Classifications

• • 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
  • G02F1/133719—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films with coupling agent molecules, e.g. silane
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • 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

Definitions

• the present invention provides a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display capable of forming a liquid crystal alignment film that controls the alignment of liquid crystal by light while suppressing a decrease in photoreactivity and further improves the response speed of liquid crystal It relates to an element.
• 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 by sandwiching and enclosing a liquid crystal layer between a pair of substrates, and orienting liquid crystals in the liquid crystal layer in a predetermined direction between the substrates.
• the liquid crystal responds and changes its orientation when a voltage is applied to electrodes provided on a pair of substrates.
• the liquid crystal display element can display a desired image using a change in the orientation of the liquid crystal due to voltage application.
• This liquid crystal display element has various liquid crystal modes in which the initial alignment state of liquid crystal molecules and the form of alignment change by voltage application are different.
• a TN (Twisted Nematic) mode in which the liquid crystal is twisted by 90 ° between a pair of substrates is known.
• liquid crystal display elements in a vertical alignment (VA) mode in which liquid crystal molecules having negative dielectric anisotropy are aligned vertically to a substrate have been actively developed (for example, see Patent Document 1 and Patent Document 2.)
• VA mode liquid crystal display element by applying a voltage, the vertically aligned liquid crystal changes its alignment so as to be parallel to the substrate while being uniformly inclined in a predetermined direction.
• the VA mode liquid crystal display element can realize a high contrast ratio, a wide viewing angle, and excellent response characteristics.
• This VA mode liquid crystal display element is required to form a state in which the liquid crystal is substantially vertically aligned as an initial alignment state of the liquid crystal when no voltage is applied in order to enable the above-described change in the alignment of the liquid crystal. That is, the VA mode liquid crystal display element is required to form an alignment state in which the liquid crystal is slightly inclined from the normal direction of the substrate toward a predetermined direction in the plane as the initial alignment state of the liquid crystal.
• VA mode liquid crystal display element several methods for realizing the above-described substantially vertical alignment state of the liquid crystal are known.
• MVA Multi-domain Vertical Alignment
• PVA Plasma-domain Vertical Alignment
• a slit structure is provided in an electrode made of ITO (Indium Tin Oxide) or the like of a substrate sandwiching a liquid crystal layer, and the tilt direction of the liquid crystal is controlled by a formed oblique electric field.
• PSA Polymer sustained Alignment
• a photopolymerizable compound is added to the liquid crystal, and an electric field is applied in a state where the liquid crystal layer is sandwiched between the substrates to tilt the liquid crystal.
• the liquid crystal layer is irradiated with light, for example, UV (ultraviolet rays) in a state where the liquid crystal is tilted and aligned.
• the photopolymerizable compound is photopolymerized, a pretilt angle is formed in the liquid crystal layer, the orientation direction of the liquid crystal that is tilted by voltage application is fixed, and the response speed of the liquid crystal is improved.
• the polymerizable compound added to the liquid crystal has low solubility, and when the addition amount is increased, it is precipitated at a low temperature.
• the addition amount of the polymerizable compound is reduced, a good alignment state and response speed cannot be obtained.
• the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity in the liquid crystal, resulting in a problem that the reliability of the liquid crystal display element is lowered.
• a technique has been proposed in which the function of the polymerizable compound described above is introduced into a polymer as a side chain structure, a liquid crystal alignment film is formed from the polymer, and a VA mode liquid crystal display element is manufactured (see Patent Document 4).
• a liquid crystal aligning agent using a polymer having a structure in which a photoreactive side chain is introduced into a polymer molecule is applied to a substrate. Then, a liquid crystal layer is sandwiched between liquid crystal alignment films formed by firing, and a liquid crystal display element is manufactured by irradiating ultraviolet rays while applying a voltage to the liquid crystal layer.
• the liquid crystal display element which uses the liquid crystal aligning film using the polymer which has a photoreactive side chain implement achieves the control of the inclination alignment direction of a liquid crystal, and the improvement of a response speed.
• a liquid crystal aligning agent using a polymer having a photoreactive side chain when the coating film is formed on a substrate and heated, unnecessary components such as a solvent are removed and a crosslinking reaction between polymer components is performed.
• the photoreactive side chain may cause a thermal reaction. That is, the photoreactive side chain of the highly reactive polymer may cause unwanted reactions due to heat.
• the photoreactivity of the side chain is partially lost and lowered before the light irradiation that requires it.
• liquid crystal alignment film with reduced photoreactivity Even if such a liquid crystal alignment film with reduced photoreactivity is used, a liquid crystal layer is sandwiched, and light such as UV is irradiated while applying a voltage to the liquid crystal layer, the liquid crystal display element has a desired liquid crystal tilt. Improvement of orientation control and response speed cannot be realized.
• liquid crystal alignment film used in a VA mode liquid crystal display element, which suppresses the reaction before light irradiation of the side chain contained therein, suppresses the decrease in photoreactivity, and controls the alignment and response speed of liquid crystal by light.
• a liquid crystal alignment film that achieves improvement. That is, there is a demand for a liquid crystal aligning agent that forms a liquid crystal alignment film that suppresses a decrease in photoreactivity before light irradiation.
• An object of the present invention is to provide a liquid crystal aligning agent capable of controlling the alignment of liquid crystal by light while suppressing a decrease in photoreactivity and further forming a liquid crystal alignment film that improves the response speed of the liquid crystal, and the liquid crystal aligning agent.
• An object of the present invention is to provide a liquid crystal alignment film obtained by use and a liquid crystal display element having the liquid crystal alignment film.
• a VA mode liquid crystal display element having a liquid crystal alignment film using a polymer having a structure in which a photoreactive side chain is introduced into a polymer molecule is configured by sandwiching a liquid crystal layer between the pair of liquid crystal alignment films. Then, a voltage is applied to the liquid crystal that is vertically aligned between a pair of liquid crystal alignment films to realize the desired tilted alignment state of the liquid crystal, and then irradiation with light such as UV is performed to polymerize the photoreactive side chain.
• the polymerization reaction of the photoreactive side chain proceeds in a state where a part of the liquid crystal in the vicinity thereof is involved.
• the photopolymerization reaction of the photoreactive side chain fixes the alignment state of a part of the liquid crystal that is tilted. Therefore, a pretilt angle is formed in the liquid crystal layer sandwiched between the liquid crystal alignment films, and as a result, the response speed of the liquid crystal of the liquid crystal display element is significantly improved.
• the liquid crystal alignment film of the liquid crystal display element has a sufficient amount of photoreactive side chains.
• the liquid crystal alignment film is formed by forming a coating film by applying a liquid crystal aligning agent and heating and baking.
• the photoreactive side chain also causes a polymerization reaction by heat. Therefore, after heating and baking of the above-mentioned coating film, a sufficient amount of side chains having photoreactivity do not remain in the liquid crystal alignment film at the stage of controlling the alignment of the liquid crystal by light irradiation.
• baking may be performed at a high temperature and / or for a long time.
• the present inventors paid attention to introducing a polymerization inhibition function into the liquid crystal alignment film. That is, the liquid crystal aligning agent containing the component which shows a polymerization prohibition function with respect to the photoreactive side chain of a polymer is used for formation of a liquid crystal aligning film, and suppresses the thermal reaction of the polymer side chain before light irradiation. For example, when the side chain undergoes radical polymerization by heating and baking, a polymerization inhibiting component that captures radicals generated during the heating and baking and inactivates radical polymerization is used for forming the liquid crystal alignment film.
• the liquid crystal alignment film enables the control of the desired liquid crystal alignment by light irradiation, and as a result, the response speed of the liquid crystal can be improved. I found it.
• R 1 Si (OR 2 ) 3 (1) R 1 is a group represented by the following formula (2), and R 2 is an alkyl group having 1 to 5 carbon atoms.
• Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
• Y 2 is a straight or branched hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond, or — (CR 17 R 18 ) b — (b is an integer of 1 to 15 , R 17 and R 18 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
• Y 4 is a divalent cyclic group selected from a single bond, a benzene ring, a cyclohexyl ring, and a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton, on the cyclic group
• Arbitrary hydrogen atoms are substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom May be.
• Y 5 is at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms.
• n1 is an integer of 0-4.
• Y 6 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
• R 21 , R 22 and R 23 are each independently —OCH 3 , —OC 2 H 5 , —OCH (CH 3 ) 2 , —OC (CH 3 ) 3 , —CH 3 , —Ph (phenyl group) ), —Cl, —OCOCH 3 , —OH, or R 24 is a hydrogen atom or a methyl group.
• Y 21 is a straight or branched hydrocarbon group having 1 to 8 carbon atoms which may contain a single bond or a double bond.
• Y 22 represents a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —N (CH 3 ) —, —NPh—, —NHCO—, —N (CH 3 ) CO—.
• the bonding group is selected from —NHCOO— and —OCONH—.
• Y 23 and Y 24 are each independently a single bond or a linear or branched hydrocarbon group having 1 to 8 carbon atoms.
• Y 25 represents a single bond, —O—, or —NZ 2 —, and Z 2 represents a hydrogen atom, a linear or branched hydrocarbon group having 1 to 18 carbon atoms, an aromatic ring group, or an aliphatic group. It is a cyclic group. Cy is an alkyl group or a divalent cyclic group selected from the following and bonded at an arbitrary substitution position.
• An arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, a carbon number It may be substituted with 1 to 3 alkoxy groups, cyano groups, fluorine atoms, or chlorine atoms.
• Z 1 is a linear or branched divalent hydrocarbon group having 1 to 18 carbon atoms which may contain an aromatic ring group or an aliphatic ring group.
• the raw material alkoxysilane further contains an alkoxysilane represented by the following formula (5) having a group having a polymerization inhibiting function, and a polymerization inhibiting component
• R a Si (OR b ) 3 (5) R a is a group having a polymerization inhibiting function, and R b is an alkyl group having 1 to 5 carbon atoms.
• the hindered phenol which the polymerization prohibition component (B) contained as a substance different from the polysiloxane component (A) is phenol, catechol, benzoquinone, hydroquinone, or an ester, etherified product or alkylated thereof.
• Liquid crystal aligning agent as described in said (1) which is phenothiazine, hindered amine, hydroxyamine, or nitrosamine.
• (6) The liquid crystal alignment according to any one of (1) to (5), wherein the polymerization-inhibiting component (B) is contained in an amount of 0.01 to 20 mol% with respect to the polysiloxane component (A). Agent.
• the raw material alkoxysilane contains 2 to 30 mol% of the alkoxysilane represented by the formula (1) and 5 to 70 mol% of the alkoxysilane represented by the formula (3).
• the liquid crystal aligning agent according to any one of the above (1) to (6).
• liquid crystal aligning agent according to any one of (1) to (7) above, which contains a polysiloxane (C) formed from an alkoxysilane represented by the following formula (6).
• Si (OR 15 ) 4 (6) R 15 is an alkyl group having 1 to 5 carbon atoms.
• At least one of the polysiloxane component (A) and the polysiloxane (C) is a polysiloxane obtained by reacting an alkoxysilane further containing an alkoxysilane represented by the following formula (7) ( The liquid crystal aligning agent according to any one of 1) to (8).
• (R 13 ) n2 Si (OR 14 ) 4-n (7) R 13 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in which the hydrogen atom may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, or a ureido group. It is.
• R 14 is an alkyl group having 1 to 5 carbon atoms, and n2 represents an integer of 0 to 3.
• a liquid crystal display element comprising the liquid crystal alignment film according to (11).
• the liquid crystal alignment film includes a pair of liquid crystal alignment films according to (11) and a liquid crystal layer sandwiched between the liquid crystal alignment films, and the liquid crystal alignment film emits light in a state where a voltage is applied to the liquid crystal layer.
• the liquid crystal aligning agent of the present invention By using the liquid crystal aligning agent of the present invention, it is possible to form a liquid crystal alignment film that suppresses the decrease in photoreactivity, controls the alignment of the liquid crystal by light, and further improves the response speed of the liquid crystal.
• a VA mode liquid crystal display element is provided. That is, in the liquid crystal display element having the liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention, the thermal reaction of the photoreactive side chain of the liquid crystal alignment film is suppressed, and the liquid crystal alignment control and response speed by light are suppressed. Will improve. In addition, the firing margin (Margin) of the liquid crystal alignment film in the manufacturing process of the liquid crystal display element can be increased.
• the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention provides a VA mode liquid crystal display element having excellent response characteristics.
• the polysiloxane component (A) contained in the liquid crystal aligning agent of the present invention is inexpensive compared with the polyimide-based material that has been conventionally used in the liquid crystal aligning film, the liquid crystal aligning agent of the present invention is It can be manufactured at a lower cost than conventional ones and is highly versatile.
• the liquid crystal aligning agent of the present invention comprises a polysiloxane component (A) formed from a raw material alkoxysilane containing an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the following formula (3), and polymerization: Contains prohibited component (B).
• polysiloxane component (A) contains an alkoxysilane represented by the following formula (1) and an alkoxysilane represented by the following formula (3). It is a polysiloxane formed from raw material alkoxysilane.
• R 1 Si (OR 2 ) 3 (1) (R 1 represents the structure of the following formula (2), and R 2 represents an alkyl group having 1 to 5 carbon atoms.)
• Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
• a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO— can be selected. It is preferable from the viewpoint of facilitating the synthesis of the chain structure. It is more preferable to select any one of a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O—, or —COO—.
• Y 2 is a straight or branched hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond, or — (CR 17 R 18 ) b — (b is an integer of 1 to 15 , R 17 and R 18 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• — (CH 2 ) b — (b is an integer of 1 to 10) is preferable from the viewpoint of significantly improving the response speed of the liquid crystal display element.
• Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
• a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO— is selected. This is preferable from the viewpoint of facilitating the synthesis of the side chain structure.
• a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO— or —OCO— is selected. Is more preferable.
• Y 4 is a single bond or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 to 3 carbon atoms. Or an alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Furthermore, Y 4 may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. Among these, an organic group having 12 to 25 carbon atoms having any one of a benzene ring, a cyclohexane ring, and a steroid skeleton is preferable.
• Y 5 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with any one of an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
• n1 is an integer of 0 to 4, preferably an integer of 0 to 2.
• Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
• an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.
• R 2 in the above formula (1) is an alkyl group having 1 to 5, preferably 1 to 3 carbon atoms. More preferably, R 2 is a methyl group or an ethyl group.
• alkoxysilane represented by the above formula (1) include, but are not limited to, the formulas [1-1] to [1-31]. Also, R 2 in the formula [1-1] - [1-31] has the same meaning as R 2 in the formula (1).
• R 5 is —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—
• R 6 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, or a fluorine-containing alkyl group. Group or fluorine-containing alkoxy group.
• R 7 is a single bond, —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, — (CH 2 ) n O— (n is an integer of 1 to 5), —OCH 2 — or — CH 2 — and R 8 is an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group having 1 to 22 carbon atoms.
• R 9 is —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 — or —O—
• R 10 is a fluorine group , Cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group.
• R 11 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
• R 12 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
• B 4 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom.
• B 3 is a 1,4-cyclohexylene group or a 1,4-phenylene group.
• B 2 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to B 3 ).
• B 1 is bonded to an oxygen atom or —COO— * (where a bond marked with “*” is bonded to (CH 2 ) a 2 ).
• a 1 is an integer of 0 or 1
• a 2 is an integer of 2 to 10
• a 3 is an integer of 0 or 1.
• the alkoxysilane represented by the above formula (1) is the solubility of the resulting polysiloxane (A) in the solvent, the orientation of the liquid crystal when it is used as a liquid crystal alignment film, the pretilt angle characteristics, the voltage holding ratio, the accumulated charge, etc. Depending on the characteristics, one type or two or more types can be used. Further, it can be used in combination with an alkoxysilane containing a long-chain alkyl group having 10 to 18 carbon atoms.
• Such an alkoxysilane represented by the formula (1) can be produced by a known method disclosed in, for example, Japanese Patent Application Laid-Open No. 61-286393.
• the alkoxysilane represented by the formula (1) is preferably 1 mol% or more in order to obtain good liquid crystal alignment in all raw material alkoxysilanes used for obtaining the polysiloxane (A). More preferably, it is 1.5 mol% or more. More preferably, it is 3 mol% or more. Further, in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed, 30 mol% or less is preferable. More preferably, it is 25 mol% or less.
• the liquid crystal alignment film of the liquid crystal aligning agent containing the polysiloxane (A) formed using the alkoxysilane represented by the above formula (3) is tilted and aligned in a desired direction by applying a voltage.
• the side chain having a cyclic group and a (meth) acryloyl group derived from the alkoxysilane of formula (3) undergoes a polymerization reaction upon receiving light irradiation.
• the tilted alignment state of the liquid crystal by voltage application is fixed, and a very small pretilt angle is formed in the liquid crystal layer sandwiched between the liquid crystal alignment films.
• Such a substantially vertical alignment state of the liquid crystal with a pretilt angle can realize a high-speed response of the liquid crystal in the VA mode liquid crystal display element of the present invention.
• R 21 , R 22 and R 23 in the above formula (3) are each independently —OCH 3 , —OC 2 H 5 , —OCH (CH 3 ) 2 , —OC (CH 3 ) 3 , —CH 3 , —Ph (phenyl group, ie, —C 6 H 5 ), —Cl, —OCOCH 3 , —OH, or —H.
• R 21 , R 22 and R 23 are preferably independently —OCH 3 or —OC 2 H 5 .
• R 24 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
• Y 21 in the above formula (3) is a linear or branched hydrocarbon group having 1 to 8 carbon atoms which may contain a single bond or a double bond.
• Y 21 is a single bond or a linear hydrocarbon group having 3 to 5 carbon atoms.
• Y 22 in the above formula (3) represents a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —N (CH 3 ) —, —NPh—, —NHCO—, — N (CH 3) CO -, - NPhCO -, - NHSO 2 -, - N (CH 3) SO 2 -, - NPhSO 2 -, - S -, - SO 2 -, - NHCONH, -N (CH 3)
• the bonding group is selected from CONH—, —NPhCONH—, —NHCOO—, and —OCONH—.
• Y 22 is preferably a single bond.
• Y 23 in the above formula (3) is a single bond or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and preferably Y 23 is a single bond.
• Y 24 is a single bond or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and preferably Y 24 is a single bond or a linear hydrocarbon group having 1 to 3 carbon atoms.
• Y 25 is a single bond, —O—, or —NZ 2 —.
• Z 2 represents a hydrogen atom, a linear or branched hydrocarbon group having 1 to 18 carbon atoms, an aromatic ring group, or an aliphatic ring group.
• Y 25 is a single bond, —O— or —NH—.
• Cy in the above formula (3) represents a divalent cyclic group selected from the following and formed at any substitution position, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms. And may be substituted with an alkoxy group having 1 to 3 carbon atoms, a cyano group, a fluorine atom, or a chlorine atom.
• Cy is a benzene ring or a biphenyl ring.
• a divalent cyclic group formed by bonding at an arbitrary substitution position means that the position of two bonds of the following cyclic group may be arbitrary.
• Z 1 represents a linear or branched divalent hydrocarbon group having 1 to 18 carbon atoms which may contain an aromatic ring group or an aliphatic ring group.
• Two or more types of alkoxysilanes represented by the above formula (1) and the above formula (3) may be contained in the raw material alkoxysilane forming the polysiloxane (A).
• the blending ratio of the alkoxysilane represented by the above formula (1) and the alkoxysilane represented by the above formula (3) when forming the polysiloxane (A) is not particularly limited.
• the alkoxysilane represented by the above formula (1) is preferably 2 to 30 mol%, particularly preferably 3 to 25 mol% in the (total) alkoxysilane used as a raw material for obtaining the polysiloxane (A). is there.
• the alkoxysilane represented by the above formula (3) is preferably 5 to 70 mol%, more preferably 5 to 60 mol% in the raw material alkoxysilane used for obtaining the siloxane (A).
• the polysiloxane (A) is an alkoxysilane other than these.
• Such other alkoxysilanes can be formed from an alkoxysilane represented by the following formula (4), and represented by the following formula (5) for introducing a polymerization inhibiting function described later. And / or alkoxysilanes represented by the following formula (7).
• R 3 in the above formula (4) is an alkyl group in which a hydrogen atom is substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group.
• the number of substituted hydrogen atoms is one or more, preferably one.
• the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
• R 4 in Formula (4) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms.
• alkoxysilane represented by the above formula (4) are given.
• the alkoxysilane represented by the above formula (4) is preferably 5 to 80 mol%, more preferably 10 to 70 mol% in the raw material alkoxysilane used to obtain the polysiloxane (A). Two or more types of alkoxysilanes represented by formula (4) can be used.
• the alkoxysilane represented by the following formula (5) used for obtaining the polysiloxane (A) is an alkoxysilane having a polymerization inhibiting function.
• a polysiloxane (A) having a polymerization inhibiting component as a constituent part can be produced.
• R a in the formula (5) represents a group having a polymerization inhibiting function, that is, a group having a polymerization inhibitor skeleton similar to a known polymerization inhibitor.
• R b represents an alkyl group having 1 to 5 carbon atoms.
• Preferred examples of Ra include hindered phenols and hydroquinone.
• the alkoxysilane represented by the formula (5) is preferably 1 to 20 mol%, more preferably 2 to 15 mol% in the raw material alkoxysilane used for obtaining the polysiloxane (A).
• Preferred examples of the alkoxysilane represented by the formula (5) include the following compounds.
• the alkoxysilane represented by the following formula (7) used for obtaining the polysiloxane (A) is improved in adhesion to the substrate of the liquid crystal alignment film of the present invention and affinity for liquid crystal.
• it is contained in the raw material alkoxysilane. Since the alkoxysilane represented by the formula (7) can impart various properties to the polysiloxane, one or more types can be selected and used.
• the alkoxysilane represented by the following formula (7) is preferably 1 to 20 mol% in the raw material alkoxysilane used for obtaining the polysiloxane (A). (R 13 ) n2 Si (OR 14 ) 4-n (7)
• R 13 in the above formula (7) is a hydrogen atom or an organic group having 1 to 10 carbon atoms.
• R 13 include ring structures such as aliphatic hydrocarbons, aliphatic rings, aromatic rings or heterocyclic rings having 1 to 10 carbon atoms, and these include unsaturated bonds, oxygen atoms, nitrogen It may contain heteroatoms such as atoms and sulfur atoms, and may be linear or branched. The number of carbon atoms is preferably 1-6.
• the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureido group, or the like.
• R 14 in the formula (7) is an alkyl group having 1 to 5, preferably 1 to 3 carbon atoms, and n2 represents an integer of 0 to 3, preferably 0 to 2.
• alkoxysilane represented by the above formula (7) are given below.
• 3- (2-aminoethylaminopropyl) trimethoxysilane 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) Triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysi
• the alkoxysilane in which n2 is 0 is tetraalkoxysilane.
• Tetraalkoxysilane is preferable for obtaining polysiloxane (A) because it easily undergoes a polycondensation reaction with the alkoxysilane represented by the above formula (1), formula (3), formula (4) and formula (5). .
• the alkoxysilane having n2 of 0 is more preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane, and particularly preferably tetramethoxysilane or tetraethoxysilane.
• n2 is 1 to 3
• the alkoxysilane represented by the formula (7) is preferably 1 to 20 mol% in the raw material alkoxysilane used for obtaining the polysiloxane (A). Particularly preferred is 1 to 10 mol%.
• the alkoxysilane represented by the formula (7) in which n2 is 0 is preferably 1 to 50 mol% in the raw material alkoxysilane used for obtaining the polysiloxane (A), and preferably 5 to 40 mol%. More preferred.
• the liquid crystal aligning agent of this invention contains the polymerization prohibition component (B) for suppressing the thermal reaction of the photoreactive side chain of a polysiloxane component (A).
• the polymerization inhibiting component (B) can introduce a polymerization inhibiting function into the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention.
• the polymerization inhibiting component (B) is a compound that retards or inhibits polymerization, and in the present invention, it is a substance that delays or inhibits the thermal reaction of the photoreactive side chain contained in the liquid crystal alignment film. .
• the polymerization inhibiting component (B) can be contained in the liquid crystal aligning agent as a constituent part of the polysiloxane component (A). That is, the polymerization-inhibiting component (B) is used in combination with the alkoxysilane of the above formula (5) for imparting a polymerization-inhibiting function when forming the polysiloxane component (A). To be included.
• the polymerization inhibiting component (B) is a component different from the polysiloxane component (A), that is, a liquid crystal aligning agent as a polymerization inhibitor which is a substance different from the polysiloxane component (A). It can be contained in the inside.
• a polymerization inhibitor has the above-described polymerization inhibition function, the molecular structure thereof is not particularly limited.
• the polymerization inhibitor should be phenol, catechol, benzoquinone, hydroquinone, their esters, etherified products or alkylated compounds Hindered phenols, phenothiazines, hindered amines, hydroxyamines such as TEMPO (2,2,6,6-tetramethylpiperidine-oxyl), and nitrosamines.
• Preferable examples of the polymerization inhibitor include the following compounds.
• the alkoxysilane of the formula (5) having the above-described polymerization inhibition function is used as a monomer in the liquid crystal aligning agent or of the formula (5) containing the alkoxysilane of the formula (5). It can be contained as a polysiloxane obtained from alkoxysilane.
• the alkoxysilane of the formula (5) functions in the same manner as the polymerization inhibitor described above, or other than, for example, polysiloxane (A) by heating and baking after forming the coating film of the liquid crystal aligning agent. It causes a polymerization reaction with the polysiloxane component, and can impart a polymerization inhibition function to the liquid crystal alignment film.
• the content of the polymerization inhibitor in the liquid crystal aligning agent is preferably 0.01 to 20 mol% based on the polysiloxane component (A), including the case where it is derived from the alkoxysilane of the formula (5). 2 to 10 mol% is more preferable.
• the liquid crystal aligning agent of this invention contains the other polysiloxane component (C) (henceforth also called polysiloxane (C)) other than a polysiloxane component (A) and a polymerization inhibition component (B). Also good.
• the polysiloxane (C) include polysiloxane obtained by reacting a raw material alkoxysilane containing an alkoxysilane represented by the following formula (6).
• the polysiloxane that is the raw material of the polysiloxane (C) preferably contains 20 to 100 mol%, more preferably 50 to 100%, of the alkoxysilane represented by the formula (6).
• Si (OR 15 ) 4 (6) However, in the above formula (6), R 15 represents an alkyl group having 1 to 5 carbon atoms.
• alkoxysilane represented by the above formula (6) tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
• the polysiloxane (C) is a polysiloxane obtained by reacting an alkoxysilane containing the alkoxysilane represented by the formula (8) in addition to the alkoxysilane represented by the formula (6). Also good.
• a liquid crystal aligning agent containing a polysiloxane (C) obtained by reacting an alkoxysilane containing an alkoxysilane represented by the formula (8) is preferable because a liquid crystal alignment film having a particularly high vertical alignment force can be formed.
• R 16 in the above formula (8) is an alkyl group having 1 to 5 carbon atoms.
• the alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.
• R 17 in the formula (8) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
• Specific examples of the alkoxysilane represented by the formula (8) include methyltriethoxysilane, methyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane and the like. However, it is not limited to these.
• the polysiloxane (C) is a polysiloxane obtained by reacting an alkoxysilane containing the alkoxysilane represented by the formula (4) in addition to the alkoxysilane represented by the formula (6). There may be.
• the content of the alkoxysilane represented by the formula (4) realizes the vertical alignment state of the liquid crystal desired by the liquid crystal alignment film of the present invention and further improves the response speed of the liquid crystal.
• a suitable amount is preferred. That is, the content of the alkoxysilane represented by the formula (4) is preferably 10 mol% or more, more preferably 20 mol% or more, particularly preferably 30 mol% or more in the raw material alkoxysilane of the polysiloxane (C). It is.
• 75 mol% or less is preferable.
• the polysiloxane (C) is a polysiloxane obtained by reacting an alkoxysilane containing the alkoxysilane represented by the formula (5) in addition to the alkoxysilane represented by the formula (6). Also good. Further, the polysiloxane (C) is further expressed by the above formula (7) unless the effects of the present invention are impaired for the purpose of imparting various properties such as adhesion to the substrate and improvement in affinity with the liquid crystal. Polysiloxane obtained by reacting the alkoxysilane represented may be used.
• the content of the alkoxysilane represented by the formula (7) is preferably 1 to 20 mol%, more preferably 1 to 10 mol% in the raw material alkoxysilane of the polysiloxane (C).
• the alkoxysilanes represented by the above formula (4), formula (5), formula (6), formula (7), and formula (8) are all two types. That's all.
• the blending ratio of the polysiloxane in the liquid crystal aligning agent containing the polysiloxane component (A) and other polysiloxane such as the polysiloxane component (C) is not particularly limited, but the total amount of polysiloxane contained in the liquid crystal aligning agent is not limited.
• the polysiloxane component (A) is preferably 10% by mass or more, and more preferably 50 to 90% by mass.
• the method for obtaining the polysiloxane component (A) and the polymerization inhibiting component (C) as the components of the liquid crystal aligning agent of the present invention is not particularly limited, and alkoxysilane may be reacted.
• alkoxysilane containing the alkoxysilane represented by the above formula (1) and the alkoxysilane represented by the above formula (3) is reacted (heavy) in an organic solvent.
• Condensation reaction usually, polysiloxane is obtained as a solution obtained by polycondensation of such alkoxysilanes and uniformly dissolved in an organic solvent.
• alkoxysilane used for formation of polysiloxane (A) together with the alkoxysilane represented by the above formula (1) and the above formula (3), for example, the alkoxysilane represented by the above formula (4), the above When producing the polysiloxane (A) using the alkoxysilane represented by (5) and / or the alkoxysilane represented by (7), the alkoxysilane can be reacted in the same manner as described above. .
• polysiloxane such as polysiloxane (A)
• a method of hydrolyzing and condensing contained alkoxysilane in a solvent such as alcohol or glycol can be mentioned.
• the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 times mole of water of all alkoxy groups in the alkoxysilane, but it is usually preferable to add an excess amount of water more than 0.5 times mole.
• the amount of water used in the above-mentioned reaction can be appropriately selected as desired, but it is usually 0.5 to 2.5 times mol of all alkoxy groups in the alkoxysilane contained in the alkoxysilane. It is preferably 0.5 to 2 moles.
• acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid, ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc.
• Catalysts such as alkali, hydrochloric acid, sulfuric acid, nitric acid and other metal salts can be used.
• a method of heating and polycondensing a mixture of alkoxysilane a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the alkoxysilane is mixed while the solution is heated.
• the amount of succinic acid used is preferably 0.2 to 2 mol, more preferably 0.5 to 2 mol, based on 1 mol of all alkoxy groups contained in the alkoxysilane contained in the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 ° C. to 180 ° C. A method of heating for several tens of minutes to several tens of hours under reflux is preferred so that evaporation or volatilization of volatile components such as solvents does not occur.
• each alkoxysilane may be mixed in advance as a mixture, or a plurality of alkoxysilanes may be sequentially added. You may mix. That is, there is no limitation on the order of reacting alkoxysilane, for example, alkoxysilane may be reacted at once,
• alkoxysilanes after reacting some alkoxysilanes, other alkoxysilanes may be added and reacted.
• the alkoxysilane represented by the above formula (1), the alkoxysilane represented by the above formula (3), and the above formula (4) are represented. May be mixed with each other to cause a polycondensation reaction.
• the alkoxysilane represented by the above formula (1) and the alkoxysilane represented by the above formula (4) may be subjected to a polycondensation reaction. You may make it react by adding the alkoxysilane represented by (3).
• alkoxysilane represented by the above formula (1) alkoxysilane represented by the above formula (3), and alkoxy represented by the above formula (5) Silane may be mixed and subjected to a polycondensation reaction. After a polycondensation reaction between the alkoxysilane represented by the above formula (1) and the alkoxysilane represented by the above formula (5), the above formula (3 ) May be added and reacted.
• the solvent used for polycondensation of the raw material alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it dissolves the alkoxysilane. Moreover, even when alkoxysilane does not melt
• Such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1 Glycols such as 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether , Ethylene glycol monobutyl
• the polysiloxane polymerization solution obtained by the above method is a concentration obtained by converting silicon atoms of all raw material alkoxysilanes charged as raw materials into SiO 2 (hereinafter referred to as SiO 2 conversion concentration). .) Is preferably 20% by mass or less, more preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.
• liquid crystal aligning agent of the present invention in addition to the polysiloxane component (A) and the polymerization inhibiting component (B), other components, for example, inorganic fine particles, metalloxane oligomers, metalloxanes, as long as the effects of the present invention are not impaired.
• Components such as a polymer, a leveling agent and a surfactant may be contained.
• the inorganic fine particles fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in the state of a colloidal solution are particularly preferable.
• This colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution.
• the inorganic fine particles preferably have an average particle size of 0.001 to 0.2 ⁇ m, more preferably 0.001 to 0.1 ⁇ m. When the average particle diameter of the inorganic fine particles exceeds 0.2 ⁇ m, the transparency of the cured film formed using the prepared coating liquid may be lowered.
• the dispersion medium for inorganic fine particles examples include water and organic solvents.
• the colloidal solution it is preferable that the pH or pKa is adjusted to 1 to 10 from the viewpoint of the stability of the coating solution for forming a film. More preferably, it is 2-7.
• organic solvent used for the dispersion medium of the colloidal solution examples include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and ⁇ -butyrolactone; And ethers such as tetrahydrofuran and 1,4-dioxane. Among these, alcohols and ketones are preferable. These organic solvents can be used alone or in combination of two or more as a dispersion medium.
• metalloxane oligomer and metalloxane polymer that can be used as other optional components
• single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used.
• the metalloxane oligomer and the metalloxane polymer may be commercial products or may be obtained from monomers such as metal alkoxides, nitrates, hydrochlorides, and carboxylates by a conventional method such as hydrolysis.
• metalloxane oligomers and metalloxane polymers include siloxane oligomers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat.
• siloxane polymers and titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.
• liquid crystal aligning agent of this invention the method of adding the other arbitrary component mentioned above may be simultaneous with polysiloxane (A), or after that, and is not specifically limited.
• the liquid crystal aligning agent of this invention is a liquid containing a polysiloxane component (C) and other components as needed in addition to the above-mentioned polysiloxane component (A) and polymerization inhibiting component (B).
• each said component is mixed uniformly.
• a polymerization inhibitor may be added to a reaction solution such as a polysiloxane polymerization solution obtained by the above method to form a liquid crystal aligning agent, or a reaction solution such as a polysiloxane polymerization solution obtained by the above method may be used. If necessary, it may be concentrated, diluted by adding a solvent, or substituted with another solvent, and a polymerization inhibitor may be added thereto to form a liquid crystal aligning agent.
• a solvent a solvent selected from the group consisting of the above-mentioned polysiloxane polymerization solvent and additive solvent can be used.
• the solvent in the liquid crystal aligning agent is not particularly limited as long as the polysiloxane component (A) and the polymerization inhibiting component (B) are preferably uniformly dissolved, and one or a plurality of types can be arbitrarily selected and used.
• a solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and esters such as methyl acetate, ethyl acetate, and ethyl lactate. These solvents can improve the applicability when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, ink jetting or the like.
• the content of polysiloxane including polysiloxane (A) in the liquid crystal aligning agent is preferably 0.5 to 15% by mass, more preferably 1 to 6% by mass in terms of SiO 2 concentration. In the case of such a SiO 2 equivalent concentration range, it is easy to obtain a desired film thickness by a single application, and a sufficient pot life (pot life) of the solution is easily obtained.
• content of polysiloxane in a liquid crystal aligning agent can be adjusted by using the solvent chosen from the group which consists of the polymerization solvent of the polysiloxane mentioned above, and the solvent to add.
• liquid crystal aligning agent of this invention contains the polysiloxane component (A) and polymerization inhibition component (B) which were mentioned above, the liquid crystal aligning film obtained suppresses the reaction before the light irradiation of the side chain to contain, light The decrease in reactivity can be suppressed, and the alignment control of liquid crystal by light and the improvement of response speed can be realized.
• the cured film obtained by drying, if necessary, heating and baking is then used. It can also be used as a liquid crystal alignment film.
• the cured film can be used by orientation treatment, specifically, rubbing, irradiation with polarized light or light having a specific wavelength, treatment with an ion beam, or the like.
• UV or other light is irradiated in a state where a voltage is applied to the liquid crystal layer sandwiched between the liquid crystal alignment films, thereby realizing desired alignment control of the liquid crystal.
• the substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate is preferable.
• Specific examples include glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile.
• a plastic plate such as triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose, and a substrate on which a transparent electrode is formed.
• liquid crystal aligning agent examples include spin coating, printing, ink jet, spraying, roll coating, and the like. From the viewpoint of productivity, the transfer printing method is widely used industrially. The present invention is also preferably used.
• the step of drying the coating film after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if it is not baked immediately after coating, it is dried. It is preferable to include a process.
• the drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like.
• the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
• the calcination temperature is usually 100 to 350 ° C., preferably 140 to 300 ° C., more preferably 150 to 230 ° C., and further preferably 160 to 220 ° C.
• the firing time is usually 5 to 240 minutes.
• the time is preferably 10 to 90 minutes, more preferably 20 to 80 minutes.
• the heating can be usually performed using a known method, for example, a hot plate, a hot air circulation oven, an IR oven, a belt furnace or the like.
• the polysiloxane derived from the polysiloxane component (A) or the like in the liquid crystal alignment film usually undergoes further polycondensation in the heating and firing steps.
• firing is performed at a temperature higher by 10 ° C. or more than the curing temperature of the sealing agent so as not to be affected by heating in a heat treatment process such as curing of the sealing agent required in the manufacturing process of the liquid crystal display element. It is preferable.
• the thickness of the liquid crystal alignment film obtained as the cured film can be selected as necessary, but is preferably 5 nm or more, more preferably 10 nm or more. When the film thickness is 10 ⁇ m or more, it is preferable because the reliability of the liquid crystal display element can be easily obtained.
• the thickness of the liquid crystal alignment film is preferably 300 nm or less, more preferably 150 nm or less. A film thickness of 150 nm or less is preferable because the power consumption of the liquid crystal display element does not become extremely large.
• the liquid crystal display element of the present invention has a pair of liquid crystal alignment films of the present invention and a liquid crystal layer sandwiched between the liquid crystal alignment films.
• the liquid crystal alignment film is preferably formed by being irradiated with light while a voltage is applied to the liquid crystal layer.
• the liquid crystal display element of the present invention can be produced by appropriately using a known method after forming a liquid crystal alignment film on a substrate by the method described above.
• a method for manufacturing a liquid crystal display element a method in which a pair of substrates on which a liquid crystal alignment film of the present invention is formed is fixed with a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed is preferable.
• the size of the spacer to be used is usually 1 to 30 ⁇ m, preferably 2 to 10 ⁇ m.
• the method for injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting the liquid crystal after reducing the pressure inside the manufactured liquid crystal cell, and a dropping method for sealing after dropping the liquid crystal.
• the liquid crystal display element After obtaining a liquid crystal display element in which the liquid crystal is introduced and the liquid crystal layer is sandwiched between the pair of liquid crystal alignment films, the liquid crystal display element is irradiated with, for example, UV light. This light irradiation is performed in a state where a voltage is applied between the electrodes on both side substrates sandwiching the liquid crystal layer, that is, in a state where the liquid crystal is inclined and oriented in a uniform direction.
• a photoreaction having, for example, an acryl group or a methacryl group in the liquid crystal alignment film by irradiating UV with a voltage applied between the electrodes on both substrates For example, a polymerization reaction is carried out in a state where the hydrophilic side chain is in contact with the tilted liquid crystal.
• the liquid crystal alignment film is partially cross-linked while interacting with the liquid crystal in the vicinity.
• the liquid crystal forms a pretilt angle in a predetermined direction and is substantially vertically aligned.
• the desired liquid crystal alignment state is formed.
• a desired very small pretilt angle is formed in a part of the liquid crystal layer, and the response speed of the liquid crystal is improved.
• the voltage applied between the electrodes is 5 to 50 V pp , but preferably 5 to 30 V pp .
• the amount of light irradiation is 1 to 60 J, preferably 40 J or less. A smaller amount of light irradiation can suppress a decrease in reliability due to light deterioration of the members constituting the liquid crystal display and can reduce a light irradiation time, so that a manufacturing tact can be improved.
• the substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate. Specifically, it is the same as the substrate described above. In this invention, it is also possible to use the board
• the liquid crystal display element of the present invention has a structure in which a line / slit electrode pattern of 1 to 10 ⁇ m is formed on one side substrate, and a slit pattern or a projection pattern is not formed on the opposite substrate, like the PSA type liquid crystal display. This simple structure can simplify the manufacturing process and obtain a high transmittance.
• a transistor element thin film transistor (TFT) formed between an electrode for driving a liquid crystal and a substrate is used.
• TFT thin film transistor
• a transmissive liquid crystal display element it is common to use a light-transmitting substrate as described above.
• a reflective liquid crystal display element such as aluminum that reflects light only on one substrate.
• a material can also be used, and an opaque substrate such as a silicon wafer can also be used.
• the liquid crystal display element having the liquid crystal alignment film of the present invention is excellent in response characteristics and display quality, and can be suitably used for a large-screen liquid crystal television or the like.
• TEOS Tetraethoxysilane
• MPMS 3-Methacryloxypropyltrimethoxysilane
• VTMS Trimethoxyvinylsilane
• GPS ⁇ -Glycidoxypropyltrimethoxysilane
• UPS 3-ureidopropyltriethoxysilane
• SMA compound represented by the following formula
• liquid crystal aligning agent [S1] 0.31 g of 3BHT (5 mol% with respect to MPMS) was dissolved to obtain a liquid crystal aligning agent [S2].
• 3BHT is a polymerization inhibitor component added to the liquid crystal aligning agent [S2] as a polymerization inhibitor.
• no polymerization inhibiting component is added to the liquid crystal aligning agent [S1].
• 17 g of the liquid crystal aligning agent [S1] 0.34 g of SMB in advance, 0.33 g of HG, and 0.
• a solution of 17 g and 0.17 g of PB dissolved in 0.38 g (5 mol% with respect to MPMS) was mixed, heated to 60 ° C. in an oil bath and stirred for 15 minutes, then allowed to cool, and SiO 2 A liquid crystal aligning agent [S3] having a 2 equivalent concentration of 5% by weight was obtained.
• the SMB used here is a polymerization inhibiting component added to the liquid crystal aligning agent [S3] as a polymerization inhibitor.
• liquid crystal aligning agent [S4] as the first component
• 7.56 g of the liquid crystal aligning agent [U2] as the second component
• 3.2 g of HG 1.07 g of BCS
• 4.B of PB 4.B
• the liquid crystal aligning agent [L1] was obtained by mixing 93g.
• the liquid crystal aligning agent [S5] is 3.24 g as the first component
• the liquid crystal aligning agent [U2] is 7.56 g as the second component
• HG is 3.2 g
• BCS is 1.07 g
• PB 4.93 g.
• the liquid crystal aligning agent [L2] was obtained by mixing.
• the liquid crystal aligning agent [S6] is 3.24 g as the first component
• the liquid crystal aligning agent [U2] is 7.56 g as the second component
• HG is 3.2 g
• BCS is 1.07 g
• PB is 4.4 g.
• the liquid crystal aligning agent [L3] was obtained by mixing 93g.
• the liquid crystal aligning agent [L3] is a liquid crystal aligning agent containing SMB as a polymerization inhibiting component separately from other polysiloxane components.
• SMB is an alkoxysilane monomer added to form a polymerization-inhibiting component as a part of polysiloxane constituting the liquid crystal alignment film.
• the polysiloxane in the obtained polysiloxane solution is formed by copolymerization of SMB with another alkoxysilane monomer. 41.7 g of the obtained polysiloxane solution, 25.15 g of HG, 14.58 g of BCS, and 18.6 g of PB were mixed to obtain a liquid crystal aligning agent [S7] having a SiO 2 equivalent concentration of 5% by weight. .
• Example 1 The liquid crystal aligning agent [S2] obtained in Synthesis Example 1 was spin-coated at 1500 rpm on a Cr substrate having a size of 30 mm ⁇ 30 mm, temporarily dried on an 80 ° C. hot plate for 90 seconds, and then heated at 200 ° C. in a hot air circulation oven The main baking was performed for 30 minutes to form a liquid crystal alignment film.
• the results are shown in Table 1.
• Example 3 Using the liquid crystal aligning agent [L2] obtained in Synthesis Example 2, spin coating was performed on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m was formed. Next, after temporary drying for 90 seconds on a hot plate at 80 ° C., main baking was performed for 30 minutes in a hot air circulation oven at 200 ° C. to form a liquid crystal alignment film having a thickness of 100 nm.
• liquid crystal alignment film surface of the other substrate was placed inside and bonded together, and then the sealing agent (manufactured by Mitsui Chemicals) was cured to produce an empty cell.
• liquid crystal MLC-6608 manufactured by Merck & Co., Inc.
• the obtained liquid crystal cell was annealed in a circulation oven at 110 ° C. for 15 minutes.
• a VA mode liquid crystal display element was manufactured by using a liquid crystal cell irradiated with UV and sandwiching it between a pair of polarizing plates arranged in crossed Nicols. Using the liquid crystal display element, the response speed of the liquid crystal was measured. Next, the voltage holding ratio of the liquid crystal display element was measured.
• Table 2 shows the type of the liquid crystal aligning agent used in this example as [L2], and also shows the type of the liquid crystal aligning agent of the first component used for the preparation of the liquid crystal aligning agent [L2].
• [S5] is shown, and the type of the liquid crystal aligning agent of the second component is shown as [U2].
• the polymerization inhibiting component contained in the used liquid crystal aligning agent [L2] was shown, and the main baking temperature and baking time for forming the liquid crystal alignment film were also shown.
• the response speed was measured by the following method.
• [Response speed measurement] A 10 V AC voltage and a rectangular wave with a frequency of 1 kHz were applied to the liquid crystal display element, and the time change of the luminance of the liquid crystal display element at that time was captured with an oscilloscope. When the voltage was not applied, the luminance was 0%, a voltage of 10 V was applied, the saturated luminance value was 100%, and the time for the luminance to change from 10% to 90% was evaluated as the rising response speed.
• Example 4 A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent [L2] was changed to the liquid crystal aligning agent [L3], and a VA mode liquid crystal display element was produced.
• Example 5 A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent [L2] was changed to the liquid crystal aligning agent [L4], and a VA mode liquid crystal display element was produced.
• Example 2 A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent [L2] was changed to the liquid crystal aligning agent [L1], and a VA mode liquid crystal display device was produced.
• Example 6 A liquid crystal cell was produced in the same manner as in Example 3 except that the conditions for the main firing were changed from 200 ° C. for 30 minutes to 200 ° C. for 40 minutes, and a VA mode liquid crystal display device was produced.
• Example 7 A liquid crystal cell was prepared in the same manner as in Example 3 except that the liquid crystal aligning agent [L2] was changed to the liquid crystal aligning agent [L3] and the conditions for the main firing were changed from 200 ° C. for 30 minutes to 200 ° C. for 40 minutes. A VA mode liquid crystal display element was manufactured.
• Example 3 A liquid crystal cell was prepared in the same manner as in Example 3 except that the liquid crystal aligning agent [L2] was changed to the liquid crystal aligning agent [L1] and the conditions for the main firing were changed from 200 ° C. for 30 minutes to 200 ° C. for 40 minutes. A VA mode liquid crystal display element was manufactured.
• Example 8 A liquid crystal cell was produced in the same manner as in Example 3 except that the conditions for the main firing were changed from 200 ° C. for 30 minutes to 230 ° C. for 30 minutes, and a VA mode liquid crystal display device was produced.
• Example 9 A liquid crystal cell was prepared in the same manner as in Example 3 except that the liquid crystal aligning agent [L2] was changed to the liquid crystal aligning agent [L3] and the conditions for the main firing were changed from 200 ° C. for 30 minutes to 230 ° C. for 30 minutes. A VA mode liquid crystal display element was manufactured.
• a liquid crystal cell was prepared in the same manner as in Example 3 except that the liquid crystal aligning agent [L2] was changed to the liquid crystal aligning agent [L1] and the conditions for the main firing were changed from 200 ° C. for 30 minutes to 230 ° C. for 30 minutes.
• a VA mode liquid crystal display element was manufactured.
• Example 2 As shown in Table 2, in the liquid crystal display elements of Examples 3 to 5 in which the polymerization inhibiting component was introduced, the response speed was improved by the liquid crystal alignment film as compared with Comparative Example 2 in which the polymerization inhibiting component was not introduced.
• SMB is added to form a polymerization inhibiting component as a part of polysiloxane constituting the liquid crystal alignment film.
• the polysiloxane contained is formed by copolymerizing SMB with other alkoxysilane monomers.
• the liquid crystal display elements of Examples 6 and 7 into which the polymerization inhibiting component was introduced exhibited the same response speed as the corresponding liquid crystal display elements of Examples 3 and 4 even when the firing time was increased.
• the firing time of the liquid crystal alignment film was the same, and the response speed was improved as compared with Comparative Example 3 in which the polymerization inhibiting component was not introduced.
• the liquid crystal display elements of Examples 8 and 9 into which the polymerization inhibiting component was introduced exhibited a response speed equivalent to that of the corresponding liquid crystal display elements of Examples 3 and 4 even when the firing temperature was increased.
• the response speed was improved as compared with Comparative Example 4 in which the polymerization inhibiting component was not introduced even when the firing temperature of the liquid crystal alignment film was the same.
• a VA mode liquid crystal display element can be manufactured.
• the liquid crystal display element constitutes a VA mode liquid crystal display element of high display quality, and can be suitably used for a portable information terminal such as a large-sized liquid crystal TV or a smartphone displaying a high-definition image.

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