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WO2014142168A1 - Agent d'alignement de cristaux liquides contenant un composé réticulable ayant un groupe photoréactif - Google Patents

Agent d'alignement de cristaux liquides contenant un composé réticulable ayant un groupe photoréactif Download PDF

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Publication number
WO2014142168A1
WO2014142168A1 PCT/JP2014/056488 JP2014056488W WO2014142168A1 WO 2014142168 A1 WO2014142168 A1 WO 2014142168A1 JP 2014056488 W JP2014056488 W JP 2014056488W WO 2014142168 A1 WO2014142168 A1 WO 2014142168A1
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Prior art keywords
liquid crystal
group
crystal aligning
aligning agent
formula
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PCT/JP2014/056488
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English (en)
Japanese (ja)
Inventor
正人 森内
亮一 芦澤
橋本　淳
耕平 後藤
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to JP2015505513A priority Critical patent/JP6387957B2/ja
Priority to CN201480014584.6A priority patent/CN105190414B/zh
Priority to KR1020157028301A priority patent/KR102114521B1/ko
Publication of WO2014142168A1 publication Critical patent/WO2014142168A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

  • the present invention relates to a liquid crystal aligning agent containing a crosslinkable compound into which a structure (photoreactive group) that causes photopolymerization by ultraviolet (UV) irradiation is introduced, a liquid crystal alignment film obtained using the same, and a liquid crystal display element About.
  • a structure photoreactive group
  • UV ultraviolet
  • VA vertical alignment
  • the VA method includes an MVA method (Multi-Vertical Alignment) in which protrusions for controlling the direction in which the liquid crystal is tilted are formed on the TFT substrate or the color filter substrate, and a direction in which the liquid crystal is tilted by forming an slit in the ITO electrode of the substrate.
  • MVA Multi-Vertical Alignment
  • a PVA Plasma Vertical Alignment
  • Another alignment method is a PSA (Polymer Sustained Alignment) method.
  • the PSA method is a technology that has attracted attention in recent years.
  • This method increases the response speed of the liquid crystal by adding a photopolymerizable compound to the liquid crystal composition and irradiating the liquid crystal panel with ultraviolet rays while the liquid crystal is tilted after applying the electric field after the liquid crystal panel is manufactured.
  • Technology see Patent Document 1.
  • a liquid crystal cell prepared using a liquid crystal composition containing a photopolymerizable compound and a liquid crystal alignment film made of polyimide or the like was irradiated with ultraviolet rays while applying a voltage, a photopolymerization reaction occurred and the liquid crystal molecules were tilted.
  • a polymer structure in which the direction is memorized is formed on the liquid crystal alignment film.
  • the alignment direction of the liquid crystal is fixed and a pretilt is generated, so that a liquid crystal display element having a better response speed can be obtained as compared with the method of controlling the inclination direction of the liquid crystal molecules only by the protrusions and slits.
  • This PSA method can be operated even in a structure in which a slit is formed in one electrode constituting a liquid crystal panel, and a protrusion such as MVA or a slit such as PVA is not provided in the opposite electrode pattern. It has a feature that simplification and excellent panel transmittance can be obtained (see Patent Document 2).
  • the PSA type liquid crystal display element has a problem that the solubility of the photopolymerizable compound added to the liquid crystal is low, and when the addition amount is increased, it is precipitated at a low temperature. On the other hand, if the addition amount of the photopolymerizable compound is reduced, a good alignment state and response speed cannot be obtained. Moreover, since the unreacted photopolymerizable compound remaining in the liquid crystal becomes an impurity in the liquid crystal, there is a problem that the reliability of the liquid crystal display element is lowered.
  • An object of this invention is to provide the liquid crystal aligning agent excellent in the storage stability at the time of frozen storage used for a vertical alignment film. Furthermore, an object of the present invention is to provide a liquid crystal display element that is produced using the liquid crystal aligning agent and exhibits a good response speed.
  • the molecular weight of the photopolymerizable compound is small, it will sublime at the time of firing.
  • the crosslinking agent used to increase the hardness and density of the liquid crystal alignment film reacts with the liquid crystal alignment film. Even if it is small, it has been confirmed that it remains in the liquid crystal alignment film. Therefore, the present inventors can introduce a photoreactive group into the liquid crystal alignment film efficiently by introducing a structure (photoreactive group) that causes photopolymerization by UV irradiation into the crosslinking agent. I thought and advanced my research.
  • a novel crosslinkable compound in which 2 or more photopolymerizable groups and 10 or less crosslinkable groups are bonded to a mother nucleus composed of a divalent or higher valent organic group has a solubility in a liquid crystal aligning agent. It has been found that the liquid crystal aligning agent containing the crosslinkable compound is excellent in storage stability during frozen storage. Furthermore, it discovered that the liquid crystal display element which shows a favorable response speed was obtained by using the liquid crystal aligning agent to which the said crosslinkable compound was added, and it came to this invention.
  • the present invention is based on such knowledge and has the following gist.
  • Crosslinkability represented by the following formula [1] in which 2 or more polymerizable groups (Py) and 10 or less crosslinkable groups (CL) are bonded to a mother nucleus composed of an organic group having a valence of 1.2 or more.
  • a liquid crystal aligning agent comprising a compound.
  • L-M-R is a mother nucleus of the crosslinkable compound, and L and R are each independently a carbocyclic or heterocyclic ring having 4 to 12 carbon atoms, and one or more of the carbocyclic or heterocyclic rings.
  • the hydrogen atom of may be substituted with a fluorine atom
  • M is a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —NHCO—, —CONH—, —COO—, —OCO—, — NH—, —CO—, or a combination thereof
  • S 1 , S 2, S 3, and S 4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms
  • One or more hydrogen atoms may be substituted with a fluorine atom or an organic group, and —CH 2 — in S 1 , S 2, S 3 and S 4 may be —O—, —NHCO—, —CONH— , —COO—, —OCO—, —NH— and —CO—.
  • Py 1 and Py 2 are each independently a polymerizable group having one of the following structures, and n and m are each independently And n + m is 10 or less.
  • p is an integer of 1 to 10, preferably 1 to 6
  • CL 1 and CL 2 are each independently a hydroxyl group, an alkoxy group, an epoxy group, an oxetanyl group, a cyclocarbonate group, or an isocyanate group masked with a blocking agent, and l and o are each independently one or more. It is an integer and l + o is 10 or less.
  • liquid crystal aligning agent according to 1, wherein L and R in the formula [1] are each independently a benzene ring, a cyclohexyl ring, a biphenyl ring, or a naphthalene ring. 3.
  • the liquid crystal aligning agent according to 1 or 2 wherein the crosslinkable compound is a formula (CL-1), a formula (CL-2) or a formula (CL-3) described later. 4).
  • the liquid crystal aligning agent according to 4 above wherein the content of the crosslinkable compound is 1 to 30% by mass with respect to 100% by mass of the polymer component. 6). 4. The liquid crystal aligning agent according to the above 1 to 3, which contains polysiloxane as a polymer component that imparts liquid crystal aligning ability. 7). 7. The liquid crystal aligning agent according to 6 above, wherein the content of the crosslinkable compound is 1 to 30% by mass with respect to 100% by mass of the polymer component in terms of SiO 2 of silicon atoms of the polysiloxane. 8). 8. The liquid crystal aligning agent according to any one of 1 to 7 further containing an organic solvent.
  • a liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of 1 to 8 on a substrate, drying and baking. 10. 10. A liquid crystal display device having the liquid crystal alignment film as described in 9 above. 11. 9. A liquid crystal display element in which ultraviolet rays are applied in a voltage-applied state to a liquid crystal cell in which liquid crystal is sandwiched between two substrates that have been coated with a liquid crystal aligning agent according to any one of 1 to 8 and baked. 12 9. A method for producing a liquid crystal display element, comprising: applying a liquid crystal aligning agent according to any one of 1 to 8 above; sandwiching a liquid crystal between two baked substrates; and irradiating ultraviolet rays with a voltage applied. 13. A photoreactive group-containing crosslinkable compound of CL-1, CL-2 or CL-3 described later.
  • the liquid crystal aligning agent of the present invention does not precipitate even when stored frozen, it can be stored for a long period of time.
  • the liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention is useful for a liquid crystal display element capable of improving the response speed after UV irradiation, and has a high quality and excellent reliability. Can be provided.
  • Crosslinkable compound having a photoreactive group In the crosslinkable compound having a photoreactive group of the present invention, two or more polymerizable groups (Py) and ten or less crosslinkable groups (CL) are bonded to a mother nucleus composed of a divalent or higher valent organic group. And is represented by the following formula [1].
  • L and R are divalent to tetravalent, preferably tetravalent, carbocyclic or heterocyclic rings having 4 to 12, preferably 5 to 12 carbon atoms.
  • the carbocycle is preferably a benzene ring, a cyclohexane ring, a biphenyl ring, or a naphthalene ring from the viewpoint of ease of synthesis.
  • the heterocyclic ring an imidazole ring, a furan ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, or an indole ring is preferable.
  • M is preferably an alkylene group having 1 to 5 carbon atoms, —O—, —COO—, —OCO—, —NH—, or —CO—.
  • M is preferably an alkylene group having 1 to 3 carbon atoms, —O—, —COO—, or —CO—.
  • S 1 , S 2, S 3 , and S 4 are preferably a single bond or an alkylene group having 1 to 8 primes.
  • S 1 , S 2, S 3 and S 4 are preferably a single bond or an alkylene group having a prime number of 1 to 6.
  • Py 1 and Py 2 have a (meth) acryloyl group, a (meth) acryloyloxy group, an ⁇ -methylene- ⁇ -butyrolactone group, or a cinnamoyl group and a (meth) acryloyl group or a (meth) acryloyloxy group.
  • Group, maleimide group, styryl group, or itaconyl group is preferred.
  • Py 1 and Py 2 are preferably a (meth) acryloyloxy group, an ⁇ -methylene- ⁇ -butyrolactone group, a group having a cinnamoyl group and a (meth) acryloyloxy group, or a styryl group.
  • CL 1 and CL 2 are preferably a hydroxyl group, an alkoxy group, an epoxy group, an oxetane group, a cyclocarbonate group, or a blocked isocyanate masked with a blocking agent.
  • L and o are preferably integers of 1 to 4, and l + o is preferably 6 or less.
  • the blocking agent for the block type isocyanate those having the following structures are particularly preferably used.
  • L-M-R in the formula [1] include the following structures, but are not limited thereto.
  • —S 3 —CL 1 and —S 4 —CL 2 in the formula [1] include the following structures, but are not limited thereto. (Wherein q is an integer of 1 to 10, preferably 1 to 6)
  • the crosslinkable compound of the formula [1] can be obtained by a known production method, for example, 3,3 ′, 5,5′-tetrakis (methoxymethyl)-[1,1′-biphenyl] -4,4′- A diol and 6-chloro-1-hexanol are reacted in the presence of potassium carbonate and potassium iodide to synthesize a precursor, and the obtained precursor and methacryloyl chloride are reacted in the presence of triethylamine to obtain a crosslinkable compound.
  • Precursor-1 and methanesulfonyl chloride were synthesized in the presence of triethylamine.
  • precursor-2 and the precursor-2 and 3,3 ′, 5,5′-tetrakis (methoxymethyl)-[1,1′-biphenyl] -4,4′-diol were carbonated.
  • Precursor-3 is synthesized by reaction in the presence of potassium.
  • Method for obtaining a crosslinkable compound by condensing precursor-3 and 2-hydroxyethyl methacrylate with 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in the presence of 4-dimethylaminopyridine , Etc.
  • the manufacturing method of the photoreactive group containing crosslinkable compound in this invention is not limited to these.
  • the content of the crosslinkable compound represented by the formula [1] is preferably 1 to 30% by mass, more preferably 3 to 15% with respect to 100% by mass of the polymer component. % By mass.
  • the liquid crystal aligning agent of the present invention is a coating liquid for forming a liquid crystal aligning film, and is a crosslinkable compound represented by the formula [1] (hereinafter referred to as photoreaction) into which a structure causing photopolymerization by UV irradiation is introduced.
  • At least one polymer selected from the group consisting of polyamic acid and polyimide, or polysiloxane as a polymer for forming a liquid crystal alignment film having a liquid crystal alignment ability) contains.
  • the polymer forming the liquid crystal alignment film having the liquid crystal alignment ability contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can align the liquid crystal on the liquid crystal alignment film formed on the substrate.
  • substrate is mentioned.
  • a polymer that can align the liquid crystal on the liquid crystal alignment film formed on the substrate perpendicularly to the substrate a polymer having a side chain that aligns the liquid crystal vertically is preferable. Examples thereof include a polyimide precursor having a side chain that is vertically aligned and a polyimide obtained by imidizing the polyimide precursor.
  • the side chain for vertically aligning the liquid crystal is not limited as long as the liquid crystal can be aligned vertically with respect to the substrate.
  • a long chain alkyl group, a ring structure or a branch in the middle of the long chain alkyl group may be used. Examples thereof include a group having a structure, a steroid group, and a group in which some or all of hydrogen atoms of these groups are replaced with fluorine atoms.
  • the side chain for vertically aligning the liquid crystal may be directly bonded to the main chain of a polymer such as polyamic acid or polyimide, or may be bonded through an appropriate bonding group. Examples of the side chain for vertically aligning the liquid crystal include those represented by the following formula (a).
  • R 7 represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—, —CONH—, Or an alkylene group-ether group having 1 to 3 carbon atoms
  • R 8 , R 9 and R 10 each independently represents a phenylene group or a cycloalkylene group
  • R 11 is a hydrogen atom or an alkyl group having 2 to 24 carbon atoms.
  • R 7 in the above formula (a) is preferably —O—, —COO—, —CONH—, an alkylene group having 1 to 3 carbon atoms or an ether group, from the viewpoint of ease of synthesis.
  • R 8 , R 9 and R 10 in the formula (a) are q, r, s, R 8 and R 9 shown in Table 1 below from the viewpoint of ease of synthesis and ability to align liquid crystals vertically. And a combination of R 10 is preferred.
  • R 11 in formula (a) is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably A hydrogen atom, an alkyl group having 2 to 12 carbon atoms, or a fluorine-containing alkyl group;
  • R 11 is preferably an alkyl group having 12 to 22 carbon atoms or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent Heterocycles and monovalent macrocyclic substituents composed of these, more preferably alkyl groups having 12 to 20 carbon atoms or fluorine-containing alkyl groups.
  • the amount of the side chain that vertically aligns the liquid crystal is not particularly limited as long as the liquid crystal alignment film can align the liquid crystal vertically.
  • the amount of side chains that vertically align the liquid crystal is possible within a range that does not impair the display characteristics of the element such as voltage holding ratio and accumulation of residual DC voltage. As few as possible is preferable.
  • the ability of a polymer having side chains for vertically aligning liquid crystals to align liquid crystals vertically varies depending on the structure of the side chains for vertically aligning liquid crystals, but in general, the side chains for vertically aligning liquid crystals. As the amount increases, the ability to align the liquid crystal vertically increases, and as the amount decreases, it decreases. Moreover, when it has a cyclic structure, compared with the case where it does not have a cyclic structure, there exists a tendency for the capability to orientate a liquid crystal vertically.
  • the polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal preferably has a photoreactive side chain.
  • a photoreactive side chain is a side chain having a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with ultraviolet rays to form a covalent bond.
  • the structure is not limited.
  • Examples of the photoreactive side chain include a vinyl group, (meth) acryloyl group, (meth) acryloyloxy group, allyl group, styryl group, cinnamoyl group, chalconyl group, coumarin group, maleimide group, and itaconyl as the photoreactive group. And a side chain having an ⁇ -methylene- ⁇ -butyrolactone group.
  • the photoreactive side chain may be directly bonded to the main chain of a polymer such as polyamic acid or polyimide, or may be bonded via an appropriate bonding group.
  • Examples of the photoreactive side chain include those represented by the following formula (b).
  • R 12 is a single bond or —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) — , —CON (CH 3 ) —, —N (CH 3 ) CO—, wherein R 13 is a single bond, an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom
  • the alkylene group —CH 2 — may be optionally replaced by —CF 2 — or —CH ⁇ CH—, and when any of the following groups is not adjacent to each other, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocycle, a divalent heterocycle
  • R 14 is a vinyl group, ( (Meth) acryloyl group, (meth)
  • R 12 in the above formula (b) can be formed by a general organic synthetic method, but from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO —, —NH— or —CH 2 O— is preferred.
  • divalent carbocycle or divalent heterocycle carbocycle or heterocycle for replacing any —CH 2 — in R 13 include the following structures, but are not limited thereto. Is not to be done.
  • R 14 is a vinyl group, (meth) acryloyl group, (meth) acryloyloxy group, allyl group, styryl group, itaconyl group, ⁇ -methylene- ⁇ -butyrolactone group, —N (CH 2 ) from the viewpoint of photoreactivity.
  • a structure represented by —CH ⁇ CH 2 ) 2 or the following formula is preferable.
  • the above formula (b) is more preferably the following structure.
  • the abundance of the photoreactive side chain is preferably within a range where the response speed of the liquid crystal can be increased by reacting with ultraviolet irradiation to form a covalent bond. In order to further increase the response speed of the crystal, it is preferable that it is as much as possible within a range that does not affect other characteristics.
  • the method for producing a polymer for forming a liquid crystal alignment film for vertically aligning such liquid crystals is not particularly limited.
  • the side chain that vertically aligns the liquid crystal in the case of producing a polyamic acid having a side chain that vertically aligns the liquid crystal, in the method of obtaining a polyamic acid by the reaction of a diamine component and a tetracarboxylic dianhydride component, the side chain that vertically aligns the liquid crystal
  • a method of copolymerizing a diamine or tetracarboxylic dianhydride having a side chain for vertically aligning a liquid crystal is convenient.
  • a polymer forming a liquid crystal alignment film for vertically aligning liquid crystals contains a photoreactive side chain
  • a diamine having a photoreactive side chain or a tetracarboxylic acid having a photoreactive side chain A dianhydride may be copolymerized.
  • Examples of the diamine having a side chain that vertically aligns the liquid crystal include a diamine having a side chain represented by the above formula (a). Specific examples include diamines represented by the following formulas (2), (3), (4), and (5), but are not limited thereto.
  • a 10 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—
  • a 11 represents a single bond or a phenylene group.
  • A represents the same structure as the side chain for vertically aligning the liquid crystal represented by the above formula (a), and a ′ is the same as the side chain for vertically aligning the liquid crystal represented by the above formula (a). (This represents a divalent group having a structure in which one element such as hydrogen is removed from the structure.)
  • a 14 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom,
  • a 17 is an oxygen atom or —COO— * (where “*” is subjected the bond is the (CH 2) binds to a 2.).
  • a 1 is an integer of 0 or 1
  • a 2 is an integer of 2 ⁇ 10
  • a 3 is 0 or 1 (It is an integer.)
  • Binding positions of the two amino group (-NH 2) in equation (2) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • a 1 is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
  • a 2 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • a 3 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, fluorine Containing alkyl group or fluorine-containing alkoxy group.
  • a 4 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, or —CH 2 —.
  • a 5 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
  • a 6 is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O —
  • a 7 represents a fluorine atom, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.
  • a 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • a 9 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • diamine represented by the formula (3) include diamines represented by the following formulas [A-25] to [A-30], but are not limited thereto.
  • a 12 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—
  • a 13 represents one having 1 to 22 carbon atoms. Represents an alkyl group or a fluorine-containing alkyl group.
  • diamine represented by the formula (4) examples include diamines represented by the following formulas [A-31] to [A-32], but are not limited thereto.
  • Adiamine of [A-25], [A-26], [A-27], [A-28], [A-29] or [A-30] is preferred.
  • the above-mentioned diamines can be used alone or in combination of two or more depending on the properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
  • the diamine having a side chain for vertically aligning the liquid crystal is preferably used in an amount of 5 to 50 mol%, more preferably 0 to 40 mol% of the diamine component used for the synthesis of the polyamic acid. Particularly preferred is 15 to 30 mol%. When an amount in this range is used, it is particularly excellent in terms of improvement in response speed and alignment fixing ability of liquid crystal.
  • Examples of the diamine having a photoreactive side chain include a diamine having a side chain represented by the above formula (b). More specifically, examples include diamines represented by the following general formula (6), but are not limited thereto.
  • the bonding position of the two amino groups (—NH 2 ) in Formula (6) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • diamine having a photoreactive group examples include, but are not limited to, the following compounds.
  • X represents a single bond or a linking group selected from the group consisting of —O—, —COO—, —NHCO— and —NH—.
  • Y represents a single bond, an unsubstituted group or a fluorine atom. Represents a substituted alkylene group having 1 to 20 carbon atoms.
  • the diamine having the photoreactive group depends on the liquid crystal orientation when used as a liquid crystal alignment film, the pretilt angle, voltage holding characteristics, characteristics such as stored charge, the response speed of the liquid crystal when used as a liquid crystal display element, One type or a mixture of two or more types can also be used.
  • the diamine having such a photoreactive group is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably 30 of the diamine component used for the synthesis of the polyamic acid. ⁇ 50 mol%.
  • diamines other than the diamine having a side chain for vertically aligning the liquid crystal and the diamine having a photoreactive group are used as a diamine component. be able to. If the liquid crystal is not required to be aligned vertically, the amount of diamine having a side chain that vertically aligns the liquid crystal may be reduced. If the liquid crystal is to be aligned horizontally, the liquid crystal is aligned vertically. If the diamine having the side chain to be used is not used.
  • the other diamines include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, , 4-Dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamino Benzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4, 4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dimethyl
  • the above-mentioned other diamines can be used alone or in combination of two or more according to properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
  • the tetracarboxylic dianhydride component to be reacted with the diamine component in the synthesis of polyamic acid is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyl Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-di Carboxyphenyl) me
  • the reaction efficiency between the polyamic acid or polyimide and the crosslinkable compound described later can be increased.
  • Specific examples of such raw materials include 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 3,3 Examples include '-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid and the like.
  • a known synthesis method can be used.
  • a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent.
  • the reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
  • the organic solvent used for producing the polyamic acid is not particularly limited as long as the generated polyamic acid can be dissolved.
  • Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, Pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl Cellosolve acetate, ethyl cellosolve acetate, butyl
  • the solvent may be used alone or in combination.
  • it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
  • water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
  • Examples of the method for reacting tetracarboxylic acid or a derivative thereof with diamine in the production of a polyamic acid in an organic solvent include the following methods.
  • C A method of alternately adding tetracarboxylic acid or a derivative thereof and diamine. Any of these methods may be used.
  • tetracarboxylic acid or a derivative thereof, or diamine when they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed to form a high molecular weight product.
  • the temperature for producing the polyamic acid can be selected in the range of ⁇ 20 ° C. to 150 ° C., but is preferably ⁇ 5 ° C. to 100 ° C.
  • reaction can be performed by arbitrary density
  • the initial reaction may be carried out at a high concentration, and then an organic solvent may be added.
  • the ratio of the number of moles of the diamine component to the number of moles of tetracarboxylic acid or its derivative is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. preferable. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
  • thermal imidization by heating and catalyst imidization using a catalyst are generally used, but the catalyst imidation in which the imidization reaction proceeds at a relatively low temperature is obtained. It is preferable that the molecular weight does not decrease.
  • Catalytic imidation can be performed by stirring polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • the reaction temperature at this time is ⁇ 20 to 250 ° C., preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization proceeds, but if it is too high, the molecular weight of the polyimide may decrease.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like, and among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the organic solvent for the catalyst imidation is not limited as long as the polyamic acid dissolves. Specific examples thereof include N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl Urea, dimethyl sulfone, hexamethyl sulfoxide, ⁇ -butyrolactone, and the like.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the produced polyimide can be obtained by collecting the reaction solution into a poor solvent and collecting the produced precipitate.
  • the poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like.
  • the polyimide that has been poured into a poor solvent and precipitated is filtered, and then can be powdered by drying at normal temperature or under reduced pressure at normal temperature or under reduced pressure.
  • the polyimide can be purified by repeating the steps of dissolving the polyimide powder in an organic solvent and reprecipitating it 2 to 10 times. When the impurities cannot be removed by a single precipitation recovery operation, it is preferable to perform this purification step.
  • the molecular weight of the polyimide used in the present invention is not particularly limited, but is preferably 2,000 to 200,000 in terms of weight average molecular weight, more preferably 4, from the viewpoint of ease of handling and stability of characteristics when a film is formed. 000 to 50,000.
  • the molecular weight is determined by GPC (gel permeation chromatography).
  • the alkoxysilane component containing the alkoxysilane represented by following formula (7) and the alkoxysilane represented by following formula (9) is made to react.
  • the resulting polysiloxane (A) can be used.
  • R 101 Si (OR 102 ) 3 (7) R 101 represents the structure of the following formula (8), and R 102 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—.
  • 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 117 R 118 ) b — (b is an integer of 1 to 15 R 117 and R 118 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 1 to 15)
  • Y 4 is selected from the group consisting of a single bond, a benzene ring, a cyclohexyl ring, and a heterocyclic ring, —O—, —CH 2 O—, —COO—, or —OCO—.
  • a divalent cyclic group or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton, on these cyclic groups Arbitrary hydrogen atoms are substituted with alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine-containing alkoxy groups having 1 to 3 carbon atoms, or fluorine atoms
  • Y 5 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 to 3 may be substituted with an alkyl group of 3, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluor
  • 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 alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents a group.
  • R 121 , R 122 , R 123 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, —H, or a combination thereof, R 124 represents a hydrogen atom or a methyl group, and Y 21 represents 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—, —NPhCO—, —NHSO 2 —, —N (CH 3 ) SO 2 —, —NPhSO 2 -, - S -, - SO 2 -, - NHCONH, -N (CH 3) CO H -, - NPhCONH -, - NHCOO-, and, .
  • Y 23 is a single bond represents a bond group selected from the group consisting of -OCONH-, or 1 to 8 carbon atoms straight-chain or branched hydrocarbon
  • Y 24 represents a single bond or a linear or branched hydrocarbon group having 1 to 8
  • any hydrogen atom on these cyclic groups includes an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a cyano group, a fluorine atom, and a chlorine atom It may be substituted with one selected from the group consisting of
  • 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.
  • the alkoxysilane component can further contain an alkoxysilane represented by the following formula (10).
  • R 103 Si (OR 104 ) 3 (10) R 103 is an alkyl group having 1 to 30 carbon atoms in which a hydrogen atom is substituted with a (meth) acryloyl group, a (meth) acryloyloxy group, or a styryl group, and R 104 is an alkyl group having 1 to 5 carbon atoms. Represents a group.
  • the liquid crystal aligning agent of this invention contains polysiloxane (B) obtained by making the alkoxysilane component containing the alkoxysilane represented by following formula (11) react. Can do. Si (OR 115 ) 4 (11) (R 115 represents an alkyl group having 1 to 5 carbon atoms.)
  • At least one of the polysiloxane (A) and the polysiloxane (B) may be a polysiloxane obtained by further reacting an alkoxysilane component containing an alkoxysilane represented by the following formula (12). .
  • R 113 is a hydrogen atom, or a hydrogen atom or a carbon atom having a carbon number of 1 to 1 that 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.
  • 10 is a hydrocarbon group
  • R 114 is an alkyl group having 1 to 5 carbon atoms
  • n2 represents an integer of 0 to 3.
  • Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. .
  • selecting a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO— It is preferable from the viewpoint of facilitating. It is more preferable to select a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • Y 2 is preferably — (CH 2 ) b — (b is an integer of 1 to 10) 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 10), —O—, —CH 2 O—, —COO— or —OCO— is selected. It is preferable from the viewpoint of facilitating the synthesis of the side chain structure.
  • Y 4 is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton.
  • n1 of Y 5 is preferably an integer of 0-2.
  • Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 10 carbon atoms. It is preferable. It is more preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.
  • R 102 of the alkoxysilane represented by the formula (7) is preferably an alkyl group of 1 to 3. More preferably, R 102 is a methyl group or an ethyl group.
  • alkoxysilane represented by the formula (7) are listed below as formulas [1-1] to [1-31], but the alkoxysilane represented by the formula (7) is not limited thereto. Absent.
  • R 2 is the same as R 102 in formula (7).
  • R 105 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—
  • R 106 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, or a fluorine-containing alkyl.
  • a cis-trans isomer of 1,4-cyclohexylene is a trans isomer.
  • R 107 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 108 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
  • R 109 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 — or —O—
  • R 110 represents a fluorine atom.
  • Cyano group trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group.
  • R 111 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • R 112 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;
  • the cis-trans isomerism of silene is the trans isomer
  • B 2 is an oxygen atom or —COO— * (where the bond marked with “*” is bonded to B 3 )
  • B 1 is oxygen An 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 formula (7) is soluble in a solvent when a siloxane polymer (polysiloxane) is used, orientation of a liquid crystal when a liquid crystal alignment film is used, pretilt angle characteristics, voltage holding ratio, accumulated charge. Depending on the characteristics, one kind or a mixture of two or more kinds 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 (7) can be produced by a known method as described in, for example, Japanese Patent Application Laid-Open No. 61-286393.
  • the proportion of the alkoxysilane represented by the formula (7) is 1 mol% or more in order to obtain good liquid crystal alignment in all alkoxysilanes used for obtaining the polysiloxane (A), that is, in the alkoxysilane component. Is preferable, 1.5 mol% or more is more preferable, and 2 mol% or more is more preferable. Further, in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed, the content is preferably 30 mol% or less, more preferably 25 mol% or less, and further preferably 20 mol% or less.
  • R 121 , R 122 and R 123 of the alkoxysilane represented by the formula (9) are preferably —OCH 3 or —OC 2 H 5 respectively.
  • Y 21 of the alkoxysilane represented by the formula (9) is preferably a single bond or a linear hydrocarbon group having 3 to 5 carbon atoms.
  • Y 22 of the alkoxysilane represented by the formula (9) is preferably a single bond.
  • Y 23 is preferably a single bond.
  • Y 24 is preferably a single bond or a linear hydrocarbon group having 1 to 3 carbon atoms.
  • Y 25 is preferably a single bond, —O— or —NH—.
  • Cy is preferably 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.
  • the alkoxysilane represented by the formula (7) and the alkoxysilane represented by the formula (9) may each be one type or two or more types.
  • the liquid crystal aligning agent used is demonstrated. It is not clear why this liquid crystal aligning agent can achieve both response speed characteristics and good vertical alignment properties (vertical alignment force), and both characteristics are remarkably good. However, it is derived from the alkoxysilane represented by the formula (7), develops vertical alignment (tilt), and has a side chain having a structure similar to the liquid crystal skeleton, and the alkoxysilane represented by the formula (9).
  • polysiloxane (A) having a side chain having a cyclic group and a (meth) acryloyl group derived from it it is presumed that the response speed and the vertical alignment which are usually in a trade-off relationship are compatible. .
  • the liquid crystal aligning agent of the present invention is less expensive than an expensive polyimide, the liquid crystal aligning agent of the present invention can be manufactured at low cost and has high versatility.
  • the blending ratio of each alkoxysilane is not particularly limited, but the alkoxysilane represented by the formula (1) is preferably a total alkoxysilane as a raw material used for obtaining the polysiloxane (A), that is, in the alkoxysilane component, It is 2 to 20 mol%, particularly preferably 3 to 15 mol%.
  • the alkoxysilane represented by the formula (3) is preferably 5 to 30 mol% in the alkoxysilane component used to obtain the polysiloxane (A).
  • an alkoxysilane represented by the above formula (10) is also used as a raw material. can do. That is, as the alkoxysilane component used for obtaining the polysiloxane (A), an alkoxysilane represented by the above formula (10) can also be used.
  • R 103 of the alkoxysilane represented by the formula (10) is an alkyl group in which a hydrogen atom is substituted with a (meth) acryloyl group, a (meth) acryloyloxy 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 104 of the alkoxysilane represented by the formula (10) is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms.
  • alkoxysilane represented by the formula (10) include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane, 3- (N-styryl) Examples include, but are not limited to, methyl-2-aminoethylamino) propyltrimethoxysilane.
  • the proportion of the alkoxysilane represented by the formula (10) is preferably 5 to 80 mol%, particularly preferably 10 to 70 mol% in the alkoxysilane component used to obtain the polysiloxane (A). Further, the alkoxysilane represented by the formula (10) may be one type or two or more types.
  • alkoxysilane represented by the above formula (12) can also be used as a raw material. That is, as the alkoxysilane component used for obtaining the polysiloxane (A), an alkoxysilane represented by the above formula (12) can also be used. Since the alkoxysilane represented by the formula (12) can impart various properties to the polysiloxane, one or more types can be selected and used according to the required properties.
  • the proportion of the alkoxysilane represented by the formula (12) is preferably 1 to 20 mol% in the alkoxysilane component used for obtaining the polysiloxane (A).
  • R 113 of the alkoxysilane represented by the formula (12) is preferably an amino group, glycidic group, a ureido group.
  • R 114 is preferably an alkyl group of 1 to 3, and n2 represents an integer of 0 to 3, preferably 0 to 2.
  • alkoxysilane represented by the formula (12) include 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, diethyldiethoxysilane , Dieth
  • the alkoxysilane in which n2 is 0 is tetraalkoxysilane.
  • Tetraalkoxysilane easily undergoes a polycondensation reaction with the alkoxysilane represented by the formulas (7), (9) and (10), so that the polysiloxane (A) contained in the liquid crystal aligning agent of the present invention is obtained. preferable.
  • tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
  • the proportion of the alkoxysilane represented by the formula (12) in which n2 is 1 to 3 is preferably 1 to 20 mol%, particularly preferably 1 to 2 in the alkoxysilane component used to obtain the polysiloxane (A). 10 mol%.
  • the proportion of the alkoxysilane represented by the formula (12) in which n2 is 0 is preferably 1 to 50 mol%, particularly preferably 5 to 5 in the alkoxysilane component used for obtaining the polysiloxane (A). 40 mol%.
  • the alkoxysilane represented by Formula (12) may be one type or two or more types.
  • the liquid crystal aligning agent of this invention may contain other polysiloxane with polysiloxane (A).
  • the other polysiloxane include polysiloxane (B), which is a polysiloxane obtained by reacting an alkoxysilane component containing an alkoxysilane represented by the above formula (11).
  • the polysiloxane component which is a raw material of the polysiloxane (B) preferably contains 20 to 100 mol%, more preferably 50 to 100%, of the polysiloxane represented by the formula (11).
  • alkoxysilane represented by the formula (11) tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
  • the polysiloxane (B) is a polysiloxane obtained by reacting an alkoxysilane component containing an alkoxysilane represented by the following formula (13) in addition to the alkoxysilane represented by the formula (11). There may be.
  • a liquid crystal aligning agent containing a polysiloxane (B) obtained by reacting an alkoxysilane component containing an alkoxysilane represented by the formula (13) is particularly desirable because of its high vertical alignment force.
  • R 119 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 120 is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms.
  • alkoxysilane represented by the formula (13) include, for example, methyltriethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxy.
  • Examples include, but are not limited to, silane.
  • the polysiloxane (B) is a polysiloxane obtained by reacting an alkoxysilane component containing an alkoxysilane represented by the above formula (10) in addition to the alkoxysilane represented by the formula (11). There may be.
  • the alkoxy represented by the formula (10) is used.
  • the proportion of silane is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more in the alkoxysilane component used to obtain polysiloxane (B).
  • 75 mol% or less is preferable and 65 mol% or less is more preferable.
  • the polysiloxane (B) is represented by the above formula (12) as long as the effects of the present invention are not impaired for the purpose of imparting various properties such as adhesion to the substrate and improvement in affinity with liquid crystal molecules. It may be a polysiloxane obtained by reacting an alkoxysilane component containing an alkoxysilane.
  • the proportion of the alkoxysilane represented by the formula (12) is preferably 1 to 20 mol%, particularly preferably 1 to 10 mol%, in the alkoxysilane component used for obtaining the polysiloxane (A).
  • Each of the alkoxysilanes may be one type or two or more types.
  • the blending ratio of the polysiloxane of the liquid crystal aligning agent containing polysiloxane (A) and other polysiloxane such as polysiloxane (B) is not particularly limited, but is based on the total amount of polysiloxane contained in the liquid crystal aligning agent.
  • the polysiloxane (A) is preferably 10% by mass or more.
  • polysiloxane (A): polysiloxane (B) 10: 90 to 50:50 in terms of mass ratio.
  • the method for obtaining the polysiloxane used in the present invention is not particularly limited, and an alkoxysilane component may be reacted.
  • an alkoxysilane component having the alkoxysilane represented by the above formula (7) and the alkoxysilane represented by the formula (10) as an essential component is reacted in an organic solvent (for example, (Polycondensation reaction).
  • organic solvent for example, (Polycondensation reaction).
  • polysiloxane is obtained as a solution in which such an alkoxysilane component is polycondensed and uniformly dissolved in an organic solvent.
  • Examples of the method of polycondensing alkoxysilane to obtain polysiloxane include a method of hydrolyzing and condensing alkoxysilane in a solvent such as alcohol or glycol.
  • 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 reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
  • acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid, alkalis such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc.
  • Catalysts such as metal salts such as hydrochloric acid, sulfuric acid and nitric acid are 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. In that case, the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. A method of heating for several tens of minutes to several tens of hours under reflux is preferred so that the liquid does not evaporate or volatilize.
  • a plurality of types of alkoxysilanes are used.
  • a mixture of alkoxysilanes in advance may be mixed, or a plurality of types of alkoxysilanes may be sequentially mixed. That is, there is no limitation on the order in which the alkoxysilane components are reacted.
  • the alkoxysilane components may be reacted at once, or after some alkoxysilanes are reacted, other alkoxysilanes are added. You may make it react.
  • an alkoxysilane represented by formula (7), an alkoxysilane represented by formula (9), and an alkoxysilane represented by formula (10) may be mixed and subjected to a polycondensation reaction.
  • the alkoxysilane represented by formula (9) is added and reacted. May be.
  • the solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it can dissolve 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 , 5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol and other glycols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether , Ethylene glycol monobutyl, ethylene
  • the polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all 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.
  • the polysiloxane polymerization solution obtained by the above method may be used as a polymer component as it is. If necessary, the solution obtained by the above method is concentrated or a solvent is added.
  • the polymer component may be diluted or substituted with another solvent.
  • the solvent to be used hereinafter also referred to as additive solvent
  • the additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one kind or plural kinds can be arbitrarily selected and used.
  • the additive solvent include, in addition to the solvents mentioned as examples of the polymerization solvent, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and esters such as methyl acetate, ethyl acetate, and ethyl lactate. It is done. 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 liquid crystal aligning agent of the present invention usually needs to form a uniform thin film having a thickness of 10 to 1000 nm on the substrate when preparing the liquid crystal aligning film, the photoreactive group-containing crosslinkable compound and the polymer component
  • a coating solution containing an organic solvent for dissolving these components is preferable.
  • the content of the organic solvent is preferably 90 to 99% by mass in the liquid crystal aligning agent from the viewpoint of forming a uniform thin film by coating. 97 mass% is more preferable. These contents can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.
  • the liquid crystal aligning agent of the present invention may contain an additive component as long as the effects of the present invention are not impaired in addition to the photoreactive group-containing crosslinkable compound, the polymer component, and the organic solvent. Good.
  • the additive component include a compound for improving the adhesion between the liquid crystal alignment film and the substrate, and a surfactant for enhancing the flatness of the coating film.
  • the compound for improving the adhesion between the coating film and the substrate include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane.
  • Silane N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N -Ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxy Cyril-1,4,7 -Triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-
  • Examples of the surfactant for improving the flatness of the coating film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 ( As mentioned above, Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, Asahi Glass Co., Ltd.) and the like can be mentioned.
  • the content of these surfactants is preferably 0.01 to 2% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the polymer component.
  • the liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation or the like, or without an alignment treatment in vertical alignment applications.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate; a plastic substrate such as an acrylic substrate or a polycarbonate substrate; Further, it is preferable to use a substrate on which an ITO or IZO electrode for driving a liquid crystal is formed from the viewpoint of simplifying the process.
  • an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as metal aluminum can be used as the electrode.
  • the application method of the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, ink jet, or the like is common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose. Firing after applying the liquid crystal aligning agent can be performed at an arbitrary temperature of 100 to 350 ° C., preferably 120 to 300 ° C., more preferably 150 to 250 ° C. This baking can be performed with a hot plate, a hot-air circulating furnace, an infrared furnace, or the like.
  • the thickness of the coating film after baking is preferably 5 to 300 nm, more preferably The thickness is 10 to 150 nm, more preferably 50 to 100 nm.
  • the liquid crystal display element of the present invention is formed by two substrates arranged to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent of the present invention provided between the substrate and the liquid crystal layer.
  • a liquid crystal display element comprising a liquid crystal cell having the liquid crystal alignment film.
  • the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other.
  • the liquid crystal aligning film formed of the liquid crystal aligning agent of the present invention ultraviolet rays were applied while applying a voltage to the liquid crystal aligning film and the liquid crystal layer, and reacted with the polyimide precursor, polyimide, and polysiloxane during firing.
  • the photopolymerizable group of the crosslinkable compound of the present invention that is, the photopolymerizable group derived from the crosslinkable compound represented by Py 1 and Py 2 in the formula [1]
  • the alignment of the liquid crystal is efficiently performed. Is fixed, and the liquid crystal display device is remarkably excellent in response speed.
  • the substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed.
  • a substrate on which a transparent electrode for driving liquid crystal As a specific example, the thing similar to the board
  • a substrate provided with a conventional electrode pattern or protrusion pattern may be used, but in the liquid crystal display element of the present invention, the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent for forming the liquid crystal aligning film. It is possible to operate even in 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 projection pattern is not formed on the opposite substrate. The process can be simplified and high transmittance can be obtained.
  • a high-performance element such as a TFT type element
  • an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.
  • the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method, for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Alternatively, MLC-2041 or the like can be used.
  • a liquid crystal material used in a conventional vertical alignment method for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Alternatively, MLC-2041 or the like can be used.
  • a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal.
  • a liquid crystal cell can also be produced by a method in which the other substrate is bonded to the inside so as to be inside and sealed.
  • the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes installed on the substrate. And applying ultraviolet rays while maintaining this electric field.
  • the voltage applied between the electrodes is, for example, 5 to 80 Vp-p, preferably 5 to 60 Vp-p.
  • the amount of ultraviolet irradiation is, for example, 1 to 60 J / cm 2 , preferably 40 J / cm 2 or less, and the smaller the amount of ultraviolet irradiation, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, In addition, the production efficiency is improved by reducing the ultraviolet irradiation time, which is preferable.
  • the photopolymerizable group of the crosslinkable compound of the present invention that has reacted with the polyimide precursor, polyimide, or polysiloxane during firing, that is, the formula [ during 1]
  • the reaction of the photopolymerizable group derived from the crosslinking compound represented by Py 1 and Py 2 proceeds, the resulting cross-linked site by the tilt directions are the liquid crystal molecules are stored, a liquid crystal display obtained
  • the response speed of the element can be increased.
  • the liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but is also produced by a rubbing process or a photo alignment process.
  • the liquid crystal alignment film can be used suitably.
  • BODA Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • TCA 2,3,5 -Tricarboxycyclopentyl acetate dianhydride
  • PCH 1,3-diamino-3- [4- (4-heptylcyclohexyl) phenoxy] benzene
  • DA-Col Cholestanyl 3,5-diaminobenzoate
  • DBA 3,5-diaminobenzoic acid
  • DA-1 2- ( Methacryloyloxy) ethyl 3,5-diaminobenzoate
  • DA-2 N 1 , N 1 -diarylbenzene-1, 2, 4-triamine
  • 3-AMP 3-Picolylamine (NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve DMF: N, N-dimethylformamide THF: Tetrahydrofuran TEOS: Tetraethoxysilane MPMS: 3-Methacryloxypropyltrimethoxysilane VTMS: Tri Methoxyvinylsilane UPS: 3-ureidopropyltriethoxysilane SMA: HG: 2-methyl-2,4-pentanediol
  • Step 1 Synthesis of CL-1 (Step 1) Synthesis of CL-1 which is a precursor of CL-1 In a 500 mL four-necked flask, 10.9 g of 3,3 ′, 5,5′-tetrakis (methoxymethyl)-[1,1′-biphenyl] -4,4′-diol, 200 mL of DMF, 6-chloro- 12.3 g of 1-hexanol, 24.9 g of potassium carbonate and 2.5 g of potassium iodide were added and stirred while heating to 100 ° C.
  • Step 2 Synthesis of CL-1 from precursor To a 300 mL four-necked flask, 16.9 g of CL-1-1, 7.30 g of triethylamine, and 160 mL of THF were added. The system was cooled to 0 ° C., 7.30 g of methacryloyl chloride was added, and the mixture was stirred at room temperature (rt: 25 ° C.). After completion of the reaction, the reaction system was poured into 500 mL of water and extracted with ethyl acetate. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated using a rotary evaporator to obtain 14.1 g of CL-1 (yellow viscous body) (yield 67%).
  • Step 2 Synthesis of CL-2 which is a precursor of CL-2
  • CL-2-1 a precursor of CL-2
  • THF triethylamine
  • the system was brought to 0 ° C., 12.6 g of methanesulfonyl chloride was added, and room temperature (rt: 25 ° C.) was added.
  • room temperature room temperature (rt: 25 ° C.) was added.
  • the reaction system was poured into 1 L of water, 500 mL of ethyl acetate was added, and extraction was performed using saturated brine.
  • Step 3 Synthesis of CL-2-3, a precursor of CL-2
  • 10.9 g of 3,3 ′, 5,5′-tetrakis (methoxymethyl)-[1,1′-biphenyl] -4,4′-diol, 200 mL of DMF, CL-2- 21.4 g of 2 and 24.9 g of potassium carbonate were added and stirred while heating to 100 ° C.
  • the reaction system was poured into 1 L of water, neutralized with 1N-hydrochloric acid (HCl) aqueous solution, and the precipitate was filtered. The filtrate was washed with methanol and dried.
  • HCl 1N-hydrochloric acid
  • the imidation ratio of polyimide in the examples was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (Kusano Kagaku, NMR sampling tube standard ⁇ 5), add 1.0 mL of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture), and ultrasonic To dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum.
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is the proton peak integrated value derived from the NH group of the amic acid
  • y is the peak integrated value of the reference proton
  • ⁇ is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%) 1 This is the ratio of the number of reference protons to one.
  • NMP 29.3 g was added to the obtained polyimide powder (A) (6.0 g) and dissolved by stirring at room temperature for 5 hours.
  • a 1% by mass 3-AMP solution 6.0 g
  • NMP 18.7 g
  • BCS 40.0 g
  • the liquid crystal aligning agent (A1) was stirred at room temperature for 10 hours. Obtained.
  • 60 mg (10% by mass with respect to the polymer component) of the crosslinking agent CL-1 was added to 10.0 g of the liquid crystal aligning agent (A1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare the liquid crystal aligning agent (A2). did.
  • Example 2> After obtaining the liquid crystal aligning agent (A1) in the same manner as in Example 1, 60 mg (10% by mass with respect to the solid content) of the crosslinking agent CL-2 was added to 10.0 g of the liquid crystal aligning agent (A1), and at room temperature. The liquid crystal aligning agent (A3) was prepared by stirring for 3 hours to dissolve.
  • ⁇ Comparative Example 1> After obtaining liquid crystal aligning agent (A1) like Example 1, 60 mg (10 mass% with respect to a polymer component) polymeric compound RM is added to 10.0 g of liquid crystal aligning agent (A1), and it is room temperature. The liquid crystal aligning agent (A4) was prepared by stirring for 3 hours to dissolve.
  • NMP 29.3 g was added to the obtained polyimide powder (B) (6.0 g), and dissolved by stirring at room temperature for 5 hours.
  • a 1% by mass 3-AMP solution 6.0 g
  • BCS 40.0 g
  • the liquid crystal aligning agent (B1) was stirred at room temperature for 10 hours. Obtained.
  • 60 mg (10% by mass with respect to the polymer component) of the crosslinking agent CL-1 was added to 10.0 g of the liquid crystal aligning agent (B1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare the liquid crystal aligning agent (B2). did.
  • TCA 5.60 g, 25.0 mmol
  • DBA 3.04 g, 20.0 mmol
  • DA-1 5.29 g, 20.0 mmol
  • DA-Col 5.23 g, 10.0 mmol
  • CBDA 4.80 g, 24.5 mmol
  • NMP 24.0 g
  • NMP (24.0 g) was added to the obtained polyimide powder (C) (6.0 g) and dissolved by stirring at room temperature for 5 hours.
  • NMP (40.0g) and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent (C1) was obtained by stirring at room temperature for 5 hours.
  • 60 mg (10% by mass with respect to the polymer component) of the crosslinking agent CL-1 was added to 10.0 g of the liquid crystal aligning agent (C1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare the liquid crystal aligning agent (C2). did.
  • Example 5 In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 21.2 g of HG, BCS 7.1 g, TEOS 24.6 g, SMA 4.1 g, MPMS 14.9 g, and VTMS 1.5 g were mixed to obtain an alkoxysilane monomer solution.
  • the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance.
  • the mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO2 equivalent concentration of 12% by weight.
  • the resulting polysiloxane solution 10.0g and BCS20.0g were mixed to obtain in terms of SiO 2 concentration of 4 wt% of the liquid crystal alignment agent (D1).
  • a solution prepared by mixing 9.9 g of HG, 3.3 g of BCS, 10.8 g of water and 1.4 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes.
  • the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance.
  • the mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by weight.
  • the resulting polysiloxane solution 10.0g and BCS20.0g were mixed to obtain in terms of SiO 2 concentration of 4 wt% of the liquid crystal alignment agent (S1).
  • the liquid crystal aligning agent intermediate (S1) and the liquid crystal aligning agent intermediate (U1) were mixed at a ratio of 2: 8 to obtain a liquid crystal aligning agent (E1) having a SiO 2 equivalent concentration of 4% by weight. Further, 40 mg of cross-linking agent CL-1 (10% by mass with respect to the polymer component in terms of SiO 2 ) was added to 10.0 g of the liquid crystal aligning agent (E1) and dissolved by stirring for 3 hours at room temperature. (E2) was prepared.
  • liquid crystal cells were prepared according to the following procedure.
  • the liquid crystal aligning agent was spin-coated on the ITO surface of the 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, and dried on an 80 ° C. hot plate for 90 seconds, Baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to produce a substrate on which a liquid crystal alignment film having a thickness of 100 nm was formed.
  • liquid crystal aligning agent used for the substrate preparation was spin-coated on the ITO surface on which no electrode pattern was formed, dried on an 80 ° C. hot plate for 90 seconds, and then heated in a hot air circulation oven at 200 ° C. for 30 minutes. Firing was performed to produce a substrate on which a liquid crystal alignment film having a thickness of 100 nm was formed.
  • a bead spacer having a diameter of 6 ⁇ m was sprayed on the liquid crystal alignment film of one of the two substrates, and a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed thereon.
  • a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed thereon.
  • the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell.
  • a negative liquid crystal (MLC-6608 manufactured by Merck & Co., Inc.) was injected into the empty cell by a reduced pressure injection method, and the liquid crystal was subjected to realignment treatment at 120 ° C. for 1 hour to produce a liquid crystal cell.
  • the response speed of the obtained liquid crystal cell was measured by the following method.
  • the liquid crystal cell produced as described above was placed between a pair of polarizing plates in a measuring apparatus configured in the order of a backlight, a set of polarizing plates to be in a crossed Nicol state, and a light amount detector.
  • the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols.
  • a rectangular wave with a voltage of ⁇ 4 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied is obtained.
  • a voltage of 0% and ⁇ 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.
  • a polymerizable compound having a ring structure mother nucleus is poor in solubility and does not precipitate during frozen storage or dissolves depending on the type of the orientation agent. It was confirmed that since the interaction between the structures is suppressed, the solubility is high, and precipitation does not occur even when stored frozen, so that the storage stability is excellent.
  • the liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention can be a liquid crystal display device having excellent pretilt angle stability, and is a vertical alignment type (VA mode) liquid crystal display element, TN liquid crystal element, STN. It is useful for liquid crystal elements, TFT liquid crystal elements, and the like. It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2013-049557 filed on March 12, 2013 is cited here as the disclosure of the specification of the present invention. Incorporated.

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Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui présente une excellente stabilité au stockage pendant un stockage réfrigéré en utilisant un composé réticulable qui comprend un groupe photoréactif et a une solubilité élevée dans des agents d'alignement de cristaux liquides. Cet agent d'alignement de cristaux liquides est capable d'améliorer la vitesse de réponse d'un élément d'affichage à cristaux liquides qui comprend un film d'alignement de cristaux liquides qui est formé à partir de cet agent d'alignement de cristaux liquides. L'invention concerne également un agent d'alignement de cristaux liquides qui contient un composé réticulable représenté par la formule [1] dans laquelle deux groupes polymérisables ou plus (Py1, Py2) et dix groupes réticulables ou moins (CL1, CL2) sont liés à un noyau parent qui est composé d'un groupe organique divalent ou de valence supérieure. (Dans la formule [1], L-M-R représente un noyau parent ; chacun de L et R représente un cycle carbone ou un cycle hétérocyclique ayant 4 à 12 atomes de carbone ; M représente une simple liaison ou similaire ; chacun de S1, S2, S3 et S4 représente une simple liaison ou similaire ; chacun de l, o, n et m représente un nombre entier de 1 ou plus, n + m vaut 10 ou moins ; et l + o vaut 10 ou moins.)
PCT/JP2014/056488 2013-03-12 2014-03-12 Agent d'alignement de cristaux liquides contenant un composé réticulable ayant un groupe photoréactif Ceased WO2014142168A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2015505513A JP6387957B2 (ja) 2013-03-12 2014-03-12 光反応性基を有する架橋性化合物を含有する液晶配向剤
CN201480014584.6A CN105190414B (zh) 2013-03-12 2014-03-12 包含具有光反应性基团的交联性化合物的液晶取向剂
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JP7438695B2 (ja) 2018-09-06 2024-02-27 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 重合性化合物を含む液晶媒体
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KR102811125B1 (ko) 2018-09-06 2025-05-22 메르크 파텐트 게엠베하 중합성 화합물을 포함하는 액정 매질
JPWO2020153311A1 (ja) * 2019-01-22 2021-11-25 日産化学株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
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CN116023951A (zh) * 2021-10-26 2023-04-28 Jsr株式会社 液晶取向剂、液晶取向膜及其制造方法、液晶元件以及聚合体

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CN105190414B (zh) 2018-02-06
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