US006312769B1
`
`
`
`
`
`
`
`(12) United States Patent
`Hiraoka et al.
`
`
`
`
`
`
`(10) Patent N0.:
`
`
`(45) Date of Patent:
`
`
`
`
`US 6,312,769 B1
`
`
`Nov. 6, 2001
`
`(54) LIQUID CRYSTAL ALIGNMENT LAYER,
`
`
`
`
`
`PRODUCTION METHOD FOR THE SAME,
`
`
`
`
`
`AND LIQUID CRYSTAL DISPLAY DEVICE
`
`
`
`
`
`COMPRISING THE SAME
`
`
`
`
`5—232472
`6—130390
`
`
`
`
`9/1993 (JP) .
`
`
`5/1994 (JP) .
`
`
`OTHER PUBLICATIONS
`
`
`
`
`Kenichiro Ohsawa, et al., pp. 1-5, “Fine Striae Forming on
`
`
`
`
`
`
`
`
`Synthesis Silica Glass by ARF Excimer Laser Beam Irra-
`
`
`
`
`
`
`
`
`diation”.
`
`H. Hiraoka, et al., SPIE, vol. 3093, pp. 204-212, “Interac-
`
`
`
`
`
`
`
`
`
`tions of Pulsed UV—Laser With Polymer Surfaces: Periodic
`
`
`
`
`
`
`
`Structures, Functional Group Alignment and Diamond
`
`
`
`
`
`
`
`Deposition”.
`H. Himmelbauer, et al., Applied Physics A, vol. 63, pp.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`336-339, “UV-Laser-Induced Surface Topology Changes
`in Polyimide”, Jun. 1996.
`
`
`
`
`Abstract of JP 05-0535143 (Mar. 1993).
`
`
`
`
`Chigrinov, V. G., et al. “Physics and applications of LC
`
`
`
`
`
`
`
`
`
`photo-alignment: recent results, ” Proceedings of the SPIE,
`
`
`
`
`
`vol. 3318, pp. 454-464, (Mar. 1997).
`
`
`
`
`
`
`Iimura Y., et al., “Alignment Control of a Liquid Crystal on
`
`
`
`
`
`
`
`a Photosensitive Polyvinlalcohol Film”, Jpn. J. Appl. Phys.,
`
`
`
`
`
`
`part 2, vol. 32, No. 1A/B, pp. L93-L96, (Jan. 1993).
`
`
`
`
`
`
`
`
`
`Lien A., et al., “UV modification of surface pretilt of
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`alignment layers for multidomain liquid crystal displays,”
`vol. 67, No. 21, pp. 3108-3109, (Nov. 1995).
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Luo, Q., et al., “Alignment of liquid crystal on the polymide
`films irradiated by pulsed ultravoilet laser,” 9”“ Int’l Sym-
`
`
`
`
`
`
`
`
`
`posium on on Electrets (ISE 9) Proceedings, pp. 662-667,
`
`
`
`
`
`
`(Sep., 1996).
`
`
`
`
`
`
`(List continued on next page.)
`
`
`
`
`Primary Examiner—C. H. Kelly
`
`
`
`(74) Attorney, Agent, or Firm—Oblon, Spivak, McClelland,
`
`
`
`
`
`Maier & Neustadt, P.C.
`
`
`
`
`
`
`(57)
`
`
`
`ABSTRACT
`
`
`
`A method of producing a liquid crystal alignment layer
`
`
`
`
`
`
`comprising exposing an organic film to polarized pulse laser
`
`
`
`
`
`
`
`beam to align molecules in a surface portion of the organic
`
`
`
`
`
`
`
`layer
`film. There is provided a liquid crystal alignment
`
`
`
`
`
`
`
`composed of a polyamide film having aligned molecules in
`
`
`
`
`
`
`a surface portion.
`
`
`
`
`13 Claims, 1 Drawing Sheet
`
`
`
`
`
`
`(75)
`
`
`
`
`
`
`
`
`Inventors: Hiroyuki Hiraoka, Kyoto; Yasumasa
`Takeuchi, Aoba-ku; Shin-ichi Kimura;
`
`
`
`Yasuo Matsuki, both of Mie, all of
`
`
`
`
`
`
`
`
`
`
`(JP); Toshihiro Ogawa, Birmingham,
`
`
`
`
`
`AL (US); Masayuki Kimura, Mie (JP)
`
`
`
`(73) Assignee: JSR Corporation, Tokyo (JP)
`
`
`
`
`
`
`
`
`( * ) Notice:
`
`
`
`
`
`
`
`
`
`Subject to any disclaimer, the term of this
`
`
`
`
`
`patent is extended or adjusted under 35
`
`
`
`
`U.S.C. 154(b) by 0 days.
`
`
`
`
`
`(21) Appl. No.: 09/069,169
`
`(22)
`
`
`
`
`Filed:
`
`
`Apr. 29, 1998
`
`
`
`
`Foreign Application Priority Data
`
`
`
`
`
`
`
`(JP) ................................................. .. 9—1127o1
`
`(30)
`
`(51)
`
`
`
`
`
`
`
`Apr. 30, 1997
`
`Int. Cl.7 ........................ .. C09K 19/00; C09K 19/56;
`
`
`
`
`
`
`
`G02F 1/133
`
`
`....................... .. 428/1.1; 252/299.4; 349/191
`(52) U.S. Cl.
`
`
`
`
`
`
`(58) Field of Search ....................... .. 252/299.4; 349/191;
`
`
`
`
`
`428/1.1
`
`
`
`(56)
`
`
`
`References Cited
`
`
`U.S. PATENT DOCUMENTS
`
`
`
`4,702,558 * 10/1987 Coles et al.
`.................... .. 349/123 X
`
`
`
`
`
`
`4,892,926 *
`1/1990 Suenaga et al.
`528/305
`
`
`
`
`
`4,983,318 *
`1/1991 Matsumoto et al.
`.. 252/299.01
`..
`
`
`
`
`
`
`5,073,294 * 12/1991 Shannon etal.
`.............. .. 252/299.01
`
`
`
`
`
`
`
`(List continued on next page.)
`
`
`
`
`FOREIGN PATENT DOCUMENTS
`
`
`
`8/1990 (JP) .
`
`
`
`
`
`2—196219
`
`
`TRANSMJTIANCE(2)
`
`
`
`VOLTAGE (v)
`
`
`
`
`Page 1 of 14
`
`Tianma Exhibit 1027
`
`Page 1 of 14
`
`Tianma Exhibit 1027
`
`

`
`
`
`US 6,312,769 B1
`Page 2
`
`
`5,858,273 *
`
`
`
`
`.................. .. 252/299.4
`1/1999 Asaoka et al.
`
`
`
`
`OTHER PUBLICATIONS
`
`
`Newsrome C J et al «Ph0t0induCedAhgn1,nent of
`
`
`
`
`
`
`
`
`
`
`
`
`
`Crystals Usirlg folyrriide Irradiated With a P01aris€d EXCi-
`mer Laser,” 17’ Int’l Liquid Crystal Conference, Vol. 329,
`
`
`
`
`
`
`
`
`
`pp. 1173_1180, (1998).
`
`
`
`* cited by examiner
`
`
`
`
`
`U.S. PATENT DOCUMENTS
`
`
`
`
`
`5,477,360 *
`
`
`5,596,435 *
`
`Sunohara 61; £11.
`
`
`
`
`
`1/1997 Sunohara et al.
`
`.................... ..
`
`
`
`.................... 349/132
`
`9/1998 Gibbons et al.
`5,807,498 *
`
`
`
`5,846,552 * 12/1998 Gibbons et al.
`
`
`
`
`
`
`
`................ .. 252/299.4
`
`................ .. 252/299.4
`
`
`
`
`
`Page 2 of 14
`
`Page 2 of 14
`
`

`
`
`
`US 6,312,769 B1
`
`1
`
`LIQUID CRYSTAL ALIGNMENT LAYER,
`
`
`
`
`PRODUCTION METHOD FOR THE SAME,
`
`
`
`
`
`AND LIQUID CRYSTAL DISPLAY DEVICE
`
`
`
`
`
`COMPRISING THE SAME
`
`
`
`DETAILED DESCRIPTION OF THE
`
`
`
`INVENTION
`
`
`The present invention relates to a liquid crystal alignment
`
`
`
`
`
`
`
`layer, a production method for the same and a liquid crystal
`
`
`
`
`
`
`
`
`display device comprising the same. More specifically, it
`
`
`
`
`
`
`
`relates to a method of producing a liquid crystal alignment
`
`
`
`
`
`
`layer by aligning molecules in a surface portion of the layer
`
`
`
`
`
`
`
`through exposure to polarized pulsed laser beam, a liquid
`
`
`
`
`
`
`
`crystal alignment layer produced by the method and a liquid
`
`
`
`
`
`
`
`crystal display device comprising the same.
`
`
`
`
`
`
`Currently, there is known an TN (Twisted Nematic) liquid
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`crystal display device having so-called TN liquid crystal
`cells, which is produced by forming a liquid crystal align-
`
`
`
`
`
`
`
`ment layer on the surface, having a transparent conductive
`
`
`
`
`
`
`
`film, of a substrate to prepare a substrate for a liquid crystal
`
`
`
`
`
`
`
`display device, arranging two of the substrate to face each
`
`
`
`
`
`
`
`
`other, forming a nematic liquid crystal layer having dielec-
`
`
`
`
`
`
`
`
`tric anisotropy between the two substrates to form a
`
`
`
`
`
`
`
`
`sandwich-structured cell and twisting the long axis of the
`
`
`
`
`
`
`
`
`
`liquid crystal molecules at 90° from one substrate toward the
`
`
`
`
`
`
`
`
`
`other substrate continuously.
`
`
`
`The alignment of the liquid crystal molecules of a liquid
`
`
`
`
`
`
`
`crystal display device such as this TN liquid crystal display
`
`
`
`
`
`
`
`
`device is generally effected by a liquid crystal alignment
`
`
`
`
`
`
`
`layer provided with an ability to align liquid crystal
`
`
`
`
`
`
`
`
`
`
`
`molecules, by rubbing.
`However, this rubbing involves the following problems:
`
`
`
`
`
`
`
`(1) Since static electricity may cause the destruction of a
`
`
`
`
`
`
`
`
`TFT device, its production machine takes generally coun-
`
`
`
`
`
`
`
`
`termeasures against static electricity. However, the counter-
`
`
`
`
`
`
`
`measures are not perfect against static electricity generated
`
`
`
`
`
`
`
`
`
`
`by rubbing.
`(2) Since rubbing produces dust, cleaning is required as a
`
`
`
`
`
`
`
`subsequent step, thereby increasing the number of steps.
`
`
`
`
`
`
`
`(3) Since a stepped portion and a flat portion of an
`
`
`
`
`
`
`
`
`
`alignment layer having the stepped portion differ from each
`
`
`
`
`
`
`
`
`
`other in rubbing conditions, alignment anchoring force and
`
`
`
`
`
`
`
`tilt angle are liable to be uneven.
`
`
`
`
`
`
`
`(4) Since rubbing is carried out in a single direction, the
`
`
`
`
`
`
`
`
`production process of an alignment layer comprising divided
`
`
`
`
`
`
`
`
`
`
`alignment pixels becomes complicated.
`(5) To uniformly rub an alignment layer for a large-sized
`
`
`
`
`
`
`
`substrate, for example, measuring 550x650 mm or more, a
`
`
`
`
`
`
`
`
`
`special equipment is required.
`To avoid the above problems, methods for providing a
`
`
`
`
`
`
`
`
`liquid crystal alignment layer with an ability to align liquid
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`crystal molecules, without necessity of rubbing treatment (to
`be referred to as “non-rubbing treatment” hereafter) have
`
`
`
`
`
`
`
`also been developed. One of the methods is to expose a
`
`
`
`
`
`
`
`
`liquid crystal alignment layer to laser beam.
`
`
`
`
`
`
`JP-A 2-196219 (the term “JP-A” as used herein means an
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`“unexamined published Japanese patent application”) dis-
`closes a method of producing a liquid crystal alignment
`
`
`
`
`
`
`layer by exposing the surface of a polymer film on an
`
`
`
`
`
`
`
`
`
`electrode substrate in a liquid crystal display device to
`
`
`
`
`
`
`
`
`high-intensity beam from an ultraviolet laser such as an XeF,
`
`
`
`
`
`
`
`XeCl, KrF, ArF or F2 excimer laser to form a periodic
`
`
`
`
`
`
`
`
`
`surface structure.
`
`
`JP-A 6-130390 discloses a method of irradiating an align-
`
`
`
`
`
`
`ment layer, which aligns the liquid crystal molecules formed
`
`
`
`
`
`
`
`
`
`
`10
`
`
`
`15
`
`
`
`20
`
`25
`
`
`
`30
`
`35
`
`
`
`40
`
`45
`
`
`
`50
`
`55
`
`
`
`60
`
`65
`
`
`
`Page 3 of 14
`
`
`
`
`
`
`2
`
`on the substrate in a predetermined direction, with beam
`
`
`
`
`
`
`
`
`from an excimer laser through a mask having a large number
`
`
`
`
`
`
`
`
`of slit holes parallel to one another, while the inside of the
`
`
`
`
`
`
`
`
`
`
`container is deaerated, in a vacuum container.
`
`
`
`
`JP-A 5-232472 discloses a method of producing an
`
`
`
`
`
`
`
`is
`electro-optic device comprising an alignment
`layer
`
`
`
`
`
`
`
`formed on the surfaces, which are arranged to face each
`
`
`
`
`
`
`
`
`
`other, of a pair of transparent substrates with liquid crystals
`
`
`
`
`
`
`
`are filled into the space between the pair of transparent
`
`
`
`
`
`
`
`
`
`
`substrates, the method comprising the steps of forming the
`
`
`
`
`
`
`
`
`alignment
`layer having spacers for supporting a liquid
`
`
`
`
`
`
`
`crystal film on the opposing surfaces of the transparent
`
`
`
`
`
`
`
`
`substrates and exposing the alignment layer to laser beam to
`
`
`
`
`
`
`
`
`
`
`
`
`
`align the liquid crystal molecules.
`In either one of the above methods, since polymer mol-
`
`
`
`
`
`
`
`
`
`ecules in a surface portion of the alignment layer are cut in
`
`
`
`
`
`
`
`
`a certain cycle and the cut atoms or molecules are oxidized
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`to gasify when the liquid crystal alignment layer is exposed
`to laser beam, a periodic surface structure is produced on the
`
`
`
`
`
`
`
`
`surface of the alignment layer. Therefore, these methods
`
`
`
`
`
`
`
`
`have defects in that the environment of a clean room is
`
`
`
`
`
`
`
`
`polluted by gasified decomposed products and that since a
`
`
`
`
`
`
`
`periodic surface structure is produced on the surface by the
`
`
`
`
`
`
`
`decomposition of the polymer molecules, the electric char-
`
`
`
`
`
`
`
`acteristics of the surface are not satisfactory.
`
`
`
`
`
`
`
`It is therefore an object of the present invention to provide
`
`
`
`
`
`
`a novel method for aligning molecules in a surface portion
`
`
`
`
`
`
`
`of an alignment layer by a non-rubbing treatment.
`
`
`
`
`
`It is another object of the present invention to provide a
`
`
`
`
`
`
`
`
`method capable of aligning molecules in a surface portion of
`
`
`
`
`
`
`an alignment layer effectively without generating dust or
`
`
`
`
`
`
`
`
`
`
`decomposed products.
`It is still another object of the present invention to provide
`
`
`
`
`
`
`
`
`a method capable of forming a periodic surface structure,
`
`
`
`
`
`
`
`
`which provide an ability to align liquid crystal molecules, on
`
`
`
`
`
`
`
`the surface of an alignment layer non-destructively without
`
`
`
`
`
`
`decomposing the molecules in a surface portion of the
`
`
`
`
`
`
`
`
`
`alignment layer.
`It is still another object of the present invention to provide
`
`
`
`
`
`
`
`a liquid crystal alignment layer composed of a polyimide
`
`
`
`
`
`
`film and having irregularities or swells formed on the
`
`
`
`
`
`
`
`
`surface non-destructively and periodically.
`
`
`
`
`It is still another object of the present invention to provide
`
`
`
`
`
`
`
`a liquid crystal display device comprising the above liquid
`
`
`
`
`
`
`
`
`crystal alignment layer of the present invention.
`
`
`
`
`
`
`Other objects and advantages of the present invention will
`
`
`
`
`
`
`
`become apparent from the following description.
`
`
`
`
`
`
`According to the present
`invention, firstly,
`the above
`
`
`
`
`
`
`
`objects and advantages of the present
`invention can be
`
`
`
`
`
`
`
`
`
`attained by a method of producing a liquid crystal film
`
`
`
`
`
`
`
`comprising exposing an organic film to polarized pulsed
`
`
`
`
`
`
`
`laser beam having a pulse energy (about 1 mJ/cm2 to 3
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`mJ/cm2) much lower than the lowest critical pulse energy
`
`
`
`
`
`
`(about 10 mJ/cm2) by which the decomposition by exposure
`of polymer molecules occurs, to align polymer molecules in
`
`
`
`
`
`
`
`a surface portion of the organic film.
`
`
`
`
`
`
`there is
`According to the present invention, secondly,
`
`
`
`
`
`
`
`provided a liquid crystal alignment layer which is composed
`
`
`
`
`
`
`
`of a polyimide film and has molecules aligned through
`
`
`
`
`
`
`
`
`exposure to polarized pulsed laser beam, in a surface portion
`
`
`
`
`
`
`
`thereof.
`
`According to the present invention, thirdly, there is pro-
`
`
`
`
`
`
`
`vided a liquid crystal display device comprising the above
`
`
`
`
`
`
`
`
`liquid crystal alignment layer of the present invention.
`
`
`
`
`
`
`
`FIG. 1 of the annexed drawing shows the relationship
`
`
`
`
`
`
`
`
`between the transmittance (%) of a liquid crystal display
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Page 3 of 14
`
`

`
`
`
`US 6,312,769 B1
`
`
`
`4
`
`1 ,3 ,3a, 4,5,9b-hexahydro-7-ethyl-5
`furan- 1 ,3-dione,
`
`
`
`
`
`
`
`(tetrahydro -2,5 -dioxo-3-furanyl)-naphtho[1 ,2-c]-furan- 1 ,3-
`dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5(tetrahydro-2,5 -
`
`
`
`
`dioxo-3-furanyl)-naphtho[1 ,2-c]-furan- 1 ,3-dione,
`1 ,3,3a, 4,
`
`
`
`
`
`
`
`
`
`5 ,9b-hexahydro-8-ethyl-5(tetrahydro -2,5 -dioxo -3-furanyl)-
`
`
`
`
`
`naphtho[1 ,2-c]-furan-1 ,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,
`
`
`
`8-dimethyl-5(tetrahydro-2,5 -dioxo -3-furanyl)-naphtho[1 ,2-
`
`
`
`
`c]-furan- 1 ,3-dione, 5 -(2,5 -dioxotetrahydrofural)-3-methyl-
`
`
`
`
`3-cyclohexene- 1 ,2-dicarboxylic dianhydride, bicyclo[2,2,
`
`
`
`
`
`
`2]-octo -7-ene -2,3,5 ,6-tetracarboxylic dianhydride, aliphatic
`and alicyclic tetracarboxylic dianhydrides such as com-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`pounds represented by the following formulas (II) and (III):
`
`0
`
`
`
`0
`
`
`
`0
`
`
`o
`
`0
`
`
`
`o
`
`
`
`o
`
`
`
`0
`
`
`
`o
`
`
`
`R1
`
`R2
`
`
`
`
`R2
`
`
`
`R4
`
`
`
`
`
`o
`
`
`
`R4
`
`
`
`(11)
`
`
`
`(III)
`
`
`
`R3
`
`
`
`o
`
`
`
`0
`
`
`
`wherein R1 and R3 are a divalent organic group having an
`
`
`
`
`
`
`aromatic ring, and each of R2’s and R4’s may be the
`
`
`
`
`
`
`
`
`
`same or different and is a hydrogen atom or an alkyl
`
`
`
`
`
`
`
`gI'O1lp,
`
`
`
`
`
`
`pyromellitic dianhydride, 3,3‘,4,4'-benzophenone tetracar-
`
`
`
`
`boxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxy-
`lic dianhydride,
`1 ,4,5,8-naphthalene tetracarboxylic
`
`
`
`
`
`
`
`dianhydride, 2,3,6,7-naphthalene tetracarboxylic
`
`
`
`tetracarboxylic
`dianhydride, 3,3‘,4,4'-biphenylether
`
`
`
`dianhydride, 3,3‘,4,4'-dimethyldiphenylsilane tetracarboxy-
`
`
`
`
`lic dianhydride, 3,3',4,4‘-tetraphenylsilane tetracarboxylic
`
`
`
`
`dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4‘-
`
`bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride,
`4,4‘-bis(3,4-dicarboxyphenoxy)diphenylsulfone
`
`dianhydride, 4,4‘-bis(3,4-dicarboxyphenoxy)
`
`
`
`dianhydride,
`diphenylpropane
`3,3‘,4,4‘-
`
`
`
`
`biphenyltetracarboxylic dianhydride, bis(phthalic acid)
`
`
`
`
`phenylphosphine oxide dianhydride, p-phenylene-bis
`
`
`
`(triphenylphthalic acid)dianhydride, m-phenylene-bis
`
`
`
`(triphenylphthalic acid)dianhydride, bis(triphenylphthalic
`
`
`
`acid)-4,4‘-diphenylether dianhydride, bis(triphenylphthalic
`
`
`
`
`acid)-4,4‘-diphenylmethane dianhydride, ethylene glycol-bis
`
`
`
`(anhydrotrimellitate), propylene glycol-bis
`
`
`(anhydrotrimellitate),
`1,4-butanediol-bis
`
`
`(anhydrotrimellitate),
`1,6-hexanediol-bis
`
`
`(anhydrotrimellitate),
`1,8-octanediol-bis
`
`
`(anhydrotrimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis
`
`
`
`
`(anhydrotrimellitate) and aromatic tetracarboxylic
`dianhydrides such as compounds represented by the follow-
`
`
`
`
`
`
`ing formulas (1) to
`They may be used alone or in
`
`
`
`
`
`
`
`
`
`
`combination of two or more.
`
`
`
`
`
`
`
`
`10
`
`15
`
`
`
`20
`
`25
`
`30
`
`35
`
`
`
`40
`
`45
`
`
`
`50
`
`55
`
`
`
`60
`
`65
`
`
`
`3
`
`
`
`
`device and voltage (volt). A curve A is drawn for a liquid
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`crystal display device comprising a liquid crystal alignment
`layer exposed to laser beam and a curve B is drawn for a
`
`
`
`
`
`
`
`
`liquid crystal display device comprising a rubbed liquid
`
`
`
`
`
`
`
`
`
`
`crystal alignment layer.
`A description is first given of the method of the present
`
`
`
`
`
`
`
`invention.
`
`In the method of the present invention, the organic film for
`
`
`
`
`
`
`
`
`
`forming a liquid crystal alignment layer is formed from an
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`organic polymer. Illustrative examples of the organic poly-
`include polyimides, polysulfones, polyesters,
`mer
`
`
`
`
`
`
`
`
`
`polyamides, poly(meth)acrylates, polycarbonates, polyphe-
`nylene sulfides, polyphenylene oxides, norbornene resins
`
`
`
`
`
`
`and the like.
`
`
`
`Any known organic polymers can be used. Of these,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`organic polymers having a secondary transition point (Tg) or
`melting point (Tm) of at least about 90° C. and an SP
`
`
`
`
`
`
`
`
`
`
`(solubility parameter) value of at least 8.5 are preferred.
`
`
`
`
`
`
`
`Tg is more preferably at least 150° C., particularly pref-
`
`
`
`
`
`
`
`
`erably at least 180° C.
`
`
`
`These organic polymers which do not swell with an
`
`
`
`
`
`
`
`
`
`ordinary solvent such as an alcohol or ketone are used
`
`
`
`
`
`
`
`
`
`
`advantageously.
`Apolyimide, one of the organic polymers, contains recur-
`
`
`
`
`
`
`
`
`
`
`
`
`
`ring units represented by the following formula (I):
`
`
`
`(1)
`
`
`wherein R01 is a tetravalent organic group and R02 is a
`
`
`
`
`
`
`
`divalent organic group.
`
`
`
`R01 is a tetravalent organic group obtained by removing
`
`
`
`
`
`
`four carboxyl groups from a tetracarboxylic acid and R02 a
`
`
`
`
`
`
`
`
`divalent organic group obtained by removing two amino
`
`
`
`
`
`
`
`
`groups from a diamine compound.
`
`
`
`
`The above polyimide can be obtained by reacting a
`
`
`
`
`
`
`
`
`tetracarboxylic dianhydride and a diamine compound in an
`
`
`
`
`
`
`organic solvent to synthesize a polyamic acid and dehydrat-
`
`
`
`
`
`
`
`ing and ring-closing the polyamic acid as required.
`
`
`
`
`
`
`
`
`
`
`[Tetracarboxylic dianhydride]
`Illustrative examples of the tetracarboxylic dianhydride
`
`
`
`
`
`include 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-
`
`
`
`
`
`
`
`
`
`cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,
`
`
`
`
`3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-
`
`
`
`
`1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-
`
`
`
`dichloro-1,2,3,4-cyclobutane tetracarboxylic dianhydride,
`
`
`1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic
`
`
`
`dianhydride, 1,2,3,4-cyclopentane tetracarboxylic
`
`
`
`dianhydride, 1,2,4,5-cyclohexane tetracarboxylic
`
`
`
`dianhydride, 3,3',4,4'-dicyclohexyl
`tetracarboxylic
`
`
`
`dianhydride, 2,3,5-tricarboxycyclopentyl acetic
`
`
`dianhydride, 3,5,6-tricarboxynorbornane-2-acetic
`
`
`
`dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic
`
`
`dianhydride, 1,3,3cz,4,5,9b-hexahydro-5(tetrahydro-2,5-
`
`
`
`dioxo- 3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,
`
`5,9b-hexahydro-5-methyl-5(tetrahydro-2,5-dioxo-3-
`
`furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3cz,4,5,9b-
`hexahydro-5-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-
`
`naphtho[1,2-c]-furan-1,3-dione, 1,3,3cz,4,5,9b-hexahya'r0-7-
`methyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-
`
`
`
`
`
`Page 4 of 14
`
`Page 4 of 14
`
`

`
`US 6,312,769 B1
`
`(|:H3
`H3(|:
`CH CH CH
`2)3
`(
`CH3
`
`H3C
`
`H3C
`
`C00
`
`OOC
`
`O
`
`0
`
`O
`
`(|:H3
`H3(|:
`CH CH CH:C
`(
`2)2
`
`CH3
`
`H3C
`
`(1)
`
`(2)
`
`H3C
`
`COO
`
`H3C
`
`CH3
`
`ooC
`
`0
`
`O
`
`0
`
`(3)
`
`(|:H3
`H3(|:
`CH(CH3)3CH
`
`C00
`
`
`
`CH3
`
`0
`
`O
`
`O
`
`0
`
`O
`
`O
`
`O
`
`0
`
`O
`
`Page 5 of 14
`
`Page 5 of 14
`
`

`
`-continued
`
`
`
`
`
`US 6,312,769 B1
`
`(4)
`
`
`
`(|3H3
`H3(|Z
`CH(CH2)3CH
`
`CH3
`
`
`
`25
`
`30
`
`35
`
`
`
`40
`
`45
`
`
`
`50
`
`55
`
`
`
`-continued
`
`
`
`CH3
`
`H3C
`
`(6)
`
`
`
`(7)
`
`
`
`(8)
`
`
`
`Of these, 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,
`
`
`
`
`
`
`
`
`
`
`3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-
`
`
`
`
`1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-
`
`
`
`
`cyclopentane tetracarboxylic dianhydride, 2,3,5-
`
`
`
`tricarboxycyclopentyl acetic dianhydride, 5-(2,5-
`dioxotetrahydrofural)-3-methyl-3-cycloheXene-1,2-
`
`
`dicarboxylic dianhydride, 1,3,3a,4,5,9b-heXahydro-5-
`(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-
`
`
`dione, 1,3,3cz,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-
`
`
`dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,
`
`9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioXo-3-
`
`
`furanyl)-naphtho[1,2-c]furan-1,3-dione, bicyclo[2,2,2]-
`
`
`
`octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic
`
`
`
`dianhydride, 3,3‘,4,4‘-benzophenone tetracarboxylic
`
`
`
`dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic
`
`
`
`dianhydride, 1,4,5,8-naphthalene tetracarboxylic
`
`
`
`
`
`
`dianhydride, compounds represented by the following for-
`mulas (5) to (7) out of the compounds represented by the
`
`
`
`
`
`
`
`
`above formula (II), and a compound represented by the
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`following formula (8) out of the compounds represented by
`the above formula (III) are preferred because they can
`
`
`
`
`
`
`
`
`
`exhibit excellent liquid crystal aligning properties. Particu-
`
`
`
`
`
`
`
`larly preferred are 1,2,3,4-cyclobutane tetracarboxylic
`
`
`
`
`
`dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracar-
`
`
`
`
`
`
`
`boxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic
`
`
`dianhydride, 1,3,3cz,4,5,9b-hexahydro-5-(tetrahydro-2,5-
`
`
`dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,
`
`9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioXo-3-
`
`
`furanyl)-naphthol[1,2-c]furan-1,3-dione, pyromellitic
`dianhydride and a compound represented by the following
`
`
`
`
`
`
`
`
`formula (5):
`
`
`
`
`
`(5)
`
`
`
`60
`
`65
`
`
`
`Page 6 of 14
`
`Page 6 of 14
`
`

`
`
`
`US 6,312,769 B1
`
`
`10
`
`
`
`phenylphenanthridine, 1,4-diaminopiperazine, 3,6-
`
`
`diaminoacridine, bis(4-aminophenyl)phenylamine and
`
`
`
`
`
`compounds represented by the following formulas (IV) and
`
`
`
`
`(V)
`
`(IV)
`
`
`
`X—R5
`
`I
`
`HZN
`
`(‘J
`
`\¢\’
`NH2
`
`wherein R5 is a monovalent organic group having a ring
`
`
`
`
`
`
`structure containing a nitrogen atom selected from the
`
`
`
`
`
`
`
`
`
`
`
`
`
`group consisting of pyridine, pyrimidine, triazine, pip-
`eridine and piperazine, and X is a divalent organic
`
`
`
`
`
`
`group,
`
`
`/
`H2N—
`
`\
`
`l—X-R6-X—l
`
`
`
`
`
`\
`—NH2
`/
`
`
`
`
`(V)
`
`
`
`wherein R6 is a divalent organic group having a ring
`
`
`
`
`
`
`
`structure containing a nitrogen atom selected from the
`
`
`
`
`
`
`
`
`
`
`
`
`
`group consisting of pyridine, pyrimidine, triazine, pip-
`eridine and piperazine, and X’s are a divalent organic
`
`
`
`
`
`
`
`
`group and may be the same or different;
`
`
`
`
`
`
`monosubstituted phenylene diamines represented by the
`
`
`
`
`
`
`
`
`following formula (VI):
`
`
`
`(V1)
`
`
`
`R7_R8
`
`
`
`I
`
`HZN
`
`(‘J
`
`\¢\’
`NH2
`
`
`
`wherein R7 is a divalent organic group selected from
`
`
`
`
`
`
`COO ,
`OCO ,
`NHCO ,
`O
`,
`
`
`
`—CONH— and —CO—, and R8 is a monovalent
`
`
`
`organic group having a steroid skeleton or an alkyl
`
`
`
`
`
`
`
`group having 6 to 30 carbon atoms;
`
`
`
`
`
`
`
`
`
`
`
`diaminoorganosiloxanes represented by the following for-
`mula (VII):
`
`
`
`
`
`
`
`
`
`
`
`
`T9
`‘F9
`H2N—(-CH2j?Ti—(-O—Tifi-(-qcH2jp—NH2
`R9
`R9
`
`
`
`(VII)
`
`
`
`
`
`wherein R9’s are a hydrocarbon group having 1 to 12
`
`
`
`
`
`
`
`carbon atoms and may be the same or different, p is an
`
`
`
`
`
`
`
`integer of 1 to 3, and q is an integer of 1 to 20;
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`and compounds represented by the following formulas (9) to
`
`(13):
`
`
`
`
`5
`
`
`
`10
`
`15
`
`20
`
`
`
`25
`
`30
`
`
`
`35
`
`
`
`40
`
`
`
`45
`
`
`
`50
`
`
`
`55
`
`
`
`60
`
`
`
`65
`
`
`
`
`9
`
`
`[diamine compound]
`Illustrative examples of the diamine compound used in
`
`
`
`
`
`
`the synthesis of the above polyamic acid include aromatic
`
`
`
`
`
`
`
`
`diamines
`such
`as
`p-phenylenediamine,
`
`
`
`
`
`
`
`m-phenylenediamine, 4,4‘-diaminodiphenylmethane, 4,4‘-
`
`
`
`
`diaminodiphenylethane, 4,4‘-diaminodiphenyl sulfide, 4,4‘-
`
`
`
`diaminodiphenyl sulfone, 3,3‘-dimethyl-4,4‘-
`diaminobiphenyl, 4,4‘-diaminobenzanilide, 4,4‘-
`
`
`
`
`
`
`
`diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3‘-
`
`
`dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4‘-
`
`
`aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4‘-
`
`
`aminophenyl)-1,3,3-trimethylindane, 3,4‘-diaminodiphenyl
`3 ,4 ‘ -
`
`
`3,3‘-diaminobenzophenone,
`
`
`
`
`diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis
`
`
`[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-
`
`
`aminophenoXy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)
`
`
`
`benzene, 1,3-bis(4-aminophenoXy)benzene, 1,3-bis(3-
`
`
`aminophenoXy)benzene, 9,9-bis(4-aminophenyl)-10-
`
`
`
`hydroanthracene, 2,7-diaminofluorene, 9,9-bis(4-
`
`
`aminophenyl)fluorene, 4,4‘-methylene-bis(2-chloroaniline),
`
`
`2,2‘,5,5'-tetrachloro-4,4‘-diaminobiphenyl, 2,2‘-dichloro-4,
`
`
`
`4'-diamino-5,5‘-dimethoxybiphenyl, 3,3'-dimethoXy- 4,4‘-
`
`
`diaminobiphenyl, 1,4,4,‘-(p-phenyleneisopropylidene)
`
`
`
`bisaniline and 4,4'-(m-phenyleneisopropylidene)bisaniline;
`aliphatic and alicyclic diamines such as 1,1-
`
`
`
`
`
`
`
`
`
`metaxylylenediamine, 1,3-propanediamine,
`
`
`tetramethylenediamine, pentamethylenediamine,
`
`
`hexamethylenediamine, heptamethylenediamine,
`
`
`
`octamethylenediamine, nonamethylenediamine, 4,4-
`
`
`
`diaminoheptamethylene diamine, 1,4-diaminocyclohexane,
`
`
`tetrahydrodicyclopentadienylene
`isophoronediamine,
`diamine,
`hexahydro-4,7-methanoindanyleneg OK? 1
`
`
`
`
`
`dimethylenediamine,
`tricyclo[6.2.1.02’7]-
`
`
`
`undecylenedimethyldiamine and 4,4‘-methylenebis
`
`
`
`
`
`
`(cyclohexylamine); diamines having two primary amino
`groups and a nitrogen atom other than the primary amino
`
`
`
`
`
`
`
`
`
`group in the molecule such as 2,3-diaminopyridine, 2,6-
`
`
`
`
`
`2,4-
`
`
`diaminopyridine, 3,4-diaminopyridine,
`
`
`
`diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-
`
`
`diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-
`
`
`
`dimethylamino-1 ,3,5-triazine, 1,4-bis(3-aminopropyl)
`
`
`
`piperazine, 2,4-diamino-6-isopropoXy-1,3,5-triazine, 2,4-
`
`
`diamino-6-methoXy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,
`3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-
`
`
`
`1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-
`
`
`
`
`
`
`5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-
`dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-
`
`
`3,8-diamino-6-
`
`
`ethoxyacridine
`lactate,
`
`
`
`
`
`ether,
`
`Page 7 of 14
`
`Page 7 of 14
`
`

`
`11
`
`
`
`US 6,312,769 B1
`
`
`
`12
`
`
`
`(9)
`
`
`
`(10)
`
`
`
`CH3
`
`
`
`
`H3(|:
`CH(CH3)3CH
`
`
`
`
`
`CH3
`
`
`
`H3C
`
`H3C
`
`
`
`Coo
`
`
`H3C
`
`H3C
`
`
`
`
`
`
`
`
`H3C
`(‘ZH3
`CH CH CH
`
`
`(
`2)3
`
`
`
`CH3
`
`
`
`H2N
`
`
`
`oo NH3
`
`
`
`
`(1 1)
`
`H3C
`
`CH3
`
`CH(CH3)3CH
`
`
`
`T“
`
`TH2
`
`(12)
`
`
`
`(13)
`
`
`
`wherein y is an integer of 2 to 12 and Z is an integer of 1
`
`
`
`
`
`
`
`to 5.
`
`
`These diamine compounds may be used alone or in
`
`
`
`
`
`
`
`
`combination of two or more.
`
`
`
`4,4‘-
`these,
`p-phenylenediamine,
`Of
`
`
`
`
`
`
`
`diaminodiphenylmethane, 4,4‘-diaminodiphenyl sulfide,
`1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4‘-
`
`
`
`
`
`
`diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoXy)phenyl]
`
`
`
`propane, 9,9-bis(4-aminophenyl)fluorene, 4,4'-(p-
`
`
`phenylenediisopropylidene)bisaniline, 4,4‘-(m-
`
`60
`
`65
`
`
`
`phenylenediisopropylidene)bisaniline, 1,4-
`
`
`cyclohexanediamine, 4,4‘-methylenebis(cycloheXylamine),
`
`
`
`1 ,4-bis(4-aminophenoXy)benzene, 4,4‘-bis(4-
`
`
`
`
`
`aminophenoXy)biphenyl, compounds represented by the
`to (13), 2,6-diaminopyridine, 3,4-
`above formulas (9)
`
`
`
`
`
`
`
`
`
`
`diaminopyridine, 2,4-diaminopyrimidine, 3,6-
`diaminoacridine, a compound represented by the following
`
`
`
`
`
`formula (14) out of the compounds represented by the above
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`formula (IV), a compound represented by the following
`
`
`
`
`
`H3N
`
`Page 8 of 14
`
`Page 8 of 14
`
`

`
`
`
`
`
`
`
`
`
`formula (15) out of the compounds represented by the above
`
`
`
`
`
`
`
`formula (V) and compounds represented by the following
`
`14
`
`
`
`
`
`
`
`
`formulas (16) to (19) out of the compounds represented by
`
`
`
`
`
`
`the above formula (VI) are preferred.
`
`
`
`US 6,312,769 B1
`
`Coo—CH3CH3
`
`\ /N
`
`
`H3N
`
`
`
`NH3
`
`
`
`
`
`H3C
`
`H3C
`
`
`
`COO
`
`
`
`H3N
`
`
`
`NH3
`
`
`
`H3C
`
`H3C
`
`
`
`COO
`
`
`
`H3N
`
`
`
`NH3
`
`
`
`
`
`
`H3(|:
`(|:H3
`CH CH CH
`
`
`2)3lCH3
`(
`
`
`
`
`
`
`
`
`
`H3(|:
`(|:H3
`CH CH CH
`
`
`(
`2)3
`
`
`
`CH3
`
`
`
`(14)
`
`
`
`(15)
`
`
`
`(1 6)
`
`
`
`
`
`(17)
`
`
`
`(18)
`
`
`
`
`(|:H3
`H3(|:
`CH CH CHiC
`
`
`lCH3
`(
`2)2
`
`
`
`
`H3C
`
`
`
`
`
`H3C
`
`
`
`COO
`
`
`H3C
`
`
`
`CH3
`
`
`
`CH3
`
`
`
`H3N
`
`NH3
`
`Page 9 of 14
`
`Page 9 of 14
`
`

`
`
`
`US 6,312,769 B1
`
`16
`
`
`
`(19)
`
`
`
`-continued
`
`
`
`
`
`(|:H3
`H3(|:
`CH CH CH=C
`
`
`(
`2)2
`
`
`
`CH3
`
`
`
`Hsc
`
`H3C
`
`
`
`COO
`
`H3C
`
`
`
`CH3
`
`
`CH3
`
`
`HZN
`
`NH2
`
`
`
`[polyamic acid]
`As for the ratio of a tetracarboxylic dianhydride and a
`
`
`
`
`
`
`
`diamine compound used in the synthesis reaction of a
`
`
`
`
`
`
`
`polyamic acid, the acid anhydride group of the tetracarboxy-
`
`
`
`
`
`
`
`
`lic dianhydride is preferably 0.2 to 2 equivalents, more
`
`
`
`
`
`
`
`preferably 0.3 to 1.2 equivalent, per 1 equivalent of the
`
`
`
`
`
`
`
`
`
`amino group contained in the diamine compound.
`
`
`
`
`
`
`The synthesis reaction of a polyamic acid is generally
`
`
`
`
`
`
`
`carried out in an organic solvent at 0° to 150° C., preferably
`
`
`
`
`
`
`
`0° to 100° C. for 1 to 48 hours. The organic solvent is not
`
`
`
`
`
`
`
`
`
`
`limited to a particular kind as long as it can dissolve a
`
`
`
`
`
`
`
`
`reaction product produced by the reaction.
`Illustrative
`
`
`
`
`
`
`
`examples of the organic solvent include aprotic polar sol-
`
`
`
`
`
`
`
`
`vents such as N-methyl-2-pyrrolidone, N,N-
`
`
`
`
`
`
`
`dimethylacetoamide, N,N-dimethylformamide,
`dimethylsulfoxide, Y -butyrolactone, tetramethyl urea and
`
`
`
`
`
`hexamethylphosphor triamide; and phenolic solvents such
`
`
`
`
`
`
`as m-cresol, xylenol, phenol and phenol halide. In general,
`
`
`
`
`
`
`
`
`
`the amount of the organic solvent used is preferably such
`
`
`
`
`
`
`
`
`that the total amount of the tetracarboxylic dianhydride and
`
`
`
`
`
`
`
`
`the diamine compound is 0.1 to 30 wt % of the total amount
`
`
`
`
`
`
`
`of the reaction solution.
`
`
`
`
`The organic solvent may be used in combination with a
`
`
`
`
`
`
`
`poor solvent for a polyamic acid such as an alcohol, ketone,
`
`
`
`
`
`
`
`
`ester, ether, halogenated hydrocarbon or hydrocarbon in
`
`
`
`
`
`such an amount that the produced polyamic acid does not
`
`
`
`
`
`
`
`
`
`precipitate. Illustrative examples of the poor solvent include
`
`
`
`
`
`
`
`methyl alcohol, ethyl alcohol,
`isopropyl alcohol,
`
`
`
`
`
`
`
`
`
`
`
`
`cyclohexanol, ethylene glycol, propylene glycol, 1,4-
`butanediol, triethylene glycol, acetone, methyl ethyl ketone,
`
`
`
`
`
`
`
`cyclohexanone, methyl acetate, ethyl acetate, butyl acetate,
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`diethyl oxalate, diethyl malonate, diethyl ether, ethylene
`
`
`
`
`
`
`
`
`glycol methyl ether, ethylene glycol ethyl ether, ethylene
`
`
`
`
`
`
`glycol monophenyl ether, ethylene glycol methylphenyl
`
`
`
`
`
`
`
`ether, ethylene glycol ethylphenyl ether, diethylene glycol
`
`
`
`
`
`
`
`dimethyl ether, diethylene glycol diethyl ether, diethylene
`
`
`
`
`
`
`glycol monomethyl ether, diethylene glycol monoethyl
`ether, diethylene glycol monomethyl ether acetate, diethyl-
`
`
`
`
`
`
`
`ene glycol monoethyl ether acetate, ethylene glycol methyl
`
`
`
`
`
`
`
`
`ether acetate, ethylene glycol ethyl ether acetate, 4-hydroxy-
`
`
`
`
`
`
`
`
`
`
`
`4-methyl-2-pentanone, 2,4-pentanedione, 2,5-hexanedione,
`
`
`
`
`ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methyl
`
`
`
`
`
`propionate, ethyl 2-hydroxy-2-methyl propionate, ethyl
`
`
`
`
`
`ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-
`
`
`
`
`
`methyl butanoate, methyl 3-methoxyp