WO2015050132A1 - 液晶配向膜の製造方法およびそれを使用した液晶表示素子 - Google Patents
液晶配向膜の製造方法およびそれを使用した液晶表示素子 Download PDFInfo
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- WO2015050132A1 WO2015050132A1 PCT/JP2014/076132 JP2014076132W WO2015050132A1 WO 2015050132 A1 WO2015050132 A1 WO 2015050132A1 JP 2014076132 W JP2014076132 W JP 2014076132W WO 2015050132 A1 WO2015050132 A1 WO 2015050132A1
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- 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
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- 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
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- 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
- G02F1/1341—Filling or closing of cells
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- 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
- G02F1/133715—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer
Definitions
- the present invention relates to a method for producing a liquid crystal alignment film and a liquid crystal display element using the liquid crystal alignment film obtained by the production method.
- the liquid crystal display element changes the state of alignment of liquid crystal molecules by an external stimulus such as an electric field, and uses the change in optical characteristics associated with the change for display.
- a liquid crystal display element has a configuration in which liquid crystal molecules are filled in a gap between two transparent substrates, and the liquid crystal molecules are placed in a specific direction on the inside of the substrate in contact with the liquid crystal molecules. An alignment treatment for arranging the layers is usually performed.
- the alignment treatment is roughly divided into a rubbing method in which a polymer film such as polyimide is formed on the surface of a substrate such as glass, and this is rubbed with a cloth or the like in one direction, and a coating film provided on the substrate is anisotropic. It is classified into a photo-alignment method in which liquid crystal alignment ability is generated by irradiating light having a property.
- the former rubbing method has characteristics such that the rubbing direction and the major axis (director) direction of the liquid crystal molecules in contact with the substrate are arranged in parallel and the alignment film manufacturing apparatus is simple, A rubbing apparatus for obtaining uniform alignment over the entire surface of the substrate and for a long time as the size of the substrate increases due to problems of alignment defects due to scratches and dust generated on the alignment film surface in the manufacturing process. There is a problem that it is difficult to design and manage.
- the latter photo-alignment method light is irradiated to a compound having a group (hereinafter, abbreviated as a photo-alignment group) having different light absorption ability depending on the direction of the electric vector of polarized light.
- the liquid crystal molecules that are aligned in the direction and exhibit the liquid crystal alignment ability for the liquid crystal molecules in contact with the photo-alignable group can be aligned for a long period of time over alignment defects and the entire substrate surface caused by scratches and dust. The problem of the rubbing method of obtaining can be solved.
- Patent Document 1 when the coating film having the substrate coated with the compound is irradiated with polarized ultraviolet rays and baked, in the uncured coating film before baking, the coating film constituent molecules are easily moved. Therefore, it is considered that the coating film constituting molecules can be oriented in a specific direction with less polarized ultraviolet energy. Also, in paragraphs “0105” to “0109” of Patent Document 2, in forming the liquid crystal alignment film, a part of the photosensitive thin film precursor is sensitive to the first radiation (150 to 800 nm) and is applied to the entire surface of the film. On the other hand, it is described that it is sensitive to the second irradiation (320 to 800 nm) and, if necessary, a heat treatment at 150 to 200 ° C. after the second irradiation.
- the object of the present invention is to solve the problem of complication of the process and to provide a method for expressing a large anchoring energy with a simple process.
- the present invention includes a step (I) of preparing a photoresponsive polymer solution by mixing a solvent and a photoresponsive polymer, and applying the photoresponsive polymer solution on a substrate for 50 minutes for 1 to 3 minutes. Drying at ⁇ 100 ° C and further drying at 120 ⁇ 180 ° C for 5 to 75 minutes to form a coating film (II), and the temperature of the coating film when irradiated with light of 200 ⁇ 350nm
- the object of the present invention is achieved by solving the above-described problems by a method for producing a liquid crystal alignment film comprising the step (III) of adjusting to 100 ° C.
- the anchoring force is improved.
- FIG. 5 is a cross-sectional view of the liquid crystal display element shown in FIG. 1 taken along the line III-III in FIG.
- FIG. 5 is a cross-sectional view of another embodiment in which the liquid crystal display element shown in FIG. It is sectional drawing of the liquid crystal display element which shows a color on filter. It is sectional drawing of the liquid crystal display element of the other form which shows a color on filter.
- FIG. 10 is a conceptual diagram showing a method for producing an alignment film according to the present invention.
- FIG. 11 shows the relationship between the polarization irradiation temperature and the anchoring energy.
- the first of the present invention is a step (I) of preparing a photoresponsive polymer solution by mixing a solvent and a photoresponsive polymer, and applying the photoresponsive polymer solution on a substrate, Drying at 50 to 100 ° C. for 3 minutes, further drying at 120 to 180 ° C. for 5 to 75 minutes to form a coating film (II), and the temperature of the coating film when irradiated with light of 200 to 350 nm And a step (III) of adjusting the temperature to 40 ° C. to 100 ° C.
- the change in the molecular structure is promoted in response to light, so that it is considered that the anchoring force is improved.
- each step will be described.
- Process (I) In the step (I) of the present invention, a solvent and a photoresponsive polymer are mixed to prepare a photoresponsive polymer solution.
- the solvent according to the present invention is not particularly limited as long as it dissolves the photoresponsive polymer, and can be appropriately selected depending on the properties of the photoresponsive polymer to be used.
- Solvents for dissolving molecules include lactones such as ⁇ -butyrolactone; ketones such as cyclopentanone, cyclohexanone, MEK, MIBK; esters such as propylene glycol monomethyl ether acetate, NMP (N-methyl-2-pyrrolidone) ).
- alcohol ethers such as 2-methoxyethanol and 2-butoxyethanol (butyl cellosolve); toluenes such as toluene may be added to the solvent as necessary.
- the photoresponsive polymer according to the present invention may be at least one selected from the group consisting of a photoresponsive decomposition polymer, a photoresponsive dimerization polymer, and a photoresponsive isomerization polymer. preferable.
- the photoresponsive dimerization polymer that forms a cross-linked structure by dimerization between side chains in response to light preferably has high photosensitivity and large orientation characteristics.
- the photoresponsive dimerization polymer used in the present invention is preferably a compound represented by the following general formula (I) and / or (II).
- L represents a group derived from a polymerizable group
- Sp is a spacer group, and is a single bond
- u represents 1 to 20
- At least one divalent linkage selected from the group consisting of —CH ⁇ CH—, —CF ⁇ CF—, —CF 2 O—, —OCF 2 —, —CF 2 CF 2 —, and —C ⁇ C—.
- one or more of the non-adjacent CH 2 groups in these substituents are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH 3 ). 2 —O—Si (CH 3 ) 2 —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR —, —CH ⁇ CH—, —C ⁇ C— or —O—CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms) .) Q represents a direct bond, —O—, —CO—O— or —O—CO—, A represents a trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other are represented by —O—, —NH—, or —S—).
- 1,4-phenylene group (one or more —CH ⁇ present in this group may be replaced by —N ⁇ ), 1,4-cyclohexenylene group, 2, 5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- A structure containing a functional group selected from the group consisting of a 2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, each functional group being unsubstituted or one
- hydrogen atoms are fluorine atoms, chlorine atoms ,
- a cyano group may be substituted by a methyl group or a methoxy group, s represents an integer of 0 to 4, and when s represents 2 to 4, a plurality of A and / /
- M represents the following general formula (IIa), the following general formula (IIb), or the following general formula (IIc).
- a broken line represents a bond to a carbon atom
- R 11 and R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms
- one methylene group or two or more methylene groups not adjacent to each other are present.
- one methylene group or two or more methylene groups that are not adjacent to one another are —O—, —CO—, —CO—O—, —O—CO—, —CO—NH—, —NH—.
- Ring C 1 , Ring C 2 and Ring C 3 are each independently of each other, (A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups not adjacent to each other are replaced by —O—, —NH— or —S—) May be) (B) a 1,4-phenylene group (one or more of —CH ⁇ present in this group may be replaced by —N ⁇ ), and (c) a 1,4-cyclohexenylene group 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo (2.2.2) octylene group, naphthalene-1,4-di
- the Sp is more preferably an alkylene oxide group having 6 to 12 carbon atoms or — (CH 2 ) m — (m is an integer of 8 to 12).
- the group derived from the polymerizable group may be a group derived from any polymerizable group selected from the group consisting of polymerizable groups represented by the following general formulas (III-1) to (III-11). preferable.
- a broken line represents a bond to Sp
- R 30 represents a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a phenoxy group
- R 31 represents a hydrogen atom.
- R 32 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- the photoresponsive dimerization polymer has the following general formula (1):
- Sp is a single bond, — (CH 2 ) u — (wherein u represents 1 to 20), —OCH 2 —, —CH 2 O—, —COO— , —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, —CF 2 O—, —OCF 2 —, —CF 2 CF 2 —, and —C ⁇ C—.
- At least one of the non-adjacent CH 2 groups independently represents —O—, —CO—, —CO—O—, —O—CO—, — Si (CH 3 ) 2 —O—Si (CH 3 ) 2 —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, — NR—CO—NR—, —CH ⁇ CH—, —C ⁇ C— or —O—CO—O— (wherein R is independently hydrogen or an alkyl group having 1 to 5 carbon atoms) Can be substituted with A 1 and A 2 are each independently (A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups not adjacent to each other are replaced by —O—, —NH— or —S—) May be) (B) a 1,4-phenylene group (one or more of —CH ⁇ present
- the broken line represents a bond to Sp or a monovalent organic group
- R a is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- a phenyl group, a halogen atom, and any hydrogen atom in each structure may be substituted with a fluorine atom, a chlorine atom, a methyl group, a phenyl group, or a methoxy group
- the broken line represents a bond to Sp
- R 1 is a tetravalent ring structure
- R 2 is a trivalent organic group
- R 3 is a hydrogen atom
- a hydroxyl group Represents an alkyl group having 1 to 15 carbon atoms and an alkoxy group having 1 to 15 carbon atoms.
- y and w represent the molar fraction of the copolymer, 0 ⁇ y ⁇ 1 and 0 ⁇ w ⁇ 1, n represents 4 to 100,000, and the monomer units of M b and M d are each independently One type or two or more types of different units may be used. ), A hydrolyzate thereof, or a condensate of the hydrolyzate is more preferable.
- the monovalent organic group is represented by the general formula (VII)
- Z 4 , Z 5 , Z 6 and Z 7 are each independently a single bond, — (CH 2 ) u — (wherein u represents 1 to 20), —OCH 2 —, —CH 2 O —, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, —CF 2 O—, —OCF 2 —, —CF 2 CF 2 — or —C ⁇ C— And at least one of the non-adjacent CH 2 groups independently represents —O—, —CO—, —CO—O—, —O—CO—, —Si (CH 3 ) 2 —O—Si.
- a 3 , A 4 , A 5 and A 6 are each independently (a) a trans-1,4-cyclohexylene group (one methylene group present in this group or two or more not adjacent to each other) The methylene group may be replaced by —O—, —NH— or —S—), (B) a 1,4-phenylene group (one or more —CH ⁇ present in this group may be replaced by —N ⁇ ), and (c) a 1,4-cyclohexenylene group 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo (2.2.2)
- the photoresponsive dimerization polymer represented by the general formula (1) according to the present invention has the following general formula (2):
- R 21 to R 24 are each independently a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms
- W represents a hydrogen atom, a fluorine atom, a methyl group, a methoxy group, an ethyl group or an ethoxy group
- W is at least one selected from the group consisting of the following general formulas (W-1) to (W-8) Represents
- X is an integer of 6 to 12, and Y is an integer of 0 to 2. ) Is more preferable.
- W is particularly preferably a group represented by (W-1) from the viewpoint of ensuring good alignment with irradiation of a small amount of polarized ultraviolet light.
- alkyl group and alkoxy group according to the present invention are preferably linear, cyclic or branched, and more preferably linear or branched.
- examples of the “alkyl group” according to the present invention include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, isopentyl group, neopentyl group, pentyl group. Group, hexyl group, heptyl group, octyl group and the like.
- examples of alkyl groups are common and are appropriately selected from the above examples depending on the number of carbon atoms of each alkyl group.
- alkoxy group examples are preferably groups in which an oxygen atom is directly bonded to the alkyl group.
- methoxy group, ethoxy group, propoxy group (n-propoxy group, i-propoxy group) , Butoxy group, pentyloxy group, and octyloxy group are more preferable.
- the example of an alkoxy group is common and is suitably selected from the said illustration according to the number of carbon atoms of each alkoxy group.
- a preferred embodiment of the method for producing a liquid crystal alignment film according to the present invention is a photoresponsive property obtained by mixing a photoresponsive dimerization polymer that forms a crosslinked structure by dimerization of side chains in response to a solvent and light.
- the photoresponsive polymer according to the present invention is particularly preferably a photoresponsive dimerization polymer.
- the light used for dimerization between side chains is preferably 200 to 350 nm, more preferably 250 to 350 nm, and more preferably 250 to 330 nm. Further preferred.
- the photoresponsive decomposable polymer according to the present invention is preferably produced by condensation of tetracarboxylic dianhydride and a diamine compound.
- tetracarboxylic dianhydride examples include the following formulas (A-1) to (A-43):
- the formula (A-14), the formula (A-15), the formula (A-16), the formula (A-17), the formula (A-20), the formula (A-21), Formula (A-28), Formula (A-29), Formula (A-30), or Formula (A-31) is preferable, and Formula (A-14) and Formula (A-21) are particularly preferable.
- diamine compound examples include the following formulas (III-1) to (VIII-17).
- R 1 to R 10 are primary amino groups, and the rest are hydrogen atoms or monovalent organic groups other than primary amino groups, which may be the same or different. Is also good.
- the diamine compound having a cinnamic acid skeleton represented by the above formulas (1) to (5) can be dimerized in response to light, and thus is preferably used as a photoresponsive dimerization polymer. be able to.
- the light used for cleaving the molecular chain is preferably 200 to 400 nm, more preferably 200 to 280 nm, and further preferably 240 to 280 nm. preferable.
- the photoresponsive isomerization polymer according to the present invention is produced by synthesis of a tetracarboxylic dianhydride and a diamine compound, and at least one of the tetracarboxylic dianhydride compound and a diamine. It is preferable to have a diazo bond.
- Examples of the tetracarboxylic dianhydride having a diazo bond include compounds represented by the following formula (1-8).
- the photoresponsive isomerization polymer according to the present invention when the formulas (I-1) to (I-7) are selected as diamine compounds having a diazo bond, tetracarboxylic acid is used.
- the dianhydride is preferably a compound represented by formula (1-8) or formula (A-1) to (A-43).
- the formula (1-8) when the formula (1-8) is selected as a tetracarboxylic dianhydride having a diazo bond, a formula (1 Compounds represented by formulas (I-1) to (I-7) and formulas (III-1) to (VIII-11), (I) and (1) to (5) are preferred.
- the light used when isomerizing in response to light and oriented substantially perpendicular to the polarization axis is preferably 200 to 500 nm, and preferably 300 to 500 nm. It is more preferable that the thickness is 300 to 400 nm.
- the weight average molecular weight of the photoresponsive decomposition type polymer according to the present invention is preferably 3000 to 300000, more preferably 5000 to 100,000, still more preferably 10,000 to 50,000, and 10,000 to 30,000. It is particularly preferred.
- the weight average molecular weight of the photoresponsive isomerization polymer according to the present invention is preferably 10,000 to 800,000, more preferably 10,000 to 400,000, still more preferably 50,000 to 400,000, and 50,000 to 300,000. It is particularly preferred that
- the weight average molecular weight of the photoresponsive dimerization polymer according to the present invention is preferably 5000 to 800,000, more preferably 5000 to 400,000, still more preferably 100,000 to 400,000, and 100,000 to 300,000. It is particularly preferred that
- the said weight average molecular weight (Mw) is obtained as a result of GPC (gel permeation chromatography, Gel Permeation Chromatography) measurement.
- the concentration of the photoresponsive polymer solution according to the present invention is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, and even more preferably 2 to 5% by mass.
- Step (II) In the step (II) of the present invention, the photoresponsive polymer solution is coated on a substrate, dried at 50 to 100 ° C. for 1 to 3 minutes, and further dried at 120 to 180 ° C. for 5 to 75 minutes. A film is formed.
- the average thickness of the coating film according to the present invention is preferably 1 to 1000 nm, more preferably 5 to 500 nm, further preferably 10 to 200 nm, and still more preferably 20 to 90 nm.
- the method for measuring the average thickness of the coating film according to the present invention is a step measurement using a contact-type film thickness meter that is applied after the photo-alignment film is applied and irradiated with light. Moreover, the measuring method of the average film thickness of the liquid crystal aligning film obtained by the manufacturing method which concerns on this invention is also the same.
- the substrate that can be used in the present invention is preferably a transparent substrate, and is not particularly limited as long as it is a material that does not dissolve in the solvent because of the relationship with the solvent used in the photoresponsive polymer solution.
- a quartz substrate etc. are mentioned.
- examples of the coating method of the present invention include spin coating, bar coating, flexographic printing, and ink jet.
- Examples of the method for drying the coating film of the present invention include heat drying and vacuum drying.
- heating at 20 to 150 ° C. for 0.1 to 20 minutes is preferable, followed by heating at 80 to 250 ° C. for 1 to 100 minutes, and heating at 30 to 120 ° C. for 0.5 to 10 minutes.
- it is preferably heated at 100 ° C. to 200 ° C. for 2 to 90 minutes, preferably heated at 50 to 100 ° C. for 1 to 3 minutes and then heated at 120 ° C. to 180 ° C. for 5 to 75 minutes, preferably 2 to 3 minutes. It is more preferable to heat at 70 to 90 ° C. and then dry at 150 to 180 ° C. for 5 minutes.
- the number of drying times of the coating film of the present invention is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less.
- the production method according to the present invention it is considered that since the change in the molecular structure is promoted by controlling the temperature of the coating film during light irradiation, the anchoring force is improved.
- the above-mentioned photoresponsive dimerization type polymer is used as the photoresponsive polymer, it was found that dimerization is promoted by controlling the temperature of the coating film during light irradiation within a specific range.
- a maintenance means such as heating with a hot plate or irradiation with polarized light in a thermostatic bath.
- step (III) it is preferable to irradiate the coating film with 200 to 350 nm light in a state where the coating film temperature is maintained at 38 ° C. to 110 ° C., and the coating film temperature is maintained at 40 ° C. to 100 ° C. It is more preferable to irradiate the coating film with 230 to 340 nm polarized light in a state, and it is even more preferable to irradiate the coating film with 250 to 330 nm polarized light while maintaining the temperature of the coating film at 50 ° C. to 90 ° C. It is particularly preferable to irradiate the coating film with polarized light of 270 to 330 nm while maintaining the temperature of the coating film at 65 ° C. to 75 ° C.
- the light irradiation in the step (III) according to the present invention imparts liquid crystal alignment ability to the coating film, and examples thereof include ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm. Of these, ultraviolet rays containing light having a wavelength of 200 nm to 350 nm are preferable.
- the irradiated light may be polarized light or non-polarized light. Further, in the case of polarized light, it may be linearly polarized light or partially polarized light. In this specification, “non-polarized light” is included in “non-polarized light” if it is substantially non-polarized light even if it is partially polarized light.
- the light applied to the coating film in the step (III) according to the present invention is preferably linear light, and more preferably linearly polarized light.
- irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination thereof. Also good.
- the direction of irradiation needs to be an oblique direction.
- the “pretilt angle” in this specification refers to the angle of inclination of liquid crystal molecules from a direction parallel to the substrate surface.
- Examples of the light source used in the present invention include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser mercury-xenon lamp (Hg-Xe lamp).
- Etc. The linearly polarized light or the partially polarized ultraviolet light is preferably obtained by means of using the light source in combination with a filter, a diffraction grating, or the like.
- the irradiation dose of light in the present invention preferably 1mJ / m 2 ⁇ 1,000mJ / m 2, more preferably from 5mJ / m 2 ⁇ 1,000mJ / m 2, 10mJ / m 2 ⁇ 500mJ / m 2 and more 10 mJ / m 2 to 100 mJ / m 2 is particularly preferable.
- a light irradiation amount of about 1,000 mJ / m 2 or more is required.
- the liquid crystal alignment film obtained by the production method according to the present invention preferably aligns liquid crystal molecules in a substantially horizontal direction with respect to the substrate.
- a lateral electric field type liquid crystal display element such as an FFS mode or an IPS mode, which will be described later
- even the lateral electric field type liquid crystal display element having an electrode structure with many surface irregularities is uneven.
- the anchoring effect can be imparted evenly, the orientation is uniform, no defects are present, and the contrast can be increased.
- linear light of 200 to 350 nm is irradiated from a substantially vertical direction with respect to the substrate of the present invention, and the amount of irradiation is linearly polarized light of 10 to 100 mJ / cm 2. is there.
- the light irradiation from the substantially vertical direction here is preferably performed from the direction of 70 to 110 degrees with respect to the substrate.
- the second of the present invention is to prepare a photoresponsive dimerization polymer solution by mixing a photoresponsive dimerization polymer that forms a crosslinked structure by dimerization of side chains in response to a solvent and light.
- (2) drying the film by drying at ⁇ 180 ° C. for 5 to 75 minutes, and irradiating with polarized light of 200 to 350 nm while maintaining the temperature of the dried film at 50 ° C. to 100 ° C.
- a step (3) of forming a liquid crystal alignment film on the surface of the first substrate and the second substrate, and a pair of substrates on which the liquid crystal alignment film is formed are bonded so that the liquid crystal alignment films face each other and are separated from each other.
- Step of filling a liquid crystal composition between a pair of formed liquid crystal alignment films 3 When a alignment method for a liquid crystal composition containing a.
- a third aspect of the present invention is a liquid crystal display element provided with the liquid crystal alignment film according to the present invention.
- liquid crystal display element As the liquid crystal display element according to the present invention, ECB-LCD, VA-LCD, VA-IPS-LCD, FFS-LCD, TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD And IPS-LCD (in-plane switching liquid crystal display element), it is particularly useful for FFS-LCD and IPS-LCD, and can be used for transmissive or reflective liquid crystal display elements.
- the two substrates of the liquid crystal cell used in the liquid crystal display element can be made of a transparent material having flexibility such as glass or plastic as described above, and one of them can be an opaque material such as silicon.
- a transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.
- the color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method.
- a method for producing a color filter by a pigment dispersion method will be described as an example.
- a curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be manufactured.
- a pixel electrode provided with an active element such as a TFT or a thin film diode may be provided on the substrate.
- the substrate After forming the liquid crystal alignment film on the transparent substrate having the transparent electrode layer and / or the transparent substrate surface by the production method according to the present invention, the substrate is placed so that the transparent electrode layer is inside (the liquid crystal alignment films face each other). ) Make them face each other. In that case, you may adjust the space
- the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good.
- a retardation film for widening the viewing angle can also be used.
- the spacer include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like.
- a normal vacuum injection method or an ODF method can be used as a method of sandwiching the liquid crystal composition (containing a polymerizable compound as necessary) between the two substrates.
- a vacuum injection method there is a problem that an injection mark remains instead of a drop mark.
- it can use more suitably for the display element manufactured using ODF method.
- a sealant such as epoxy photothermal curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and then removed.
- a liquid crystal display element can be manufactured by bonding a front plane and a back plane after dropping a predetermined amount of the liquid crystal composition in the air.
- the liquid crystal composition of the present invention can be preferably used because the liquid crystal composition can be stably dropped in the ODF process.
- the liquid crystal display device using the liquid crystal composition of the present invention is useful for achieving both high-speed response and suppression of display failure, and is particularly useful for a liquid crystal display device for active matrix driving, including VA mode, PSVA mode, It can be applied to liquid crystal display elements for PSA mode, IPS (in-plane switching) mode, VA-IPS mode, FFS (fringe field switching) mode or ECB mode.
- liquid crystal display element an example of a liquid crystal display
- FIG. 1 is a cross-sectional view showing a liquid crystal display element including two substrates facing each other, a sealing material provided between the substrates, and liquid crystal sealed in a sealing region surrounded by the sealing material. It is.
- the TFT layer 102 and the pixel electrode 103 are provided on the first substrate 100, the backplane on which the passivation film 104 and the first alignment film 105 are provided, and the black matrix on the second substrate 200.
- 202, a color filter 203, a planarization film (overcoat layer) 201, and a transparent electrode 204 are provided, and a second alignment film 205 is provided thereon, provided between the front plane facing the back plane and the substrate.
- a sealing material 301 and a liquid crystal layer 303 sealed in a sealing region surrounded by the sealing material, and protrusions (columnar spacers) 302 and 304 are provided on a substrate surface in contact with the sealing material 301. The specific aspect of a liquid crystal display element is shown.
- the first substrate or the second substrate is not particularly limited as long as it is substantially transparent, and glass, ceramics, plastics, or the like can be used.
- Plastic substrates include cellulose derivatives such as cellulose, triacetyl cellulose, diacetyl cellulose, polycycloolefin derivatives, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, polyethylene, etc.
- Inorganic-organic composite materials such as glass fiber-acrylic resin can be used.
- the function of the barrier film is to reduce the moisture permeability of the plastic substrate and to improve the reliability of the electrical characteristics of the liquid crystal display element.
- the barrier film is not particularly limited as long as it has high transparency and low water vapor permeability. Generally, vapor deposition, sputtering, chemical vapor deposition method (CVD method) using an inorganic material such as silicon oxide is used. ) Is used.
- the same material or different materials may be used as the first substrate or the second substrate, and there is no particular limitation.
- Use of a glass substrate is preferable because a liquid crystal display element having excellent heat resistance and dimensional stability can be manufactured.
- a plastic substrate is preferable because it is suitable for a manufacturing method using a roll-to-roll method and is suitable for weight reduction or flexibility. For the purpose of imparting flatness and heat resistance, good results can be obtained by combining a plastic substrate and a glass substrate.
- a substrate is used as the material of the first substrate 100 or the second substrate 200.
- the TFT layer 102 and the pixel electrode 103 are provided on the first substrate 100. These are manufactured by a normal array process.
- a backplane is obtained by providing a passivation film 104 and a first alignment film 105 thereon.
- a passivation film 104 (also referred to as an inorganic protective film) is a film for protecting the TFT layer.
- a nitride film (SiNx), an oxide film (SiOx), or the like is formed by a chemical vapor deposition (CVD) technique or the like.
- first liquid crystal alignment film 105 and the second alignment film 205 are films having a function of aligning liquid crystals obtained by the method for manufacturing a liquid crystal alignment film according to the present invention. Since the alignment film may hinder the adhesive force with the sealing material, a pattern is applied in the sealing region.
- the reaction mechanism for inducing the photo-alignment method according to the present invention includes molecular orientation induction (isomerization reaction) (eg, azobenzene group) and dimerization reaction (eg: cinnamoyl group) due to Weigert effect resulting from photodichroism. ), Or those having a group (hereinafter abbreviated as photoalignable group) that causes a photoreaction that causes liquid crystal alignment ability, such as a photodecomposition reaction (eg, polyimide group).
- a photoalignable group that causes a photoreaction that causes liquid crystal alignment ability, such as a photodecomposition reaction (eg, polyimide group).
- the method of forming a photo-alignment film by is particularly preferable. After the solvent is evaporated by temporary drying, the applied alignment agent solution has an alignment ability in any direction by controlling the temperature of the coating film when irradiating light (polarized light) having an arbitrary deflection. It is preferable to obtain
- One front plane is provided with a black matrix 202, a color filter 203, a planarizing film 201, a transparent electrode 204, and a second alignment film 205 on a second substrate 200.
- the black matrix 202 is produced by, for example, a pigment dispersion method. Specifically, a color resin solution in which a black colorant is uniformly dispersed for forming a black matrix is applied on the second substrate 200 provided with the barrier film 201 to form a colored layer. Subsequently, the colored layer is baked and cured. A photoresist is applied on this and prebaked. After exposing the photoresist through a mask pattern, development is performed to pattern the colored layer. Thereafter, the photoresist layer is peeled off and the colored layer is baked to complete the black matrix 202.
- a color resin solution in which a black colorant is uniformly dispersed for forming a black matrix is applied on the second substrate 200 provided with the barrier film 201 to form a colored layer. Subsequently, the colored layer is baked and cured. A photoresist is applied on this and prebaked. After exposing the photoresist through a mask pattern, development is performed to pattern the colored layer. Thereafter, the photo
- a photoresist type pigment dispersion may be used.
- a photoresist-type pigment dispersion is applied, pre-baked, exposed through a mask pattern, and then developed to pattern the colored layer. Thereafter, the photoresist layer is peeled off and the colored layer is baked to complete the black matrix 202.
- the color filter 203 is produced by a pigment dispersion method, an electrodeposition method, a printing method, a dyeing method, or the like.
- a pigment dispersion method as an example, a color resin liquid in which a pigment (for example, red) is uniformly dispersed is applied onto the second substrate 200, and after baking and curing, a photoresist is applied thereon and prebaked. After the photoresist is exposed through a mask pattern, development is performed and patterning is performed. Thereafter, the photoresist layer is peeled off and baked again to complete the (red) color filter 203. There is no particular limitation on the color order to be produced. Similarly, a green color filter 203 and a blue color filter 203 are formed.
- the transparent electrode 204 is provided on the color filter 203 (if necessary, an overcoat layer (201) is provided on the color filter 203 for surface flattening).
- the transparent electrode 204 preferably has a high transmittance, and preferably has a low electrical resistance.
- the transparent electrode 204 is formed by sputtering an oxide film such as ITO.
- a passivation film may be provided on the transparent electrode 204 for the purpose of protecting the transparent electrode 204.
- the second alignment film 205 is the same as the first alignment film 105 described above.
- the shape of the columnar spacer is not particularly limited, and the horizontal cross section can be various shapes such as a circle and a polygon such as a quadrangle. A polygonal shape is particularly preferable.
- the protrusion shape is preferably a truncated cone or a truncated pyramid.
- the material of the columnar spacer is not particularly limited as long as it is a sealing material, an organic solvent used for the sealing material, or a material that does not dissolve in liquid crystal, but it may be a synthetic resin (curable resin) in terms of processing and weight reduction. preferable.
- the protrusion can be provided on the surface of the first substrate in contact with the sealing material by a photolithography method or a droplet discharge method. For these reasons, it is preferable to use a photocurable resin suitable for a photolithography method or a droplet discharge method.
- FIG. 2 is a diagram of an exposure process using a columnar spacer preparation pattern formed on a black matrix as a photomask pattern.
- a resin solution for forming columnar spacers (not containing a colorant) is applied on the transparent electrode 204 of the front plane. Subsequently, the resin layer 402 is baked and cured. A photoresist is applied on this and prebaked. After exposing the photoresist through the mask pattern 401, development is performed to pattern the resin layer. Thereafter, the photoresist layer is peeled off, and the resin layer is baked to complete columnar spacers (302 and 304 in FIG. 1).
- the formation position of the columnar spacer can be determined at a desired position by the mask pattern. Therefore, both the inside of the sealing region of the liquid crystal display element and the outside of the sealing region (sealed material application portion) can be manufactured simultaneously.
- the columnar spacer is preferably formed so as to be positioned on the black matrix so that the quality of the sealing region does not deteriorate.
- a columnar spacer manufactured by a photolithography method in this way is sometimes called a column spacer or a photospacer.
- a mixture of a negative water-soluble resin such as PVA-stilbazo photosensitive resin, a polyfunctional acrylic monomer, an acrylic acid copolymer, a triazole initiator, or the like is used.
- a color resin in which a colorant is dispersed in a polyimide resin there is no particular limitation, and a spacer can be obtained from a known material in accordance with the compatibility with the liquid crystal or the sealing material to be used.
- a sealing material (301 in FIG. 1) is applied to the surface of the backplane that contacts the sealing material.
- the material of the sealing material is not particularly limited, and a curable resin composition in which a polymerization initiator is added to an epoxy or acrylic photocurable, thermosetting, or photothermal combination curable resin is used.
- a curable resin composition in which a polymerization initiator is added to an epoxy or acrylic photocurable, thermosetting, or photothermal combination curable resin is used.
- fillers made of inorganic or organic substances may be added.
- the shape of these fillers is not particularly limited, and includes a spherical shape, a fiber shape, and an amorphous shape.
- a spherical or fibrous gap material having a monodisperse diameter is mixed, or in order to further strengthen the adhesive force with the substrate, a fibrous substance that is easily entangled with the protrusion on the substrate is used. You may mix.
- the diameter of the fibrous material used at this time is desirably about 1/5 to 1/10 or less of the cell gap, and the length of the fibrous material is desirably shorter than the seal coating width.
- the material of the fibrous substance is not particularly limited as long as a predetermined shape can be obtained, and synthetic fibers such as cellulose, polyamide, and polyester, and inorganic materials such as glass and carbon can be appropriately selected.
- the sealing material As a method for applying the sealing material, there are a printing method and a dispensing method, but a dispensing method with a small amount of the sealing material used is desirable.
- the application position of the sealing material is usually on the black matrix so as not to adversely affect the sealing area.
- the sealing material application shape is a closed loop shape.
- the liquid crystal is dropped on the closed loop shape (sealing region) of the front plane coated with the sealing material.
- a dispenser is used. Since the amount of liquid crystal to be dropped coincides with the volume of the liquid crystal cell, the amount is basically the same as the volume obtained by multiplying the height of the column spacer and the seal application area. However, in order to optimize liquid crystal leakage and display characteristics in the cell bonding process, the amount of liquid crystal to be dropped may be adjusted as appropriate, or the liquid crystal dropping position may be dispersed.
- the back plane is bonded to the front plane where the sealing material is applied and the liquid crystal is dropped.
- the front plane and the back plane are adsorbed on a stage having a mechanism for adsorbing a substrate such as an electrostatic chuck, and the second alignment film on the front plane and the first alignment film on the back plane face each other.
- it is arranged at a position (distance) where the sealing material does not contact the other substrate.
- the system is depressurized. After decompression is completed, the positions of both substrates are adjusted while confirming the bonding position between the front plane and the back plane (alignment operation).
- the substrate is brought close to a position where the sealing material on the front plane and the back plane are in contact with each other.
- the system is filled with an inert gas, and the pressure is gradually returned to normal pressure while releasing the reduced pressure.
- the front plane and the back plane are bonded together by atmospheric pressure, and a cell gap is formed at the height of the columnar spacer.
- the sealing material is irradiated with ultraviolet rays to cure the sealing material, thereby forming a liquid crystal cell.
- a heating step is added in some cases to promote curing of the sealing material. A heating process is often added to enhance the adhesive strength of the sealing material and improve the reliability of electrical characteristics.
- a second preferred embodiment of the liquid crystal display device includes a first substrate having an electrode layer including a first alignment layer and a thin film transistor on the surface, and a second substrate having a second alignment layer on the surface. Are arranged so as to face each other and the liquid crystal layer containing the liquid crystal composition is filled between the first substrate and the second substrate, and includes the thin film transistor.
- the electrode layer includes a plurality of gate wirings and data wirings arranged in a mesh pattern, a thin film transistor provided at each intersection of the gate wiring and the data wiring, a pixel electrode connected to the thin film transistor, and the pixel And a common electrode provided on the first substrate apart from the electrode.
- the first alignment layer and the second alignment layer provided in the vicinity of the liquid crystal layer are preferably alignment films that induce homogeneous alignment with respect to the liquid crystal composition.
- the liquid crystal display element includes a second polarizing plate, a second substrate, an electrode layer including a thin film transistor (or also referred to as a thin film transistor layer), a liquid crystal alignment film obtained by the manufacturing method of the present invention, and a liquid crystal A configuration in which a liquid crystal layer containing the composition, an alignment film, a color filter, a first substrate, and a first polarizing plate are sequentially laminated is preferable.
- the electric field (E) generated between the common electrode and the pixel electrode can have a planar component. Therefore, for example, when an alignment film that induces homogeneous alignment with respect to the liquid crystal composition is used for the alignment layer, the alignment layer is aligned in the plane direction that is the alignment direction of the alignment film before voltage is applied between the common electrode and the pixel electrode.
- the liquid crystal molecules that block light, and when a voltage is applied, the liquid crystal molecules rotate horizontally by the electric field (E) applied in the plane direction, and can be arranged along the electric field direction to provide an element that blocks light. .
- the liquid crystal display element according to the present invention may be a so-called color filter on array (COA), or a color filter may be provided between an electrode layer including a thin film transistor and a liquid crystal layer, or the thin film transistor.
- COA color filter on array
- a color filter may be provided between the electrode layer containing and the second substrate.
- “on the substrate” in this specification includes not only a direct contact with the substrate but also a indirectly supported state in which the substrate is supported.
- Another more preferable embodiment (FFS) of the second embodiment in the liquid crystal display composition according to the present invention includes a first substrate having an electrode layer including a first alignment layer and a thin film transistor on the surface, and a second alignment layer.
- the electrode layer including the thin film transistor includes a plurality of gate wirings and data wirings arranged in a mesh pattern, a thin film transistor provided at each intersection of the gate wiring and the data wiring, and connected to the thin film transistor And a common electrode that is spaced apart from the pixel electrode and arranged in parallel on the first substrate, and the shortest separation distance between the adjacent common electrode and the pixel electrode It is preferred but shorter than the shortest distance G between the alignment layer.
- a liquid crystal display element in which the shortest separation distance d between the common electrode and the pixel electrode is longer than the shortest separation distance G between the alignment layers is referred to as an IPS liquid crystal display element.
- An element in which the shortest distance d from the electrode is shorter than the shortest distance G between the alignment layers is referred to as FFS. Accordingly, the only requirement for the FFS method is that the shortest separation distance d between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers. Therefore, the surface of the common electrode and the surface of the pixel electrode There is no limitation on the positional relationship in the thickness direction. Therefore, in the FSS mode liquid crystal display element according to the present invention, the pixel electrode may be provided on the liquid crystal layer side from the common electrode as shown in FIGS. 3 to 9, and the pixel electrode and the common electrode are on the same plane. May be provided.
- the photo-alignment film according to the present invention is used for a liquid crystal display element of an FFS driving system (FFS-LCD), it is preferable from the viewpoint of high-speed response and reduction of image sticking.
- FFS-LCD FFS driving system
- FIG. 3 is an exploded perspective view schematically showing a structure of one embodiment of the liquid crystal display element, which is a so-called FFS type liquid crystal display element.
- a liquid crystal display element 10 according to the present invention includes a second polarizing plate 8, a second substrate 7, an electrode layer (also referred to as a thin film transistor layer) 3 including a thin film transistor, an alignment film 4, and a liquid crystal composition. It is preferable that the liquid crystal layer 5, the alignment film 4, the color filter 6, the first substrate 2, and the first polarizing plate 1 are sequentially stacked. Further, as shown in FIG.
- the second substrate 7 and the first substrate 2 may be sandwiched between a pair of polarizing plates 1 and 8. Further, in FIG. 3, a color filter 6 is provided between the second substrate 7 and the alignment film 4. Further, a pair of alignment films 4 may be formed on the (transparent) electrode (layer) 3 so as to be close to the liquid crystal layer 5 according to the present invention and to directly contact the liquid crystal composition constituting the liquid crystal layer 5.
- a so-called color filter on array may be used, and the color filter 6 may be provided between the thin film transistor layer 3 and the liquid crystal layer 5.
- a color filter 6 may be provided between the thin film transistor layer 3 and the first substrate 2.
- the FFS mode liquid crystal display element uses a fringe electric field.
- the shortest separation distance d between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers, the common electrode and the pixel electrode A fringe electric field is formed between them, and the horizontal and vertical alignments of the liquid crystal molecules can be used efficiently. That is, in the case of the FFS liquid crystal display element, a horizontal electric field formed in a direction perpendicular to a line forming the comb-teeth of the pixel electrode 21 and a parabolic electric field can be used.
- FIG. 4 is an enlarged plan view of a region II of the electrode layer 3 (or also referred to as the thin film transistor layer 3) including the thin film transistor formed on the substrate in FIG.
- the thin film transistor 20 including the source electrode 27, the drain electrode 24, and the gate electrode 28 serves as a switch element that supplies a display signal to the pixel electrode 21. 21 is provided.
- FIG. 4 shows a configuration in which a flat plate-like common electrode 22 is formed on the back surface of an interdigital pixel electrode 21 via an insulating layer (not shown).
- the surface of the pixel electrode 21 may be covered with a protective insulating film and an alignment film layer.
- a storage capacitor 23 for storing a display signal supplied through the data wiring 25 may be provided in a region surrounded by the plurality of gate wirings 26 and the plurality of data wirings 25. Further, a common line 29 is provided in parallel with the gate wiring 26. The common line 29 is connected to the common electrode 22 in order to supply a common signal to the common electrode 22.
- FIG. 5 is an example of a cross-sectional view of the liquid crystal display element taken along the line III-III in FIG.
- the substrate 7 is spaced apart from the alignment layer at a predetermined gap G, and the liquid crystal layer 5 containing a liquid crystal composition is filled in this space.
- a gate insulating film 12 is formed on a part of the surface of the first substrate 2
- a common electrode 22 is formed on a part of the surface of the gate insulating film 12, and the common electrode 22 and the thin film transistor 20 are further formed.
- An insulating film 18 is formed so as to cover it.
- a pixel electrode 21 is provided on the insulating film 18, and the pixel electrode 21 is in contact with the liquid crystal layer 5 through the alignment layer 4. Therefore, the minimum distance d between the pixel electrode and the common electrode can be adjusted as the (average) film thickness of the gate insulating film 12. In other words, in the embodiment of FIG. 5, the distance in the horizontal direction on the substrate between the pixel electrode and the common electrode is zero.
- the electrode width of the comb-like portion of the pixel electrode 21: l and the width of the gap of the comb-like portion of the pixel electrode 21: m are such that all the liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable to form the width.
- the major axis direction is
- a voltage is applied to the liquid crystal molecules arranged parallel to the alignment direction of the alignment layer, an equipotential line of a parabolic electric field is formed between the pixel electrode 21 and the common electrode 22 between the pixel electrode 21 and the common electrode 22.
- the liquid crystal molecules in the liquid crystal layer 5 rotate in the liquid crystal layer 5 along the formed electric field and function as a switching element.
- the plane direction that is the alignment direction of the alignment film before voltage is applied between the common electrode and the pixel electrode
- the common electrode and the pixel electrode are separated from each other on the same substrate (or electrode layer).
- the vertical component electric field (fringe field) derived from the edges of these electrodes is generated when the shortest separation distance d between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers.
- the amount of the compound having a high dielectric anisotropy ( ⁇ ), which has a high characteristic of the liquid crystal composition itself, can be reduced as much as possible, so that the liquid crystal composition itself can contain a large amount of a low-viscosity compound. .
- the alignment film obtained by the manufacturing method according to the present invention can exhibit a high anchoring effect, since there are many types of liquid crystal compositions that can be used, a relatively low dielectric constant that can be used. Many liquid crystal compositions can be driven.
- the configuration of another preferred embodiment of the second embodiment in the liquid crystal display composition according to the present invention is (FFS), a first substrate having an electrode layer including a first alignment layer and a thin film transistor on the surface, and a second A liquid crystal in which a liquid crystal layer containing a liquid crystal composition is filled between the first substrate and the second substrate.
- the electrode layer including the thin film transistor which is a display element, includes a common electrode, a plurality of gate wirings and data wirings arranged in a mesh shape, and a thin film transistor provided at each intersection of the gate wiring and the data wiring And a pixel electrode connected to the thin film transistor, and the pixel electrode is preferably provided so as to protrude from the common electrode toward the second substrate.
- the first alignment layer and the second alignment layer provided in the vicinity of the liquid crystal layer are preferably alignment films that induce homogeneous alignment with respect to the liquid crystal composition.
- FIG. 6 is another form of a plan view in which the region II of the electrode layer 3 including the thin film transistor (also referred to as the thin film transistor layer 3) formed on the substrate in FIG. 3 is enlarged.
- the thin film transistor 20 including the source electrode 27, the drain electrode 24, and the gate electrode 28 serves as a switch element that supplies a display signal to the pixel electrode 21.
- the pixel electrode 21 may have a structure cut out by at least one notch, and an example thereof is shown in FIG.
- the pixel electrode 21 has a shape in which the center and both ends of a rectangular flat plate are cut out by a triangular cutout, and the remaining region is cut out by eight rectangular cutouts.
- Reference numeral 22 denotes a comb tooth body (not shown).
- the surface of the pixel electrode may be covered with a protective insulating film and an alignment film layer.
- a storage capacitor 23 for storing a display signal supplied through the data wiring 24 may be provided in a region surrounded by the plurality of gate wirings 25 and the plurality of data wirings 24. Note that the shape and number of the notches are not particularly limited.
- FIG. 7 shows another example of the cross-sectional view of the liquid crystal display element taken along the line III-III in FIG. That is, the difference from the structure of the liquid crystal display element shown in FIG. 5 is that the liquid crystal display element shown in FIG. 5 has a common electrode as a flat plate and a pixel electrode as a comb.
- the pixel electrode 21 has a rectangular flat plate whose center and both ends are cut out by a triangular cutout, and a remaining area is 8. It has a shape cut out by two rectangular cutouts, and the common electrode has a comb-like structure.
- the minimum separation distance d between the pixel electrode and the common electrode is equal to or greater than the (average) film thickness of the gate insulating film 12 and less than the alignment layer separation distance G.
- the common electrode has a comb-like structure, but the common electrode may be a flat plate in this embodiment.
- the FFS mode liquid crystal display element according to the present invention only needs to satisfy the condition that the shortest separation distance d between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers.
- the pixel electrode 21 is covered with the protective film 18, but in the configuration of the liquid crystal display element shown in FIG. 5, the pixel electrode 21 is covered with the alignment layer 4. .
- the pixel electrode may be covered with either a protective film or an alignment film.
- a polarizing plate is formed on one surface of the first substrate 2, and a gate insulating film 12 is formed so as to cover the comb-like common electrode 22 formed on a part of the other surface.
- a pixel electrode 21 is formed on a part of the surface of the gate insulating film 12, and an insulating film 18 is formed so as to cover the pixel electrode 21 and the thin film transistor 20.
- an alignment layer 4, a liquid crystal layer 5, an alignment layer 4, a color filter 6, a second substrate 7 and a polarizing plate 8 are laminated on the insulating film 18.
- the minimum separation distance d between the pixel electrode and the common electrode is adjusted by both electrode positions, the electrode width of the comb-like portion of the pixel electrode 21: l, or the width of the gap of the comb-like portion of the pixel electrode 21: m. can do.
- an electric field (E) having a thickness direction component can be applied at the same time because an electric field having a planar direction component is formed and the height in the thickness direction is different between the surface of the pixel electrode and the surface of the common electrode.
- the FFS mode liquid crystal display element uses a fringe electric field, and is particularly limited as long as the shortest distance d between the adjacent common electrode and the pixel electrode is shorter than the shortest distance G between the alignment layers.
- the plurality of teeth of the comb-shaped pixel electrode and the plurality of teeth of the comb-shaped common electrode are provided on the substrate in a state of being separated and engaged with each other. Also good.
- a fringe electric field can be used if the distance between the teeth of the common electrode and the teeth of the pixel electrode is shorter than the shortest distance G between the alignment layers.
- the alignment film obtained by the method for manufacturing a liquid crystal alignment film according to the present invention is used in an FFS mode liquid crystal display element, a high anchoring effect can be exhibited, and thus an effect of reducing burn-in can be achieved. it can.
- the color filter 6 is preferably formed on the same substrate side as the first substrate on which the electrode layer 3 including a thin film transistor is formed.
- This form is generally called a color filter on array (COA) or the like.
- COA color filter on array
- FIG. 8 is another form of a cross-sectional view of the liquid crystal display element taken along the line III-III in FIG.
- the configuration of the liquid crystal composition is that the alignment layer 4, the thin film transistor 20 (11, 13, 15, 16, 17), the color filter 6 and the pixel electrode 21 are formed on the first substrate 2, the alignment layer 4, A second substrate 7 having a common electrode 22 formed on the surface thereof is spaced apart from the alignment layers, and the liquid crystal layer 5 containing a liquid crystal composition is filled in the space. Further, a thin film transistor 20 and a gate insulating film 12 are formed on a part of the surface of the first substrate 2, and a buffer layer 30 that is also a flat film is formed so as to cover the thin film transistor 20, The color filter 6, the pixel electrode 21, and the alignment layer 4 are stacked on the insulating layer 30 in this order. Therefore, unlike FIG. 5 and the like, the color filter 6 does not exist on the second substrate 7.
- the liquid crystal display element has a rectangular display region R1 located in the center and a frame-like non-display region R2 located along the periphery of the display region.
- a blue color filter is formed in the display region R1. More specifically, the periphery of the color filter is disposed so as to overlap the signal line (data wiring, gate wiring, etc.).
- a plurality of pixel electrodes 21 formed of a transparent conductive film such as ITO (indium tin oxide) are provided on the color filter.
- Each pixel electrode 21 is connected to a corresponding thin film transistor through an insulating film 18 and a through hole (not shown) formed in each colored layer. More specifically, the pixel electrode 21 is connected to the thin film transistor via the contact electrode described above.
- a plurality of columnar spacers (not shown) may be provided on the pixel electrode 21.
- An alignment film 4 is formed on the color filter and the pixel electrode 21.
- FIG. 9 is a view showing a color filter-on-array having a different form from that in FIG. 8, and is an enlarged view showing the portions of the thin film transistor 20 and the substrate 2 in FIG.
- the color filter is present on the liquid crystal layer side of the thin film transistor.
- the thin film transistor is present on the liquid crystal layer side of the color filter. Are joined via a buffer layer.
- the reaction solution was filtered, and the reaction solution was washed with 200 ml of 10% hydrochloric acid, then washed with 200 ml of saturated brine three times, and dried over anhydrous magnesium sulfate.
- the solvent was distilled off to some extent, 70 g of silica gel was added thereto to form a slurry, packed in a 100 g alumina / 200 g silica gel column, and eluted with dichloromethane.
- the solvent was distilled off, and recrystallization was performed with a mixed solvent of ethyl acetate / heptane to obtain 31.8 g of the target compound of formula 5 as a white solid. Purity 99% (HPLC). M + 566.
- reaction solution was filtered, and the reaction solution was washed with 100 ml of 10% hydrochloric acid, then washed with 100 ml of saturated brine three times, and dried over anhydrous magnesium sulfate.
- Purification was performed using a 30 g alumina / 300 g silica gel column and an ethyl acetate / dichloromethane mixed solvent. The solid from which the solvent had been distilled off was recrystallized using methanol to obtain 16.4 g of the compound of formula I-1-1 as a white solid. Purity 99.5% (HPLC). M + 563.
- the washed organic layer was concentrated under reduced pressure to obtain 50 g of a colorless liquid compound (a-1-1).
- a reaction vessel 23 g of p-hydroxybenzaldehyde, 46 g of potassium carbonate, and 46 g of compound (a-1-1) were suspended in 300 mL of DMF and stirred at 90 ° C. for 6 hours to complete the reaction.
- 650 mL of water was added dropwise to the reaction solution to precipitate a solid.
- the solid was collected by filtration to obtain 72 g of a compound (a-1-2) as a brown granular solid.
- the weight average molecular weight was measured by GPC (gel permeation chromatography) under the following measurement conditions.
- Tosoh GPC equipment HLC-8220GPC is used as the measurement device, TSKgel GMHXL x 2, TSKgel G2000XL x 1, TSKgel G1000XL x 1 in series for the analytical column, and differential refractive index for the detector
- polystyrene standard sample STANDARD SM-105 molecular weight range 1,300 to 3,800,000 manufactured by Showa Denko was used.
- the obtained polymer was dissolved in THF so as to have a concentration of 1 ⁇ g / mL, and the mobile phase was measured with THF, the liquid feed rate was 1 mL / min, the column temperature was 40 ° C., and the sample injection amount was 300 ⁇ L.
- Example 2 The polymer photo-alignment material PI-1-1 synthesized above was dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and then 2-butoxyethanol was added, and the weight ratio was NMP: 2-butoxyethanol: high.
- Molecular photo alignment material 1 adjusted to be 47.5: 47.5: 5, and filtered using MS PTFE syringe filter (5 um, 1 um, 0.45 um) manufactured by menbrane solutions. Obtained.
- the solution was E. coli. H.
- the substrate SZ-B107MIN up / low) manufactured by C Co., Ltd. was spin-coated using a spin coater IH-DX2 manufactured by Mikasa Co., Ltd.
- Example 3 The polymer photo-alignment material PI-1-1 synthesized above was dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and then 2-butoxyethanol was added, and the weight ratio was NMP: 2-butoxyethanol: high.
- NMP N-methyl-2-pyrrolidone
- Molecular photo alignment material 1 adjusted to be 47.5: 47.5: 5, and filtered using MS PTFE syringe filter (5 um, 1 um, 0.45 um) manufactured by menbrane solutions. Obtained.
- the solution was E. coli. H.
- the substrate SZ-B107MIN (up / low) manufactured by C Co., Ltd. was spin-coated using a spin coater IH-DX2 manufactured by Mikasa Co., Ltd. to a thickness of about 90 nm, and then hot manufactured by AS ONE Co., Ltd.
- the plate was dried on a plate digital hot plate NINOS ND1 at 80 ° C. for 3 minutes, and further dried at 180 ° C. for 5 minutes in an air atmosphere using an oven-made DO-600FA manufactured by AS ONE. After drying, it was gradually cooled to room temperature. Next, after the drying step, 313 nm linearly polarized light was irradiated for 5 seconds at 100 mJ / cm 2 with the temperature of the film dried using the irradiation apparatus shown in FIG. A membrane was prepared.
- Example 4 The polymer photo-alignment material PI-1-1 synthesized above was dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and then 2-butoxyethanol was added, and the weight ratio was NMP: 2-butoxyethanol: high.
- NMP N-methyl-2-pyrrolidone
- Molecular photo alignment material 1 adjusted to be 47.5: 47.5: 5, and filtered using MS PTFE syringe filter (5 um, 1 um, 0.45 um) manufactured by menbrane solutions. Obtained.
- the solution was E. coli. H.
- the substrate SZ-B107MIN (up / low) manufactured by C Co., Ltd. was spin-coated using a spin coater IH-DX2 manufactured by Mikasa Co., Ltd. to a thickness of about 90 nm, and then hot manufactured by AS ONE Co., Ltd.
- the plate was dried on a plate digital hot plate NINOS ND1 at 80 ° C. for 3 minutes, and further dried at 180 ° C. for 5 minutes in an air atmosphere using an oven-made DO-600FA manufactured by AS ONE. After drying, it was gradually cooled to room temperature. Next, after the drying step, 313 nm linearly polarized light was irradiated for 5 seconds at 100 mJ / cm 2 with the temperature of the film dried using the irradiation apparatus shown in FIG. A membrane was prepared.
- Example 5 The polymer photo-alignment material PI-1-1 synthesized above was dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and then 2-butoxyethanol was added, and the weight ratio was NMP: 2-butoxyethanol: high.
- NMP N-methyl-2-pyrrolidone
- Molecular photo alignment material 1 adjusted to be 47.5: 47.5: 5, and filtered using MS PTFE syringe filter (5 um, 1 um, 0.45 um) manufactured by menbrane solutions. Obtained.
- the solution was E. coli. H.
- the substrate SZ-B107MIN (up / low) manufactured by C Co., Ltd. was spin-coated using a spin coater IH-DX2 manufactured by Mikasa Co., Ltd. to a thickness of about 90 nm, and then hot manufactured by AS ONE Co., Ltd.
- the plate was dried on a plate digital hot plate NINOS ND1 at 80 ° C. for 3 minutes, and further dried at 180 ° C. for 5 minutes in an air atmosphere using an oven-made DO-600FA manufactured by AS ONE. After drying, it was gradually cooled to room temperature. Next, after the drying step, 313 nm linearly polarized light was irradiated for 5 seconds at 100 mJ / cm 2 with the temperature of the film dried using the irradiation apparatus shown in FIG. A membrane was prepared.
- Example 6 to 13 The polymer photo-alignment material PI-1-2 synthesized above was dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and then 2-butoxyethanol was added, and the weight ratio was NMP: 2-butoxyethanol: high.
- NMP N-methyl-2-pyrrolidone
- Molecular photo-alignment material 1 67.5: 47.5: 6, and six photo-alignment films by filtering using MS PTFE syringe filter (5 um, 1 um, 0.45 um) manufactured by menbrane solutions A solution was obtained.
- Each of the six solutions was E. coli. H.
- the substrate SZ-B107MIN (up / low) manufactured by C Co., Ltd. was spin-coated using a spin coater IH-DX2 manufactured by Mikasa Co., Ltd. to a thickness of about 90 nm, and then hot manufactured by AS ONE Co., Ltd.
- the plate was dried at 80 ° C. for 3 minutes on a plate digital hot plate NINOS ND1, and further dried at 180 ° C. for 5 minutes in an air atmosphere using an oven-made oven DO-600FA. After drying, it was gradually cooled to room temperature. Next, after the drying step, the temperature of the film dried using the irradiation apparatus shown in FIG.
- the azimuth anchoring energy of the photo-alignment film was measured by a method called the torque balance method (the method reported on pages 251 to 252 of the Proceedings of the Annual Meeting of the Japanese Liquid Crystal Society (2001)). .
- the liquid crystal composition (A) prepared in Reference Example 7 was poured into a liquid crystal cell, heated at 92 ° C. for 2 minutes, and then cooled to room temperature.
- a polarizer and an analyzer of an optical measuring device OMS-DI4RD, manufactured by Chuo Seiki Co., Ltd.
- Place this liquid crystal cell rotate the polarizer and analyzer, detect the amount of transmitted light with a detector, find the rotation angle of the polarizer and analyzer, the detected light amount is the smallest, this angle It was used as a twist angle ⁇ 1.
- liquid crystal composition (A) was taken out from the liquid crystal cell, and the liquid crystal composition (B) was injected instead, heated at 2 ° C. for 2 minutes, and then cooled to room temperature.
- this liquid crystal cell seeking rotation angle of the polarizer and the analyzer in the same manner as described above, it was the angle and the twist angle phi 2.
- the azimuth anchoring energy A was determined by equation (1).
- K 22 is the twist elastic modulus of the liquid crystal
- d is the cell gap
- p is the helical pitch of the chiral liquid crystal.
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Abstract
Description
本発明の工程(I)は、溶媒および光応答性高分子を混合して光応答性高分子溶液を調製する。
Spはスペーサー基であり、単結合、-(CH2)u-(式中、uは1~20を表す。)、-OCH2-、-CH2O-、―COO-、-OCO-、-CH=CH-、-CF=CF-、-CF2O-、-OCF2-、-CF2CF2-および-C≡C-からなる群から選択される少なくとも1種の二価の連結基であり、これらの置換基において非隣接のCH2基の一つ以上は独立して、-O-、-CO-、-CO-O-、-O-CO-、-Si(CH3)2-O-Si(CH3)2―、-NR-、-NR-CO-、-CO-NR-、-NR-CO-O-、-O-CO-NR-、-NR-CO-NR-、-CH=CH-、-C≡C-又は-O-CO-O-(式中、Rは独立して水素又は炭素原子数1から5のアルキル基を表す。)で置換することができ、
Qは、直接結合、-O-、-CO-O-又は-O-CO-を表し、
Aは、トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は互いに隣接していない2個以上のメチレン基は-O-、-NH-又は-S-に置き換えられてもよい)、1,4-フェニレン基(この基中に存在する1個以上の-CH=は-N=に置き換えられてもよい)、1,4-シクロヘキセニレン基、2,5-チオフェニレン基、2,5-フラニレン基、1,4-ビシクロ[2.2.2]オクチレン基、ナフタレン-1,4-ジイル基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基及び1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基からなる群より選ばれる官能基を含む構造を表し、官能基はそれぞれ無置換であるか又は1個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていてもよく、
sは、0~4の整数を表し、sが2~4を表す場合は、複数存在するAおよび/またはQは同一であっても異なっていてもよく、
X及びYは、それぞれ独立して水素原子、フッ素原子、塩素原子、シアノ基又は炭素原子数1~20のアルキル基を表し、アルキル基中に存在する水素原子はフッ素原子に置換されていてもよく、アルキル基中に1個のメチレン基又は互いに隣接しない2個以上のメチレン基が存在する場合は、1個のメチレン基又は互いに隣接しない2個以上のメチレン基は、-O-、-CO-O-、-O-CO-又は-CH=CH-で置き換えられていてもよく、
Mは、下記一般式(IIa)、下記一般式(IIb)又は下記一般式(IIc)
R11及びR12は、それぞれ独立に水素原子又は炭素原子数1~30のアルキル基を表し、前記R11及びR12中に、1個のメチレン基又は互いに隣接しない2個以上のメチレン基が存在する場合、1個のメチレン基又は互いに隣接しない2個以上のメチレン基は、-O-、-CO-、-CO-O-、-O-CO-、-CO-NH-、-NH-CO-、-NCH3-、-CH=CH-、-CF=CF-又は-C≡C-で置き換えられていてもよく、R11及びR12中に存在する水素原子は、炭素原子数1~20のアルキル基、シアノ基若しくはハロゲン原子で置換されていてもよく、
環C1、環C2及び環C3はそれぞれ互いに独立して、
(a) トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は-O-、-NH-又は-S-に置き換えられてもよい)、
(b) 1,4-フェニレン基(この基中に存在する1個又は2個以上の-CH=は-N=に置き換えられてもよい)、及び
(c) 1,4-シクロヘキセニレン基、2,5-チオフェニレン基、2,5-フラニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ナフタレン-1,4-ジイル基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基及び1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基
からなる群より選ばれる基を表し、上記の基(a)、基(b)及び基(c)はそれぞれ無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基、メトキシ基又はエトキシ基によって置換されていてもよく、
Z1a及びZ1bはそれぞれ互いに独立して、単結合、-(CH2)v-、-O-、-CO-、-CO-O-、-O-OC-、-NR7-、-CO-NR7-、-NR7-CO-、-(CH2)u-O-、-O-(CH2)u-、-(CH2)u-NR7-又は-NR7-(CH2)u-であり、その際にR7は水素原子又は低級アルキル基を意味し;vは1~4の整数を意味し;uは1~3の整数であり、
i及びjはそれぞれ互いに独立して、0又は1である。)を表す。
さらに、前記光応答性二量化型高分子は、下記の一般式(1):
A1、A2はそれぞれ独立して、
(a) トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は-O-、-NH-又は-S-に置き換えられてもよい)、
(b) 1,4-フェニレン基(この基中に存在する1個又は2個以上の-CH=は-N=に置き換えられてもよい)、及び
(c) 1,4-シクロヘキセニレン基、2,5-チオフェニレン基、2,5-フラニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ナフタレン-1,4-ジイル基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基及び1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基
からなる群より選ばれる基を表し、上記の基(a)、基(b)又は基(c)はそれぞれ無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良く、
Z1、Z2およびZ3は、それぞれ独立して、単結合、-(CH2)u-(式中、uは1~20を表す。)、-OCH2-、-CH2O-、―COO-、-OCO-、-CH=CH-、-CF=CF-、-CF2O-、-OCF2-、-CF2CF2-又は-C≡C-を表すが、これらの置換基において非隣接のCH2基の一つ以上は独立して、-O-、-CO-、-CO-O-、-O-CO-、-Si(CH3)2-O-Si(CH3)2―、-NR-、-NR-CO-、-CO-NR-、-NR-CO-O-、-O-CO-NR-、-NR-CO-NR-、-CH=CH-、-C≡C-又は-O-CO-O-(式中、Rは独立して水素又は炭素原子数1から5のアルキル基を表す。)で置換することができ、
Xは、-O-、-NR-またはフェニレン基であり、
Rbは、重合性基、アルコキシ基、シアノ基または炭素原子数1~12個のフッ化アルキル基であり、
mは、0、1、または2であり、
Mb及びMdはそれぞれ独立して同一であっても異なっていても良く、以下の一般式(U-1)~(U-13)のいずれか1種のモノマー単位を表し、
上記一般式(U-11)~(U-13)中、破線はSpへの結合を表し、R1は4価の環構造、R2は3価の有機基、R3は水素原子、水酸基、炭素原子数1~15個のアルキル基、炭素原子数1~15個のアルコキシ基を表す。)
y及びwは、コポリマーのモル分率を表し、0<y≦1かつ、0≦w<1であり、nは4~100,000を表し、Mb及びMdのモノマー単位は各々独立して1種類でも2種類以上の異なる単位からなっていても良い。)で表される高分子、その加水分解物または加水分解物の縮合物であることがより好ましい。
Z4、Z5、Z6及びZ7は、それぞれ独立して単結合、-(CH2)u-(式中、uは1~20を表す。)、-OCH2-、-CH2O-、―COO-、-OCO-、-CH=CH-、-CF=CF-、-CF2O-、-OCF2-、-CF2CF2-又は-C≡C-を表すが、これらの置換基において非隣接のCH2基の一つ以上は独立して、-O-、-CO-、-CO-O-、-O-CO-、-Si(CH3)2-O-Si(CH3)2―、-NR-、-NR-CO-、-CO-NR-、-NR-CO-O-、-O-CO-NR-、-NR-CO-NR-、-CH=CH-、-C≡C-又は-O-CO-O-(式中、Rは独立して水素又は炭素原子数1から5のアルキル基を表す。)で置換することができ、
A3、A4、A5及びA6は、それぞれ独立して
(a)トランス-1,4-シクロへキシレン基(この基中に存在する1個のメチレン基又は隣接していない2個以上のメチレン基は-O-、-NH-又は-S-に置き換えられてもよい)、
(b)1,4-フェニレン基(この基中に存在する1個又は2個以上の-CH=は-N=に置き換えられてもよい)、及び
(c)1,4-シクロヘキセニレン基、2,5-チオフェニレン基、2,5-フラニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ナフタレン-1,4-ジイル基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基及び1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基
からなる群より選ばれる基を表し、上記の基(a)、基(b)又は基(c)はそれぞれ無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良く、
r1、s1、t1及びu1は、それぞれ独立して0又は1を表し、
R12は水素、フッ素、塩素、シアノ基又は炭素数1~20のアルキル基を表し、前記アルキル基中の水素原子はフッ素原子に置換されていてもよく、1つのCH2基若しくは2以上の非隣接CH2基は-O-、-CO-O-、-O-CO-及び/又は-CH=CH-で置換されていても良い。)で表される
また、上記本発明に係る一般式(1)で表される光応答性二量化型高分子の好ましい形態として、Z2が単結合である高分子が好ましい。
Wは、水素原子、フッ素原子、メチル基、メトキシ基、エチル基又はエトキシ基を表し、Wは、下記一般式(W-1)~(W-8)からなる群から選択される少なくとも1種を表し、
「工程(II)」
本発明の工程(II)は、前記光応答性高分子溶液を基板上に塗布した後、1~3分間50~100℃で乾燥し、更に120℃~180℃で5~75分間乾燥し塗膜を形成する。
本発明に係る塗膜の平均厚みの測定方法は、光配向膜を塗布及び光照射後に行う接触式膜厚測定計を用いた段差測定である。また、本発明に係る製造方法により得られた液晶配向膜の平均膜厚の測定方法も同様である。
「工程(III)」
本発明の工程(III)は、200~350nmの光を照射した時の前記塗膜の温度を40℃~100℃に調整する。
本発明の第三は、本発明に係る液晶配向膜を備えた、液晶表示素子である。
(合成例1)
(実施例1)
上記で合成した高分子光配向材料P-I-1-1をN-メチル-2-ピロリドン(以下NMP)に溶解した後に2-ブトキシエタノールを加え、重量比としてNMP:2-ブトキシエタノール:高分子光配向材料1=47.5:47.5 :5 となるよう調整し、menbrane solutions 社製のMS PTFE syringe filter(5um, 1um, 0.45um)を用いてろ過して光配向膜溶液を得た。
該溶液をE.H.C(株)社製の基板SZ-B107MIN(up/low)に約90nmの厚さになるようミカサ(株)製スピンコーターIH-DX2を用いてスピンコートし、その後AS ONE(株)製ホットプレートdigital hot plate NINOS ND1上で80℃で3分間乾燥し、さらにAS ONE社製オーブンDO-600FAを用いて空気雰囲気下で180℃で5分間乾燥した。乾燥後室温まで徐冷した。次いで、前記乾燥工程の後、図10に示した照射装置を用いて乾燥した膜の温度を25℃に維持した状態で313nmの直線偏光を5秒間100mJ/cm2照射して本発明の光配向膜を調製した。
上記で合成した高分子光配向材料P-I-1-1をN-メチル-2-ピロリドン(以下NMP)に溶解した後に2-ブトキシエタノールを加え、重量比としてNMP:2-ブトキシエタノール:高分子光配向材料1=47.5:47.5 :5 となるよう調整し、menbrane solutions 社製のMS PTFE syringe filter(5um, 1um, 0.45um)を用いてろ過して光配向膜溶液を得た。
該溶液をE.H.C(株)社製の基板SZ-B107MIN(up/low)に約90nmの厚さになるようミカサ(株)製スピンコーターIH-DX2を用いてスピンコートし、その後AS ONE(株)製ホットプレートdigital hot plate NINOS ND1上で80℃で3分間乾燥し、さらにAS ONE社製オーブンDO-600FAを用いて空気雰囲気下で180℃で5分間乾燥した。乾燥後室温まで徐冷した。次いで、前記乾燥工程の後、図10に示した照射装置を用いて乾燥した膜の温度を50℃に維持した状態で313nmの直線偏光を5秒間100mJ/cm2照射して本発明の光配向膜を調製した。
上記で合成した高分子光配向材料P-I-1-1をN-メチル-2-ピロリドン(以下NMP)に溶解した後に2-ブトキシエタノールを加え、重量比としてNMP:2-ブトキシエタノール:高分子光配向材料1=47.5:47.5 :5 となるよう調整し、menbrane solutions 社製のMS PTFE syringe filter(5um, 1um, 0.45um)を用いてろ過して光配向膜溶液を得た。
上記で合成した高分子光配向材料P-I-1-1をN-メチル-2-ピロリドン(以下NMP)に溶解した後に2-ブトキシエタノールを加え、重量比としてNMP:2-ブトキシエタノール:高分子光配向材料1=47.5:47.5 :5 となるよう調整し、menbrane solutions 社製のMS PTFE syringe filter(5um, 1um, 0.45um)を用いてろ過して光配向膜溶液を得た。
上記で合成した高分子光配向材料P-I-1-1をN-メチル-2-ピロリドン(以下NMP)に溶解した後に2-ブトキシエタノールを加え、重量比としてNMP:2-ブトキシエタノール:高分子光配向材料1=47.5:47.5 :5 となるよう調整し、menbrane solutions 社製のMS PTFE syringe filter(5um, 1um, 0.45um)を用いてろ過して光配向膜溶液を得た。
上記で合成した高分子光配向材料P-I-1-2をN-メチル-2-ピロリドン(以下NMP)に溶解した後に2-ブトキシエタノールを加え、重量比としてNMP:2-ブトキシエタノール:高分子光配向材料1=47.5:47.5 :5 となるよう調整し、menbrane solutions 社製のMS PTFE syringe filter(5um, 1um, 0.45um)を用いてろ過して6つの光配向膜溶液を得た。
実施例1~13にて作成した基板を用い、DIC(株)製の液晶PA0500を挟持した液晶セルを組み立てた。当該液晶セルのアンカリングエネルギーを測定したところ偏光照射時の温度によりアンカリングエネルギーが変化することが確認された(図11参照)。
得られた方位角アンカリングエネルギーは、図11に示す通りであった。
112 紫外線ランプ
113 無偏光紫外線(全波長)
114 干渉フィルター
115 無偏光紫外線(313nm)
116 偏光フィルター
117 偏光紫外線(313nm)
118 光配向膜
119 ガラス基板
1110 加熱プレート
100 第1基板
102 TFT層
103 画素電極
104 パッシベーション膜
105 第1配向膜
200 第2基板
201 平坦化膜(オーバーコート層)
202 ブラックマトリックス
203 カラーフィルタ
204 透明電極
205 第2配向膜
301 シール材
302 突起(柱状スペーサー)
303 液晶層
304 突起(柱状スペーサー)
401 マスクパターン
402 レジン層
L 光
1,8 偏光板
2 第一の基板
3 電極層
4 配向膜
5 液晶層
6 カラーフィルタ
6G カラーフィルタ緑
6R カラーフィルタ赤
7 第二の基板
11 ゲート電極
12 ゲート絶縁膜
13 半導体層
14 絶縁層
15 オーミック接触層
16 ドレイン電極
17 ソース電極
18 絶縁保護層
21 画素電極
22 共通電極
23 ストレイジキャパシタ
25 データ配線
27 ソース配線
29 共通ライン
30 バッファー層
Claims (9)
- 溶媒および光応答性高分子を混合して光応答性高分子溶液を調製する工程(I)と、
前記光応答性高分子溶液を基板上に塗布した後、1~3分間50~100℃で乾燥し、更に120℃~180℃で5~75分間乾燥し塗膜を形成する工程(II)と、
200~350nmの光を前記塗膜に照射した時の前記塗膜の温度を40℃~100℃に調整する工程(III)と、
を含むことを特徴とする液晶配向膜の製造方法。 - 溶媒および光に応答して側鎖同士の二量化により架橋構造を形成する光応答性二量化型高分子を混合して光応答性二量化型高分子溶液を調製する工程(I)と、
前記光応答性二量化型高分子溶液を基板上に塗布した後、1~3分間50~100℃で乾燥し、更に120℃~180℃で5~75分間乾燥し塗膜を形成する工程(II)と、
200~350nmの光を前記塗膜に照射した時の前記塗膜の温度を40℃~100℃に調整する工程(III)と、
を含むことを特徴とする、請求項1に記載の液晶配向膜の製造方法。 - 前記200~350nmの光は、前記基板に対して略垂直方向から照射し、照射量は10~100mJ/cm2の直線光である、請求項1または2に記載の液晶配向膜の製造方法。
- 液晶分子を基板に対して略水平方向に配向させる、請求項1~3に記載の液晶配向膜の製造方法。
- 前記工程(II)で得られた塗膜の平均厚みは、10~100nmである、請求項1~4のいずれか1項に記載の液晶配向膜の製造方法。
- 前記光は、250~330nmの波長の偏光である、請求項1~5のいずれか1項に記載の液晶配向膜の製造方法。
- 溶媒および光応答性高分子を混合して光応答性型高分子溶液を調製する工程(1)と、
第1の基板および第2の基板の表面に前記光応答性高分子溶液の被膜を形成した後、1~3分間50~100℃で乾燥し、更に120℃~180℃で5~75分間乾燥して前記被膜を乾燥する工程(2)と、
乾燥された前記被膜の温度を50℃~100℃に維持した状態で200~350nmの光を照射して前記第1の基板および第2の基板表面に液晶配向膜を形成する工程(3)と、
前記液晶配向膜が形成された一対の基板を前記液晶配向膜同士が対向して離間するよう貼りあわせて形成される一対の液晶配向膜間に液晶組成物を充填する工程(3)と、を含む液晶組成物の配向方法。 - 前記光応答性高分子は、光に応答して側鎖同士の二量化により架橋構造を形成する光応答性二量化型高分子である、請求項7に記載の配向方法。
- 請求項1~6のいずれか1項に記載の方法により得られた液晶配向膜を備えた、液晶表示素子。
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US15/027,141 US10423033B2 (en) | 2013-10-02 | 2014-09-30 | Method for producing liquid crystal alignment film and liquid crystal display element using same |
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JP6854452B2 (ja) * | 2015-09-29 | 2021-04-07 | パナソニックIpマネジメント株式会社 | ガラスパネルユニット,これを備えたガラス窓、及びガラスパネルユニットの製造方法 |
CN106371254A (zh) * | 2016-10-28 | 2017-02-01 | 上海中航光电子有限公司 | 阵列基板及显示面板 |
TW201910305A (zh) * | 2017-08-09 | 2019-03-16 | 瑞士商羅立克科技股份公司 | 製備光配向聚合物材料和組成物的方法 |
JP2019152835A (ja) * | 2018-03-06 | 2019-09-12 | シャープ株式会社 | 配向膜付き基板の製造方法 |
TWI683159B (zh) * | 2018-11-20 | 2020-01-21 | 友達光電股份有限公司 | 顯示面板 |
CN113552736B (zh) | 2020-04-23 | 2024-01-30 | 中强光电股份有限公司 | 电控视角切换器及显示装置 |
CN112375168B (zh) * | 2020-10-28 | 2022-03-29 | 华南理工大学 | 侧链棒状极性液晶聚合物及其制备方法与在非线性光学领域的应用 |
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