with a dehydrating agent having hydrolysis ability. The dehydrating agent to be used is selected from the group consisting of aliphatic carboxylic acid anhydrides represented by anhydrous acetic acid, trifluoroacetic anhydride, polyphosphoric acid, phosphoric acid derivatives represented by phosphorus pentoxide, mixed acid anhydrides thereof, methanesulfonic acid chloride, phosphorus pentachloride and thionyl chloride There may be mentioned representative acid chlorides. These dehydrating agents may be used alone or in combination of two or more. The amount of the dehydrating agent used is 2 to 10 molar equivalents, preferably 2.1 to 4 molar equivalents relative to 1 mol of the diamine used.
    [617] In the chemical imidation method, a base catalyst may be coexistent. The base catalyst used can also be used as the base catalyst in the amine-based solvent of the above p). In addition to them, organic bases such as imidazole, N, N-dimethylaniline and N, N-diethylene aniline; And inorganic bases typified by potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate. The amount of these catalysts to be used is 0.001 to 0.50 molar ratio, preferably 0.05 to 0.2 molar ratio with respect to 1 mol of the diamine to be used.
    [618] The reaction temperature, the reaction time and the reaction pressure of the chemical imidation method are not particularly limited, and known conditions can be applied. That is, the reaction temperature is preferably -10 ° C to 120 ° C, more preferably about room temperature to about 70 ° C, and most preferably room temperature. The reaction time varies depending on the kind of solvent used and other reaction conditions, but is preferably about 1 to 24 hours, more preferably about 2 to 10 hours. The reaction pressure is sufficient at normal pressure. As the atmosphere, air, nitrogen, helium, neon, and argon are used, and nitrogen or argon, which is an inert gas, is preferably selected although there is no particular limitation.
    [619] The heat imidization method
    [620] I) a method of thermally dehydrating polyamic acid by heating the polyamide acid by the above method;
    [621] Ii) Monomers and dicarboxylic acid anhydrides used for simultaneous polymerization and dehydromidation reaction to obtain a polyimide acid without isolating the polyamic acid are directly heated in the state of being dissolved or suspended in a solvent, In which dehydration is carried out in the presence of a catalyst. In the above item i), any form of a solution in which polyamide acid is dissolved in a solvent, a suspension in which the polyamide acid is dispersed, and a solid of polyamic acid isolated from the solution or suspension solution may be used. When the solution or suspension is heated, the solvent may be refluxed even if the solvent used is evaporated and removed while the dehydration is carried out. The former is most suitably applied to the film formation of the film, and the latter is suitable for dehydration and the like in the reactor. Particularly preferred solvents used in the process of the above ii) are phenolic solvents of the above item m).
    [622] In addition, the thermal imidation method may be performed by coexistence of a base catalyst as well as a chemical imidation method. The base catalyst to be used and its amount to be used are the same as those described in the above-mentioned chemical imidation method.
    [623] In addition, other solvents may be coexisted to remove water generated by the dehydration-imidization reaction. The solvent to be used herein is at least one solvent selected from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, , m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, . These solvents may be used alone or in combination of two or more. Further, one or a mixture of two or more of them may be further used by using the solvents described in the above items m) to q). In the case of using them in combination, it is not necessary to select a combination of solvents which are mutually dissolved in an arbitrary ratio. There is no restriction on the amount of dehydrating agent used.
    [624] The reaction temperature, the reaction time and the reaction pressure of the thermal imidation method are not particularly limited, and known conditions can be applied. That is, the reaction temperature is preferably 80 ° C to 400 ° C, more preferably approximately 100 ° C to 300 ° C, and most preferably approximately 150 ° C to 250 ° C. The reaction time varies depending on the type of the solvent to be used and other reaction conditions, but is preferably from 0.5 to 24 hours, more preferably from 2 to 10 hours. Further, the reaction pressure is sufficient at normal pressure. Air, nitrogen, helium, neon, and argon are used as the atmosphere, and nitrogen or argon, which is an inert gas, is preferably selected, although there is no particular limitation.
    [625] As a method of combining the chemical imidation method and the thermal imidation method
    [626] I) a method in which the heating is simultaneously carried out in the execution of the chemical imidation method;
    [627] And ii) a method in which the dehydrating agent used in the chemical imidization coexists when the heat imidizing method is performed.
    [628] With regard to the method of manufacturing the optical member, a usual manufacturing method can be applied. The polyimide solution for an optical lens of the present invention or a polyamic acid solution which is a precursor of a polyimide is encapsulated in a mold having a shape of an optical member or cast on a substrate having an optical lens shape, By performing desolvation, the optical lens can be easily formed. The thermoplastic polyimide can be easily made into an optical lens by a method such as injection molding in a mold having a shape of an optical lens. Further, regardless of the thermoplastic and non-thermoplastic properties, the optical lens can be formed by cutting and polishing a rod-like or sheet-like polyimide resin.
    [629] The polyimide optical member obtained by the above method can be used as it is, or after the surface is protected. When the surface is protected, a commonly used cover coat material, a cover glass, or the like can be used. When the cover glass is protected by a cover glass, a commonly used method such as adhesion by an adhesive or heat pressing by heating can be applied as a method for attaching the cover glass.
    [630] In the method of the present invention, when the structure capable of introducing a crosslinked structure is used in the general formula (7) or (8), the resulting polyimide resin molded article is subjected to heat treatment and crosslinking.
    [631] The optical member made of the polyimide resin according to the present invention is obtained by heat-treating a polyimide containing a crosslinkable group. The "heat treatment" in the present invention means that the carbon-carbon double bond or the triple bond in the crosslinking group-containing dicarboxylic acid anhydride introduced into the molecular end of the chemical reaction thermally reacts to generate crosslinking between the molecular chains . The temperature, time, pressure and method of the heat treatment are not particularly limited, but are shown below as typical examples.
    [632] The heat treatment temperature is usually about 250 to 350 占 폚, preferably about 250 to 330 占 폚, and most preferably about 260 to 300 占 폚. The crosslinking reaction is unlikely to occur at a temperature lower than 250 DEG C, and the crosslinking polyimide tends to undergo denaturation at temperatures exceeding 350 DEG C, and it is difficult to sufficiently obtain the characteristics as the optical lens.
    [633] The heat treatment time varies depending on other heat treatment conditions, but is preferably 0.1 to 100 hours, more preferably about 1 to 30 hours, and most preferably about 2 to 10 hours. If the heat treatment time is shorter than 0.1 hour, Is insufficient, and when it exceeds 100 hours, the crosslinking polyimide tends to undergo denaturation, and it is difficult to sufficiently obtain the properties.
    [634] The heat treatment pressure is usually atmospheric pressure, but it can also be performed under pressure. The heat treatment atmosphere is not particularly limited, but is usually air, nitrogen, helium, neon or argon, preferably nitrogen or argon, which is inert gas.
    [635] Further, a metal catalyst containing gallium, germanium, indium and lead, molybdenum, manganese, nickel, cadmium, cobalt, chromium, iron and the like may be added for the purpose of controlling the reaction rate by promoting or suppressing the cross- , Copper, tin and platinum, and a phosphorus compound, a silicon compound, a nitrogen compound, and a sulfur compound. For the same purpose, irradiation with infrared rays, ultraviolet rays, alpha, beta, gamma rays, electron beams and X rays, plasma treatment or doping treatment may be performed.
    [636] The optical member made of the polyimide resin obtained by the heat treatment as described above has excellent chemical resistance.
    [637] Test methods for various tests common to the examples and comparative examples are as follows.
    [638] [Logarithmic Viscosity of Polyamic Acid] ( Inh )
    [639] N, N-dimethylacetamide at a concentration of 0.50 g / 100 ml, and then measured at 35 ° C.
    [640] [Production method of film]
    [641] The polyamic acid varnish was cast on a glass plate and heated at 100 DEG C and 200 DEG C for 30 minutes and then at 250 DEG C for 1 hour under a nitrogen atmosphere to desolvate and imidize the polyimide film.
    [642] [Evaluation method of film]
    [643] A film was prepared from the polyamic acid varnish by the above method and evaluated by the following method.
    [644] 1) Glass transition temperature (Tg)
    [645] DSC measurement, value measured at a heating temperature of 16 캜 / min
    [646] 2) 5% weight reduction temperature (Td 5 )
    [647] DATA-TG measurement, value measured at a heating temperature of 10 ° C / min
    [648] 3) Refractive index (n)
    [649] TE value measured by METRICON prism coupler 2010/633 nm
    [650] 4) The birefringence ( N)
    [651] The TE-TM value measured by a METRICON prism coupler 2010/633 nm
    [652] 5) T% 500 nm
    [653] The light transmittance at 500 nm (measured by Shimadzu UV-3100PC)
    [654] 6) T% 420 nm
    [655] The light transmittance at 420 nm (measured by Shimadzu UV-3100PC)
    [656] 7) Solvent resistance: A polyimide film of 1 cm x 2 cm was immersed in various solvents at room temperature, and after 24 hours, the solvent resistance was observed by visual observation.
    [657] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
    [658] Example A
    [659] [Example A1]
    [660] 36.03 g (0.100 mol) of 1,3-bis (3-aminophenoxy) -4-trifluoromethylbenzene and 194.58 g of N, N-dimethylacetamide as a solvent were placed in a vessel equipped with a stirrer, And the mixture was stirred and dissolved in a nitrogen atmosphere for 30 minutes. Thereafter, 28.83 g (0.098 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added in portions while paying attention to the rise of the solution temperature, followed by stirring at room temperature for 6 hours. The logarithmic viscosity of the polyamic acid thus obtained was 0.69 dl / g. From the obtained polyamide acid varnish, a film was prepared by the above-mentioned method, and the thermo-physical properties and optical properties of the obtained polyimide film were evaluated.
    [661] The amount of diamine, tetracarboxylic dianhydride and the physical properties of the obtained polyamic acid varnish are shown in Table A1, and the physical properties of the polyimide film are shown in Table A2.
    [662] [Examples A2 to A40]
    [663] Various diamines and acid anhydrides were used to prepare various polyamide acid varnishes in the same manner as in Example 1. A polyimide film was prepared from the polyamide acid varnish by the above method and evaluated for thermal and optical properties did. The amount of the diamine, tetracarboxylic dianhydride used and the physical properties of the obtained polyamic acid varnish are shown in Table A1, and the physical properties of the polyimide film are shown in Table A2.
    [664] [Example A41]
    [665] A polyamic acid varnish was synthesized in the same manner as in Example A1, 0.59 g (0.004 mol) of phthalic anhydride was added, and the mixture was stirred for another 6 hours. Using the obtained polyamic acid varnish, a polyimide film was produced by the same method as above, and the thermal properties and the optical properties were evaluated. The amounts of diamine, tetracarboxylic dianhydride, end-capping agent used and physical properties of the obtained polyamic acid varnish are shown in Table A3, and the physical properties of the polyimide film are shown in Table A4.
    [666] [Examples A42 to A80]
    [667] Various polyamidic acid varnishes were prepared in the same manner as in Example A1 using various diamines, acid anhydrides, dicarboxylic acid anhydrides and aromatic monoamines. A polyimide film was prepared from the polyamide acid varnish by the above-mentioned method, and the thermal and optical properties were evaluated. The amounts of diamine, tetracarboxylic dianhydride, end-capping agent used and physical properties of the obtained polyamic acid varnish are shown in Table A3, and the physical properties of the polyimide film are shown in Table A4.
    [668] [Comparative Examples A1 to A4]
    [669] A polyamic acid varnish was synthesized by using a polyimide monomer other than the polyimide monomer of the present invention. From the polyamic acid varnish thus obtained, a polyimide film was prepared by the above-mentioned method, and thermal properties and optical properties were evaluated. The amount of the diamine, tetracarboxylic dianhydride, the endcapping agent used, and the physical properties of the resulting polyamide acid varnish are shown in Table A5, and the physical properties of the polyimide film are shown in Table A6.
    [670] From the basic physical properties of the polyimide film, it has been confirmed that the polyimide resin of the present invention is useful as an optical member.
    [671] In the Examples and Comparative Examples, the diamine component, tetracarboxylic dianhydride, monoamine, and dicarboxylic acid anhydride components used are represented by the following abbreviations.
    [672] 3,4'-ODA-CF 3: 3,4'- diamino a 2'-trifluoromethyl-diphenyl-ether;
    [673] 4,4'-ODA-CF 3: 4,4'- diamino-2'-trifluoromethyl-diphenyl-ether;
    [674] APB-CF 3 -1: 1,3- bis (3-aminophenoxy) benzene, methyl-4-trifluoromethyl;
    [675] APB-CF 3 -2: 1,3- bis (3-aminophenoxy) benzene, methyl-5-trifluoromethyl;
    [676] APB-CN: 2,6-bis (3-aminophenoxy) benzonitrile;
    [677] APB-Cl: 1,3-bis (3-aminophenoxy) -5-chlorobenzene;
    [678] APB-Br: 1,3-bis (3-aminophenoxy) -5-bromobenzene;
    [679] APB-2CF 3 : 3-bis (3-amino-5-trifluoromethylphenoxy) benzene;
    [680] APB-3CF 3 : 1,3-bis (3-amino-5-trifluoromethylphenoxy) -4-trifluoromethylbenzene;
    [681] P-BP-CF 3: 4,4'- bis (4-amino-2-methylphenoxy trifluoromethyl) biphenyl;
    [682] m-BP-CF 3: 4,4'- bis (3-methylphenoxy-5-trifluoromethyl) biphenyl;
    [683] p-BO-CF 3: bis [4- (4-methylphenoxy-amino-2-trifluoromethyl) phenyl] ether;
    [684] m-BO-CF 3: bis [4- (3-methylphenoxy-5-trifluoromethyl) phenyl] ether;
    [685] PAPS-CF 3: bis [4- (4-methylphenoxy-amino-2-trifluoromethyl) phenyl] sulfide;
    [686] MPAS-CF 3: bis [4- (4-methylphenoxy-amino-2-trifluoromethyl) phenyl] sulfide;
    [687] p-BS-CF 3: bis [4- (4-amino-2-methylphenoxy trifluoromethyl) phenyl] sulfone;
    [688] m-BS-CF 3: bis [4- (3-methylphenoxy-5-trifluoromethyl) phenyl] sulfone;
    [689] p-CO-CF 3: bis [4- (4-methylphenoxy-amino-2-trifluoromethyl) phenyl] ketone;
    [690] m-CO-CF 3: bis [4- (3-methylphenoxy-5-trifluoromethyl) phenyl] ketone;
    [691] 6F-BAPP-CF 3 -1: 2,2- bis [4- (4-amino-2-methylphenoxy tree Paul Luo) phenyl -1,1,1,3,3,3-- hexafluoro Propane;
    [692] 6F-BAPP-CF 3 -2: 2,2- bis [4- (3-amino-5-methylphenoxy tree Paul Luo) phenyl -1,1,1,3,3,3-- hexafluoro Propane;
    [693] PA; phthalic anhydride; PPA: 4-phenylphthalic anhydride
    [694] DPEA: 3,4-diphenyl ether dicarboxylic acid anhydride;
    [695] NDA: 1,8-naphthalene dicarboxylic acid anhydride;
    [696] AN: aniline; ClAN: 4-chloroaniline; MAN: 4-methylaniline;
    [697] ABP: 4-aminobiphenyl.
    [698] It can be seen from the examples and the comparative examples that the polyimide of the present invention has a higher refractive index than that of the polyimide of the comparative example but has a high light transmittance and a sufficiently low birefringence. It is also understood that any of the polyimides of the present invention is useful as a lens having a glass transition temperature of 150 ° C or higher, a 5% weight reduction temperature of 500 ° C or higher, a 5% weight reduction temperature of 500 ° C or higher and heat resistance.
    [699] Example B
    [700] [Example B1]
    [701] 20.03 g (0.100 mol) of 3,3'-diaminodiphenyl ether and 146.58 g of N, N-dimethylacetamide as a solvent were charged in a vessel equipped with a stirrer, a nitrogen introducing tube and a thermometer and stirred for 30 minutes in a nitrogen atmosphere And dissolved. Thereafter, 28.83 g (0.098 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added in portions while paying attention to the rise of the solution temperature, followed by stirring at room temperature for 6 hours. The logarithmic viscosity of the polyamic acid thus obtained was 0.72 dl / g.
    [702] From the obtained polyamide acid varnish, a film was prepared by the above-mentioned method, and the thermo-physical properties and optical properties of the obtained polyimide acid film were evaluated.
    [703] The amount of diamine, tetracarboxylic dianhydride and the physical properties of the obtained polyamic acid varnish are shown in Table B1, and the physical properties of the polyimide film are shown in Table B2.
    [704] [Examples B2 to B40]
    [705] Various diamines and acid anhydrides were used to prepare various polyamide acid varnishes in the same manner as in Example B1, and polyimide films were prepared from the polyamide acid varnishes by the above-mentioned method, and the thermal and optical properties were evaluated did. The amount of the diamine, tetracarboxylic dianhydride used and the physical properties of the obtained polyamic acid varnish are shown in Table B1, and the physical properties of the polyimide film are shown in Table B2.
    [706] [Example B41]
    [707] A polyarylate varnish was synthesized in the same manner as in Example B1, and 0.59 g (0.004 mol) of phthalic anhydride was added thereto, followed by stirring for another 6 hours. Using the obtained polyamic acid varnish, a polyimide film was produced by the same method as above, and the thermal properties and the optical properties were evaluated. The amounts of diamine, tetracarboxylic dianhydride, end-capping agent used and physical properties of the obtained polyamic acid varnish are shown in Table B3, and the physical properties of the polyimide film are shown in Table B4.
    [708] [Examples B42 to B80]
    [709] Various polyamidic acid varnishes were prepared in the same manner as in Example B1 using various diamines, acid anhydrides, dicarboxylic acid anhydrides and aromatic monoamines. A polyimide film was prepared from the polyamide acid varnish by the above-mentioned method, and the thermal and optical properties were evaluated. The amounts of diamine, tetracarboxylic dianhydride, end-capping agent used and physical properties of the obtained polyamic acid varnish are shown in Table B3, and the physical properties of the polyimide film are shown in Table B4.
    [710] [Comparative Examples B1 to B4]
    [711] A polyamic acid varnish was synthesized by using a polyimide monomer other than the polyimide monomer of the present invention. From the polyamic acid varnish thus obtained, a polyimide film was prepared by the above-mentioned method, and thermal properties and optical properties were evaluated. The amount of the diamine component, the tetracarboxylic dianhydride, the amount of the end-capping agent, and the physical properties of the obtained polyamic acid varnish are shown in Table B5 and the physical properties of the polyimide film are shown in Table 6.
    [712] The diamine component, tetracarboxylic dianhydride, monoamine and dicarboxylic acid anhydride components used in Examples and Comparative Examples are represented by the following abbreviations.
    [713] 4,4'-ClBP: 4,4'-diamino-2,2'-dichlorobiphenyl;
    [714] 4,4'-CF 3 BP: 4,4'-diamino-2,2'-ditrifluoromethylbiphenyl;
    [715] 4,4'-CH 3 BP: 4,4'- diamino-3,3'-dimethyl biphenyl;
    [716] 3,3'-ODA: 3,3'-diaminodiphenyl ether;
    [717] 3,4'-ODA: 3,4'-diaminodiphenyl ether;
    [718] 4,4'-ODA: 4,4'-diaminodiphenyl ether;
    [719] 3,3'-DASO 2 : 3,3'-diaminodiphenylsulfone;
    [720] 4,4'-DASO 2 : 4,4'-diaminodiphenylsulfide;
    [721] 3,3'-DAS: 3,3'-diaminodiphenylsulfide;
    [722] 3,3'-MDA: 3,3'-diaminodiphenylmethane;
    [723] 3,3'-DABP: 3,3'-diaminobenzophenone;
    [724] APB: 1,3-bis (3-aminophenoxy) benzene;
    [725] pm-APB: 1,3-bis (4-aminophenoxy) benzene;
    [726] mp-APB: 1,4-bis (3-aminophenoxy) benzene;
    [727] pp-APB: 1,4-bis (4-aminophenoxy) benzene;
    [728] m-BP: 4,4'-bis (3-aminophenoxy) biphenyl;
    [729] p-BP: 4,4'-bis (4-aminophenoxy) biphenyl;
    [730] MAPS: bis [4- (3-aminophenoxy) phenyl] sulfide;
    [731] m-BS: bis [4- (3-aminophenoxy) phenyl] sulfone;
    [732] m-BO: bis [4- (3-aminophenoxy) phenyl] ether;
    [733] m-CO: bis [4- (3-aminophenoxy) phenyl] ketone;
    [734] m-BAPP: 2,2-bis [4- (3-aminophenoxy) phenyl] propane;
    [735] 6F-BAPP: 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane;
    [736] PA: phthalic anhydride;
    [737] PPA: 4-phenylphthalic anhydride;
    [738] DPEA: 3,4-diphenyl ether dicarboxylic acid anhydride;
    [739] NDA: 1,8-naphthalene dicarboxylic acid anhydride;
    [740] AN: aniline;
    [741] ClAN: 4-chloroaniline;
    [742] MAN: 4-methylaniline;
    [743] APB: 4-aminobiphenyl.
    [744] From the examples and comparative examples, it can be seen that the polyimide of the present invention has a higher refractive index than the polyimide of the comparative example, but has a higher light transmittance. In addition, all of the polyimides of the present invention are useful as microlenses, guide lenses, and optical filters having a glass transition temperature of 150 ° C or higher and a 5% weight reduction temperature of 500 ° C or higher and having heat resistance.
    [745] According to the present invention, it is possible to provide a polyimide excellent in physical properties inherent to the polyimide, that is, excellent in heat resistance, mechanical properties, sliding characteristics, low absorptivity, electrical properties, thermal oxidation stability, chemical resistance and radiation resistance, It has become possible to provide a polyimide microlens for optical use.
    [746] Example C
    [747] [Example C1]
    [748] 10.02 g (0.05 mol) of 3,3'-diaminodiphenyl ether and 73.29 g of N, N-dimethylacetamide were charged in a vessel equipped with a stirrer and a nitrogen inlet tube and stirred for 30 minutes under a nitrogen atmosphere. Thereafter, 14.42 g (0.049 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added in portions while paying attention to the rise of the solution temperature, and the mixture was stirred at room temperature for 6 hours. Then, 0.20 g (0.002 mol) of maleic anhydride was added and stirred for another 10 hours. The logarithmic viscosity of the polyamic acid thus obtained was 0.68 dl / g.
    [749] A part of the above polyamic acid solution was taken and cast on a glass plate and then heated at 100 ° C, 200 ° C and 250 ° C for 1 hour, respectively, to produce polyimide film-1 (measurement of thermal properties, light transmittance, For evaluation).
    [750] Further, the polyamide acid varnish was spin-coated on a silicon wafer, and then heated at 100 DEG C, 200 DEG C, and 250 DEG C for 1 hour under a nitrogen atmosphere to produce polyimide film-2 (refractive index measurement).
    [751] The polyimide film-1,2 (polyimide film) was heat-treated again at 280 占 폚 to prepare a heat-treated polyimide film-1, 2 (collectively referred to as a heat-treated polyimide film).
    [752] The thermal properties, optical properties and chemical resistance of the polyimide film and the heat-treated polyimide film were evaluated. The evaluation results are shown in Table C1.
    [753] [Example C2, C3]
    [754] Various evaluations were carried out in the same manner as in Example C1 except that the polyimide film was obtained from the polyamide acid varnish obtained in Example C1 and then the heat treatment temperature was changed to 300 占 폚 and 320 占 폚. Evaluation results and the like are shown in Table C1.
    [755] [Examples C4 to C84]
    [756] Diamine, tetracarboxylic acid dianhydride and dicarboxylic acid anhydride were used in the same manner as in Examples C1 to C3 except that the kind and amount of the diamine, tetracarboxylic acid dianhydride and dicarboxylic acid anhydride were changed to those shown in Table C1 and the heat treatment was conducted again at the temperature shown in Table C1. And the results of each test are shown in Table C1.
    [757] [Comparative Examples C1, C2] (Reference Example)
    [758] A polyamide acid varnish or polyimide film was obtained in the same manner as in Example C1 except that the dicarboxylic acid anhydride was not used. The obtained polyimide film was heated at the heat treatment temperature shown in Table C2 to obtain a heat-treated polyimide film. The physical properties of the polyamic acid varnish and the results of the respective tests are shown in Table C2.
    [759] [Comparative Example C3, C4] (Reference Example)
    [760] A polyamic acid varnish or polyimide film was obtained in the same manner as in Example C1 except that phthalic anhydride was used in the dicarboxylic acid anhydride. The obtained polyimide film was heated at the heat treatment temperature shown in Table C2 to obtain a heat-treated polyimide film. The physical properties of the polyamic acid varnish and the results of the respective tests are shown in Table C2.
    [761] [For comparison, C5 to C8] (Reference Example)
    [762] The physical properties of the polyamic acid varnish when heated at the heat treatment temperature outside the scope of the present invention and the results of the respective tests are shown in Table C2.
    [763] [Comparative Example C9, C10]
    [764] A polyamic acid varnish was synthesized by using a polyimide monomer other than the polyimide monomer of the present invention. A polyimide film and a heat-treated polyimide film were prepared from the obtained polyamic acid varnish by the above-mentioned method, and the results of the respective tests are shown in Table C2.
    [765] In Examples and Comparative Examples, diamines, tetracarboxylic dianhydrides, dicarboxylic acid anhydrides, and used drugs are represented by the following abbreviations.
    [766] [Diamine]
    [767] 3,3'-ODA: 3,3'-diaminodiphenyl ether;
    [768] 4,4'-ODA: 4,4'-diaminodiphenyl ether;
    [769] 4,4'-ClBP: 4,4'-diamino-2,2'-dichlorobiphenyl;
    [770] 4,4'-CF 3 BP: 4,4'-diamino-2,2'-ditrifluoromethylbiphenyl;
    [771] 3,3'-DAS: 3,3'-diaminodiphenylsulfone;
    [772] APB: 1,3-bis (3-aminophenoxy) benzene;
    [773] APB-CF 3: 1,3- bis (3-aminophenoxy) -4-trifluoromethyl benzene;
    [774] APB-CN: 2,6-bis (3-aminophenoxy) benzonitrile;
    [775] APB-Cl: 1,3-bis (3-aminophenoxy) -5-chlorobenzene;
    [776] APB-2CF3: 1,3-bis (3-amino-5-trifluoromethylphenoxy) benzene;
    [777] APB-3CF3: 1,3-bis (3-amino-5-trifluoromethylphenoxy) -4-trifluoromethylbenzene;
    [778] m-BP: 4,4'-bis (3-aminophenoxy) biphenyl;
    [779] MAPS: bis [4- (3-aminophenoxy) phenyl] sulfide;
    [780] m-BS: bis [4- (3-aminophenoxy) phenyl] sulfone;
    [781] m-BO: bis [4- (3-aminophenoxy) phenyl] ether;
    [782] m-BAPP: 2,2-bis [4- (3-aminophenoxy) phenyl] propane;
    [783] 6F-BAPP: 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane;
    [784] MAPS-CF3: bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] sulfide;
    [785] m-BS-CF3: bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] sulfone;
    [786] m-BO-CF3: bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] ether;
    [787] 6F-BAPP-CF3: 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane;
    [788] (Tetracarboxylic dianhydride)
    [789] BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride;
    [790] ODPA: bis (3,4-dicarboxyphenyl) ether dianhydride;
    [791] 6FDA: 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride;
    [792] PMDA: pyromellitic dianhydride
    [793] (Dicarboxylic acid anhydride)
    [794] MA: maleic anhydride
    [795] NCA: 5-norbornene-2,3-dicarboxylic acid anhydride
    [796] EPA: 6-ethynyl phthalic anhydride;
    [797] HPA: cis-1,2,3,4-tetrahydrophthalic anhydride;
    [798] MM-MA: 2-methylmaleic anhydride;
    [799] DM-MA: 2,3-dimethyl maleic anhydride;
    [800] PA: phthalic anhydride
    [801] From the examples and comparative examples, it can be seen that the polyimide of the present invention is superior in chemical resistance to the polyimide of the comparative example. Further, if heating is performed in excess of the heat treatment temperature of the present invention, the chemical resistance is improved but the light transmittance is deteriorated, which is a problem in performance as a lens. The polyimide of the present invention has a high light transmittance and a sufficiently low birefringence. It is also understood that any of the polyimides of the present invention is useful as a lens having a glass transition temperature of 150 ° C or higher and a 5% weight reduction temperature of 500 ° C or higher and having heat resistance.
    [802] According to the present invention, the polyimide has inherent properties of being resistant to aging, that is, heat resistance, mechanical properties, sliding characteristics, low absorptivity, electrical properties, thermal oxidation stability, chemical resistance and radiation resistance, It becomes possible to provide optical members such as optical polyimide lenses, microlenses, guide lenses and optical filters, which are excellent in transparency and have high refractive index and low refractive index.
    [803] Example D
    [804] It was confirmed that the optical basic performance was measured in Examples A to C and could be used as various optical members. In Example D, concrete optical members were manufactured and their performance was confirmed.
    [805] Example D1 (Guide Lens)
    [806] 50.45 g (0.100 mol) of 4.4'-bis (3-amino-5-trifluoromethylphenoxy) biphenyl and 188.65 g (0.100 mol) of N, N-dimethylacetamide as a solvent were placed in a vessel equipped with a stirrer, And the mixture was stirred and dissolved in a nitrogen atmosphere for 30 minutes. Thereafter, 30.40 g (0.098 mol) of 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride was added in portions while paying attention to the rise of the solution temperature, followed by stirring at room temperature for 6 hours. The logarithmic viscosity of the polyamic acid thus obtained was 0.062 dl / g.
    [807] The obtained polyamic acid varnish was coated on a glass plate using a doctor blade, and then heated at 100 DEG C, 200 DEG C, and 250 DEG C for 1 hour, respectively, to obtain a polyimide film having a thickness of 50 mu m.
    [808] The thus obtained polyimide film was punched with a punch having a diameter of 38 mm, and 20 sheets of the polyimide film were superposed and thermoformed under the conditions of a temperature of 300 占 폚, a pressure of 98 MPa, and a time of 30 minutes to prepare a disk-shaped polyimide molding having a thickness of 1 mm. This molded article was a homogeneous polyimide molded article in which the films were completely fused and integrated with each other.
    [809] The ultraviolet-visible ray spectrum of the obtained molded article was measured, and the cut-off (wavelength at which the transmittance became zero) was 380 nm and the total light transmittance was 78%. Further, when the specimen had a specific gravity of 1.35 and a refractive index of 1.64 and subjected to a pressurized cooker test at 121 캜 for 12 hours and 24 hours, no apparent change was observed at all.
    [810] From the above results, the polyimide can completely absorb ultraviolet rays in the range of 200 to 300 nm, and has transparency to transmit most of the visible light in the 380 to 780 nm range. Therefore, in the state where it is buried in the guide, harmful ultraviolet rays are absorbed and cut to protect the retina, and since it is transparent in the visible region, sufficient visual acuity can be given. The transparent polyimide has a specific gravity as small as 1.35 and a refractive index of 1.64, which is larger than that of conventional PMMA. Therefore, the transparent polyimide is 3 to 50 times thinner than that of PMMA, and thus can be made light. Therefore, when it is buried in the guide, the burden on the eyes is light. Further, since the lens part in the guide lens uses a colorless transparent polyimide excellent in heat resistance, it can be easily sterilized by using the autoclave steam sterilization method.
    [811] [Example D2 (Guide lens)]
    [812] A polyamic acid varnish was synthesized in the same manner as in Example D1, 0.59 g (0.004 mol) of phthalic anhydride was added, and the mixture was stirred for another 6 hours. The logarithmic viscosity of the obtained polyamic acid was 0.61 dl / g. Using this polyamide acid varnish, coating and drying were carried out in the same manner as in Example D1 to obtain a polyimide film having a thickness of 50 탆. Further, molding was carried out in the same manner as in Example D1 to obtain a homogeneous polyimide molding having a thickness of 1 mm.
    [813] The ultraviolet-visible light spectrum of the obtained molded article was measured. The cut-off (wavelength at which the transmittance became zero) was 380 nm and the total light transmittance was 81%. Further, when the specific gravity was 1.35 and the refractive index was 1.64, and a presser cooker test of 12 atm and 24 hours was carried out, no apparent change was observed at all.
    [814] The total light transmittance was improved by 3% as compared with the polyimide of Example D1 in which the terminal was not sealed, and a guide lens having a light transmittance better than that of the polyimide rod end seal of the same structure was obtained.
    [815] [Example 3 (Guide lens)]
    [816] A polyamic acid varnish was synthesized by the same method as in Example D1, 0.39 g (0.004 mol) of phthalic anhydride was added, and the mixture was stirred for another 6 hours. The logarithmic viscosity of the obtained polyamic acid varnish was 0.60 dl / g. Using this polyamide acid varnish, coating and drying were conducted in the same manner as in Example D1 to obtain a polyimide film having a thickness of 50 占 퐉. Further, molding was carried out in the same manner as in Example D1 to obtain a homogeneous polyimide molding having a thickness of 1 mm.
    [817] The ultraviolet-visible ray spectrum of the obtained molded article was measured, and the cut-off (wavelength at which the transmittance became zero) was 380 nm and the total light transmittance was 80%. Further, when the specimen had a specific gravity of 1.35 and a refractive index of 1.64, and subjected to a pressurized cooker test at 121 캜 for 12 hours and 24 hours, no apparent change was observed at all.
    [818] The obtained polyimide molded product was heat-treated at 300 캜 for 2 hours, then immersed in DMF and chloroform, and the surface state was visually observed. As a result, no change was observed on the surface of any of the solvents. The refractive index after heat treatment was 1.64 and the total light transmittance was 76%. Further, the polyimide molded article not subjected to the heat treatment at 300 占 폚 was likewise immersed in DMF and chloroform, and the surface thereof became cloudy.
    [819] From the above results, it was found that the polyimide formed article after crosslinking obtained by heat-treating the polyimide treated with the crosslinkable end-capping agent had excellent solvent resistance.
    [820] [Example D4 (color filter)]
    [821] 36.03 g (0.100 mol) of 1,3-bis (3-aminophenoxy) -4-trifluoromethylbenzene and 151.34 g of N, N-dimethylacetamide as a solvent were placed in a vessel equipped with a stirrer, And the mixture was stirred and dissolved in a nitrogen atmosphere for 30 minutes. Thereafter, 28.83 g (0.098 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added in portions while paying attention to the rise of the solution temperature, followed by stirring at room temperature for 6 hours. The logarithmic viscosity of the polyamic acid thus obtained was 0.69 dl / g.
    [822] 100 g of the obtained polyamic acid varnish was transferred to a 250 ml polyethylene bottle and 20 g of phthalocyanine blue powder was added thereto and mixed well by a three-roll mill to obtain a heat-resistant coloring paste for a color filter. The varnish was applied on a glass plate using a doctor blade and heated and dried at 100 DEG C, 200 DEG C, and 250 DEG C for 1 hour, respectively, in a nitrogen atmosphere to prepare a test piece having a thickness of about 10 mu m on a glass plate. The sample was observed with naked eyes, and a clear blue filter without color turbidity was obtained.
    [823] [Example D5 (color filter)]
    [824] A polyamic acid varnish was synthesized by the same method as in Example D4, 0.59 g (0.004 mol) of phthalic anhydride was added, and the mixture was stirred for another 6 hours. The logarithmic viscosity of the obtained polyamic acid varnish was 0.66 dl / g. Phthalocyanine powders were mixed in the same manner as in Example D4 using this polyamide acid varnish to obtain a heat-resistant coloring paste for a color filter. This varnish was applied and dried in the same manner as in Example D4 to prepare a test piece of about 10 탆 on a glass plate.
    [825] The sample was observed with naked eyes, and a clear blue filter without color turbidity was obtained.
    [826] [Example D6 (color filter)]
    [827] A polyamic acid varnish was synthesized in the same manner as in Example D4, 0.39 g (0.004 mol) of maleic anhydride was added, and the mixture was stirred for another 6 hours. The logarithmic viscosity of the obtained polyamic acid varnish was 0.67 dl / g, and the polyamic acid varnish was used to mix the phthalocyanine powder in the same manner as in Example D4 to obtain a heat-resistant coloring paste for a color filter. This varnish was applied and dried in the same manner as in Example D4 to prepare a test piece of about 10 탆 on a glass plate.
    [828] The sample was heat-treated at 280 ° C for 2 hours, immersed in DMF and chloroform, and the surface state was visually observed. No change in the surface was observed in any of the solvents.
    [829] Further, a color filter not subjected to heat treatment at 280 占 폚 was likewise immersed in DMF and chloroform, and its surface was cloudy.
    [830] From the above results, it can be seen that the polyimide after crosslinking obtained by heat-treating the polyimide treated with the crosslinkable end-capping agent has excellent solvent resistance.
    [831] [Example D7 (micro lens)]
    [832] 36.85 g (0.100 mol) of 4,4'-bis (3-aminophenoxy) -biphenyl and 156.92 g of N, N-dimethylacetamide as a solvent were charged in a vessel equipped with a stirrer, And dissolved by stirring in a nitrogen atmosphere for 30 minutes. Thereafter, 30.40 g (0.098 mol) of 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride was added in portions while paying attention to the rise of the solution temperature, followed by stirring at room temperature for 6 hours. The logarithmic viscosity of the polyamic acid thus obtained was 0.52 dl / g.
    [833] The obtained polyamide acid varnish was coated on a glass plate having a plurality of hemispherical concavities each having a diameter of 30 占 퐉 using a doctor blade and then heated and dried at 100 占 폚, 200 占 폚 and 250 占 폚 for one hour, Was obtained as a microlens.
    [834] The refractive index of the obtained microlens was 1.68, the light transmittance at 420 nm was 65%, the light transmittance at 500 to 700 nm was 90% or more, and the shape of the microlens was good.
    [835] [Example D8 (micro lens)]
    [836] A polyamic acid varnish was synthesized by the same method as in Example D7, 0.59 g (0.004 mol) of phthalic anhydride was added, and the mixture was stirred for another 6 hours. The logarithmic viscosity of the obtained polyamic acid varnish was 0.51 dl / g. Using this polyamic acid varnish, a glass substrate containing polyamide as a microlens was obtained in the same manner as in Example D7.
    [837] The refractive index of the obtained microlens was 1.68, the light transmittance at 420 nm was 68%, the light transmittance at 500 to 700 nm was 90% or more, and the shape of the microlens was good. The light transmittance at 420 nm was 3% higher than that of the polyimide of Example D7 in which the terminal was not encapsulated, and a microlens having a better light transmittance was obtained by polyimide end-cap sealing of the same structure.
    [838] [Example D9 (micro lens)]
    [839] A polyamic acid varnish was synthesized by the same method as in Example D7, 0.39 g (0.004 mol) of maleic anhydride was added, and the mixture was stirred for another 6 hours. Using the obtained polyamic acid varnish, a glass substrate having polyimide as a microlens was obtained in the same manner as in Example D7. The refractive index of this microlens was 1.68, the light transmittance at 420 nm was 65%, the light transmittance at 500 to 700 nm was 90% or more, and the shape of the microlens was good.
    [840] The obtained glass substrate having the microlenses was heat-treated at 300 캜 for 2 hours, immersed in DMF and chloroform, and the surface state was visually observed. As a result, no change was observed on the surface of any of the solvents. The refractive index of the microlens after the heat treatment was 1.68, the light transmittance at 420 nm was 63%, the light transmittance at 500 to 700 nm was 88% or more, and the shape of the microlens was good. A glass substrate having a microlens not subjected to heat treatment at 300 占 폚 was likewise immersed in DMF and chloroform, and the surface of the glass substrate was opaque.
    [841] From the above results, it can be seen that the polyimide after crosslinking obtained by heat-treating the polyimide treated with the crosslinkable end-capping agent has excellent solvent resistance.
    权利要求:
    Claims (8)
    [1" claim-type="Currently amended] An optical member obtained by using a polyimide resin comprising a repeating structural unit represented by the general formula (1) as an essential component.
    In the general formula (1), A represents a general formula (2), (3) or (4), and X represents a direct bond, -o -, -SO 2 -, or -C (CF 3 ) 2 Display.
    In the general formula (2), A 1 represents a direct bond, -O-, -S-, -SO 2 -, -CO-, C (CH 3 ) 2 or -C (CF 3 ) 2 -.
    In the general formula (3), R 3 , R 4 and R 5 represent H, Cl, Br, CN, CH 3 or CF 3 .
    In the general formula (4), A 2 represents a direct bond, -O-, -S-, -SO 2 -, -CO-, C (CH 3 ) 2 or -C (CF 3 ) 2 -. In the general formula (4), R 6 and R 7 represent H or CF 3 .
    [2" claim-type="Currently amended] The positive resist composition according to claim 1, which comprises a polyimide resin in which the terminal of the polyimide represented by the general formula (1) according to claim 1 is encapsulated by a structure represented by the following general formula (5) or (6) .
    [In the formula (5), Ar1 represents one species selected from the group of the formula (I), and Y represents one species selected from the group of the formula (II).
    In the general formula (6), Ar2 represents one species selected from the group of the formula (III), and Z represents one species selected from the group of the formula (IV).
    [3" claim-type="Currently amended] The polyimide resin composition according to claim 1, wherein the terminal of the polyimide represented by the general formula (1) according to claim 1 is encapsulated by a structure capable of introducing a crosslinking structure represented by the following general formula (7) or (8) An optical member comprising a polyimide resin.
    In the general formula (7), Ar 3 represents one kind selected from the group of the formula (V), and R 6 to R 13 in the formula (V) each represent H, F, CF 3 , CH 3 , C 2 H 5 Or a phenyl group, and they may be the same or different.
    In the general formula (8), Ar4 represents one species selected from the group of the formula (VI).] [4" claim-type="Currently amended] The optical member according to any one of claims 1 to 3, wherein the optical member is a microlens.
    [5" claim-type="Currently amended] The optical member according to claim 3, wherein the optical member is selected from the group consisting of an optical lens, a guide lens, or a microlens.
    [6" claim-type="Currently amended] An optical member obtained by using a polyimide resin having a repeating structural unit represented by the general formula (9) as an essential component.
    Display or -C (CF 3) 2 - [In the general formula (9), A is represented by the general formula 10, 11 or the display 12, and X is a direct bond, -O -, - SO 2 do.
    In formula (10), A 1 represents a direct bond, -O-, -S-, -SO 2 -, -CO-, -C (CH 3 ) 2 - or -C (CF 3 ) 2 - do. In the general formula (10), R 1 and R 2 represent Cl, Br, CH 3 or CF 3 , respectively.
    R 3 , R 4 and R 5 each represent H, Cl, Br, CN, CH 3 or CF 3 , and at least one of R 3 , R 4 and R 5 represents a group other than H Display.
    In the general formula (12), A 2 represents a direct bond, -O-, -S-, -SO 2 -, -CO-, -C (CH 3 ) 2 - or -C (CF 3 ) 2 - do. In the general formula (12), R 6 and R 7 each represent CF 3 .
    [7" claim-type="Currently amended] The optical member according to claim 6, wherein the optical member is selected from the group consisting of an optical lens, a guide lens or an optical filter.
    [8" claim-type="Currently amended] An optical lens obtained by using a polyimide resin having the structure described in claim 2 and / or 3 and at least one of R 3 , R 4 and R 5 being a group other than H, a micro lens, Optical member selected from the group of filters.
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    同族专利:
    公开号 | 公开日
    JP4786859B2|2011-10-05|
    US20030064235A1|2003-04-03|
    EP1237015A1|2002-09-04|
    TW499569B|2002-08-21|
    CN1388904A|2003-01-01|
    WO2002012926A1|2002-02-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-08-09|Priority to JP2000241371
    2000-08-09|Priority to JPJP-P-2000-00241372
    2000-08-09|Priority to JPJP-P-2000-00241371
    2000-08-09|Priority to JP2000241372
    2001-04-02|Priority to JP2001103843
    2001-04-02|Priority to JPJP-P-2001-00103843
    2001-08-08|Application filed by 사토 아키오, 미쯔이카가쿠 가부시기가이샤
    2001-08-08|Priority to PCT/JP2001/006820
    2002-06-14|Publication of KR20020044160A
    优先权:
    申请号 | 申请日 | 专利标题
    JP2000241371|2000-08-09|
    JPJP-P-2000-00241372|2000-08-09|
    JPJP-P-2000-00241371|2000-08-09|
    JP2000241372|2000-08-09|
    JPJP-P-2001-00103843|2001-04-02|
    JP2001103843|2001-04-02|
    PCT/JP2001/006820|WO2002012926A1|2000-08-09|2001-08-08|Optical members made of polyimide resins|
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