Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
  • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/56—Aligning agents
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
  • G02F1/133723—Polyimide, polyamide-imide

Definitions

• the present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element for producing a liquid crystal display element having excellent image sticking characteristics.
• the liquid crystal display element is known as a light, thin, and low power consumption display device and has been remarkably developed in recent years.
• the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
• an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.
• the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates.
• the liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate.
• alignment control ability is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
• the rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction).
• This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements.
• an organic film used for the liquid crystal alignment film a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.
• Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.
• a decomposition type photo-alignment method is known as a main photo-alignment method.
• the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (see, for example, Patent Document 1).
• photocrosslinking type and photoisomerization type photo-alignment methods are also known.
• polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1).
• a method using a polyamic acid produced using a diamine containing a cyclobutane ring and an imide group is known as a photo-alignment film that improves afterimage characteristics by AC driving (see, for example, Patent Document 3).
• the liquid crystal alignment film alignment treatment method by the photo alignment method does not require rubbing, and there is no fear of generation of dust or static electricity.
• An alignment process can also be performed on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial soot production process.
• the photo-alignment method eliminates the rubbing process itself as compared with the rubbing method that has been used industrially as an alignment treatment method for liquid crystal display elements, and thus has a great advantage. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light.
• the photo-alignment method in order to achieve the same degree of alignment control ability as in the rubbing method, a large amount of polarized light irradiation may be required or stable liquid crystal alignment may not be realized. .
• the present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, which has high efficiency and orientation control ability, and has excellent image sticking characteristics, a horizontal electric field drive type liquid crystal display element having the substrate, and a method for manufacturing the same
• the purpose is to provide.
• each R is independently an alkyl group having 1 to 5 carbon atoms.
• liquid crystal aligning agent according to 1 above wherein the polymer is at least one selected from the group consisting of a polyimide precursor and an imidized polyimide. 3. 3. The liquid crystal aligning agent according to any one of the above 1 or 2, wherein R in the formula (2-2) is a methyl group. 4). 4. The liquid crystal aligning agent according to any one of the above 1 to 3, wherein the polymer is represented by the following formula (3).
• X 1 is a tetravalent organic group derived from the tetracarboxylic acid derivative containing at least one structure selected from the above equation (2-1) and (2-2), Y 1 Is a divalent organic group derived from a diamine containing the structure of formula (1), and R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• a liquid crystal alignment film for a transverse electric field drive type liquid crystal display device obtained by using the liquid crystal alignment agent according to any one of 1 to 5 above. 7). 7. A substrate having the liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element as described in 6 above. 8). 8. A lateral electric field drive type liquid crystal display device comprising the substrate according to 7 above.
• a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate.
• the polymer composition used in the production method of the present invention has a photosensitive main chain polymer (hereinafter, also simply referred to as main chain polymer) capable of expressing self-organization ability, and the polymer
• the coating film obtained by using the composition is a film having a photosensitive main chain type polymer that can exhibit self-organization ability.
• This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it passes through the process of heating the main chain type polymer film, and becomes a coating film (hereinafter also referred to as a liquid crystal alignment film) to which alignment control ability is imparted.
• the slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the main chain polymer itself is efficiently reoriented by self-organization.
• a highly efficient alignment process can be realized as the liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.
• the liquid crystal alignment film formed by the polymer composition of the present invention has excellent film strength. Thereby, when it is set as a liquid crystal display element, even if thin processing by slimming (chemical polishing) is performed, the liquid crystal alignment film is less likely to be scraped or peeled off.
• the liquid crystal aligning agent of the present invention includes a diamine component containing a diamine represented by the above formula (1), a cyclobutanetetracarboxylic dianhydride represented by the above formula (2-1), and the above formula (2-2).
• a liquid crystal aligning agent containing a polymer obtained from an acid component containing at least one selected from cyclobutanetetracarboxylic acid diesters hereinafter also referred to as a specific polymer or a main chain polymer.
• the liquid crystal aligning agent of the present invention includes a diamine component containing a diamine represented by the above formula (1) (also referred to as a specific diamine in the present invention), and a cyclobutanetetracarboxylic acid represented by the above formula (2-1).
• a dianhydride also referred to as a specific tetracarboxylic dianhydride in the present invention
• a cyclobutane tetracarboxylic acid diester represented by the above formula (2-2) (also referred to as a specific tetracarboxylic acid diester in the present invention).
• the liquid crystal aligning agent containing the polymer obtained from the acid component containing at least 1 sort (s) selected from these, and the organic solvent.
• the polymer used in the liquid crystal aligning agent of the present invention includes a diamine component containing a diamine represented by the above formula (1), a cyclobutanetetracarboxylic dianhydride represented by the above formula (2-1), and the above It is a polymer obtained from an acid component containing at least one selected from cyclobutanetetracarboxylic acid diesters represented by the formula (2-2). Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide and the like. From the viewpoint of use as a liquid crystal aligning agent, a polyimide precursor containing a structural unit represented by the following formula (3), And at least one selected from polyimides which are imidized products thereof. In the heating step after irradiation with polarized light, a polyimide precursor is more preferable in that the polymer is reoriented more highly because there are many free rotation sites in the polymer.
• X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative containing at least one structure selected from the above formulas (2-1) and (2-2), and Y 1 Is a divalent organic group derived from a diamine having the structure of formula (1), and R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• R 11 is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom, from the viewpoint of ease of imidization by heating.
• X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative containing at least one structure selected from the above formulas (2-1) and (2-2).
• each R is independently an alkyl group having 1 to 5 carbon atoms.
• R is preferably a methyl group from the viewpoint of ease of imidization by heating.
• Y 1 is a structure obtained by removing two amino groups from the diamine represented by Formula (1).
• the polyimide precursor containing the structural unit represented by the formula (3) is at least selected from the structural unit represented by the following formula (4) and a polyimide that is an imidized product thereof, as long as the effects of the present invention are not impaired.
• One kind may be included.
• X 2 is a tetravalent organic group derived from a tetracarboxylic acid derivative
• Y 2 is a divalent organic group derived from a diamine
• R 12 is R in the formula (3).
• 11 and R 22 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Moreover, it is preferable that at least one of two R ⁇ 22 > is a hydrogen atom.
• X 2 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited.
• X 2 in the polyimide precursor is required for the solubility of the polymer in the solvent, the coating property of the liquid crystal aligning agent, the orientation of the liquid crystal when it is used as the liquid crystal alignment film, the voltage holding ratio, the accumulated charge, etc.
• one type may be used in the same polymer, or two or more types may be mixed.
• Y 2 in the polyimide precursor is a divalent organic group derived from diamine, and its structure is not particularly limited. Y 2 depends on the degree of required properties such as the solubility of the polymer in the solvent, the coating property of the liquid crystal aligning agent, the orientation of the liquid crystal when it is used as the liquid crystal alignment film, the voltage holding ratio, and the accumulated charge. 1 type may be selected in the same polymer, and 2 or more types may be mixed.
• a preferable structure of Y 2 includes a structure of the following formula (5).
• R 32 is a single bond or a divalent organic group, and a single bond is preferable.
• R 33 is a structure represented by — (CH 2 ) n —. n is an integer of 2 to 10, preferably 3 to 7. Arbitrary —CH 2 — may be replaced with an ether, ester, amide, urea, or carbamate bond under the condition that they are not adjacent to each other.
• R 34 is a single bond or a divalent organic group. Any hydrogen atom on the benzene ring may be replaced by a monovalent organic group, and a fluorine atom or a methyl group is preferred.
• diamine to give a structure of Y 2 preferably diamines represented by the following formula (10).
• L is a divalent organic group having 2 or more carbon atoms containing alkylene and either a bond selected from an ether bond and an ester bond
• R 1 and R 2 are each independently 1
• p1 and p2 are each independently an integer of 0 to 4
• p is 0 or 1
• q1 and q2 are each independently 1 or 2.
• Examples of the monovalent organic group herein include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms.
• a monovalent organic group a methyl group is preferable.
• the divalent organic group a group composed of an alkylene and an ether bond, a group composed of an alkylene and an ester bond, or an alkylene and ether bond in which some or all of the hydrogen atoms are replaced by halogens. And groups composed of alkylene and ester bonds in which some or all of the hydrogen atoms are replaced by halogens.
• the divalent organic group is preferably a group composed of an alkylene and an ether bond.
• the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably 2 or more and 10 or less.
• the resulting polymer has high linearity.
• the heating step it is preferable to realign in a higher order because a liquid crystal alignment film having a high alignment control ability can be obtained.
• the total number of carbon atoms and oxygen atoms involved in the length of the main chain is 1 per methylene, 1 per ether bond, and 1 ester bond per main chain. This is the total when the number is 2.
• P1 and p2 are preferably 0 in that the steric hindrance is small, so that the phenyl groups are easily overlapped with each other and re-orientated in a higher order.
• P is preferably 1 in that it has higher order of reorientation when it has alkylene functioning as a free rotation site.
• diamines of the above formula (10) specific examples of diamines where p is 1 include the following, but are not limited thereto.
• p-phenylenediamine is a specific example of a diamine in which p is 0.
• the structural unit represented by Formula (4) is the liquid crystal alignment film obtained.
• the content is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, and particularly preferably 30 mol%, based on the sum of the formulas (3) and (4). Mol% to 70 mol%.
• the molecular weight of the polyimide precursor used in the present invention is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, still more preferably 10,000 to 100,000. is there.
• the polyimide used in the present invention examples include polyimides obtained by ring-closing the polyimide precursor.
• the ring closure rate (also referred to as imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the use and purpose.
• the imidation ratio is preferably 0 to 70%, more preferably 0 to 50%.
• the imidation rate here is an imidation rate calculated excluding the imide structure derived from the diamine represented by Formula (1).
• the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
• the liquid crystal aligning agent of the present invention includes a diamine component containing a diamine represented by the above formula (1), a cyclobutanetetracarboxylic dianhydride represented by the above formula (2-1), and the above formula (2-2).
• a polymer (specific polymer) obtained from an acid component containing at least one selected from cyclobutanetetracarboxylic acid diesters represented by Two or more specific polymers having a structure may be contained.
• polystyrene-phenylmaleimide poly (meta ) Acrylate and the like.
• the ratio of the specific polymer to the total polymer components is preferably 10% by mass or more, and an example thereof is 10 to 100% by mass.
• the liquid crystal aligning agent is used for producing a liquid crystal aligning film, and generally takes the form of a coating liquid from the viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is a coating liquid containing an above-described polymer component and the organic solvent in which this polymer component is dissolved. At that time, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, the content is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8% by mass.
• the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component is uniformly dissolved.
• Specific examples are N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl.
• -Imidazolidinone methyl ethyl ketone, cyclohexanone, cyclopentanone and the like.
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or ⁇ -butyrolactone is preferably used.
• the organic solvent contained in the liquid crystal aligning agent uses a mixed solvent that is used in combination with a solvent that improves the coating properties and the surface smoothness of the coating film when the liquid crystal aligning agent is applied in addition to the above-described solvents.
• a mixed solvent is also preferably used in the liquid crystal aligning agent of the present invention. Specific examples of the organic solvent to be used in combination are given below, but the organic solvent is not limited to these examples.
• ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Ethane All, 1,2-propanediol, 1,3-propan
• D 1 represents an alkyl group having 1 to 3 carbon atoms
• D 2 represents an alkyl group having 1 to 3 carbon atoms
• D-3 represents an alkyl group having 1 to 4 carbon atoms.
• Such a solvent are appropriately selected according to the liquid crystal aligning agent coating apparatus, coating conditions, coating environment, and the like.
• the liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the organic solvent as long as the effects of the present invention are not impaired.
• additional components include an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing material, a crosslinking agent for increasing the strength of the liquid crystal alignment film, and the liquid crystal alignment.
• examples thereof include dielectrics and conductive materials for adjusting the dielectric constant and electric resistance of the film. Specific examples of these additional components are as disclosed in various known literatures relating to liquid crystal aligning agents. If an example is given, pages 53 [0105] to 55 of the pamphlet of Japanese Unexamined Patent Publication No. 2015/060357. And the like as disclosed in [0116].
• the method for producing a substrate having the liquid crystal alignment film of the present invention is as follows.
• a lateral electric field drive type liquid crystal display element can be obtained.
• the second substrate instead of using a substrate having no lateral electric field driving conductive film instead of a substrate having a lateral electric field driving conductive film, the above steps [I] to [III] (for lateral electric field driving) Since a substrate having no conductive film is used, for the sake of convenience, in this application, the steps [I ′] to [III ′] may be abbreviated as steps), thereby providing a first liquid crystal alignment film having alignment controllability. Two substrates can be obtained.
• the manufacturing method of the horizontal electric field drive type liquid crystal display element is: [IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween; Have Thereby, a horizontal electric field drive type liquid crystal display element can be obtained.
• step [I] a polymer composition containing a photosensitive main chain polymer and an organic solvent is applied to a substrate having a conductive film for driving a lateral electric field, and then dried to form a coating film.
• ⁇ Board> Although it does not specifically limit about a board
• the substrate has a conductive film for driving a lateral electric field.
• the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
• examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto.
• a method for forming a conductive film on a substrate a conventionally known method can be used.
• the method for applying the polymer composition described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
• the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like.
• Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
• the polymer composition After the polymer composition is applied on the substrate having the conductive film for driving the transverse electric field, it is 30 to 150 ° C., preferably 70 to 70 ° C. by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven.
• the solvent can be evaporated at 110 ° C. to obtain a coating film. If the drying temperature is too low, the solvent tends to be insufficiently dried, and if the heating temperature is too high, thermal imidization proceeds, resulting in excessive photodegradation reaction due to polarized light exposure. In some cases, reorientation in one direction due to self-assembly becomes difficult, and orientation stability may be impaired.
• the drying temperature at this time is preferably a temperature at which the thermal imidization of the specific polymer does not substantially proceed from the viewpoint of liquid crystal alignment stability. If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is. In addition, it is also possible to provide the process of cooling the board
• step [II] the coating film obtained in step [I] is irradiated with polarized ultraviolet rays.
• the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
• ultraviolet rays to be used ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used.
• the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used.
• ultraviolet light having a wavelength in the range of 240 nm to 400 nm can be selected and used so that a photodegradation reaction can be selectively induced.
• the ultraviolet light for example, light emitted from a high-pressure mercury lamp or a metal halide lamp can be used.
• the irradiation amount of polarized ultraviolet rays depends on the coating film used.
• the amount of irradiation is polarized ultraviolet light that realizes the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light.
• the amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%.
• step [III] the ultraviolet-irradiated coating film polarized in step [II] is heated.
• An orientation control ability can be imparted to the coating film by heating.
• a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used.
• the heating temperature can be determined in consideration of the temperature at which good liquid crystal alignment stability and electrical characteristics are exhibited in the coating film used.
• the heating temperature is preferably within a temperature range in which the main chain polymer exhibits good liquid crystal alignment stability. If the heating temperature is too low, the anisotropy effect due to heat and thermal imidization tend to be insufficient, and if the heating temperature is too high, the anisotropy imparted by polarized light exposure In this case, it may be difficult to reorient in one direction due to self-organization.
• the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason described in the step [I].
• the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board
• the step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving.
• the obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is placed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is formed by a known method.
• This is a step of manufacturing a lateral electric field drive type liquid crystal display element.
• a substrate having no lateral electric field driving conductive film was used in place of the substrate having the lateral electric field driving conductive film in the step [I].
• steps [I] to [III] It can be carried out in the same manner as in steps [I] to [III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.
• the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside.
• the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
• Etc. can be illustrated.
• the diameter of the spacer at this time is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.
• substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply
• high-efficiency anisotropy is introduced into the main chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
• the coating film used in the present invention the introduction of highly efficient anisotropy into the coating film is realized by utilizing the principle of molecular reorientation induced by self-assembly based on the photoreaction of the main chain.
• the main chain type polymer has a photodegradable group as a photoreactive group
• a liquid crystal display element is formed.
• the coating film used in the method of the present invention is a liquid crystal alignment film having anisotropy introduced with high efficiency and excellent alignment control ability by sequentially performing irradiation of polarized ultraviolet rays on the coating film and heat treatment. can do.
• the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.
• the optimal irradiation amount of polarized ultraviolet light for introducing highly efficient anisotropy into the coating film used in the present invention is the irradiation amount of polarized ultraviolet light that optimizes the amount of photodegradation reaction of the photosensitive group in the coating film.
• the amount of photoreaction is not sufficient. In that case, sufficient self-organization does not proceed even after heating.
• the optimum amount of the photolytic reaction of the photosensitive group by irradiation with polarized ultraviolet light is preferably 0.1 to 90 mol% of the polymer film. More preferably, it is 1 mol% to 80 mol%.
• the amount of photodecomposition reaction of the photosensitive group in the main chain of the polymer film is optimized by optimizing the irradiation amount of polarized ultraviolet rays. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.
• the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the vertical direction after the irradiation with the polarized ultraviolet ray are measured.
• ⁇ A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.
• the maximum value of ⁇ A ( ⁇ Amax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained.
• a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of polarized ultraviolet rays to realize this ⁇ Amax.
• the above-described main chain type polymer provides liquid crystal alignment stability as a reference, as described above.
• a suitable heating temperature should be determined. Therefore, for example, the temperature range in which the main chain polymer used in the present invention provides liquid crystal alignment stability is determined in consideration of the temperature at which good liquid crystal alignment stability and electrical characteristics are exhibited in the coating film used. And can be set in a temperature range according to a liquid crystal alignment film made of a conventional polyimide or the like. That is, the heating temperature after irradiation with polarized ultraviolet rays is preferably 150 ° C. to 300 ° C., more preferably 180 ° C. to 250 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.
• the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.
• the lateral electric field drive type liquid crystal display element substrate manufactured using the polymer of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability and a large screen. And can be suitably used for high-definition liquid crystal televisions.
• the liquid crystal alignment film manufactured by the method of the present invention has excellent liquid crystal alignment stability and reliability, it can be used for a variable phase shifter using liquid crystal. For example, it can be suitably used for an antenna that can vary the resonance frequency.
• DA-1 Structural formula (DA-1)
• DA-2 Structural formula below (DA-2)
• DA-3 Structural formula below (DA-3)
• DA-4 Structural formula below (DA-4)
• DA-5 Structural formula below (DA-5)
• DA-6 Structural formula below (DA-6)
• DA-7 Structural formula below (DA-7)
• DA-8 Structural formula below (DA-8)
• DA-9 Structural formula below (DA-9)
• DA-10 Structural formula below (DA-10)
• CA-1 Structural formula below (CA-1)
• CA-2 Structural formula below (CA-2)
• DE-1 Structural formula shown below (DE-1)
• DBOP Diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate
• Boc is a group represented by the following formula.
• the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24), temperature 25 Measured at ° C.
• the viscosity of this polyamic acid-polyimide copolymer solution at a temperature of 25 ° C. was 268 mPa ⁇ s. 7.8 g of this polyamic acid-polyimide copolymer solution was taken in a 100 mL Erlenmeyer flask containing a stir bar, added with 6.8 g of NMP and 6.2 g of BCS, stirred at room temperature for 2 hours, and liquid crystal An aligning agent (A-1) was obtained.
• polyamic acid ester-polyimide copolymer powder 2.11 g of the obtained polyamic acid ester-polyimide copolymer powder was placed in a 100 mL Erlenmeyer flask containing a stir bar, 15.5 g of NMP was added, and the mixture was dissolved by stirring at room temperature for 20 hours. Subsequently, 15.2 g of NMP and 14.1 g of BCS were added and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (A-2).
• A-2 liquid crystal aligning agent
• polyamic acid- A polyimide copolymer solution was obtained.
• the viscosity of this polyamic acid-polyimide copolymer solution at a temperature of 25 ° C. was 347 mPa ⁇ s. 14.5 g of this polyamic acid-polyimide copolymer solution was dispensed into a 100 mL Erlenmeyer flask containing a stir bar, 12.6 g of NMP and 11.6 g of BCS were added, and the mixture was stirred at room temperature for 2 hours.
• An aligning agent (A-3) was obtained.
• the viscosity of this polyamic acid-polyimide copolymer solution at a temperature of 25 ° C. was 104 mPa ⁇ s. 15.3 g of this polyamic acid-polyimide copolymer solution was dispensed into a 100 mL Erlenmeyer flask containing a stirring bar, 6.1 g of NMP and 9.2 g of BCS were added, and the mixture was stirred at room temperature for 2 hours. An aligning agent (A-4) was obtained.
• the viscosity of this polyamic acid-polyimide copolymer solution at a temperature of 25 ° C. was 142 mPa ⁇ s. 15.6 g of this polyamic acid-polyimide copolymer solution was dispensed into a 100 mL Erlenmeyer flask containing a stir bar, 6.2 g of NMP and 9.4 g of BCS were added, and the mixture was stirred at room temperature for 2 hours. An aligning agent (A-5) was obtained.
• the viscosity of this polyamic acid-polyimide copolymer solution at a temperature of 25 ° C. was 117 mPa ⁇ s. 15.2 g of this polyamic acid-polyimide copolymer solution was dispensed into a 100 mL Erlenmeyer flask containing a stir bar, 6.1 g of NMP and 9.1 g of BCS were added, and the mixture was stirred at room temperature for 2 hours. An aligning agent (A-6) was obtained.
• the viscosity of the polyamic acid-polyimide copolymer solution at a temperature of 25 ° C. was 139 mPa ⁇ s. 15.6 g of this polyamic acid-polyimide copolymer solution was dispensed into a 100 mL Erlenmeyer flask containing a stir bar, 6.2 g of NMP and 9.4 g of BCS were added, and the mixture was stirred at room temperature for 2 hours. An aligning agent (A-7) was obtained.
• the viscosity of this polyamic acid-polyimide copolymer solution at a temperature of 25 ° C. was 191 mPa ⁇ s. 14.7 g of this polyamic acid-polyimide copolymer solution was taken into a 100 mL Erlenmeyer flask containing a stirring bar, 5.9 g of NMP and 8.8 g of BCS were added, and the mixture was stirred at room temperature for 2 hours. An aligning agent (A-8) was obtained.
• the viscosity of this polyamic acid-polyimide copolymer solution at a temperature of 25 ° C. was 108 mPa ⁇ s. 15.1 g of this polyamic acid-polyimide copolymer solution was taken into a 100 mL Erlenmeyer flask containing a stir bar, 6.0 g of NMP and 9.1 g of BCS were added, and the mixture was stirred at room temperature for 2 hours. An aligning agent (A-9) was obtained.
• the viscosity of this polyamic acid-polyimide copolymer solution at a temperature of 25 ° C. was 326 mPa ⁇ s.
• 7.5 g of this polyamic acid-polyimide copolymer solution was dispensed into a 100 mL Erlenmeyer flask containing a stir bar, 6.5 g of NMP and 6.0 g of BCS were added, and the mixture was stirred at room temperature for 2 hours.
• An aligning agent (B-1) was obtained.
• a method for manufacturing a liquid crystal cell for evaluating the liquid crystal alignment will be described below.
• a liquid crystal cell having a configuration of an FFS liquid crystal display element was manufactured.
• a substrate with electrodes was prepared.
• the substrate is a glass substrate having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm.
• an IZO electrode constituting the counter electrode as the first layer was formed on the entire surface.
• a SiN (silicon nitride) film formed by the CVD method was formed as the second layer.
• the second layer SiN film has a thickness of 500 nm and functions as an interlayer insulating film.
• a comb-like pixel electrode formed by patterning an IZO film is arranged as a third layer, and two pixels, a first pixel and a second pixel, are formed. .
• the size of each pixel is 10 mm long and about 5 mm wide.
• the first-layer counter electrode and the third-layer pixel electrode are electrically insulated by the action of the second-layer SiN film.
• the pixel electrode of the third layer is a comb tooth formed by arranging a plurality of U-shaped electrode elements whose central portion is bent, as in the figure described in Japanese Patent Application Laid-Open No. 2014-77845 (Japan Published Patent Publication). It has a shape. The width in the short direction of each electrode element is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m. Since the pixel electrode forming each pixel is configured by arranging a plurality of bent-shaped electrode elements having a bent central portion, the shape of each pixel is not rectangular but bent at the central portion in the same manner as the electrode elements. It has a shape that is similar to a bold, Kumon character. Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side.
• the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the direction of a line segment projected onto the substrate with the polarization plane of polarized ultraviolet rays to be described later is used as a reference, in the first region of the pixel, the electrode element of the pixel electrode forms an angle of + 10 ° (clockwise). In the second region of the pixel, the electrode element of the pixel electrode is formed at an angle of ⁇ 10 ° (clockwise).
• the direction of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the substrate plane is It comprised so that it might become a mutually reverse direction.
• the liquid crystal aligning agent obtained in the synthesis example and the comparative synthesis example was filtered through a 1.0 ⁇ m filter, and then applied to the prepared substrate with electrodes by spin coating. Subsequently, it was dried for 90 seconds on a hot plate set to 70 ° C. Next, using an exposure apparatus manufactured by Ushio Electric Co., Ltd .: APL-L050121S1S-APW01, the substrate was irradiated with linearly polarized ultraviolet light from a vertical direction through a wavelength selection filter and a polarizing plate.
• the direction of the polarization plane was set so that the direction of the line segment obtained by projecting the polarization plane of polarized ultraviolet rays onto the substrate was inclined by 10 ° with respect to the third-layer IZO comb-teeth electrode. Subsequently, baking was performed for 30 minutes in an IR (infrared) oven set at 230 ° C., and a substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm subjected to alignment treatment was obtained.
• IR infrared
• substrate with a polyimide liquid crystal aligning film by which the alignment process was performed similarly to the above was also obtained for the glass substrate which has the columnar spacer of 4 micrometers in height with the ITO electrode formed in the back surface as a counter substrate.
• a set of these two substrates with a liquid crystal alignment film is used as one set, and a sealing agent is printed on the other substrate leaving a liquid crystal injection port.
• the polarizing planes were bonded and pressure-bonded so that the line segments projected onto the substrate were parallel. Thereafter, the sealing agent was cured to produce an empty cell having a cell gap of 4 ⁇ m.
• Liquid crystal MLC-7026-100 (negative liquid crystal manufactured by Merck & Co., Inc.) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 30 minutes and allowed to stand at 23 ° C. overnight, and then used for evaluation of liquid crystal alignment.
• the liquid crystal cell After leaving, the liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal, and the backlight is turned on with no voltage applied so that the brightness of the transmitted light is minimized.
• the arrangement angle of the liquid crystal cell was adjusted. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel became darkest to the angle at which the first region became darkest was calculated as an angle ⁇ .
• the second area was compared with the first area, and a similar angle ⁇ was calculated. Then, the average value of the angle ⁇ values of the first pixel and the second pixel was calculated as the angle ⁇ of the liquid crystal cell.
• the value of the angle ⁇ of this liquid crystal cell was less than 0.2 °, it was defined as “good”, and when the value of the angle ⁇ was 0.2 ° or more, it was defined as “bad”.
• the liquid crystal aligning agent obtained in the synthesis example and the comparative synthesis example was filtered through a 1.0 ⁇ m filter, and then applied to the prepared substrate with electrodes by spin coating. Subsequently, it was dried for 90 seconds on a hot plate set to 70 ° C. Subsequently, baking was performed for 30 minutes in an IR (infrared) oven set at 230 ° C., and a substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm subjected to alignment treatment was obtained.
• IR infrared
• This polyimide film was rubbed with a rayon cloth manufactured by Yoshikawa Kako: YA-20-R (roller diameter 120 mm, roller rotation speed 1000 rpm, moving speed 20 mm / sec, indentation length 0.3 mm).
• the presence or absence of scratches or scraps on the polyimide film surface was observed with a confocal laser microscope. Those having no scratches or scraps were defined as “good”, and those having scratches or scraps were defined as “bad”.
• Example 1 Using the liquid crystal aligning agent (A-1) obtained in Synthesis Example 1, a liquid crystal cell was produced as described above. Irradiation with polarized ultraviolet rays was performed using a high pressure mercury lamp through a wavelength selection filter: 240LCF and a 254 nm type polarizing plate. Dose of polarized ultraviolet radiation light amount measured using Ushio KK luminometer UVD-S254SB, three liquid crystal cells polarized ultraviolet irradiation amount of wavelength 254nm is 200,300,400mJ / cm 2 Produced.
• the polarized UV irradiation dose with the best angle ⁇ was 300 mJ / cm 2 , and the angle ⁇ was 0.05 °, which was good.
• the film strength was evaluated as described above using the liquid crystal aligning agent (A-1) obtained in Synthesis Example 1, and the result was good.
• Example 2 The liquid crystal orientation and film strength were evaluated in the same manner as in Example 1 except that the liquid crystal aligning agents obtained in Synthesis Examples 2 to 10 were used.
• Comparative Example 1 The liquid crystal orientation and film strength were evaluated in the same manner as in Example 1 except that the liquid crystal aligning agent obtained in Comparative Synthesis Example 1 was used.
• Table 1 shows the results of evaluation of polarized UV irradiation amount, liquid crystal orientation evaluation, and film strength evaluation with the best angle ⁇ when using the liquid crystal aligning agents obtained in the synthesis examples and comparative synthesis examples. Show.
• the angle ⁇ which is the difference between the orientation azimuth angles before and after AC driving, is good at less than 0.2 °, which is excellent in improving the display quality of the liquid crystal display element. . Further, since the film strength is also good, when a liquid crystal display element is formed, even if thin processing is performed by slimming (chemical polishing), the liquid crystal alignment film is less likely to be scraped or peeled off. On the other hand, in Comparative Example 1, the angle ⁇ was not good when it was 0.2 ° or more, and the film strength was also poor.
• the liquid crystal display device manufactured by the method of the present invention exhibits very excellent afterimage characteristics and film strength.
• a substrate for a horizontal electric field drive type liquid crystal display element manufactured using the composition of the present invention or a horizontal electric field drive type liquid crystal display element having the substrate has excellent long-term stability of liquid crystal alignment, and has a large screen and high stability. It can be suitably used for a fine liquid crystal television.
• a lateral electric field driving type liquid crystal display element substrate manufactured using the composition of the present invention or a lateral electric field driving type liquid crystal display element having the substrate has excellent film strength, and thus is a small portable device for slimming. It can be suitably used for telephones and smartphones.
• the liquid crystal alignment film manufactured by the method of the present invention can also be used for a variable phase shifter using liquid crystal, and this variable phase shifter can be suitably used for an antenna that can vary the resonance frequency, for example.

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