WO2014148569A1 - 横電界駆動型液晶表示素子の製造方法 - Google Patents

横電界駆動型液晶表示素子の製造方法 Download PDF

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WO2014148569A1
WO2014148569A1 PCT/JP2014/057587 JP2014057587W WO2014148569A1 WO 2014148569 A1 WO2014148569 A1 WO 2014148569A1 JP 2014057587 W JP2014057587 W JP 2014057587W WO 2014148569 A1 WO2014148569 A1 WO 2014148569A1
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Prior art keywords
side chain
group
ring
liquid crystal
photosensitive
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PCT/JP2014/057587
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English (en)
French (fr)
Japanese (ja)
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耕平 後藤
亮一 芦澤
洋一 山之内
淳彦 萬代
悟志 南
達哉 名木
喜弘 川月
瑞穂 近藤
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日産化学工業株式会社
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Priority to CN201480029107.7A priority Critical patent/CN105339837B/zh
Priority to KR1020157030091A priority patent/KR102258545B1/ko
Priority to JP2015506834A priority patent/JPWO2014148569A1/ja
Publication of WO2014148569A1 publication Critical patent/WO2014148569A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • 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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • 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
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]

Definitions

  • the present invention relates to a method of manufacturing a horizontal electric field drive type liquid crystal display element, and more particularly to a method of manufacturing a horizontal electric field drive type 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.
  • a photo-alignment method has been actively studied as another alignment treatment method for a liquid crystal alignment film that is not rubbed.
  • 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. For example, irradiate a polyimide film with polarized UV light, cause anisotropic decomposition by utilizing the polarization direction dependency of UV absorption of the molecular structure, and align the liquid crystal with the remaining polyimide without decomposition.
  • the method of making is known (for example, refer 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).
  • 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 be performed even 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 production process.
  • the photo-alignment method eliminates the rubbing process itself as compared with the rubbing method that has been industrially performed 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. .
  • An object of the present invention is to provide a lateral electric field drive type liquid crystal display element which is imparted with high efficiency and orientation control ability and excellent in reliability.
  • the present inventors have developed a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range on a substrate having a conductive film for driving a lateral electric field.
  • the present invention has been completed by finding that it is achieved by applying a lateral electric field driving type liquid crystal display element to which an alignment control ability is imparted by applying a photosensitive composition containing, and then applying ultraviolet light irradiation and subsequent heating.
  • the present invention has the following gist.
  • the amount of UV irradiation in step [II] maximizes ⁇ A, which is the difference between the UV absorbance in the direction parallel to the polarization direction of the polarized UV light and the UV absorbance in the direction perpendicular to the polarization direction of the polarized UV light.
  • the production method according to 1 above which is in the range of 1% to 70% of the ultraviolet irradiation amount.
  • 3. The production method according to 1 or 2 above, wherein the ultraviolet irradiation amount in the step [II] is in the range of 1% to 50% of the ultraviolet irradiation amount that maximizes the ⁇ A. 4).
  • the heating temperature in the step [III] is a temperature in the range from a temperature 10 ° C.
  • the ultraviolet irradiation amount in the step [IV] is an irradiation amount with which 20 mol or more reacts with respect to 100 mol of the photosensitive group of the side chain polymer film. 7). 7. The production method according to any one of 1 to 6, wherein the step [IV] is performed after the production of the liquid crystal display element. 8). 8. The production method according to any one of 1 to 7 above, wherein the component (A) has a side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.
  • the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even if it is continuously driven for a long time.
  • the photosensitive composition used in the production method of the present invention has a photosensitive side chain polymer (hereinafter also referred to as a side chain polymer) that can exhibit liquid crystallinity, and the photosensitive composition.
  • a film obtained by using a product is a film of a photosensitive side chain type polymer that can exhibit liquid crystallinity. Without subjecting this film to rubbing treatment, alignment treatment can be performed by irradiation of polarized light to form a liquid crystal alignment film.
  • a film (liquid crystal alignment film) to which alignment control ability is imparted is obtained through a step of heating the side chain polymer film after irradiation of polarized light on the side chain polymer film.
  • the slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the liquid crystalline side 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 unreacted photosensitive groups can be reduced by irradiating the liquid crystal alignment film with ultraviolet rays. By doing so, it is possible to obtain a liquid crystal display element with excellent reliability while maintaining highly efficient alignment control ability.
  • a photosensitive composition containing a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and an organic solvent on a substrate having a conductive film for driving a lateral electric field (hereinafter, (Also referred to as a photosensitive composition) to form a polymer film.
  • the substrate is not particularly limited, and for example, a transparent substrate such as a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used in addition to a glass substrate.
  • a substrate on which ITO (Indium Tin Oxide) electrodes for driving liquid crystals are formed in order to simplify the process of manufacturing liquid crystal display elements.
  • ITO Indium Tin Oxide
  • a reflective liquid crystal display element an opaque substrate such as a silicon wafer can be used, and a light reflecting material such as aluminum can be used as an electrode in this case.
  • Application method is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an inkjet method or the like is common.
  • 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 solvent is evaporated at 20 to 180 ° C., preferably 40 to 150 ° C. by a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven, and the photosensitive composition is exposed. Can be obtained.
  • the drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer. If the thickness of the polymer 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, so it is preferably 5 to 300 nm, more preferably 10 to 10 nm. 150 nm.
  • step [II] the photosensitive side chain polymer 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 200 to 400 nm can be used.
  • the optimum wavelength is selected through a filter or the like depending on the type of the photosensitive side chain polymer film to be used.
  • ultraviolet light having a wavelength in the range of 290 to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
  • the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
  • the maximum value of ⁇ A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays in the photosensitive side chain polymer film to be used.
  • ⁇ Amax is preferably in the range of 1% to 70%, more preferably in the range of 1 to 50% of the amount of polarized ultraviolet light that realizes (hereinafter also referred to as ⁇ Amax).
  • step [III] the side chain polymer film irradiated with the ultraviolet light polarized in step [II] is heated.
  • a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven is used.
  • the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the side chain type polymer film to be used is developed.
  • the surface Tg glass transition temperature
  • the bulk Tg that is, even in the liquid crystal temperature range of the liquid crystal alignment film surface. It is expected to be lower than the liquid crystal temperature range seen in bulk.
  • the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the liquid crystal temperature range in which the side chain polymer film used exhibits liquid crystallinity, and 10 ° C. lower than the upper limit of the liquid crystal temperature range. It is preferable that it is the temperature of the range made into an upper limit.
  • step [IV] the side chain polymer film obtained in step [III] is further irradiated with ultraviolet rays.
  • the side chain polymer film on the substrate may be directly irradiated with ultraviolet rays immediately after the step [III], and then the liquid crystal display element using the substrate with the side chain polymer film is used.
  • Ultraviolet rays may be irradiated in the step of manufacturing the liquid crystal display device, or after the liquid crystal display device is manufactured, the obtained liquid crystal display device may be irradiated with ultraviolet rays. By doing in this way, since the unreacted photosensitive group can be quenched while the alignment control ability is imparted with high efficiency, it becomes possible to manufacture a liquid crystal display element having excellent reliability.
  • the liquid crystal temperature range in the present invention is a value obtained by differential scanning calorimetry.
  • the photosensitive composition used in the production method of the present invention includes a photosensitive side chain polymer that can exhibit liquid crystallinity, and a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range. Including. And the side chain which has photosensitivity has couple
  • the structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, the achieved orientation control ability can be stably maintained for a long period of time even when exposed to external stress such as heat.
  • the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, stable liquid crystal alignment can be obtained when the side chain polymer film is used as a liquid crystal alignment film.
  • the structure of the side chain polymer has, for example, a main chain and a side chain bonded to the main chain, and the side chain is a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, or an azobenzene group.
  • a photosensitive group bonded to the tip and capable of undergoing a crosslinking reaction or an isomerization reaction in response to light can be set as the structure which has a phenylbenzoate group which has a main chain and the side chain couple
  • More specific examples of the structure of the photosensitive side chain polymer that can exhibit liquid crystallinity include at least one selected from the group consisting of hydrocarbon, acrylate, methacrylate, maleimide, norbornene, and siloxane.
  • a structure having a main chain and at least one photosensitive side chain selected from the group consisting of the following formulas (1) to (13) is preferable.
  • A, B, and D each independently represent a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, or —NH—CO—.
  • a ′ and B ′ are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O—, Or, —O—CO—CH ⁇ CH— is represented.
  • Y 1 is a group selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and a hydrogen atom bonded to them is Each may be independently substituted with —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, or an alkyl or alkoxy group having 1 to 4 carbon atoms.
  • Y 2 is a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and the hydrogen atom bonded to them is Each may be independently substituted with —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkoxy group.
  • R represents OH, NH 2 , an alkoxy group having 1 to 6 carbon atoms or an alkylamino group having 1 to 6 carbon atoms.
  • R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, or an alkyl or alkoxy group having 1 to 12 carbon atoms.
  • One or more of the benzene rings in the formulas (1) to (13) may be substituted with the same or different rings selected from a naphthalene ring, an anthracene ring and a fluorene ring.
  • the side chains represented by the above formulas (1) to (13) have a structure having groups such as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azobenzene, naphthalene, anthracene, and fluorene as mesogenic components. And at the tip, it has a photosensitive group that undergoes a dimerization reaction in response to light and undergoes a crosslinking reaction, or has a main chain and a side chain bonded thereto, and the side chain also becomes a mesogenic component. And having at least one of phenylbenzoate groups that undergo a photo-Fries rearrangement reaction.
  • a photosensitive side chain type polymer film is formed on a substrate using a photosensitive composition, and then irradiated with polarized ultraviolet rays.
  • high-efficiency anisotropy is introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
  • Side-chain polymer membranes utilize the principle of molecular reorientation induced by side-chain photoreaction and self-organization based on liquid crystallinity to provide highly efficient anisotropy to side-chain polymer membranes. Realize the introduction.
  • FIG. 1 schematically shows an anisotropy introduction process in a method for producing a liquid crystal alignment film using a side chain polymer having a photocrosslinkable group as a photosensitive group in the first embodiment of the present invention.
  • An example to explain is shown.
  • the ultraviolet irradiation amount in the step [II] is in the range of 1 to 15% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • FIG. 1A is a diagram schematically showing the state of the side chain polymer film 1 before polarized light irradiation, and has a structure in which the side chains 2 are randomly arranged.
  • FIG. 1 (b) is a diagram schematically showing the state of the side chain polymer film 1 after irradiation with polarized light.
  • the photosensitive groups in the side chain 2 arranged in a direction parallel to the polarization direction of ultraviolet rays are shown.
  • the photosensitive group of the side chain 2a possessed preferentially causes a photoreaction such as a dimerization reaction.
  • FIG. 1C is a diagram schematically showing the state of the side chain polymer film 1 after heating.
  • the side chain polymer film 1 In the side chain polymer film 1, the direction perpendicular to the direction parallel to the polarization direction of the irradiated ultraviolet light is shown. The amount of the cross-linking reaction that occurs. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet ray is very small, this crosslinking reaction site functions as a plasticizer.
  • the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is higher than the liquid crystallinity in the parallel direction, and the side chain 2 containing the mesogenic component is reoriented by self-organizing in the direction parallel to the polarization direction of the irradiated ultraviolet light.
  • the very small anisotropy of the side chain polymer film 1 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is given to the side chain polymer film 1.
  • FIG. 2 schematically shows an anisotropic introduction process in the method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photosensitive group in the first embodiment of the present invention.
  • An example to explain is shown.
  • the ultraviolet irradiation amount in the step [II] is in the range of 15 to 70% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • FIG. 2A is a diagram schematically showing the state of the side chain polymer film 3 before polarized light irradiation, and has a structure in which the side chains 4 are randomly arranged.
  • FIG. 2 (b) is a diagram schematically showing the state of the side chain polymer film 3 after irradiation with polarized light.
  • the photosensitive groups in the side chains 4 arranged in a direction parallel to the polarization direction of ultraviolet rays are shown.
  • the photosensitive group of the side chain 4a possessed preferentially causes a photoreaction such as a dimerization reaction.
  • FIG. 2 (c) is a diagram schematically showing the state of the side chain polymer film 3 after heating.
  • the side chain polymer film 3 the direction perpendicular to the direction parallel to the polarization direction of the irradiated ultraviolet light The amount of the cross-linking reaction that occurs. Therefore, the side chain 4 containing the mesogenic component is reoriented by self-organizing in a direction parallel to the polarization direction of the irradiated ultraviolet light.
  • the small anisotropy of the side chain polymer film 3 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is given to the side chain polymer film 3.
  • FIG. 3 shows a liquid crystal alignment film using a side chain type polymer having a structure having a light Fleece rearrangement group represented by the above formula (5) or (7) as a photosensitive group in the second embodiment of the present invention.
  • FIG. 3 shows a figure of one example which illustrates typically the introduction process of anisotropy in this manufacturing method.
  • the ultraviolet irradiation amount in the step [II] is in the range of 1 to 15% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • FIG. 1 shows a schematic diagram in the case.
  • FIG. 3A is a diagram schematically showing the state of the side chain polymer film 5 before irradiation with polarized light, and has a structure in which the side chains 6 are randomly arranged. According to the random arrangement of the side chain 6, the mesogenic component and the photosensitive group of the side chain 6 are also randomly oriented, and the side chain polymer film 5 is isotropic.
  • FIG. 3B is a diagram schematically showing the state of the side chain polymer film 5 after irradiation with polarized light.
  • the photosensitive groups in the side chains 6 arranged in a direction parallel to the polarization direction of ultraviolet rays are shown.
  • the photosensitive group of the side chain 6a has preferentially photoreaction such as photofleece rearrangement.
  • FIG. 3C is a diagram schematically showing the state of the side chain polymer film 5 after heating.
  • the direction perpendicular to the direction parallel to the polarization direction of the irradiated ultraviolet rays In the side chain polymer film 5, the direction perpendicular to the direction parallel to the polarization direction of the irradiated ultraviolet rays. And the amount of photo-Fries rearrangement reaction that occurs.
  • the liquid crystal alignment force of the light fleece rearrangement generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is stronger than the liquid crystal alignment force of the side chain before the reaction, it is self-organized in the direction perpendicular to the polarization direction of the irradiated ultraviolet light.
  • the side chain 6 containing the mesogenic component is reoriented.
  • the very small anisotropy of the side chain polymer film 5 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is given to the side chain polymer film 5. become.
  • FIG. 4 shows a liquid crystal alignment film using a side chain polymer having a structure having a photo-Fries rearrangement group represented by the above formula (6) or (8) as a photosensitive group in the second embodiment of the present invention.
  • FIG. 4 shows a figure of one example which illustrates typically the introduction process of anisotropy in this manufacturing method.
  • the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ⁇ A.
  • FIG. 1 shows a liquid crystal alignment film using a side chain polymer having a structure having a photo-Fries rearrangement group represented by the above formula (6) or (8) as a photosensitive group in the second embodiment of the present invention.
  • FIG. 4A is a diagram schematically showing a state of the side chain polymer film 7 before irradiation with polarized light, and has a structure in which the side chains 8 are randomly arranged. According to the random arrangement of the side chain 8, the mesogenic component and the photosensitive group of the side chain 8 are also randomly oriented, and the side chain polymer film 7 is isotropic.
  • FIG. 4B is a diagram schematically showing the state of the side chain polymer film 7 after irradiation with polarized light.
  • the photosensitive groups in the side chains 8 arranged in a direction parallel to the polarization direction of ultraviolet rays are shown.
  • the photosensitive group of the side chain 8a has a photoreaction such as photofleece rearrangement preferentially.
  • FIG. 4C is a diagram schematically showing the state of the side chain polymer film 7 after heating.
  • the anchoring force of the optical fleece rearrangement 8a is stronger than that of the side chain 8 before the rearrangement, if a certain amount or more of the optical fleece rearrangement is generated, it self-assembles in a direction parallel to the polarization direction of the irradiated ultraviolet light, and the mesogenic component is formed.
  • the containing side chain 8 is reoriented.
  • the small anisotropy of the side chain polymer film 7 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is given to the side chain polymer film 7. .
  • the side chain polymer film is a liquid crystal alignment with high anisotropy introduced and high alignment control ability by sequentially irradiating the side chain polymer film with polarized ultraviolet rays and heat treatment. It can be a membrane.
  • the irradiation amount of polarized ultraviolet rays to the side chain polymer film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the side chain type polymer film can be realized with high efficiency.
  • the optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the side chain polymer film is such that the photo-sensitive group in the side chain polymer film undergoes photocrosslinking reaction or photoisomerization reaction, or It corresponds to the irradiation amount of polarized ultraviolet rays that optimizes the amount of photofleece rearrangement reaction.
  • the obtained side chain type polymer film becomes rigid and may hinder the progress of self-assembly by subsequent heating.
  • the side chain type polymer film when the side chain type polymer film is irradiated with polarized ultraviolet rays to the structure having the light fleece rearrangement group, the side chain type polymer film becomes excessive if the side chain photosensitive group that undergoes the light fleece rearrangement reaction becomes excessive.
  • the liquid crystallinity of the film will be too low. In that case, the liquid crystallinity of the obtained side chain polymer film is also lowered, which may hinder the progress of self-assembly by subsequent heating.
  • the optimum amount of the photopolymerization reaction, photoisomerization reaction, or photofleece rearrangement reaction of the photosensitive group of the side chain by irradiation with polarized ultraviolet rays is the same as that of the side chain polymer film.
  • the content is preferably 0.1 mol% to 40 mol%, more preferably 0.1 mol% to 20 mol% of the photosensitive group.
  • the amount of photo-crosslinking reaction, photoisomerization reaction, or photofleece rearrangement reaction of photosensitive groups in the side chain of the side-chain polymer film by optimizing the irradiation amount of polarized ultraviolet rays To optimize.
  • high-efficiency introduction of anisotropy into the side chain polymer film is realized.
  • a suitable amount of polarized ultraviolet light can be determined based on the evaluation of ultraviolet absorption of the side chain polymer film.
  • the UV absorption in the direction parallel to the polarization direction of the polarized UV light and the UV absorption in the vertical direction after the irradiation with the polarized UV light are measured for the side chain type polymer film.
  • ⁇ 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 ( ⁇ Amax) of ⁇ A realized in the side chain type polymer film and the irradiation amount of polarized ultraviolet rays 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 irradiation amount of the polarized ultraviolet rays on the side chain polymer film is preferably in the range of 1% to 70% of the amount of the polarized ultraviolet rays that realizes ⁇ Amax. % Is more preferable.
  • the irradiation amount of polarized ultraviolet light within the range of 1% to 50% of the amount of polarized ultraviolet light that realizes ⁇ Amax is 0.1% of the entire photosensitive group of the side chain polymer film.
  • the mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.
  • the side chain polymer film is heated after being irradiated with polarized ultraviolet rays.
  • This side chain type polymer film is a polymer film that can exhibit liquid crystallinity in a predetermined temperature range.
  • the heat treatment after irradiation with polarized ultraviolet rays can be determined based on the temperature at which the liquid crystallinity of the side chain polymer film is developed.
  • the temperature at which the surface of the side chain polymer film develops liquid crystallinity is expected to be lower than the temperature at which liquid crystallinity develops when viewed in bulk. That is, the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. from the temperature range 10 ° C. lower than the temperature range in which the side chain polymer film exhibits liquid crystallinity (hereinafter also referred to as the liquid crystal temperature range).
  • a temperature in the range up to a low temperature is preferred.
  • the side chain type polymer film used in the present invention is heated after being irradiated with polarized ultraviolet rays to be in a liquid crystal state, and is self-organized and reoriented in a direction parallel to the polarization direction.
  • the small anisotropy of the side chain polymer film induced by the photocrosslinking reaction, photoisomerization reaction, and photofleece rearrangement reaction is amplified by heat.
  • the heating temperature is lower by 10 ° C. or more from the lower limit of the liquid crystal temperature range of the side chain polymer film, the effect of anisotropy amplification by heat in the side chain polymer film may be sufficient. Can not.
  • the side chain polymer film is in a liquid crystal state by heating, when the heating temperature is high, the state of the side chain polymer film becomes close to an isotropic liquid state, and the side chain polymer film is made uniform by self-organization. It becomes difficult to reorient in the direction.
  • the heating temperature is higher than the temperature lower by 10 ° C. from the upper limit of the liquid crystal temperature range of the side chain polymer film, the anisotropy amplification effect due to heat in the side chain polymer film is sufficient. I can't.
  • a suitable heating temperature is determined based on the liquid crystal temperature range of the side chain polymer film.
  • the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the liquid crystal temperature range of the side chain polymer film, and the upper limit is 10 ° C. lower than the upper limit of the liquid crystal temperature range.
  • the temperature is within the range. Therefore, for example, when the liquid crystal temperature range of the side chain polymer film is 100 to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 90 to 190 ° C. By so doing, greater anisotropy is imparted to the side chain polymer film. By doing so, the obtained liquid crystal display element shows high reliability against external stresses such as light and heat.
  • the photosensitive composition used in the present invention contains a side chain polymer that reacts with light in a wavelength range of 250 to 400 nm and exhibits liquid crystallinity in a temperature range of 100 to 250 ° C.
  • the polymer serving as a component of the photosensitive composition preferably has a photosensitive group that reacts with light in the wavelength range of 250 to 400 nm.
  • the polymer as a component of the photosensitive composition preferably has a mesogenic group in order to exhibit liquid crystallinity in a certain temperature range of 100 to 250 ° C.
  • the above-mentioned photosensitive side chain polymer capable of exhibiting liquid crystallinity can be obtained by polymerizing the above photosensitive side chain monomer and / or liquid crystalline side chain monomer having the above photosensitive group.
  • the photosensitive side chain monomer is a monomer having a photosensitive group at a side chain portion of a polymer when a polymer is formed.
  • the photosensitive group possessed by the side chain the following structures or derivatives thereof are preferable.
  • photosensitive side chain monomer examples include a main chain composed of at least one selected from the group consisting of hydrocarbon, (meth) acrylate, maleimide, norbornene and siloxane, and the following formula (1):
  • a structure having at least one photosensitive side chain selected from the group consisting of (13) to (13) is preferable.
  • A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—.
  • a ′ and B ′ are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O—, Or, —O—CO—CH ⁇ CH— is represented.
  • Y 1 is a group selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, cyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and the hydrogen atom bonded to them is Each may be independently substituted with —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkoxy group.
  • Y 2 is a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and the hydrogen atom bonded to them is Each may be independently substituted with —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkoxy group.
  • R represents —OH, —NH 2 , an alkoxy group having 1 to 6 carbon atoms or an alkylamino group having 1 to 6 carbon atoms.
  • R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkoxy group.
  • One or more of the benzene rings in the formulas (1) to (8) may be substituted with the same or different rings selected from a naphthalene ring, an anthracene ring and a fluorene ring.
  • the liquid crystalline side chain monomer is a monomer in which the polymer exhibits liquid crystallinity and has a mesogenic group at the side chain portion of the polymer.
  • the mesogenic group possessed by the side chain biphenyl, phenylbenzoate, or the like alone may have a mesogen structure, or a side chain may form a mesogen structure by hydrogen bonding, such as benzoic acid.
  • the mesogenic group possessed by the side chain the following structure is preferable.
  • liquid crystalline side chain monomer a main chain composed of at least one selected from the group consisting of hydrocarbon, (meth) acrylate, maleimide, norbornene and siloxane, and the following formula ( A structure having at least one liquid crystalline side chain selected from the group consisting of 5) to (8) and (14) to (22) is preferable.
  • a and B each independently represents a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—.
  • a ′ and B ′ each represent Independently, a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—O—, or —O—CO—CH
  • Y 1 is a group selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, cyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and Each hydrogen atom bonded to may be independently substituted with —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group, or an alkoxy group.
  • Z 1 and Z 2 each independently represent —CO—, —CH 2 O—, —CH ⁇ N—, —CF 2 —.
  • R 2 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • L represents an integer of 1 to 12
  • m represents an integer of 0 to 2
  • m1 and m2 each independently represents an integer of 1 to 3.
  • One or more of them may be substituted with the same or different ring selected from naphthalene ring, anthracene ring and fluorene ring.
  • the side chain type polymer that is a component of the photosensitive composition used in the present invention can be obtained by the polymerization reaction of the photosensitive side chain monomer that exhibits the liquid crystal properties described above. Moreover, it can obtain by copolymerization of the photosensitive side chain monomer and liquid crystalline side chain monomer which do not express liquid crystallinity, and the copolymerization of the photosensitive side chain monomer and liquid crystalline side chain monomer which express liquid crystallinity. Moreover, it can copolymerize with another monomer in the range which does not impair liquid crystallinity expression ability.
  • Examples of other monomers include industrially available monomers capable of radical polymerization reaction. Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound, vinyl compound and the like.
  • unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
  • acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
  • (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, and the like are also used. Can do.
  • Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether and the like.
  • Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
  • Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.
  • the method for producing the photosensitive side chain type polymer in the present invention is not particularly limited, and a general-purpose method handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or a photosensitive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
  • a known compound such as a radical polymerization initiator or a reversible addition-cleavage chain transfer (RAFT) polymerization reagent can be used.
  • the radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation).
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
  • examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (
  • the radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
  • the organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.
  • organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer
  • the polymerization temperature at the time of radical polymerization can be arbitrarily selected from 30 to 150 ° C., but is preferably in the range of 50 to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1 to 50, more preferably 5 to 30.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is
  • the content is preferably 0.1 to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
  • the polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the molecular weight of the photosensitive side chain polymer capable of expressing liquid crystal contained in the photosensitive composition used in the present invention is the strength of the resulting side chain polymer film, the workability during film formation, and In consideration of the uniformity of the film, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.
  • the photosensitive composition used in the present invention comprises a photosensitive side chain polymer that can exhibit liquid crystallinity. And it is preferable to prepare as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. That is, the photosensitive composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent.
  • a resin component is a resin component containing the photosensitive side chain type polymer which can express the said liquid crystallinity.
  • the content of the resin component is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass in the photosensitive composition.
  • the resin component may be a photosensitive side chain polymer that can all exhibit liquid crystallinity, but other than those as long as the liquid crystal expression ability and the photosensitive performance are not impaired.
  • a polymer may be mixed.
  • the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
  • examples of such other polymers include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.
  • Organic solvent used for the photosensitive composition used for this invention will not be specifically limited if it is an organic solvent in which a resin component is dissolved. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ket
  • the photosensitive composition used in the present invention may contain components other than those described above. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when the photosensitive composition is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
  • solvent poor solvent which improves the uniformity of film thickness and surface smoothness.
  • solvents may be used alone or in combination.
  • it is preferably 5 to 80% by mass, more preferably 20%, so that the solubility of the entire solvent contained in the photosensitive composition is not significantly reduced. ⁇ 60% by mass.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-Top 301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710 (Asahi Glass Co., Ltd.), Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC10 (AGC Seimi Chemical Co., Ltd.) and the like.
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the photosensitive composition. .
  • the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
  • phenoplasts and epoxy group-containing compounds for the purpose of preventing the deterioration of electrical characteristics due to the backlight when the liquid crystal display element is constructed
  • An agent may be contained in the photosensitive composition. Specific phenoplast additives are shown below, but are not limited to this structure.
  • Specific epoxy group-containing compounds include 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 ′
  • the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the photosensitive composition.
  • the amount is preferably 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • a photosensitizer can also be added to the photosensitive composition used in the present invention.
  • the photosensitizer a colorless sensitizer and a triplet sensitizer are preferable.
  • Specific examples of photosensitizers include aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino acids.
  • Substituted aromatic 2-hydroxy ketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoyl) Methylene-3-methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoyl) Methylene) -3-methylben Thiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methyl- ⁇ -naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl- ⁇ -naphthothiazoline, 2- (p-fluorobenzoylmethylene)-
  • Aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, or acetophenone ketal is preferable.
  • a dielectric, a conductive substance, or the like for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired.
  • a crosslinkable compound may be added for the purpose of increasing the hardness and density of the liquid crystal alignment film.
  • the photosensitive composition used in the present invention after being applied on a substrate and subjected to photo-alignment treatment by light irradiation, imparts alignment control ability with high efficiency by heating to a temperature at which the liquid crystal alignment film exhibits liquid crystallinity, Furthermore, the alignment state obtained by heating can be fixed by irradiating ultraviolet rays. In this way, the photosensitive composition can form a liquid crystal alignment film through a photo-alignment treatment, a heating step up to the liquid crystal phase transition temperature, and irradiation with non-polarized ultraviolet rays. Can be used.
  • the liquid crystal display element is obtained by obtaining a substrate with a liquid crystal alignment film from the photosensitive composition used in the present invention, and then preparing a liquid crystal cell by a known method to obtain a lateral electric field drive type liquid crystal display element.
  • a liquid crystal cell To give an example of the production of a liquid crystal cell, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside. A method of laminating the other substrate and injecting liquid crystal under reduced pressure, or a method of laminating liquid crystal on the liquid crystal alignment film surface on which spacers are dispersed, and then laminating the substrate and sealing, etc. It can be illustrated. At this time, it is preferable to use a substrate having an electrode having a structure like a comb for driving a horizontal electric field as the substrate on one side.
  • 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.
  • the liquid crystal phase transition temperature of the polymer obtained in the example was measured using differential scanning calorimetry (DSC) and DSC3100SR (manufactured by Mac Science).
  • Example 1 [Production of liquid crystal cell] Using the liquid crystal aligning agent (A) obtained in Synthesis Example 1, a liquid crystal cell was prepared according to the procedure shown below.
  • the substrate used was a glass substrate having a size of 30 mm ⁇ 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged.
  • the pixel electrode has a comb-like shape configured by arranging a plurality of “ ⁇ ”-shaped electrode elements having a bent central portion. The width in the short direction of each electrode element is 10 ⁇ m, and the distance between the electrode elements is 20 ⁇ m.
  • the pixel electrode forming each pixel is formed by arranging a plurality of bent “ ⁇ ”-shaped electrode elements at the center, so that the shape of each pixel is not rectangular but is the same as the electrode element. It has a shape that resembles the bold “ ⁇ ” character that bends at the part.
  • 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. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different.
  • the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
  • the electrode elements of the pixel electrode are formed so as to form an angle of ⁇ 15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
  • the liquid crystal aligning agent (A) obtained in Example 1 was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the photosensitive side chain type polymer film with a film thickness of 100 nm. Next, the film surface was irradiated with 5 mJ / cm 2 of 313 nm ultraviolet light through a polarizing plate and heated on a hot plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film made of a side chain polymer film.
  • a photosensitive side chain polymer film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which an electrode was not formed as a counter substrate, and an orientation treatment was performed.
  • a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate.
  • the other substrate was bonded so that the liquid crystal alignment film surfaces of both substrates faced each other and the alignment direction was 0 °, and then the sealing agent was thermally cured to produce an empty cell.
  • a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element is prepared by injecting liquid crystal, MLC-2041 (manufactured by Merck) into the empty cell by a reduced pressure injection method, sealing the injection port. Obtained.
  • IPS In-Planes Switching
  • the voltage holding ratio of the liquid crystal cell was measured by applying a voltage of 5 V for 60 ⁇ s at a temperature of 70 ° C., and calculating how much the voltage could be held after 1667 ms as the voltage holding ratio.
  • VHR-1 manufactured by Toyo Corporation was used.
  • the IPS mode liquid crystal cell prepared in Example 1 is installed between two polarizing plates arranged so that their polarization axes are orthogonal to each other, and the backlight is turned on in the state where no voltage is applied.
  • the arrangement angle of the liquid crystal cell was adjusted so as to be the smallest.
  • the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the pixel was darkest to the angle at which the first region was darkest was calculated as the initial orientation azimuth.
  • an alternating voltage of 16 V PP was applied at a frequency of 30 Hz in an oven at 60 ° C. for 336 hours.
  • Example 2 In the secondary irradiation process, a cell was produced in the same procedure as in Example 1 except that ultraviolet rays that passed through a 313 nm bandpass filter were irradiated with 5 J / cm 2 (secondary irradiation). The evaluation results are shown in Table 1.
  • Example 3 In the same manner as in Example 1, the liquid crystal aligning agent (A) obtained in Synthesis Example 1 was spin-coated on a substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the surface of the photosensitive side chain polymer film was irradiated with 5 mJ / cm 2 of 313 nm ultraviolet light through a polarizing plate, heated on a hot plate at 150 ° C. for 10 minutes, the substrate was cooled for 30 minutes, and the side chain was further cooled.
  • a substrate with a liquid crystal alignment film was obtained by irradiating ultraviolet rays through a 365 nm band-pass filter with 1 J / cm 2 (secondary irradiation) on the surface of the mold polymer film. Moreover, it carried out similarly to Example 1, and obtained the liquid crystal cell provided with the structure of the IPS mode liquid crystal display element combining the opposing board
  • Example 4 In the secondary irradiation process on the substrate, the same procedure as in Example 3 was used, except that the side chain polymer film surface was irradiated with 500 mJ / cm 2 of ultraviolet light (secondary irradiation) through a 313 nm bandpass filter. A cell was produced. The evaluation results are shown in Table 1.
  • Examples 5 to 8> Using the liquid crystal aligning agent (B) obtained in Synthesis Example 2, a liquid crystal cell was produced in the same manner as in Examples 1 to 4. Table 1 summarizes the liquid crystal aligning agent used, the ultraviolet irradiation amount (primary irradiation), the secondary irradiation wavelength, the secondary irradiation amount, and the evaluation results.
  • Comparative Example 1 a liquid crystal cell was prepared in the same procedure as in Example 1, and then realignment treatment was performed in an oven at 120 ° C. for 60 minutes, but the secondary irradiation process was not performed. This liquid crystal cell was also subjected to voltage holding ratio measurement, afterimage evaluation, and cell observation after aging. The liquid crystal aligning agent used and the evaluation results are shown in Table 1.
  • Comparative example 2 a liquid crystal cell was prepared in the same procedure as in Example 5, and then re-aligned in an oven at 120 ° C. for 60 minutes, but the secondary irradiation process was not performed. This liquid crystal cell was also subjected to voltage holding ratio measurement, afterimage evaluation, and cell observation after aging. The liquid crystal aligning agent used and the evaluation results are shown in Table 1.
  • the liquid crystal cell in which the secondary irradiation process was introduced showed a higher voltage holding ratio than the cell not subjected to the secondary irradiation. This is presumably because unreacted photosensitive groups were reduced and cross-linking proceeded between the polymers by the photodimerization reaction.
  • This horizontal electric field drive type liquid crystal display element is a large-screen high-definition liquid crystal television. It can utilize suitably for various display uses, such as. It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2013-57047 filed on March 19, 2013 is cited here as the disclosure of the specification of the present invention. Incorporated.

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PCT/JP2014/057587 2013-03-19 2014-03-19 横電界駆動型液晶表示素子の製造方法 WO2014148569A1 (ja)

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