Liquid Crystal Aligning Agent and Liquid Crystal Display Device

专利摘要:
PURPOSE: Provided are a liquid crystal aligning agent which provides a liquid crystal alignment film having excellent aligning properties and pre-tilt angle developing stability through exposure to linearly polarized radiation without rubbing, a method of forming a liquid crystal alignment film from the liquid crystal aligning agent and a liquid crystal display element having this liquid crystal alignment film. CONSTITUTION: A liquid crystal aligning agent is characterized by comprising a polymer having (A) an optically crosslinkable structure and (B) at least one group selected from the group consisting of a fluorine-containing organic group, alkyl group having 10 to 30 carbon atoms and alicyclic organic group having 10 to 30 carbon atoms.
公开号:KR20030029476A
申请号:KR1020020060153
申请日:2002-10-02
公开日:2003-04-14
发明作者:쇼이찌 나까따；마사유끼 기무라
申请人:제이에스알 가부시끼가이샤；
IPC主号:

专利说明:

Liquid crystal aligning agent and liquid crystal display device {Liquid Crystal Aligning Agent and Liquid Crystal Display Device}
[2] This invention relates to the liquid crystal aligning agent, the formation method of a liquid crystal aligning film, and a liquid crystal display element. More specifically, the liquid crystal aligning agent which can obtain the liquid crystal aligning film excellent in the orientation characteristic and the pretilt angle expression stability by irradiation of the linearly polarized radiation, without performing a rubbing process, and the method of forming a liquid crystal aligning film using this liquid crystal aligning agent. And a liquid crystal display element comprising the liquid crystal alignment film.
[3] Conventionally, a nematic liquid crystal having positive dielectric anisotropy has a sandwich structure on a transparent electrode portion substrate having a liquid crystal alignment film, and the long axis of the liquid crystal molecules is twisted more than 90 degrees continuously between substrates, a twisted nematic (TN) type, BACKGROUND ART A liquid crystal display device having a STN (Super Twisted Nematic) type liquid crystal cell is known.
[4] The means for orienting the liquid crystal in the liquid crystal cell,
[5] 1) a method of forming an organic film on the substrate surface, and then rubbing the organic film surface in one direction with a cloth member such as rayon to impart liquid crystal alignment capability (performing a rubbing treatment),
[6] 2) a method of depositing silicon oxide on the substrate surface in all directions;
[7] 3) There is a method of forming a monomolecular film having a long chain alkyl group using the Langmuir broth method (LB method), but the method of 2) of these methods is limited in the size of the substrate to be processed or the orientation uniformity of the liquid crystal Because of insufficient, industrially, alignment of liquid crystals by rubbing treatment, which is advantageous in terms of processing time and processing cost, is generally performed.
[8] On the other hand, when liquid crystal orientation is performed by a rubbing process, there exists a problem that dust generate | occur | produces in the process and static electricity becomes easy to generate | generate. When static electricity is generated, dust adheres to the surface of the alignment film, which causes display defects, and in the case of a substrate having a thin film transistor (TFT) device, circuit breakdown of the TFT device occurs due to the generated static electricity, which causes a decrease in yield. It can also be. In addition, in the liquid crystal display device which is increasingly finer and finer in the future, the uniformity of the rubbing treatment becomes a problem because of irregularities on the surface of the substrate accompanied by higher density of the pixels.
[9] In the liquid crystal cell, another means for orienting the liquid crystal is to introduce anisotropy into the alignment film and impart liquid crystal alignment ability by irradiating linearly polarized ultraviolet rays to a photosensitive organic film such as polyvinylcinnamate formed on the substrate surface. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust.
[10] As a photosensitive organic film used for this photo-alignment method, photodegradation like a polyimide, photoisomerization like an azobenzene derivative, polyvinyl cinnamate, poly (4 ((2-methacryloyloxy)) And an optical crosslinking reaction such as ethoxy) chalcon). Among these, it is considered that the organic thin film which produces a photocrosslinking reaction is preferable at the point of the thermal stability and electrical characteristics as an oriented film.
[11] However, in the alignment film obtained by the conventional photo-alignment method, sufficient liquid crystal alignment regulating force cannot be obtained, and therefore, when used in a liquid crystal display element, orientation defects such as flow orientation and declining are likely to occur. As a method for obtaining stable alignment characteristics, a method of increasing the liquid crystal alignment regulating power by heating the liquid crystal alignment film oriented by light irradiation has been proposed (see Japanese Patent Laid-Open No. 2001-290155). The angle becomes unstable and causes deterioration of device display quality such as generation of pretilt domains, generation of disclination lines, and in-plane irregularities of electro-optic properties.
[12] On the other hand, as one of the operation modes of the liquid crystal display element, a vertical (homeotropic) alignment is known in which liquid crystal molecules having negative dielectric anisotropy are oriented perpendicular to the substrate. However, in this operation mode, when a voltage is applied between the substrates, Is inclined in a direction parallel to the substrate. In order to make the liquid crystal molecules incline toward one direction in the substrate plane from the substrate normal direction at the time of voltage application, an orientation has been proposed in which the liquid crystal molecules are slightly inclined with respect to the substrate normal without applying a voltage.
[13] However, when controlling the inclination direction of liquid crystal molecules by this method, there is a problem that orientation disturbance is likely to occur due to the influence of the transverse electric field generated between pixels because the orientation regulation of the liquid crystal molecules in the in-plane direction of the liquid crystal molecules is not sufficient. . In this case, the alignment regulation of the liquid crystal molecules in the in-plane direction of the substrate can be improved by increasing the inclination angle in the substrate normal direction. For example, when the inclination angle is 5 degrees or more in the substrate normal direction, the voltage is not applied. As the light transmittance increases, a new problem arises in which the contrast decreases.
[14] The objective of this invention is providing the liquid crystal aligning agent which can obtain the liquid crystal aligning film which has the orientation control force and the pretilt angle expression stability of the liquid crystal aligning film oriented by the photo-alignment method.
[15] Another object of the present invention is to provide a method for forming a liquid crystal alignment film using the liquid crystal aligning agent of the present invention.
[16] Another object of the present invention is to provide a liquid crystal display device having excellent display characteristics having the liquid crystal alignment film of the present invention.
[17] Still another object of the present invention is to provide a vertical alignment liquid crystal aligning agent capable of forming a liquid crystal alignment film capable of imparting the alignment regulating force of the substrate in-plane direction with respect to the liquid crystal molecules even when no inclination angle from the substrate normal is expressed. To provide.
[18] Still other objects and advantages of the present invention will become apparent from the following description.
[1] 1 is a graph showing the results of evaluation of the pretilt angle expression stability of Example 4 and Comparative Example 2.
[19] According to the present invention, the above objects and advantages of the present invention firstly,
[20] (A) a structure capable of photocrosslinking reaction (hereinafter referred to as "structure (A)"), and
[21] (B) contains a polymer having a structure (hereinafter referred to as "structure (B)") having at least one group selected from a fluorine-containing organic group, an alkyl group having 10 to 30 carbon atoms, and an alicyclic organic group having 10 to 30 carbon atoms It is achieved by the liquid crystal aligning agent (henceforth "liquid crystal aligning agent ①") characterized by the above-mentioned.
[22] According to the present invention, the above objects and advantages of the present invention are second,
[23] Structures (A), (B), and (C) polymers having a heat crosslinkable structure (hereinafter referred to as "structure (C)") or the group consisting of the above structures (A), (B) and (C) A liquid crystal aligning agent, which is a mixture of a polymer having at least one structure selected from and comprises a polymer mixture having all of the above structures (A), (B) and (C) (hereinafter referred to as "liquid crystal aligning agent ②") Is achieved by
[24] The above objects and advantages of the present invention are third,
[25] A polymer having structures (A) and (B) or a mixture of polymers having at least one structure selected from the group consisting of the above structures (A) and (B), comprising together structures (A) and (B) A liquid crystal aligning agent (hereinafter referred to as "liquid crystal aligning agent ③"), which contains a polymer mixture, and a compound having a structure crosslinked by heat (C ') (hereinafter referred to as "compound (C')"). Moreover, the liquid crystal aligning agent (1), the liquid crystal aligning agent (2), and the liquid crystal aligning agent (3) are combined together and it is achieved by "the liquid crystal aligning agent of this invention."
[26] Fourthly, the above objects and advantages of the present invention are achieved by a method for forming a liquid crystal aligning film, wherein the film obtained from the liquid crystal aligning agent of the present invention is irradiated with polarized ultraviolet light while heating at room temperature or more.
[27] Fifth, the above objects and advantages of the present invention are achieved by a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.
[28] <Embodiment of the Invention>
[29] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
[30] Liquid crystal aligning agent ①
[31] Liquid crystal aligning agent (1) has a structure (A) and a structure (B), It is characterized by containing the polymer (henceforth "specific polymer") which does not have the following structure (C).
[32] There is no restriction | limiting in particular in the skeleton of a specific polymer. Examples thereof include polyamic acid, polyimide, polymaleimide, polystyrene, maleimide / styrene copolymer, polyester, polyamide, poly (meth) acrylate, polysiloxane, and copolymers thereof. In particular, polyimide, polyamic acid, polystyrene and maleimide / styrene copolymer are preferable in view of excellent heat resistance and electrical properties.
[33] As a content ratio of structure (A) and a structure (B) in a specific polymer, the repeating unit which has a structure (A) with respect to all the repeating units becomes like this. Preferably it is 10 to 95%, More preferably, it is 50 to 90% The repeating unit having the structure (B) is preferably 5 to 50%, more preferably 10 to 25%.
[34] Each structural component of the liquid crystal aligning agent ① is mentioned later.
[35] Liquid crystal aligning agent ②
[36] The liquid crystal aligning agent ② is characterized by including a polymer having a structure (A), a structure (B) and a structure (C) or a polymer mixture. The polymer here is a copolymer having a structure (A), a structure (B) and a structure (C), and the polymer mixture is one kind selected from the group consisting of structure (A), structure (B) and structure (C). It is a polymer mixture which has a structure (A), a structure (B), and a structure (C) as a whole using two or more polymers which have the above structure.
[37] Preferred polymer components include the following 1-3.
[38] 1.A mixture of the specific polymer described above with a polymer having structure (C).
[39] 2. Copolymer having structure (A), structure (B) and structure (C).
[40] 3. A mixture of a polymer having a structure (A), a polymer having a structure (B) and no structure (A), and a polymer having a structure (C) and no structure (A), (B) .
[41] The skeleton of the polymer used in the present invention is not particularly limited, but may be a polymer having structure (A), a polymer having structure (B), no structure (A), or a specific polymer (collectively referred to as "polymer I"). For example, polyamic acid, polyimide, polymaleimide, polystyrene, maleimide / styrene copolymer, polyester, polyamide, poly (meth) acrylate, polysiloxane, and copolymers thereof are mentioned, for example. . In particular, polyimide, polyamic acid, polystyrene and maleimide / styrene copolymer are preferable in view of excellent heat resistance and electrical properties. Moreover, as a polymer which has a structure (C) and does not have a structure (A) and (B), an epoxy resin, the (meth) acrylate type polymer which has an epoxy structure in a side chain, etc. are mentioned, for example. Examples of the copolymer having the structure (A) and the structure (B) and the structure (C) include polystyrene and maleimide / styrene copolymers.
[42] As content ratio of the structure (A)-(C) in all the polymer components, the repeating unit which has a structure (A) with respect to all the repeating units in a polymer component becomes like this. It is 90%, The repeating unit which has a structure (B) becomes like this. Preferably it is 5 to 50%, More preferably, it is 10 to 25%, The repeating unit which has a structure (C) becomes like this. Preferably it is 0.1 to 5%, More preferably. Preferably it is 1 to 4%.
[43] Each structural component of the liquid crystal aligning agent ② is mentioned later.
[44] Liquid crystal aligning agent ③
[45] The liquid crystal aligning agent ③ is characterized by containing a polymer or polymer mixture having a structure (A) and a structure (B) and a compound (C '). The polymer here is a specific polymer, and the polymer mixture is a mixture of a polymer having structure (A) and a polymer having structure (B) and not having structure (A).
[46] Although there is no restriction | limiting in particular in the skeleton of a polymer, The structure of the polymer I mentioned above is mentioned as a preferable thing. In particular, it is preferable to use a polyimide and / or polyamic acid as the polymer component and to use a compound having an epoxy structure as the compound (C ′).
[47] As the content ratio of the structure (A) and the structure (B) in the polymer or the polymer mixture, the repeating unit having the structure (A) is preferably 10 to 95%, more preferably to the total repeating units in the polymer or the polymer mixture. Is 50 to 90%, and the repeating unit having the structure (B) is preferably 5 to 50%, more preferably 10 to 25%.
[48] In addition, the content ratio of the compound (C ′) is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight based on 100 parts by weight of the polymer or polymer mixture.
[49] Each structural component of the liquid crystal aligning agent ③ is mentioned later.
[50] Structure (A)
[51] The structure (A) is not particularly limited as long as it is a structure capable of photocrosslinking reaction. Preferably, at least one conjugated enone structure selected from the following general formulas (1), (2), (3) and (4) is mentioned.
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[56] In formula, P <^1> , P <^2> , P <^3> , P <^4> , Q <^1> , Q <^2> , Q <^3> and Q <^4> represent the organic group containing an aromatic ring, and P <^1> , P <^4> , Q <^1> and Q <^3> represent an aromatic ring. Is a divalent organic group having, P ² , P ³ and Q ⁴ are monovalent organic groups having an aromatic ring, Q ² is a trivalent organic group having an aromatic ring, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group.
[57] ^{P 1, P 2, P 3} , P 4, Q 1, an organic group containing an aromatic ring of Q ^2, Q ³ and Q ⁴ are particularly, preferred may be an organic group having 6 to 20 carbon atoms.
[58] Such an organic group may contain a halogen atom. Specifically, as P ² , P ³ and Q ⁴ , for example, 4-pentylphenyl group, 4-fluorophenyl group, 3,4-difluorophenyl group, 3,4,5-trifluorophenyl group, 4-octyl Phenyl group, 4-pentylbiphenyl group, 4-octylbiphenyl group, 4-fluorobiphenyl group, 3,4-difluorobiphenyl group, 3,4,5-trifluorobiphenyl group, 4-octyl-1-naphthyl group, 5 -Pentyl-1-naphthyl group, 6-octyl-2-naphthyl group, 9-anthtolyl group, 10-pentyl-9-anthtolyl group, etc. are mentioned.
[59] As P ¹ , P ⁴ , Q ¹ and Q ³ , for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 4,4′-biphenylene group, etc. may be used. Can be mentioned.
[60] Moreover, as Q <^2> , all are trivalent skeleton, For example, a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, an anthsen skeleton, etc. are mentioned.
[61] These groups may be the same or different from each other.
[62] In addition, in formula, R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , R <^6> , R <^7> and R <^8> are a hydrogen atom or an alkyl group, Preferably they are a hydrogen atom or a C1-C6 alkyl group. Such alkyl groups may be linear or branched and may be the same or different from one another.
[63] Other examples of the structure (A) include cinnamic acid derivative structure, stilbene derivative structure, benzophenone derivative structure, cinnamoyl structure and the like. Such a structure may be linear or part of a cyclic structure, such as in a coumarin structure. Such a structure (A) may be used alone or in combination in the polymer component.
[64] Structure (B)
[65] The structure (B) is at least one group selected from a fluorine-containing organic group, an alkyl group having 10 to 30 carbon atoms, and an alicyclic organic group having 10 to 30 carbon atoms, and a pretilt angle is applied to the liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention. Has a role to provide.
[66] As a fluorine-containing organic group, a trifluoromethyl group, pentafluoroethyl group, 4-fluorocyclohexyl group, pentafluorocyclohexyl group, 4-fluorophenyl group, pentafluorophenyl group, etc. are mentioned, for example. Examples of the alkyl group having 10 to 30 carbon atoms include n-decyl group, n-dodecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-octadecyl group and n-ecosyl group. Etc. are mentioned. Moreover, as a C10-C30 alicyclic organic group, a cholesteryl group, a cholestanyl group, etc. are mentioned, for example. In the structure (B), the fluorine-containing organic group and the alkyl group may be bonded through a linking group such as -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH- or -S-. It may be.
[67] Structure (C)
[68] The structure (C) is not particularly limited as long as it is a heat crosslinkable structure. Preferably, an epoxy group is mentioned, for example.
[69] Polymer I
[70] The polyamic acid and the polyimide, which are specific examples of the polymer I, are obtained by reacting (a) tetracarboxylic dianhydride and (b) a diamine compound to produce a polyamic acid, followed by dehydration and ring closure to produce a polyimide. At this time, in the production of polyamic acid and polyimide, a compound having structure (A) and / or a compound having structure (B) is used in at least one of the components (A) and (B).
[71] As a tetracarboxylic dianhydride which has a structure (A), it is 2,2'-bis (4-chalconyloxy) -3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, for example. , 3,3'-bis (4-chalconyloxy) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (4-chalconyloxy) -4, 4 ', 5,5'-biphenyltetracarboxylic dianhydride, 4,4'-bis (4-chalconyloxy) -2,2', 3,3'-biphenyltetracarboxylic dianhydride, 6,6'-bis (4-chalconyloxy) -2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 5,5'-bis (4-chalconyloxy) -2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2'-bis (4-chalconyloxy) -3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3'-bis (4-chalconyloxy) -4,4 ', 5,5'-diphenylethertetracarboxylic dianhydride, 2,2'-bis (4-chalconyloxy) -4, 4 ', 5,5'-diphenylethertetracarboxylic dianhydride, 4,4'-bis (4-chalconyloxy) -2,2', 3,3'-diphenylethertetracarboxylic dianhydride Water, 6,6'-bis (4-chalconyloxy) -2,2 ', 3,3'-diphenylethertetracarboxylic dianhydride, 5,5'-bis (4-chalconyl) -2 , 2 ', 3,3'-diphenylethertetracarboxylic dianhydride, 2,2'-bis (6 (4-chalconyloxy) hexyloxy) -3,3', 4,4'-ratio Phenyltetracarboxylic dianhydride, 2,2'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -3,3 ', 4,4'-biphenyltetracarboxylic acid Dianhydrides, 3,3'-bis (6 (4-chalconyloxy) hexyloxy) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 3,3'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (6 (4-chalconyl Oxy) hexyloxy) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy ) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 4,4'-bis (6 (4-chalconyloxy) hexyloxy) -2,2', 3,3 ' -Biphenyltetracarboxylic dianhydride, 4,4'-bis (6 (4'-fluoro -4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 6,6'-bis (6 (4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 6,6'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -2,2' , 3,3'-biphenyltetracarboxylic dianhydride, 5,5'-bis (6 (4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-biphenyltetracarboxylic Acid dianhydrides, 5,5'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2 , 2'-bis (6 (4-chalconyloxy) hexyloxy) -3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 2,2'-bis (6 (4' -Fluoro-4-chalconyloxy) hexyloxy) -3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3'-bis (6 (4-chalconyloxy) Hexyloxy) -4,4 ', 5,5'-diphenylethertetracarboxylic dianhydride, 3,3'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -4,4 ', 5,5'-diphenylethertetracar Acid dianhydride, 2,2'-bis (6 (4-chalconyloxy) hexyloxy) -4,4 ', 5,5'-diphenylethertetracarboxylic dianhydride, 2,2'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -4,4 ', 5,5'-diphenylethertetracarboxylic dianhydride, 4,4'-bis (6 (4 -Chalconyloxy) hexyloxy) -2,2 ', 3,3'-diphenylethertetracarboxylic dianhydride, 4,4'-bis (6 (4'-fluoro-4-chalconyloxy ) Hexyloxy) -2,2 ', 3,3'-diphenylethertetracarboxylic dianhydride, 6,6'-bis (6 (4-chalconyloxy) hexyloxy) -2,2' , 3,3'-diphenylethertetracarboxylic dianhydride, 6,6'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -2,2 ', 3,3 '-Diphenylethertetracarboxylic dianhydride, 5,5'-bis (6 (4-chalconyloxy) hexyloxy) -2,2', 3,3'-diphenylethertetracarboxylic dianhydride Water, 5,5'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-diphenylethertetracarboxylic dianhydride, 2, 2'-rain (6 (4-chalconyloxy) hexyloxy) -3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2'-bis (6 (4'-fluoro-4- Chalconyloxy) hexyloxy) -3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3'-bis (6 (4-chalconyloxy) hexyloxy) -4, 4 ', 5,5'-benzophenonetetracarboxylic dianhydride, 3,3'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -4,4', 5, 5'-benzophenonetetracarboxylic dianhydride, 2,2'-bis (6 (4-chalconyloxy) hexyloxy) -4,4 ', 5,5'-benzophenonetetracarboxylic dianhydride , 2,2'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -4,4 ', 5,5'-benzophenonetetracarboxylic dianhydride, 4,4' -Bis (6 (4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 4,4'-bis (6 (4'-fluoro- 4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 6,6'-bis (6 (4-chalconyloxy) hexyloxy)- 2,2 ', 3,3'-benzophenonetetracarboxyl Dianhydrides, 6,6'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 5, 5'-bis (6 (4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 5,5'-bis (6 (4'-fluor Ro-4-chalconyloxy) hexyloxy) -2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3 (6 (4-chalconyloxy) hexyloxy) -pyromellitic acid Dianhydrides, 3 (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -pyromellitic dianhydride, 3,6-bis (6 (4-chalconyloxy) hexyloxy) -pyro Mellitic dianhydride, 3,6-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) -pyromellitic dianhydride, a compound represented by the following formula 5 to 26,
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[93]
[94] 2,2'-bis (4 (4-chalconyl) phenoxy) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3'-bis (4 (4-chalconyl ) Phenoxy) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (4 (4-chalconyl) phenoxy) -4,4', 5,5 '-Biphenyltetracarboxylic dianhydride, 4,4'-bis (4 (4-chalconyl) phenoxy) -2,2', 3,3'-biphenyltetracarboxylic dianhydride, 6, 6'-bis (4 (4-chalconyl) phenoxy) -2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 5,5'-bis (4 (4-chalconyl) phenoxy C) -2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2'-bis (4 (4-chalconyl) phenoxy) -3,3', 4,4'- Diphenylethertetracarboxylic dianhydride, 3,3'-bis (4 (4-chalconyl) phenoxy) -4,4 ', 5,5'-diphenylethertetracarboxylic dianhydride, 2, 2'-bis (4 (4-chalconyl) phenoxy) -4,4 ', 5,5'-diphenylethertetracarboxylic dianhydride, 4,4'-bis (4 (4-chalconyl) Phenoxy) -2,2 ', 3,3'-diphenylethertetracarboxylic dianhydride, 6,6'-bis (4 ( 4-chalconyl) phenoxy) -2,2 ', 3,3'-diphenylethertetracarboxylic dianhydride, 5,5'-bis (4 (4-chalconyl) phenoxy) -2,2 ", 3,3"-diphenyl ether tetracarboxylic dianhydride etc. are mentioned. These can be used individually or in combination of 2 or more types.
[95] Examples of the diamine compound having the structure (A) include 4 (3,5-diaminophenoxy) -4'-isopropylchalcone and 4 (3,5-diaminophenoxy) -4'-pentylchalcone , 4 (3,5-diaminophenoxy) -4'-pentylchalcone, 4 (3,5-diaminophenoxy) -4'-octylchalcone, 4 (2,4-diaminophenoxy) -4 '-Pentylchalcone, 4 (2,4-diaminophenoxy) -4'-octylchalcone, 4 (3,5-diaminobenzoyloxy) -4'-pentylchalcone, 4' (4-pentylphenyl)- 4 (3,5-diaminophenoxy) chalcone, 6 (4-chalconyloxy) hexyloxy (2,4-diaminobenzene), 6 (4'-fluoro-4-chalconyloxy) hexyloxy C (2,4-diaminobenzene), 8 (4-chalconyloxy) octyloxy (2,4-diaminobenzene), 8 (4'-fluoro-4-chalconyloxy) octyloxy (2, 4-diaminobenzene), 10 (4-chalconyloxy) decyloxy (2,4-diaminobenzene), 10 (4'-fluoro-4-chalconyloxy) decyloxy (2,4- Diaminobenzene), 2 (2 (4-chalconyloxy) ethoxy) ethyl (3,5-diaminobenzoate), 2 (2 (4'-fluoro-4-chalconyloxy) ethoxy) ethyl (3,5-diaminoben Ate), 2 (2 (4-chalconyloxy) ethoxy) ethoxy (2,4-diaminobenzene), 2 (2 (4'-fluoro-4-chalconyloxy) ethoxy) ethoxy ( 2,4-diaminobenzene), 1 ((4-chalconyloxy) ethoxy) -2 ((2,4-diaminophenoxy) ethoxy) ethane, 1 ((4'-fluoro-4- Chalconyloxy) ethoxy) -2 ((2,4-diaminophenoxy) ethoxy) ethane, 1-((4-chalconyloxy) ethoxy) -2-((3,5-diaminobenzoyl Oxy) ethoxy) ethane, 1-((4'-fluoro-4-chalconyloxy) ethoxy) -2-((3,5-diaminobenzoyloxy) ethoxy) ethane, 6 (4-cal Conyloxy) hexyloxy (3,5-diaminobenzoyl), 6 (4'-fluoro-4-chalconyloxy) hexyloxy (3,5-diaminobenzoyl), 8 (4-chalconyloxy ) Octyloxy (3,5-diaminobenzoyl), 8 (4'-fluoro-4-chalconyloxy) octyloxy (3,5-diaminobenzoyl), 10 (4-chalconyloxy) decyloxy (3,5-diaminobenzoyl), 10 (4'-fluoro-4-chalconyloxy) decyloxy (3,5-diaminobenzoyl), 6 (4-chalconyloxy) hexanoic acid (2, 4-diaminophenyl), 6 ( 4'-fluoro-4-chalconyloxy) hexanoic acid (2,4-diaminophenyl), 8 (4-chalconyloxy) -octanoic acid- (2,4-diaminophenyl), 8 (4 ' -Fluoro-4-chalconyloxy) -octanoic acid- (2,4-diaminophenyl), 10 (4-chalconyloxy) -decanoic acid- (2,4-diaminophenyl), 10 (4 ' -Fluoro-4-chalconyloxy) -decanoic acid- (2,4-diaminophenyl), adipic acid mono (4-chalconyl) mono (2,4-diaminophenyl), adipic acid mono ( 4'-fluoro-4-chalconyl) mono (2,4-diaminophenyl), suveric acid mono (4-chalconyl) mono (2,4-diaminophenyl), suveric acid mono (4 ' -Fluoro-4-chalconyloxy) mono (2,4-diaminophenyl), sebacic acid mono (4-chalconyl) mono (2,4-diaminophenyl), sebacic acid mono (4'- Fluoro-4-chalconyloxy) mono (2,4-diaminophenyl), bis-1,1 (4-aminophenyl) -6 (4-chalconyloxy) hexane, bis-1,1 (4- Aminophenyl) -6 (4'-fluoro-4-chalconyloxy) hexane, bis-1,1 (4-aminophenyl) -8 (4-chalconyloxy) octane, bis-1,1 (4- Aminophenyl) -8 (4'-flu Oro-4-chalconyloxy) octane, bis-1,1 (4-aminophenyl) -10 (4-chalconyloxy) decane, bis-1,1 (4-aminophenyl) -10 (4'-fluor Ro-4-chalconyloxy) decane, bis-N, N- (4-aminophenyl) -N- (6 (4-chalconyloxy) hexaneoxyphenyl) amine, bis-N, N- (4-amino Phenyl) -N- (6 (4'-fluoro-4-chalconyloxy) hexaneoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (8 (4-chalconyloxy) Octaneoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (8 (4'-fluoro-4-chalconyloxy) octaneoxyphenyl) amine, bis-N, N- (4 -Aminophenyl) -N- (10 (4-chalconyloxy) decanoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (10 (4'-fluoro-4-chalconyl Oxy) decaneoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (2 (2 (4-chalconyloxy) ethoxy) ethoxyphenyl) amine, bis-N, N- ( 4-aminophenyl) -N- (4 (2 (2 (4'-fluoro-4-chalconyloxy) ethoxy) ethoxy) phenyl) amine, 4 (4 (2,4-diaminophenoxy) Phenyl) chalcone, 4 (4 (2 (2,4-diaminophenoxy) ethoxy) phenyl) kal , 4 (4 (6 (2,4-diaminophenoxy) hexaneoxy) phenyl) chalcone, 4 (2 (2,4-diaminophenoxy) ethyl) chalconcarboxylate, 4 (6 (2,4 -Diaminophenoxy) hexyl) chalconcarboxylate, 4 (4 (2,4-diaminophenoxy) benzoyloxy) chalcone, 4 (4 (2,4-diaminophenoxy) phenyl) chalconcarboxylate , 4 (4 (2 (2,4-diaminophenoxy) ethoxy) benzoyloxy) chalcone, 4 (4 (2 (2,4-diaminophenoxy) ethoxy) phenyl) chalconcarboxylate, 4 (4 (6 (2,4-diaminophenoxy) hexaneoxy) benzoyloxy) chalcone, 4 (4 (6 (2,4-diaminophenoxy) hexaneoxy) phenyl) chalconcarboxylate, 4 (4 (3,5-diaminobenzoyloxy) phenyl) chalcone, 4 (4 (2 (3,5-diaminobenzoyloxy) ethoxy) phenyl) chalcone, 4 (4 (6 (3,5-diaminobenzoyloxy ) Hexaneoxy) phenyl) chalcone, 4 (2 (3,5-diaminobenzoyloxy) ethyl) chalconcarboxylate, 4 (6 (3,5-diaminobenzoyloxy) hexyl) chalconcarboxylate, 4 ( 4 (3,5-diaminobenzoyloxy) benzoyloxy) chalcone, 4 (4 (3, 5-diaminobenzoyloxy) phenyl) chalconcarboxylate, 4 (4 (2 (3,5-diaminobenzoyloxy) ethoxy) benzoyloxy) chalcone, 4 (4 (2 (3,5-diaminobenzoyl) Oxy) ethoxy) phenyl) chalconcarboxylate, 4 (4 (6 (3,5-diaminobenzoyloxy) hexaneoxy) benzoyloxy) chalcone, 4 (4 (6 (3,5-diaminobenzoyloxy) Hexaneoxy) phenyl) chalconcarboxylate, etc. are mentioned. These can be used individually or in combination of 2 or more types.
[96] Moreover, as tetracarboxylic dianhydride which has a structure (B), the compound represented by following formula (27)-40 is mentioned, for example. These can be used individually or in combination of 2 or more types.
[97]
[98]
[99]
[100]
[101]
[102]
[103]
[104]
[105]
[106]
[107]
[108]
[109]
[110]
[111] Examples of the diamine compound having the structure (B) include 1-dodecaneoxy-2,4-diaminobenzene, 1-tetradecaneoxy-2,4-diaminobenzene, 1-pentadecanoxy-2, 4-diaminobenzene, 1-hexadecaneoxy-2,4-diaminobenzene, 1-octadecaneoxy-2,4-diaminobenzene, 1-cholesteryl oxy2,4-diaminobenzene, 1- Cholestanyloxy-2,4-diaminobenzene, dodecaneoxy (3,5-diaminobenzoyl), tetradecaneoxy (3,5-diaminobenzoyl), pentadecaneoxy (3,5-diaminobenzoyl ), Hexadecaneoxy (3,5-diaminobenzoyl), octadecaneoxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3,5 -Diaminobenzoyl), (2,4-diaminophenoxy) palmitate, (2,4-diaminophenoxy) stearylate, (2,4-diaminophenoxy) -4-trifluoromethyl Benzoate and the compound represented by following formula (41) are mentioned.
[112]
[113] The polyimide used by this invention can use together the other tetracarboxylic dianhydride and / or diamine compound of the grade which does not impair the effect of this invention. Such other components are preferably used at 60 mol% or less, more preferably 20 mol% or less, based on the total of the compound having the structure (A) and the compound having the structure (B), for example.
[114] As another tetracarboxylic dianhydride, For example, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride Water, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5,6-tricarboxy Norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3- Aliphatic and alicyclic tetracarboxes such as cyclohexene-1,2-dicarboxylic dianhydride and bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Acid dianhydrides; Pyromellitic dianhydride, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3 , 3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furtetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy ) Diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride Water, 3,3 ', 4,4'-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphate Pinoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride Aromatic tetracarboxylic dianhydride, such as an aqueous substance, bis (triphenyl phthalic acid) -4,4'- diphenyl ether dianhydride, and bis (triphenyl phthalic acid) -4,4'- diphenylmethane dianhydride, are mentioned. .
[115] Among these, 2,3,5-tricarboxycyclopentyl acetic dianhydride, butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride and 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride are preferable. These can be used individually or in combination of 2 or more types.
[116] As another diamine compound, p-phenylenediamine, m-phenylenediamine, 4,4'- diaminodiphenyl methane, 4,4'- diamino diphenylethane, 4,4'- diamino, for example Diphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diamino Diphenyl ether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1 (4'-aminophenyl) -1,3,3-trimethylindan, 6-amino-1 (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenylether, 2,2-bis (4-aminophenoxy) propane, 2,2 -Bis [4 (4-aminophenoxy) phenyl] propane, 2,2-bis [4 (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro 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, 4,4 '(p-phenyleneisopropylidene) bisaniline, 4,4' (m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4 ( 4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [ Aromatic diamines such as (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl; Aromatic diamines having hetero atoms such as diaminotetraphenylthiophene; 1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine , 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6.2.1.0 _2,7 ] -undecylene Aliphatic and alicyclic diamines such as dimethyldiamine and 4,4'-methylenebis (cyclohexylamine); Diamino organosiloxane, such as diamino hexamethyl disiloxane, is mentioned.
[117] Among them, p-phenylenediamine, 4,4'-diaminodiphenyl methane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 4, 4 '(p-phenyleneisopropylidene) bisaniline, 2,2-bis [4 (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane , 2,2'-bis [4 (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) Biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl is preferred. These can be used individually or in combination of 2 or more types.
[118] The polyimide used in the present invention is polycondensed with the (A) tetracarboxylic dianhydride component and the (B) diamine component to obtain a polyamic acid, and subsequently heated in the presence of a dehydrating agent and an imidization catalyst, if necessary, It is obtained by imidization. The reaction temperature in the case of imidating by heating is 60-300 degreeC normally, Preferably it is 100-170 degreeC. When reaction temperature is less than 60 degreeC, advancing of reaction will be delayed and when it exceeds 300 degreeC, the molecular weight of polyamic acid will fall largely. In addition, the reaction in the case of imidizing in presence of a dehydrating agent and an imidation catalyst can be performed in an organic solvent. Reaction temperature is 0-180 degreeC normally, Preferably it is 60-150 degreeC. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used. As the imidation catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. The amount of the dehydrating agent is preferably 1.6 to 20 moles with respect to 1 mole of the repeating unit of the polyamic acid. In addition, it is preferable that the usage-amount of an imidation catalyst shall be 0.5-10 mol with respect to 1 mol of dehydrating agents to be used. The content rate of the amic acid residue in a polyimide can be adjusted according to the usage-amount of this imidation catalyst and a dehydrating agent.
[119] Polystyrene and styrene / maleimide copolymers, which are embodiments of Polymer I, are obtained by radical polymerization of styrene derivatives or styrene derivatives and phenylmaleimide derivatives in the presence of an initiator. The polystyrene and styrene / maleimide copolymers used in the present invention are obtained using a compound having structure (A) and at least one component of a styrene derivative and a phenylmaleimide derivative component and a compound having structure (B).
[120] As a styrene derivative which has a structure (A), for example, 4- (4-chalconyloxy) styrene, 4- (4-chalconyloxy) (alpha) -methylstyrene, 4- (2- (4-chalconyloxy) ) Ethoxy) styrene, 4- (2- (4-chalconyloxy) ethoxy) α-methylstyrene, 4- (4- (4-chalconyloxy) butoxy) styrene, 4- (4- (4 -Chalconyloxy) butoxy) α-methylstyrene, 4- (6- (4-chalconyloxy) hexaneoxy) styrene, 4- (6- (4-chalconyloxy) hexaneoxy) α-methylstyrene, 4- (8- (4-chalconyloxy) octaneoxy) styrene, 4- (8- (4-chalconyloxy) octaneoxy) α-methylstyrene, 4- (4-chalconylcarboxy) styrene, 4- (4-chalconylcarboxy) α-methylstyrene, 4- (2- (4-chalconylcarboxy) ethoxy) styrene, 4- (2- (4-chalconylcarboxy) ethoxy) α-methylstyrene, 4 -(4- (4-chalconylcarboxy) butoxy) styrene, 4- (4- (4-chalconylcarboxy) butoxy) α-methylstyrene, 4- (6- (4-chalconylcarboxy) hexaneoxy ) Styrene, 4- (6- (4-chalconylcarboxy) hexaneoxy) α-methylstyrene, 4- (8- (4-chalconylcarboxy) jade Tanoxy) styrene, 4- (8- (4-chalconylcarboxy) octaneoxy) α-methylstyrene, 4- (2- (4-chalconyl) ethoxy) styrene, 4- (2- (4-cal Conyl) ethoxy) α-methylstyrene, 4- (4- (4-chalconyl) butoxy) styrene, 4- (4- (4-chalconyl) butoxy) α-methylstyrene, 4- (6- (4-chalconyl) hexaneoxy) styrene, 4-(6- (4-chalconyl) hexaneoxy) α-methylstyrene, 4- (8- (4-chalconyl) octaneoxy) styrene, 4- ( 8- (4-chalconyl) octaneoxy) α-methylstyrene, 4- (2- (4-chalconyloxy) ethyl) styrene, 4- (2- (4-chalconyloxy) ethyl) α-methylstyrene , 4- (4- (4-chalconyloxy) butyl) styrene, 4- (4- (4-chalconyloxy) butyl) α-methylstyrene, 4- (6- (4-chalconyloxy) hexyl) Styrene, 4- (6- (4-chalconyloxy) hexyl) α-methylstyrene, 4- (8- (4-chalconyloxy) octyl) styrene, 4- (8- (4-chalconyloxy) octyl ) α-methylstyrene, 4- (2- (4-chalconylcarboxy) ethyl) styrene, 4- (2- (4-chalconylcarboxy) ethyl) α-methylstyrene, 4- (4- (4-cal Conylcarboxy) butyl) styrene, 4- (4- (4-chalconylcarboxy) Butyl) α-methylstyrene, 4- (6- (4-chalconylcarboxy) hexyl) styrene, 4- (6- (4-chalconylcarboxy) hexyl) α-methylstyrene, 4- (8- (4- Chalconylcarboxy) octyl) styrene, 4- (8- (4-chalconylcarboxy) octyl) α-methylstyrene, 4- (2- (4-chalconyl) ethyl) styrene, 4- (2- (4- Chalconyl) ethyl) α-methylstyrene, 4- (4- (4-chalconyl) butyl) styrene, 4- (4- (4-chalconyl) butyl) styrene, 4- (4- (4-chalconyl ) Butyl) α-methylstyrene, 4- (6- (4-chalconyl) hexyl) styrene, 4- (6- (4-chalconyl) hexyl) α-methylstyrene, 4- (8- (4-cal Conyl) octyl) styrene, 4- (8- (4-chalconyl) octyl) α-methylstyrene, 4- (4-chalconyloxymethyl) styrene, 4- (4-chalconyloxymethyl) α-methylstyrene , 4- (2- (4-chalconyloxy) ethoxymethyl) styrene, 4- (2- (4-chalconyloxy) ethoxymethyl) α-methylstyrene, 4- (4- (4-chalconyl Oxy) butoxymethyl) styrene, 4- (4- (4-chalconyloxy) butoxymethyl) α-methylstyrene, 4- (6- (4-chalconyloxy) hexaneoxymethyl) styrene, 4- ( 6- (4-chalconyloxy) hexaneoxymethyl ) α-methylstyrene, 4- (8- (4-chalconyloxy) octaneoxymethyl) styrene, 4- (8- (4-chalconyloxy) octaneoxymethyl) α-methylstyrene, 4- (4- Chalconylcarboxymethyl) styrene, 4- (4-chalconylcarboxymethyl) α-methylstyrene, 4- (2- (4-chalconylcarboxy) ethoxymethyl) styrene, 4- (2- (4-chalconyl Carboxy) ethoxymethyl) α-methylstyrene, 4- (4- (4-chalconylcarboxy) butoxymethyl) styrene, 4- (4- (4-chalconylcarboxy) butoxymethyl) α-methylstyrene, 4- (6- (4-chalconylcarboxy) hexaneoxymethyl) styrene, 4- (6- (4-chalconylcarboxy) hexaneoxymethyl) α-methylstyrene, 4- (8- (4-chalconylcarboxy ) Octaneoxymethyl) styrene, 4- (8- (4-chalconylcarboxy) octaneoxymethyl) α-methylstyrene, 4- (2- (4-chalconyl) ethoxymethyl) styrene, 4- (2- (4-Calconyl) ethoxymethyl) α-methylstyrene, 4- (4- (4-chalconyl) butoxymethyl) styrene, 4- (4- (4-chalconyl) butoxymethyl) α-methyl Styrene, 4- (6- (4-chalconyl) hexaneoxymethyl) styrene, 4- (6- (4-chalco ) Hexaneoxymethyl) α-methylstyrene, 4- (8- (4-chalconyl) octaneoxymethyl) styrene, 4- (8- (4-chalconyl) octaneoxymethyl) α-methylstyrene, 4- ( 4'-fluoro-4-chalconyloxy) styrene, 4- (4'-fluoro-4-chalconyloxy) α-methylstyrene, 4- (2- (4'-fluoro-4-chalconyl Oxy) ethoxy) styrene, 4- (2- (4'-fluoro-4-chalconyloxy) ethoxy) α-methylstyrene, 4- (4- (4'-fluoro-4-chalconyloxy ) Butoxy) styrene, 4- (4- (4'-fluoro-4-chalconyloxy) butoxy) α-methylstyrene, 4- (6- (4'-fluoro-4-chalconyloxy) Hexaneoxy) styrene, 4- (6- (4'-fluoro-4-chalconyloxy) hexaneoxy) α-methylstyrene, 4- (8- (4'-fluoro-4-chalconyloxy) octane Oxy) styrene, 4- (8- (4'-fluoro-4-chalconyloxy) octaneoxy) α-methylstyrene, 4- (4'-fluoro-4-chalconylcarboxy) styrene, 4- ( 4'-fluoro-4-chalconylcarboxy) α-methylstyrene, 4- (2- (4'-fluoro-4-chalconylcarboxy) ethoxy) styrene, 4- (2- (4'-fluoro Ro-4-kal Nylcarboxy) ethoxy) α-methylstyrene, 4- (4- (4'-fluoro-4-chalconylcarboxy) butoxy) styrene, 4- (4- (4'-fluoro-4-chalconyl Carboxy) butoxy) α-methylstyrene, 4- (6- (4'-fluoro-4-chalconylcarboxy) hexaneoxy) styrene, 4- (6- (4'-fluoro-4-chalconylcarboxy) ) Hexaneoxy) α-methylstyrene, 4- (8- (4'-fluoro-4-chalconylcarboxy) octaneoxy) styrene, 4- (8- (4'-fluoro-4-chalconylcarboxy) Octaneoxy) α-methylstyrene, 4- (2- (4'-fluoro-4-chalconyl) ethoxy) styrene, 4- (2- (4'-fluoro-4-chalconyl) ethoxy) α-methylstyrene, 4- (4- (4'-fluoro-4-chalconyl) butoxy) styrene, 4- (4- (4'-fluoro-4-chalconyl) butoxy) α-methyl Styrene, 4- (6- (4'-fluoro-4-chalconyl) hexaneoxy) styrene, 4- (6- (4'-fluoro-4-chalconyl) hexaneoxy) α-methylstyrene, 4 -(8- (4'-fluoro-4-chalconyl) octaneoxy) styrene, 4- (8- (4'-fluoro-4-chalconyl) octaneoxy) α-methylstyrene, 4- (2 -(4'-fluoro-4- Chalconyloxy) ethyl) styrene, 4- (2- (4'-fluoro-4-chalconyloxy) ethyl) α-methylstyrene, 4- (4- (4'-fluoro-4-chalconyloxy ) Butyl) styrene, 4- (4- (4'-fluoro-4-chalconyloxy) butyl) α-methylstyrene, 4- (6- (4'-fluoro-4-chalconyloxy) hexyl) Styrene, 4- (6- (4'-fluoro-4-chalconyloxy) hexyl) α-methylstyrene, 4- (8- (4'-fluoro-4-chalconyloxy) octyl) styrene, 4 -(8- (4'-fluoro-4-chalconyloxy) octyl) α-methylstyrene, 4- (2- (4'-fluoro-4-chalconylcarboxy) ethyl) styrene, 4- (2 -(4'-fluoro-4-chalconylcarboxy) ethyl) α-methylstyrene, 4- (4- (4'-fluoro-4-chalconylcarboxy) butyl) styrene, 4- (4- (4 '-Fluoro-4-chalconylcarboxy) butyl) α-methylstyrene, 4- (6- (4'-fluoro-4-chalconylcarboxy) hexyl) styrene, 4- (6- (4'-fluoro Ro-4-chalconylcarboxy) hexyl) α-methylstyrene, 4- (8- (4'-fluoro-4-chalconylcarboxy) octyl) styrene, 4- (8- (4'-fluoro-4 -Chalconylcarboxy) jade Tyl) α-methylstyrene, 4- (2- (4'-fluoro-4-chalconyl) ethyl) styrene, 4- (2- (4'-fluoro-4-chalconyl) ethyl) α-methyl Styrene, 4- (4- (4'-fluoro-4-chalconyl) butyl) styrene, 4- (4- (4'-fluoro-4-chalconyl) butyl) α-methylstyrene, 4- ( 6- (4'-fluoro-4-chalconyl) hexyl) styrene, 4- (6- (4'-fluoro-4-chalconyl) hexyl) α-methylstyrene, 4- (8- (4 ' -Fluoro-4-chalconyl) octyl) styrene, 4- (8- (4'-fluoro-4-chalconyl) octyl) α-methylstyrene, 4- (4'-fluoro-4-chalconyl Oxymethyl) styrene, 4- (4'-fluoro-4-chalconyloxymethyl) α-methylstyrene, 4- (2- (4'-fluoro-4-chalconyloxy) ethoxymethyl) styrene, 4- (2- (4'-fluoro-4-chalconyloxy) ethoxymethyl) α-methylstyrene, 4- (4- (4'-fluoro-4-chalconyloxy) butoxymethyl) styrene , 4- (4- (4'-fluoro-4-chalconyloxy) butoxymethyl) α-methylstyrene, 4- (6- (4'-fluoro-4-chalconyloxy) hexaneoxymethyl) Styrene, 4- (6- (4'-fluoro-4-chalconyloxy) hexanocta Methyl) α-methylstyrene, 4- (8- (4'-fluoro-4-chalconyloxy) octaneoxymethyl) styrene, 4- (8- (4'-fluoro-4-chalconyloxy) octane Oxymethyl) α-methylstyrene, 4- (2- (4'-fluoro-4-chalconyl) ethoxymethyl) styrene, 4- (2- (4'-fluoro-4-chalconyl) ethoxy Methyl) α-methylstyrene, 4- (4'-fluoro-4-chalconylcarboxymethyl) styrene, 4- (4'-fluoro-4-chalconylcarboxymethyl) α-methylstyrene, 4- (2 -(4'-fluoro-4-chalconylcarboxy) ethoxymethyl) styrene, 4- (2- (4'-fluoro-4-chalconylcarboxy) ethoxymethyl) α-methylstyrene, 4- ( 4- (4'-fluoro-4-chalconylcarboxy) butoxymethyl) styrene, 4- (4- (4'-fluoro-4-chalconylcarboxy) butoxymethyl) α-methylstyrene, 4- (6- (4'-fluoro-4-chalconylcarboxy) hexaneoxymethyl) styrene, 4- (6- (4'-fluoro-4-chalconylcarboxy) hexaneoxymethyl) α-methylstyrene, 4 -(8- (4'-fluoro-4-chalconylcarboxy) octaneoxymethyl) styrene, 4- (8- (4'-flu Chloro-4-chalconylcarboxy) octaneoxymethyl) α-methylstyrene, 4- (2- (4'-fluoro-4-chalconyl) ethoxymethyl) styrene, 4- (2- (4'-fluoro Ro-4-chalconyl) ethoxymethyl) α-methylstyrene, 4- (4- (4'-fluoro-4-chalconyl) butoxymethyl) styrene, 4- (4- (4'-fluoro -4-chalconyl) butoxymethyl) α-methylstyrene, 4- (6- (4'-fluoro-4-chalconyl) hexaneoxymethyl) styrene, 4- (6- (4'-fluoro- 4-chalconyl) hexaneoxymethyl) α-methylstyrene, 4- (8- (4'-fluoro-4-chalconyl) octaneoxymethyl) styrene, 4- (8- (4'-fluoro-4 -Chalconyl) octaneoxymethyl) α-methylstyrene, 4- (3- (4-vinylphenyl)) propionyloxy) -4'-fluorochalcone, 4- (3- (4-vinylphenyl)) propy Onyloxy) chalcone, the compound represented by following formula (42)-(49), etc. are mentioned.
[121]
[122]
[123]
[124]
[125]
[126]
[127]
[128]
[129] Among these, 4- (6- (4-chalconyloxy) hexaneoxy) styrene, 4- (6- (4-chalconyloxy) octaneoxy) styrene and the compounds represented by the above formulas 42 to 49 are preferable. These can be used individually or in combination of 2 or more types.
[130] Examples of the maleimide derivative having the structure (A) include 4- (4-chalconyloxy) phenylmaleimide, 4- (2- (4-chalconyloxy) ethoxy) phenylmaleimide, 4- ( 4- (4-chalconyloxy) butoxy) phenylmaleimide, 4- (6- (4-chalconyloxy) hexaneoxy) phenylmaleimide, 4- (8- (4-chalconyloxy) octaneoxy) Phenylmaleimide, 4- (4-chalconylcarboxy) phenylmaleimide, 4- (2- (4-chalconylcarboxy) ethoxy) phenylmaleimide, 4- (4- (4-chalconylcarboxy) butoxy ) Phenylmaleimide, 4- (6- (4-chalconylcarboxy) hexaneoxy) phenylmaleimide, 4- (8- (4-chalconylcarboxy) octaneoxy) phenylmaleimide, 4- (2- (4 -Chalconyl) ethoxy) phenylmaleimide, 4- (4- (4-chalconyl) butoxy) phenylmaleimide, 4- (6- (4-chalconyl) hexaneoxy) phenylmaleimide, 4- ( 8- (4-chalconyl) octaneoxy) phenylmaleimide, 4- (2- (4-chalconyloxy) ethyl) phenylmaleimide, 4- (4- (4-chalconyloxy) butyl) phenylmaleimide 4- (6- (4-chalconyloxy) hex ) Phenyl maleimide, 4- (8- (4-chalconyloxy) octyl) phenyl maleimide, 4- (2- (4-chalconylcarboxy) ethyl) phenyl maleimide, 4- (4-chalconylcarboxy) Butyl) phenylmaleimide, 4- (6- (4-chalconylcarboxy) hexyl) phenylmaleimide, 4- (8- (4-chalconylcarboxy) octyl) phenylmaleimide, 4- (2- (4- Chalconyl) ethyl) phenylmaleimide, 4- (4- (4-chalconyl) butyl) phenylmaleimide, 4- (6- (4-chalconyl) hexyl) phenylmaleimide, 4- (8- (4 -Chalconyl) octyl) phenylmaleimide, 4- (4'-fluoro-4-chalconyloxy) phenylmaleimide, 4- (2- (4'-fluoro-4-chalconyloxy) ethoxy) Phenylmaleimide, 4- (4- (4'-fluoro-4-chalconyloxy) butoxy) phenylmaleimide, 4- (6- (4'-fluoro-4-chalconyloxy) hexaneoxy) Phenylmaleimide, 4- (8- (4'-fluoro-4-chalconyloxy) octaneoxy) phenylmaleimide, 4- (4'-fluoro-4-chalconylcarboxy) phenylmaleimide, 4- (2- (4'-fluoro-4-chalconylcarboxy) ethoxy) phenyl Imide, 4- (4- (4'-fluoro-4-chalconylcarboxy) butoxy) phenylmaleimide, 4- (6- (4'-fluoro-4-chalconylcarboxy) hexaneoxy) phenyl Maleimide, 4- (8- (4'-fluoro-4-chalconylcarboxy) octaneoxy) phenylmaleimide, 4- (2- (4'-fluoro-4-chalconyl) ethoxy) phenylmaleimide Mid, 4- (4- (4'-fluoro-4-chalconyl) butoxy) phenylmaleimide, 4- (6- (4'-fluoro-4-chalconyl) hexaneoxy) phenylmaleimide, 4- (8- (4'-fluoro-4-chalconyl) octaneoxy) phenylmaleimide, 4- (2- (4'-fluoro-4-chalconyloxy) ethyl) phenylmaleimide, 4- (4- (4'-fluoro-4-chalconyloxy) butyl) phenylmaleimide, 4- (6- (4'-fluoro-4-chalconyloxy) hexyl) phenylmaleimide, 4- (8 -(4'-fluoro-4-chalconyloxy) octyl) phenylmaleimide, 4- (2- (4'-fluoro-4-chalconylcarboxy) ethyl) phenylmaleimide, 4- (4- ( 4'-fluoro-4-chalconylcarboxy) butyl) phenylmaleimide, 4- (6- (4'-fluoro-4-chalconylcar Carboxy) hexyl) phenylmaleimide, 4- (8- (4'-fluoro-4-chalconylcarboxy) octyl) phenylmaleimide, 4- (2- (4'-fluoro-4-chalconyl) ethyl ) Phenylmaleimide, 4- (4- (4'-fluoro-4-chalconyl) butyl) phenylmaleimide, 4- (6- (4'-fluoro-4-chalconyl) hexyl) phenylmaleimide 4- (8- (4'-fluoro-4-chalconyl) octyl) phenylmaleimide, 4- (8- (4'-fluoro-4-chalconyloxy) octaneoxymethyl) phenylmaleimide, 4- (8- (4'-fluoro-4-chalconylcarboxy) octaneoxymethyl) phenylmaleimide, 4- (2- (4'-fluoro-4-chalconyl) ethoxymethyl) phenylmaleimide , 4- (4- (4'-fluoro-4-chalconyl) butoxymethyl) phenylmaleimide, 4- (6- (4'-fluoro-4-chalconyl) hexaneoxymethyl) phenylmaleimide , 4- (8- (4'-fluoro-4-chalconyl) octaneoxymethyl) phenylmaleimide, the compound represented by the following general formula (50) -53, etc. are mentioned.
[131]
[132]
[133]
[134]
[135] Among them, 4- (6- (4-chalconyloxy) hexaneoxy) phenylmaleimide, 4- (8- (4-chalconyloxy) octaneoxy) phenylmaleimide, 4- (6- (4'- Fluoro-4-chalconyloxy) hexyl) phenylmaleimide, 4- (8- (4'-fluoro-4-chalconyloxy) octyl) phenylmaleimide, compounds represented by the above formulas 50 to 53 are preferable. Do. These can be used individually or in combination of 2 or more types.
[136] Examples of the styrene derivative having the structure (B) include p-trifluoromethylstyrene, p-trifluoromethyl-α-methylstyrene, p-trifluoromethoxystyrene, and p-trifluoromethoxy-α -Methyl styrene, 4- (2,2,2-trifluoroethoxy) styrene, 4- (2,2,2-trifluoroethoxy) -α-methylstyrene, p-cetyloxystyrene, p- Cetyloxy-α-methylstyrene, p-palmitoyloxystyrene, p-palmitoyloxy-α-methylstyrene, p-stearyloxystyrene, p-stearyloxy-α-methylstyrene, p-stearoyloxy Styrene, p-stearoyloxy-α-methylstyrene, p-cholesteryloxystyrene, p-cholesteryl oxymethylstyrene, p-cholestanyloxystyrene, p-cholestanyloxy-α-methylstyrene Can be mentioned.
[137] As the maleimide derivative having the structure (B), for example, 4-trifluoromethylphenylmaleimide, 4-trifluoromethoxyphenylmaleimide, 4- (2,2,2-trifluoroethoxy ) Phenyl maleimide, 4-cetyloxyphenyl maleimide, 4-palmitoyloxyphenyl maleimide, 4-stearyloxyphenyl maleimide, 4-stearoyloxyphenyl maleimide, 4-cholesteryloxyphenyl maleimide And 4-cholestanyloxyphenylmaleimide and the like.
[138] The polystyrene and styrene / maleimide copolymer used in the present invention may be copolymers having a structure (A), a structure (B) and a structure (C) by copolymerizing a monomer having a structure (C).
[139] As a monomer which has a structure (C), for example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycine (alpha)-n-butyl acrylate Cydyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6, 7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned. These monomers are used alone or in combination.
[140] The polystyrene and styrene / maleimide copolymer used in the present invention may be used in combination with other radically polymerizable monomers to the extent that the effects of the present invention are not impaired. The other radically polymerizable monomer is preferably used at 50 mol% with respect to styrene in polystyrene and relative to the sum of styrene and maleimide in the styrene / maleimide copolymer.
[141] As another radically polymerizable monomer, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, 2-hydroxyethyl (meth Aliphatic (meth), such as) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate, and trimethylolpropane tri (meth) acrylate Acrylate compounds;
[142] Tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl Alicyclic (meth) acrylate compounds such as (meth) acrylate and isobornyl (meth) acrylate;
[143] 4- (meth) acryloyloxychalcone, 4- (meth) acryloyloxy-4'-phenylchalcone, 4- (meth) acryloyloxy-4'-pentylchalcone, 4- (meth) acrylo Iloxy-4 '-(4-pentylphenyl) chalcone, benzyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tree Aromatic (meth) acrylate compounds such as (meth) acrylate;
[144] Ethylene, propylene, butene, styrene, p-methylstyrene, p-trifluoromethylstyrene, α-methylstyrene, p-trifluoromethyl-α-methylstyrene, 4 (4-trifluoromethylbenzoyloxy) styrene , p-cetyloxystyrene, p-palmitoyloxystyrene, 4-trifluoromethylphenyl-3 (4-vinylphenyl) propionate, 4-cetyl-3 (4-vinylphenyl) propionate, 4-ste Vinyl compounds such as aryl-3 (4-vinylphenyl) propionate, vinyl chloride, vinyl acetate and acrylonitrile;
[145] Maleic acid derivatives such as maleic anhydride and phenylmaleimide;
[146] And dienes such as butadiene, isoprene and chloroprene.
[147] Among them, styrene, p-methyl styrene and α-methyl styrene are preferable. These can be used individually or in combination of 2 or more types.
[148] The polystyrene and styrene / maleimide copolymer used in the present invention are polymerized with the styrene derivative and / or maleimide derivative in the presence of a catalyst such as an azo compound such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide as necessary. It is obtained by. These polymers can be used alone or in combination of two or more thereof.
[149] Alternative methods for obtaining the polystyrene and styrene / maleimide copolymers used in the present invention include monomers having structure (B) with acetoxy substituted styrene derivatives and / or acetoxy substituted phenylmaleimide derivatives, structure (C) After radical polymerization of the monomer etc. which have a, the said acetyl group is substituted by the functional group which has a structure (A).
[150] Polymer having structure (C)
[151] As a polymer which has a structure (C), the polymer obtained by copolymerizing the monomer which has the structure (C) mentioned above as needed with the other radical polymerization monomer mentioned above, and an epoxy resin are mentioned as a preferable thing.
[152] As an epoxy resin, For example, epoxy resin represented by following formula 54, such as a bisphenol-A epoxy resin and a bisphenol F-type epoxy resin; Epoxy resins represented by the following general formula (55), such as a phenol novolak type epoxy resin and a cresol novolak type epoxy resin; The epoxy resin shown by following formula 56, such as a polyfunctional epoxy resin, etc. can be used.
[153]
[154]
[155]
[156] In formula, X is a methylene group, a C2-C6 alkylene group, a C2-C6 fluoroalkylene group, or a bivalent organic group which has an alicyclic skeleton, R is a C1-C3 alkyl group, Y is p Is an organic group, m is an integer of 0-4, m 'is an integer of 0-3, n and p are two or more numbers.
[157] These can be obtained as a commercial item. For example, as bisphenol A epoxy resin, epicoat 828, copper 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010 (above, manufactured by Yuka Shell Epoxy Co., Ltd.) Epicoat 807, copper 834 (above, manufactured by Yuka Shell Epoxy Co., Ltd.), and the like, and epiphenol 152, copper 154, copper 157H65 (above, Yuka Shell Epoxy Co., Ltd.) ), EPPN201, copper 202 (above, manufactured by Nihon Kayaku Co., Ltd.), and the like, as the cresol novolak type epoxy resin, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Nihon Kayaku Co., Ltd.), epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like as cyclic aliphatic epoxy resins include Araldite CY175, copper CY177, copper CY179 (above, Shiba Specialty Chemical Co., Ltd.), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (above, manufactured by UCB), Shodine 509 (manufactured by Showa Denko Co., Ltd.), Araldite CY-182 , CY-192, CY-184, Ciba Specialty Chemical Co., Ltd., Epiclone 200, Copper 400 (above, Dainippon Ink Industries Co., Ltd.), Epicoat 871, Copper 872, EP1032H60 (above, Yuka Shell Epoxy Co., Ltd.), ED- 5661, ED-5662 (above, manufactured by Celanese Co., Ltd.), and the like, as the aliphatic polyglycidyl ether, epicoat 190P and copper 191P (above, manufactured by Yuka Shell Epoxy Co., Ltd.) epolite 100 MF Eisha Chemical Co., Ltd. make, Epiol TMP (made by Japan Yushi Co., Ltd.), etc. are mentioned.
[158] Compound (C ')
[159] As a compound (C ') used by this invention, an epoxy compound is preferable. As an epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- diaminodiphenyl methane, etc. are mentioned preferably.
[160] solvent
[161] The liquid crystal aligning agent of this invention consists of a solution of the said polymer component. The solvent used at this time is not particularly limited as long as it is an organic solvent that can dissolve the polymer component. For example, when a polyimide is used as the polymer component, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetra Aprotic polar solvents such as methylurea, dimethylimidazolidinone, and hexamethylphosphortriamide;
[162] Ester solvents such as butyl cellosolve acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate and isopentyl acetate;
[163] Ketone solvents such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone and methylcyclohexanone;
[164] Halogen solvents such as chlorobenzene, orthodichlorobenzene, tetrachloroethylene and 1,1,1-trichloroethane;
[165] Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, can be illustrated. These can be used individually or in combination of 2 or more types of solvents. In addition, the poor solvent of the polymer used for the said solvent can be used together in the range which a polymer does not precipitate.
[166] In addition, the liquid crystal aligning agent of this invention can contain a functional silane containing compound for the purpose of improving the adhesiveness with a board | substrate. As a functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrier Methoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-tri Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl- 3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-ami Propyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N And a bis (oxyethylene) -3-aminopropyltriethoxysilane and a reaction product of tetracarboxylic dianhydride and amino group-containing silane compound described in JP-A-63-291922.
[167] Liquid crystal alignment film
[168] As a method of forming a liquid crystal aligning film using the liquid crystal aligning agent of this invention, the following method is mentioned, for example. First, the liquid crystal aligning agent of this invention is apply | coated to the transparent conductive film side of the board | substrate with a transparent conductive film by roll coating method, a spinner method, the printing method, etc., and it heats at the temperature of 40-200 degreeC, and forms a coating film. The film thickness of a coating film becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.
[169] As said board | substrate, the transparent substrate which consists of plastics, such as glass, such as float glass and a soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, can be used, for example.
[170] As the transparent conductive film, for example, an NESA film made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. A photo etching method or a method of using a mask in advance is used for the image.
[171] In application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate, a transparent conductive film, and a coating film further favorable, a functional silane containing compound, titanate, etc. can be apply | coated previously on a board | substrate and a transparent conductive film.
[172] Next, the coating film is irradiated with light, preferably linearly polarized radiation. The radiation used is preferably ultraviolet light and visible light having a wavelength of 150 nm to 800 nm, and particularly preferably ultraviolet light having a wavelength of 240 nm to 450 nm.
[173] As the light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a quenon lamp, an excimer laser, or the like can be used.
[174] Moreover, when liquid crystal aligning agent (2) or liquid crystal aligning agent (3) is used, it is preferable to irradiate, heating the said coating film at room temperature or more. At this time, heating temperature becomes like this. Preferably it is 30-300 degreeC, More preferably, it is 30-200 degreeC.
[175] More preferably, the coating film is heated at a temperature of room temperature (25 ° C) or higher. As heat processing temperature, 30 to 300 degreeC is preferable and 30 to 200 degreeC is especially preferable. Moreover, 1 second-1 hour are preferable, and, as for the time of heat processing, 1 second-5 minutes are especially preferable.
[176] In addition, this heat treatment process can be performed simultaneously with the thermosetting process of the sealing agent at the time of sealing the peripheral part of a liquid crystal cell with a sealing agent in the manufacturing process of a liquid crystal display element.
[177] Liquid crystal display element
[178] The liquid crystal display element of this invention can be obtained as follows. The two substrates on which the liquid crystal alignment film is formed are opposed to each other so that the polarization direction of the linearly polarized radiation irradiated with the liquid crystal alignment film is a predetermined angle. Configure And it makes a liquid crystal display element by bonding a polarizing plate so that the polarization direction of a polarizing plate may form a predetermined angle with the polarization direction of the linearly polarized radiation which irradiated the liquid crystal aligning film of a board | substrate, respectively, on both surfaces. The liquid crystal display element which has a TN type or STN type liquid crystal cell can be obtained by adjusting the angle which the polarization direction of the linearly polarized radiation irradiated on the two board | substrates with a liquid crystal aligning film, and the angle of each board | substrate and a polarizing plate make.
[179] As the sealant, for example, an epoxy resin or the like containing an aluminum oxide sphere as a curing agent and a spacer can be used.
[180] Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable, and for example, a sipe salt liquid crystal, a cyan salt liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, A terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. Moreover, it is sold to these liquid crystals as cholesteric liquid crystals, such as a cholesteryl chloride, a cholesteryl nonaate, a cholesteryl carbonnet, and a brand name "C-15" "CB-15" (made by Merck), for example. The chiral agent etc. which are like can be added. In addition, ferroelectric liquid crystals such as p-disiloxybensilidene-p-amino-2-methylbutylcinnamate can also be used.
[181] As a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate which sandwiched the polyvinyl alcohol, and absorbed the iodine, the polarizing plate called H film, the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned. .
[182] Since the liquid crystal alignment film formed by the method of the present invention has a higher liquid crystal alignment control force and a higher pretilt angle expression stability than the conventional photo alignment film, when the liquid crystal display element is configured using this, It has the effect of preventing the pretilt domain generation and can prevent the misalignment. Therefore, the liquid crystal display element which has no display unevenness, has uniform electro-optical characteristics in surface inside, and has high contrast can be comprised.
[183] <Example>
[184] Hereinafter, although an Example demonstrates this invention more concretely, this invention is not restrict | limited to these Examples.
[185] Synthesis Example 1
[186] 4- (6- (4-chalconyloxy) hexaneoxy) styrene 0.04 mol (17.1 g), p-cetyloxystyrene 0.01 mol (3.45 g), 4- (6- (4-chalconyloxy) hexaneoxy) 0.05 mol (24.8 g) of phenylmaleimide and 3.0 g of azobisisobutyronitrile were dissolved in 500 ml of dimethylacetamide, and reacted at 80 ° C. for 10 hours under a nitrogen atmosphere. The viscous reaction mixture was poured into methanol, and the polymer was precipitated and dried to obtain 44.5 g of a poly (styrene-phenylmaleimide) copolymer (hereinafter referred to as "polymer 1").
[187] Synthesis Example 2
[188] 0.1 mol (42.8 g) of 4- (6- (4-chalconyloxy) hexaneoxy) styrene, 0.01 mol (1.72 g) of p-trifluoromethylstyrene and 3.0 g of azobisisobutyronitrile were added to dimethylacetamide 500 It dissolved in ml and reacted for 10 hours at 80 degreeC under nitrogen atmosphere. 37.8 g of polystyrene copolymers (hereinafter, referred to as "polymer 2") were obtained by pouring a viscous reaction mixture into methanol to precipitate and dry the polymer.
[189] Synthesis Example 3
[190] Polymerization of Polyamic Acid
[191] 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 0.05 mol (21.5 g) of 1- (6- (4-chalconyloxy) hexyloxy) -2,4-diaminobenzene And 0.05 mol (17.4 g) of 1-cetyloxy-2,4-diaminobenzene were dissolved in 300 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Subsequently, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to give 60.7 g of polyamic acid (hereinafter referred to as “polymer 3a”).
[192] Imidization reaction
[193] 380 g of N-methyl-2-pyrrolidone, 16 g of pyridine, and 20.5 g of acetic anhydride were added to 60.7 g of the obtained polymer 3a, and it imidated at 120 degreeC for 4 hours. Subsequently, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to give 54.4 g of polyimide (hereinafter referred to as "polymer 3b").
[194] Comparative Synthesis Example
[195] Polymerization of Polyamic Acid
[196] 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 0.05 mol (5.4 g) of p-phenylenediamine and 0.05 mol (17.4 g) of 1-cetyloxy-2,4-diaminobenzene Was dissolved in 300 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Subsequently, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to give 45.0 g of polyamic acid (hereinafter referred to as “polymer 3a ′”).
[197] Imidization reaction
[198] 380 g of N-methyl-2-pyrrolidone, 16 g of pyridine, and 20.5 g of acetic anhydride were added to 45 g of the obtained polymer 3a ', and it imidated at 120 degreeC for 4 hours. Subsequently, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to give 40.5 g of polyimide (hereinafter referred to as "polymer 3b '").
[199] <Example 1>
[200] The polymer 1 obtained in the synthesis example 1 was melt | dissolved in (gamma) -butyrolactone, it was made into the solution of 4 weight% of solid content concentration, and it filtered with the filter of 1 micrometer of pore diameters, and produced the liquid crystal aligning agent solution. This solution was applied onto the glass substrate attached to the ITO transparent electrode film using a spinner so as to have a film thickness of 0.1 µm, and dried at 180 ° C. for 1 hour to form a thin film. Next, using a Hg-Xe lamp on the surface of the thin film, the light having a shorter wavelength than 320 nm was cut by sandwiching a Pyrex (registered trademark) glass polarizing plate SPF-50C-32 (manufactured by Sigma Photonics Co., Ltd.) to obtain 365 nm. 1.0 J / cm <^{2> was} irradiated to the linearly polarized light which mainly takes the wavelength of in the normal line direction of a board | substrate surface.
[201] After screen-printing the epoxy resin adhesive containing the aluminum oxide sphere of 17 micrometers in the surface in which the liquid crystal aligning film was formed, about the said pair of irradiated process board | substrates, it overlaps so that the direction of the polarizing surface of the irradiated ultraviolet-ray may be mutually parallel. The adhesive was cured by pressing. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) was injected through the injection port, and then sealed with an epoxy adhesive. Moreover, in order to remove the flow orientation at the time of liquid crystal injection, after heating to 120 degreeC, it cooled gradually to room temperature. The polarizing plate was adhered to the manufactured cell so that the polarization direction of the polarizing plate was consistent with the polarization plane of the irradiated ultraviolet rays to make a liquid crystal display element.
[202] In this liquid crystal display device, the liquid crystal was homeotropically aligned, and its orientation was good. When voltage 12V was applied to this, the liquid crystal orientation parallel to the polarization plane of the irradiated ultraviolet ray was observed.
[203] <Example 2>
[204] A liquid crystal display device was produced in the same manner as in Example 1 except that Polymer 2 obtained in Synthesis Example 2 was used, whereby a compound having a good alignment state was obtained. When voltage was applied under the same conditions as in Example 1, an orientation parallel to the polarization plane of the irradiated ultraviolet rays was observed.
[205] <Example 3>
[206] Except having used the polymer 3b obtained by the synthesis example 3, the liquid crystal display element was produced like Example 1, and the thing which has a favorable orientation state was obtained. When voltage was applied under the same conditions as in Example 1, an orientation parallel to the polarization plane of the irradiated ultraviolet rays was observed.
[207] Comparative Example 1
[208] Using the polymer 3b 'obtained by the comparative synthesis example, the thin film was formed on the board | substrate similarly to Example 1 and irradiated with linearly polarized ultraviolet-ray, and the liquid crystal display element was manufactured using this. In this liquid crystal display element, favorable homeotropic alignment was obtained in the same manner as in Example 1, but no liquid crystal alignment was observed when voltage was applied under the same conditions as in Example 1.
[209] <Example 4>
[210] (1) 0.04 mol (17.1 g) of 4- (6- (4-chalconyloxy) hexaneoxy) styrene, 0.01 mol (3.45 g) of p-cetyloxystyrene, 4- (6- (4-chalconyloxyhexane 0.05 mole (24.8 g) of oxy) phenylmaleimide and 3.0 g of azobisisobutyronitrile were dissolved in 500 ml of dimethylacetamide and reacted for 10 hours at 80 ° C. under a nitrogen atmosphere. The polymer was precipitated and dried to give 44.5 g of maleimide / styrene copolymer.
[211] (2) To the obtained maleimide / styrene copolymer, 2% by weight of bisphenol F-type epoxy resin (Yukaka Epoxy Co., Ltd., Epicoat 828) was added to dissolve in γ-butyrolactone to obtain a solid content of 4% by weight. It was made into% solution, and it filtered with the filter of 1 micrometer of pore diameters, and manufactured the liquid crystal aligning agent of this invention.
[212] (3) The obtained liquid crystal aligning agent was spin-coated so that the film thickness might be 80 nm on the glass substrate attached to the ITO electrode, and it dried at 130 degreeC for 2 minutes, and formed the thin film. Subsequently, while heating this thin film surface at 180 degreeC, using a high pressure Hg lamp, the light of wavelength shorter than 320 nm was cut out by inserting the Pyrex (trademark) glass polarizing plate SPF-50C-32 (made by Sigma photonics company), The linearly polarized light which mainly takes the wavelength of 365 nm was irradiated for 240 second from the angle inclined 45 degree | times in the normal line direction of a board | substrate surface, and it was set as the liquid crystal aligning film. The irradiation amount was 5.3 J / cm ² .
[213] (4) About the pair of board | substrates which formed the said liquid crystal aligning film, screen-printed the epoxy resin adhesive containing the aluminum oxide sphere of diameter 17micrometer on the liquid crystal aligning film formation surface, and board | substrate so that the polarization directions of the irradiated ultraviolet-ray might be mutually parallel. The adhesive was cured by overlapping and pressing. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) was injected through the injection port, and then sealed with an epoxy adhesive. In addition, in order to remove the flow orientation at the time of liquid crystal injection, after heating to 120 degreeC, it cooled gradually to room temperature. The liquid crystal display device was manufactured by adhering a polarizing plate to the manufactured cell so that the polarization direction of the polarizing plate might correspond with the polarization direction of the irradiated ultraviolet ray.
[214] (5) When voltage was applied to the obtained liquid crystal display element, the orientation of the liquid crystal was good, and in response to the ON-OFF of the applied voltage, a change in contrast of the liquid crystal display element was observed, and the contrast was good. In addition, the pretilt angle was 3 degrees.
[215] (6) After heating the obtained liquid crystal display element at 70 degreeC, 100 degreeC, 120 degreeC, 150 degreeC, and 170 degreeC, respectively, for 60 minutes, the pretilt angle was measured, and as shown in FIG. It was ± 0.2 degrees and was excellent in pretilt angle expression stability.
[216] Example 5
[217] (1) 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 0.05 mol of 1- (6- (4-chalconyloxy) hexyloxy) -2,4-diaminobenzene ( 21.5 g) and 0.05 mol (17.4 g) of 1-cetyloxy-2,4-diaminobenzene were dissolved in 300 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. The reaction mixture was then poured into excess methanol to precipitate the reaction product. Thereafter, the mixture was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure, thereby obtaining 60.7 g of polyamic acid.
[218] 380 g of N-methyl-2-pyrrolidone, 16 g of pyridine, and 20.5 g of acetic anhydride were added to the obtained polyamic acid, and imidation reaction was performed at 120 degreeC for 4 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product, washed with methanol and dried under reduced pressure for 15 hours, thereby obtaining 54.4 g of polyimide.
[219] (2) To the obtained polyimide, 2% by weight of N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane was dissolved in γ-butyrolactone to obtain a solid content. It was made into the solution of 4 weight% of concentration, and it filtered with the filter of 1 micrometer of pore diameters, and manufactured the liquid crystal aligning agent of this invention.
[220] (3) Except using the obtained liquid crystal aligning agent, it carried out similarly to Example 1, and manufactured the liquid crystal display element. When voltage was applied to the obtained liquid crystal display element, the orientation of the liquid crystal was good, and in response to the ON-OFF of the applied voltage, a change in contrast of the liquid crystal display element was observed, and the contrast was good. In addition, the pretilt angle was 3 degrees.
[221] (6) After heating the obtained liquid crystal display element at 70 degreeC, 100 degreeC, 120 degreeC, 150 degreeC, and 170 degreeC, respectively, for 60 minutes, the pretilt angle was measured, and all the pretilt angles were 3 degrees +/- 0.3 degree, and it was free. The tilt angle expression stability was excellent.
[222] Comparative Example 2
[223] Using the maleimide / styrene polymer obtained in Example 4 (1), the liquid crystal aligning agent and the liquid crystal display element were obtained like Example 4 except not using bisphenol F-type epoxy resin. Although the orientation and contrast of a liquid crystal were favorable in the obtained liquid crystal display element, when it evaluated on the conditions similar to Example 4 (6), the pretilt angle fluctuates to 1.5 degrees-3 as shown in FIG. This was degraded.
[224] According to the formation method of the liquid crystal aligning film using the liquid crystal aligning agent of this invention as mentioned above, since the adhesion of the dust by the static electricity generate | occur | produced at the time of the conventional rubbing process, and the circuit breakdown of a TFT element do not arise, a liquid crystal aligning film is formed with a high yield. can do. Moreover, since the liquid crystal aligning agent formed by the method of this invention has high liquid crystal aligning force and pretilt angle expression stability, when it is used for display, such as TN type and STN type, undesirable orientation defect hardly arises, A liquid crystal display element having a high display quality can be obtained and can be effectively used for various devices. For example, it is used suitably for display apparatuses, such as a table calculator, a wristwatch, a table clock, a counting board, a word processor, a personal computer, and a liquid crystal television.

权利要求:
Claims (16)
[1" claim-type="Currently amended] (A) a structure capable of photocrosslinking reaction, and
(B) at least one group selected from the group consisting of a fluorine-containing organic group, an alkyl group having 10 to 30 carbon atoms, and an alicyclic organic group having 10 to 30 carbon atoms
It contains a polymer which has a liquid crystal aligning agent.
[2" claim-type="Currently amended] (A) a structure capable of photocrosslinking reaction,
(B) at least one group selected from the group consisting of a fluorine-containing organic group, an alkyl group having 10 to 30 carbon atoms, and an alicyclic organic group having 10 to 30 carbon atoms, and
(C) heat crosslinkable structure
Or a mixture of polymers having at least one structure selected from the group consisting of the structures (A), (B) and (C), and having all of the structures (A), (B) and (C) A liquid crystal aligning agent comprising a polymer mixture.
[3" claim-type="Currently amended] The polymer mixture according to claim 2, wherein the polymer mixture has at least one structure selected from the group consisting of the above structures (A) and (B), and a polymer having no structure (C) and a polymer having structure (C). Phosphorus liquid crystal aligning agent.
[4" claim-type="Currently amended] The polymer composition of claim 2, wherein the polymer mixture has a polymer having the structure (A), a polymer having the structure (B), no polymer having the structure (A), and a structure (C), Liquid crystal aligning agent which is a mixture of the polymer which does not have (B).
[5" claim-type="Currently amended] (A) a structure capable of photocrosslinking reaction, and
(B) at least one group selected from the group consisting of a fluorine-containing organic group, an alkyl group having 10 to 30 carbon atoms, and an alicyclic organic group having 10 to 30 carbon atoms
Or a polymer mixture comprising at least one structure selected from the group consisting of the above-mentioned structures (A) and (B), and simultaneously comprising said structures (A) and (B), and (C ' A liquid crystal aligning agent containing the compound which has a structure bridge | crosslinked by heat.
[6" claim-type="Currently amended] The liquid crystal aligning agent according to claim 5, wherein the polymer mixture is a mixture of a polymer having the structure (A) and a polymer having the structure (B) and no structure (A).
[7" claim-type="Currently amended] The polymer according to any one of claims 4 to 6, wherein the polymer having the structure (A) or the polymer having the structure (B) and without the structure (A) is selected from polyamic acid, polyimide, polystyrene and maleic. A liquid crystal aligning agent, which is a polymer having at least one main chain structure selected from the group consisting of a mid / styrene copolymer.
[8" claim-type="Currently amended] The liquid crystal aligning agent according to any one of claims 1 to 7, wherein the structure capable of photocrosslinking reaction is at least one structure selected from the group consisting of structures represented by the following formulas (1), (2), (3) and (4). .
<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

In formula, P <^1> , P <^4> , Q <^1> and Q <^3> are the same or different, and represent the divalent organic group which has an aromatic ring, P <^2> , P <^3> and Q <^4> are the same or different, and monovalent which has an aromatic ring An organic group, Q ² represents a trivalent organic group including an aromatic ring, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or An alkyl group is shown.
[9" claim-type="Currently amended] The liquid crystal aligning agent of Claim 2 whose structure which crosslinks by (C) heat is an epoxy structure.
[10" claim-type="Currently amended] The liquid crystal aligning agent of Claim 3 whose compound which has a structure bridge | crosslinked by (C ') heat is a compound which has an epoxy structure.
[11" claim-type="Currently amended] Polarizing ultraviolet-ray is irradiated to the film | membrane obtained from the liquid crystal aligning agent of Claim 1, The formation method of the liquid crystal aligning film characterized by the above-mentioned.
[12" claim-type="Currently amended] The polarizing ultraviolet-ray is irradiated to the film | membrane obtained from the liquid crystal aligning agent of Claim 2, heating at room temperature or more, The formation method of the liquid crystal aligning film characterized by the above-mentioned.
[13" claim-type="Currently amended] The polarizing ultraviolet-ray is irradiated to the film | membrane obtained from the liquid crystal aligning agent of Claim 3, heating at room temperature or more, The formation method of the liquid crystal aligning film characterized by the above-mentioned.
[14" claim-type="Currently amended] The liquid crystal display element which has a liquid crystal aligning film obtained from the liquid crystal aligning agent of Claim 1.
[15" claim-type="Currently amended] The liquid crystal display element which has a liquid crystal aligning film obtained from the liquid crystal aligning agent of Claim 2.
[16" claim-type="Currently amended] The liquid crystal display element which has a liquid crystal aligning film obtained from the liquid crystal aligning agent of Claim 3.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-10-03|Priority to JP2001307203A

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2001-10-03|Priority to JPJP-P-2001-00307203

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2002-01-31|Priority to JP2002022855A

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2002-01-31|Priority to JPJP-P-2002-00022855

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2002-10-02|Application filed by 제이에스알 가부시끼가이샤

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2003-04-14|Publication of KR20030029476A

优先权:

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申请号 | 申请日 | 专利标题

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JP2001307203A|JP3985261B2|2001-10-03|2001-10-03|Liquid crystal aligning agent and liquid crystal display element|

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JPJP-P-2001-00307203|2001-10-03|

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JP2002022855A|JP4207430B2|2002-01-31|2002-01-31|Liquid crystal aligning agent, method for forming liquid crystal aligning film, and liquid crystal display element|

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JPJP-P-2002-00022855|2002-01-31|