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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/56—Aligning agents

Definitions

• Silicon-based liquid crystal aligning agent, liquid crystal aligning film, and production method thereof are Silicon-based liquid crystal aligning agent, liquid crystal aligning film, and production method thereof.
• the present invention relates to a liquid crystal aligning agent mainly containing a polysiloxane mixture obtained by polycondensation of alkoxysilane, a method for producing the same, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and the liquid crystal aligning film
• the present invention relates to a liquid crystal display element having
• a liquid crystal display element has a structure in which two substrates, each having a liquid crystal alignment film mainly composed of polyamic acid or polyimide on a transparent electrode, are arranged to face each other, and a liquid crystal material is filled in a gap between the two substrates. It is generally known that there is. The most well-known method is the power of a TN (Twisted Nematic) type liquid crystal display device. A higher contrast ratio can be realized. 3 ⁇ 4 STN (Super Twisted Nematic) type and IPS (less viewing angle dependency) In-plane switching (VA) and vertical alignment (VA) types have been developed.
• TN Transmission Nematic
• vertical alignment type liquid crystal display elements driven by thin film transistors have the characteristics of an ultra-wide viewing angle and high contrast, which have a fast response speed, and demanded further improvements in quality.
• a new vertical alignment type liquid crystal display device has been proposed, such as MVA (Multi_domain Vertical Alignment), ASV (Advanced Super View) and PVA (Patterned Vertical Alignment).
• liquid crystal alignment film provided in these liquid crystal display elements aligns the liquid crystal and has a great influence on various characteristics such as electrical characteristics of the liquid crystal display element. Therefore, a liquid crystal alignment film suitable for such a new vertical alignment type display element has been developed.
• liquid crystal display elements The reliability of liquid crystal display elements is very important because it directly affects the yield improvement in the manufacturing process, not just the reliability of the display characteristics of monitors and televisions.
• the yield in the manufacturing process has a greater influence on the productivity of the liquid crystal display element than in the past.
• Sex has become very important. That is, to improve the productivity of large liquid crystal display elements, it is essential to improve the reliability of the liquid crystal display elements.
• the liquid crystal alignment film is excellent in liquid crystal alignment and has a high voltage holding ratio in element driving at a low frequency under high temperature. There is a great demand.
• Patent Document 1 Japanese Patent Laid-Open No. 06-3678
• Patent Document 2 Japanese Patent Laid-Open No. 09-278724
• Patent Document 3 Japanese Patent Laid-Open No. 2001-311080
• Patent Document 4 Japanese Patent Laid-Open No. 2005-250244
• Patent Document 5 JP 2001-264805 A
• the present invention relates to a silicon-based liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having good liquid crystal alignment and having a high voltage holding ratio in element driving at a low frequency under high temperature, and a method for producing the same.
• Another object of the present invention is to provide a liquid crystal alignment film obtained from a silicon-based liquid crystal alignment agent, and a liquid crystal display device having the liquid crystal alignment film.
• the present invention has the following gist.
• a liquid crystal aligning agent comprising the following polysiloxane (A), polysiloxane (B), and an organic solvent that dissolves these polysiloxanes.
• R 3 represents a hydrocarbon group having 1 to 5 carbon atoms.
• a liquid crystal aligning agent comprising the following polysiloxane (A) solution and polysiloxane (B) solution.
• Polysiloxane (A) solution a polysiloxane solution obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (1) in an organic solvent,
• R 3 represents a hydrocarbon group having 1 to 5 carbon atoms.
• R 4 is a hydrocarbon group having 1 to 5 carbon atoms
• R 5 is a hydrogen atom or an organic group having 1 to 5 carbon atoms
• n is an integer of 0 to 3
• Polysiloxane (B) is further at least one alkoxysilane represented by the formula (4): 4.
• R 6 represents a hydrocarbon group having 1 to 5 carbon atoms
• R 7 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms
• m represents an integer of 1 or 2.
• Polysiloxane (A) is a polysiloxane obtained by polycondensation of alkoxysilane and tetraethoxysilane represented by formula (1), and polysiloxane (B) is obtained by converting tetraethoxysilane. 3.
• the liquid crystal aligning agent of description The liquid crystal aligning agent of description.
• a liquid crystal display device having the liquid crystal alignment film as described in 8 above.
• a method for producing a liquid crystal aligning agent comprising a step of mixing a polysiloxane (A) solution and a polysiloxane (B) solution described below.
• Polysiloxane (A) solution a polysiloxane solution obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (1) in an organic solvent,
• R 3 represents a hydrocarbon group having 1 to 5 carbon atoms.
• liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal aligning film having good liquid crystal alignment and having a high voltage holding ratio in element driving at a low frequency under high temperature. Therefore, a highly reliable liquid crystal display element can be provided.
• FIG. 1 is a result of analyzing the distribution of elements in the direction from the surface of the film to the substrate of the liquid crystal alignment film obtained from the liquid crystal aligning agent (L5) of the present invention.
• FIG. 2 shows the result of analyzing the distribution of elements from the surface of the film to the substrate with respect to the coating film obtained from the polysiloxane solution (P2) of Comparative Example 1.
• the polysiloxane (A) used in the present invention is obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (1).
• R 1 in the formula (1) is an organic group having 8 to 30 carbon atoms, but has a ring structure such as an aliphatic hydrocarbon, an aliphatic ring, an aromatic ring, and a hetero ring, or an unsaturated bond. In addition, it may have a branched structure that may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
• the organic group may be substituted with a halogen atom, a bur group, an amino group, a glycidoxy group, a mercapto group, a urea group, a methacryloxy group, an isocyanate group, an attaryloxy group, or the like.
• an organic group R 1 examples include an alkyl group, a perfluoroalkyl group, an arolekenyl group, an allyloxyalkyl group, a phenethyl group, a perfluorophenylalkyl group, a phenylaminoalkyl group, Styrylalkyl group, naphthyl group, benzoyloxylalkyl group, alkoxyphenoxyalkyl group, cycloalkylaminoalkyl group, epoxycycloalkyl group, N- (aminoalkyl) aminoalkynole group, N- (aminoalkyl) An aminoalkylphenethyl group, a bromoalkyl group, a diphenylphosphino group, an N— (methacrylaminoalkyl group, and the like can be given.
• organic group R 1 an alkyl group having 8 to 30 carbon atoms is preferable.
• More preferred is an alkyl group of 0.
• R 2 in the formula (1) represents a hydrocarbon group, but a smaller hydrocarbon number is more reactive, so a saturated hydrocarbon group having 1 to 5 carbon atoms is preferable. More preferred are a methyl group, an ethyl group, a propyl group, and a butyl group.
• At least one of the alkoxysilanes represented by the formula (1) may be used, but plural kinds may be used as necessary.
• alkoxysilane represented by the formula (1) include octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decinotritriethoxysilane, , Hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecinoletrimethoxysilane, octadecinoletriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyl Triethoxysilane, undecyltrimethoxysilane, 21-docosenyltriethoxysilane, allyloxyundecyltriethoxysilane, tridecafluorooctyltrimethoxysilane,
• the polysiloxane (A) used in the present invention is obtained by polycondensation of an alkoxysilane containing the formula (1), but it is in a homogeneous solution state in a solvent.
• the polysiloxane (A) used in the present invention is preferably one obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the following formula (3).
• R 4 in the formula (3) represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having carbon numbers:! To 5 and more preferably a methyl group, an ethyl group, A propyl group and a butyl group.
• R 5 in formula (3) is a hydrogen atom or an organic group having 1 to 5 carbon atoms.
• the organic group is not particularly limited as long as it has 1 to 5 carbon atoms. This organic group may contain a hetero atom such as an oxygen atom, a nitrogen atom and a sulfur atom, or may have an unsaturated bond or a ring structure.
• saturated hydrocarbon groups such as methinole group, ethyl group, isopropyl group and n-propyl group
• unsaturated hydrocarbon groups such as bur group, amino group, glycidoxy group, mercapto group, ureido group and isocyanate group. It may be substituted with.
• N in the formula (3) represents an integer of 0 to 3.
• n when n is 0, it represents tetraalkoxysilane.
• alkoxysilane represented by the formula (3) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methinoretriethoxysilane, Ethinotritrimethoxysilane, Ethinotritriethoxysilane, Provirtrimethoxysilane, Propyltriethoxysilane, Methyltripropoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, N-2 ( Aminoethyl) 3-Aminopropyltriethoxysilane, N-2 (Aminoethyl) 3-Aminopropyltrimethoxysilane, 3- (2-Aminoethylaminopropyl) trimethoxysilane, 3- (2-Aminoethyl) trimethoxys
• alkoxysilane represented by the formula (3) used in the present invention may be used singly or as needed as needed.
• the use of tetraalkoxysilanes in which n is 0 is easy to polycondense with the alkoxysilane represented by the formula (1). Les, so it is preferred to obtain polysiloxane (A).
• the use ratio of the alkoxysilane represented by the formula (1) is less than 2 mol% in the total alkoxysilane used to obtain the polysiloxane (A)
• good liquid crystal orientation is obtained. In some cases, 2 mol% or more is preferable. More preferably, it is 3 mol% or more.
• the liquid crystal alignment film to be formed may not be cured sufficiently, so 30 mol% or less is preferred. More preferably, the content is 22 mol% or less.
• one or more of the above-described polysiloxanes (A) can be used.
• the solution of polysiloxane (A) described above is preferably a uniformly dissolved solution obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (1) in an organic solvent.
• a solution of polysiloxane (A) is a solution in which an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the formula (3) are used in combination for polycondensation and dissolved uniformly in an organic solvent. preferable.
• the polycondensation method of the polysiloxane (A) used in the present invention is not particularly limited, and examples thereof include a method of hydrolysis and polycondensation of alkoxysilane in an alcohol solvent.
• the hydrolysis' polycondensation reaction may be either partial hydrolysis or complete hydrolysis.
• complete hydrolysis theoretically, 0.5 to 5 moles of water of all alkoxy groups in the alkoxysilane may be added, but it is usually preferable to add an excess amount of water over 0.5 moles.
• the amount of water used in the above reaction is a force that can be appropriately selected as desired. Usually, it is preferably 0.5 to 2.5 moles of all alkoxy groups in the alkoxysilane.
• acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, alkalis such as ammonia, methenoreamine, ethylamine, ethanolanol, and triethylamine are used.
• Catalysts such as metal salts such as hydrochloric acid, sulfuric acid and nitric acid are used.
• the heating temperature and the heating time can be appropriately selected as desired. Examples thereof include heating and stirring at 50 ° C. for 24 hours, and heating and stirring for 1 hour under reflux.
• a method of heating and polycondensing a mixture of an alkoxysilane, a solvent and oxalic acid can be mentioned.
• a method in which oxalic acid is previously added to alcohol to form an alcohol solution of oxalic acid, and then the alkoxysilane is mixed while the solution is heated is generally 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of the alkoxysilane.
• the heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and preferably, for example, in a sealed container or under reflux, several tens to ten times so as not to cause evaporation or volatilization of the liquid. Done for a few hours.
• the alkoxysilanes may be mixed in advance to form a mixture, or a plurality of alkoxysilanes may be sequentially mixed.
• the solvent used for polycondensation of alkoxysilane is not particularly limited as long as it dissolves alkoxysilane.
• alcohols, glycols, or organic solvents having good compatibility with alcohols are used.
• organic solvent examples include methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, hexyl glycolol, methyl cecrosolve, ethinoreserosonoreb, butylcellosonolev, Ethyl canolitol, Butinorecanolbitolole, Ethylene glycol monomethyl ether, Ethylene glycol noremethylenotenol, Ethylene glycololene n-Butinoleethenole, Diethyleneglycololinoremonomethylenoleetenore, Diethyleneglycolenoremonobutinore Etherenole, diethyleneglycone resin methinoleatenore, propylene glycol monomethino ethenore, propylene glycol monobutyl ether, N-methyl _2 pyrrolidone, , Nyu- dimethyl
• the solution of polysiloxane (A) obtained by such a method is a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO (hereinafter referred to as SiO-concentrated concentration).
• the solution obtained by the above-described method may be used as it is as the polysiloxane (A) solution, and the solution obtained by the above-described method may be concentrated or dissolved as necessary. It is also possible to dilute the medium with a solvent or replace it with another solvent to prepare a solution of polysiloxane (A).
• the solvent used may be the same solvent used for the polycondensation or may be another solvent.
• the solvent is not particularly limited as long as the polysiloxane (A) is uniformly dissolved, and one kind or a plurality of kinds can be arbitrarily selected and used.
• Such a solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethylene glycol, diethylene glycol, Glycols such as propylene glycol and hexylene glycol; methyl cetosolve, ethylcete solve, butylcetosolve, ethyl carbitol, butinorecanolebitonore, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol nole Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl Glycol-no-ethers such as ether and propylene glycol monobutyl ether; esters such as acetic acid methyl ester, acetic acid e
• the polysiloxane (A) solution obtained as described above may be used singly or in combination.
• the polysiloxane (B) used in the present invention is a tetraalkoxysilane represented by the formula (2) Is a polysiloxane obtained by polycondensation of an alkoxysilane containing.
• R 3 in the above formula (2) is a hydrocarbon group having 1 to 5 carbon atoms, and is preferably a saturated hydrocarbon group having 1 to 5 carbon atoms because it has a low reactive force with a small number of carbon atoms. More preferred are a methyl group, an ethyl group, a propyl group and a butyl group.
• tetraalkoxysilane represented by the above formula (2) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, and are easily available as commercial products. .
• the polysiloxane (B) can be used in combination with a tetraalkoxysilane represented by the formula (2) and at least one of the alkoxysilanes represented by the following formula (4):
• the alkoxysilane represented by the above formula (4) is a so-called bifunctional or trifunctional alkoxysilane having preferably two or three alkoxy groups.
• R 6 in the formula (4) is a hydrocarbon group having 1 to 5 carbon atoms, like R 3 , but has a low carbon number, and is highly reactive, so a saturated hydrocarbon group having 1 to 5 carbon atoms. Is preferred. More preferred are a methyl group, an ethyl group, a propyl group, and a butyl group.
• R 7 in the above formula (4) represents a hydrogen atom or an organic group having carbon atoms:! To 6, preferably 1 to 5.
• organic groups include aromatic groups, aliphatic groups, and groups having an alicyclic structure.
• aliphatic groups having carbon numbers of 5 to 5 are preferable, and saturated hydrocarbon groups having 1 to 5 carbon atoms are more preferable.
• Specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
• a specific example of the alkoxysilane represented by the formula (4) is methyltrimethoxy. Silane, methinoretriethoxysilane, ethinoretrimethoxysilane, ethinoretriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyl trimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoaminoethylaminopropinole) triethoxysilane, 2_aminoethylaminomethyltrimethoxysilane,
• At least one tetraalkoxysilane represented by the formula (2) may be used, but a plurality of types may be used as necessary.
• an alkoxysilane represented by the formula (4) can be used in combination. In this case, a plurality of alkoxysilanes represented by the formula (4) may be used.
• polysiloxanes such as methyl silicate 51 and ethyl silicate 40 manufactured by Colcoat can be used in combination.
• the polysiloxane (B) used in the present invention is obtained by polycondensation of a tetraalkoxysilane containing the formula (2), but it may be in a homogeneous solution state in a solvent. In the present invention, one or more of the above-described polysiloxanes (B) can be used.
• the solution of polysiloxane (B) described above is preferably a uniformly dissolved solution obtained by polycondensing an alkoxysilane containing tetraalkoxysilane represented by the formula (2) in an organic solvent.
• the alkoxysilane represented by the formula (1) is not used in combination.
• a solution in which tetraalkoxysilane represented by the formula (2) alone or a polyoxycondensation of the formula (2) and the alkoxysilane represented by the formula (4) is uniformly dissolved is preferable.
• the solution of polysiloxane (B) is obtained as a solution uniformly dissolved in an organic solvent.
• the method for obtaining the polysiloxane (B) used in the present invention is not particularly limited.
• the polysiloxane (B) can be obtained by a method of hydrolysis / polycondensation of an alcoholoxysilane in an alcohol / daricol solvent.
• the hydrolysis' polycondensation reaction may be either partial hydrolysis or complete hydrolysis.
• complete hydrolysis theoretically, it is sufficient to add 0.5 to 5 moles of water of all alkoxy groups in the alkoxysilane, but usually an excess of 0.5 moles of water is added.
• the amount of water used in the above reaction is a force that can be appropriately selected as desired. Usually, it is 0.5 to 2.5 moles of all alkoxy groups in the alkoxysilane.
• acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, alkalis such as ammonia, methylolamine, ethylamine, ethanolamine, triethylamine, hydrochloric acid, Catalysts such as metal salts such as sulfuric acid and nitric acid are used.
• heating temperature and the heating time can be appropriately selected as desired. Examples thereof include heating and stirring at 50 ° C. for 24 hours, and heating and stirring for 1 hour under reflux.
• 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 make an alcoholic solution of oxalic acid, the alkoxysilane is mixed while the solution is heated. It is a method to do. In this case, the amount of succinic acid is generally 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of alkoxysilane.
• the heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and preferably, for example, in a sealed container or under reflux, several tens to ten times so as not to cause evaporation or volatilization of the liquid. Done for a few hours.
• the alkoxysilanes may be mixed as a premixed mixture, or a plurality of alkoxysilanes may be sequentially mixed. Also good.
• the solvent used for polycondensation of alkoxysilane is not particularly limited as long as it dissolves alkoxysilane.
• an organic solvent having good compatibility with alcohols, glycols and alcohols is used.
• organic solvent examples include methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, methyl cecrosolve, ethinorecerosoreb, butylcellosoleb, Ethyl canolitol, Butinorecanolitol, Ethylene glycol monomethyl ether, Ethylene glycol dimethyl ether, Ethylene glycol n butyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, Propylene glycol monomethyl ether, Propylene glycol mono Butyl ether, N-methyl-2-pyrrolidone, ⁇ , ⁇ Dimethylformamide, ⁇ , ⁇ Dimethyl Ruasetoamido, gamma Buchirorataton, dimethyl sulfoxide, tetramethylurea, to hexa methyl
• a plurality of the above organic solvents may be mixed and used.
• the solution of polysiloxane (B) obtained by such a method has an SiO equivalent concentration of 20 quality.
• the amount is not more than%.
• the solution obtained by the above-described method may be used as it is as the polysiloxane (B) solution. If necessary, the solution obtained by the above-described method may be concentrated or dissolved. A solution of polysiloxane (B) may be prepared by diluting with a medium or substituting with another solvent. Les.
• the solvent used may be the same solvent used for the polycondensation or may be another solvent.
• the solvent is not particularly limited as long as the polysiloxane (B) is uniformly dissolved, and one kind or a plurality of kinds can be arbitrarily selected and used.
• solvents include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutynole ketone; ethylene glycol , Glycols such as diethylene glycol, propylene glycol, hexylene glycol; methyl cetosolve, ethylcete solve, butylcete solve, ethyl carbitol, butinorecanolebitonore, ethyleneglycone monomethino ethenore , Ethylene Glyco-Resino Methylatenore, Ethylene Glyco-Nole _n_Butyl Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycole Monobutinoleate Tenole Glycol-no-ethers such as propylene glycol monomethyl ether and propylene glycol mono
• the polysiloxane (B) solution obtained as described above may be used singly or in combination.
• polysiloxane (A) and polysiloxane (B) may be used as long as the effects of the present invention are not impaired. It may be included.
• the inorganic fine particles are particularly preferably those in a colloidal solution in which fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferred.
• This colloidal solution may be a dispersion of inorganic fine particle powder in a dispersion medium, or a commercially available colloidal solution.
• the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions.
• Inorganic fine particles The average particle size is preferably 0.001-0.2 / im, more preferably 0.001 -0.1 ⁇ . If the average particle size of the inorganic fine particles exceeds 0.2 ⁇ , the transparency of the cured film formed using the prepared coating liquid may be lowered.
• Examples of the dispersion medium for the inorganic fine particles include water and organic solvents.
• ⁇ or pKa is adjusted to 2 to 10 from the viewpoint of the stability of the coating solution for film formation. More preferably, it is 3-7.
• Examples of the organic solvent used for the dispersion medium of the colloidal solution include methanol, propanol, ethylene glycol, butanol, ethylene glycol monopropinoate, and other ketones such as methyl ethyl ketone and methyl isobutyl ketone.
• Aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide, and N-methylpyridone; esters such as ethyl acetate, butyl acetate, and ⁇ -butylate rataton; tetrahydrofuran, 1 , 4_dioxane and the like.
• alcohols and ketones are preferred.
• These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
• leveling agent and the surfactant known ones can be used, and a commercially available product is particularly preferable because it is easily available.
• the method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. It is sufficient that polysiloxane ( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ) and polysiloxane ( ⁇ ) and other components as necessary are uniformly mixed. Usually, polysiloxane ( ⁇ ) and polysiloxane ( ⁇ ) are polycondensed in a solvent and thus obtained in a solution state. Therefore, the above-described solution of polysiloxane ( ⁇ ⁇ ) and polysiloxane ( ⁇ ) ) Is easy to mix. If necessary, the solvent can be removed after mixing the polysiloxane ( ⁇ ⁇ ⁇ ⁇ ⁇ ) solution and the polysiloxane ( ⁇ ) solution.
• the SiO equivalent concentration in the liquid crystal aligning agent is preferably 0.5 to 15% by mass. like this
• concentration range is equivalent to SiO, sufficient solution that makes it easy to obtain the desired film thickness with a single coating.
• a pot life is easy to obtain.
• polysiloxane (A) solution and the polysiloxane (B) solution were added after mixing.
• the solvent the same solvent as described in the solution of polysiloxane (A) and the solution of polysiloxane (B) can be used.
• the method of mixing the other components described above is not particularly limited, either at the same time as the solution of polysiloxane (A) and the solution of polysiloxane (B) or after mixing them.
• the proportion of polysiloxane (A) used is such that the total amount of silicon atoms in polysiloxane (A) is 3% of the total amount of silicon atoms in polysiloxane (A) and polysiloxane (B).
• Mole 0 /. Les Shi preferred is to 80 mole 0/0,. More preferably 5 mol 0 /. ⁇ 75 mol 0/0. If the total amount of silicon atoms in the polysiloxane (A) is less than 3 ⁇ 4 mol%, good liquid crystal orientation may not be obtained. If it exceeds 80 mol%, the element with low frequency at high temperature In some cases, it is difficult to obtain high power and high voltage holding ratio during driving.
• liquid crystal aligning agent In the present invention, specific examples of the liquid crystal aligning agent are listed below.
• the polysiloxane (B) is an alkoxysilane represented by the formula (2) or a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (2) and the formula (4).
• the liquid crystal aligning agent according to any one of [1] to [3] above.
• [5] A liquid crystal aligning agent containing the liquid crystal aligning agent according to any one of [1] to [4] and inorganic fine particles.
• the liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film by drying and baking after coating on a substrate.
• Examples of the method for applying the liquid crystal aligning agent include spin coating, printing, inkjet, and spray. Forces including one method, roll coating method, etc. From the viewpoint of productivity, the transfer printing method is widely used industrially, and it is also suitably used in the liquid crystal aligning agent of the present invention.
• the drying process after applying the liquid crystal aligning agent is not necessarily required, but the time from application to baking is constant for each substrate. If not baked, it is preferable to include a drying step.
• the drying means is not particularly limited as long as the solvent evaporates to such an extent that the shape of the coating film is not deformed by transporting the substrate. For example, a method of drying on a hot plate at a temperature of 50 to 150 ° C, preferably 80 to 120 ° C for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.
• the coating film formed by applying the liquid crystal aligning agent by the above method can be fired to form a liquid crystal aligning film.
• the firing temperature can be any temperature of 100 to 350 ° C., but is preferably 150 to 300. C, more preferably f or 150-220. C, particularly preferably ⁇ to 150-200 ° C.
• the polysiloxane (A) and polysiloxane (B) in the liquid crystal alignment film undergo polycondensation in the firing step.
• firing is preferably performed at a temperature higher by 10 ° C or more than the heat treatment temperature required for the manufacturing process of the liquid crystal cell, such as curing of a sheet agent.
• the thickness of the liquid crystal alignment film can be selected as necessary. When the thickness of the liquid crystal alignment film is 5 nm or more, it is preferable because the reliability of the liquid crystal display element is easily obtained. More preferably, it is 10 nm or more. Moreover, the case of 300 nm or less is preferable because the power consumption of the liquid crystal display element does not increase. More preferably, it is 150 nm or less.
• the liquid crystal alignment film of the present invention formed by the method as described above has a structure in which polysiloxane (A) is unevenly distributed near the surface layer of the liquid crystal alignment film. This can be ensured by analyzing the elemental distribution of the liquid crystal alignment film of the present invention from the surface of the film to the substrate by a method such as X-ray photoelectron spectroscopy.
• the liquid crystal alignment film of the present invention has a good liquid crystal alignment property
• the liquid crystal display element having the liquid crystal alignment film of the present invention has a high voltage holding ratio in driving an element at a low frequency at a high temperature. It has the characteristic.
• the liquid crystal alignment film of the present invention has a small amount of alkoxysilane represented by the formula (1) which is a constituent component of the polysiloxane (A) contained in the liquid crystal aligning agent of the present invention.
• the voltage holding ratio in driving the device at a low frequency at a high temperature is very high.
• the amount of the alkoxysilane represented by the formula (1) in the polysiloxane (A) is 2 to 12 mol%, and it exhibits good liquid crystal orientation and low frequency at high temperatures. It has a feature that the voltage holding ratio in driving the element is very high.
• the liquid crystal alignment film of the present invention is obtained from a liquid crystal aligning agent containing polysiloxane (A) and polysiloxane (B), and therefore, a liquid crystal aligning film obtained from a liquid crystal aligning agent of polysiloxane (A) alone.
• the voltage holding ratio in driving the element at a low frequency at a high temperature shows a high value.
• the liquid crystal alignment agent of the present invention forms a liquid crystal alignment film having a structure in which polysiloxane (A) is unevenly distributed on the film surface as shown in FIG. (A) It is not obtained from a single liquid crystal aligning agent, and has the characteristics as described above as a liquid crystal aligning film.
• the liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the method described above and then preparing a liquid crystal cell by a known method.
• An example of liquid crystal cell production is generally a method in which a pair of substrates on which a liquid crystal alignment film is formed is fixed with a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed.
• the size of the spacer used is:! To 30 ⁇ m, preferably 2 to ⁇ ⁇ m.
• the method for injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting liquid crystal after reducing the pressure inside the manufactured liquid crystal cell, and a dropping method for sealing after dropping the liquid crystal.
• the substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate. However, it is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate. Specific examples include glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysenolephone, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) talylonitrile trinole, triacetiate.
• Examples thereof include substrates on which a transparent electrode is formed on a plastic plate such as noresenorelose, dicetinoresenorelose, acetate butyratesenoleose.
• a high-performance element such as a thin film transistor (TFT) type element, an element such as a transistor formed between an electrode for driving a liquid crystal and a substrate is used.
• TFT thin film transistor
• a substrate in the case of a transmissive liquid crystal element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as long as the substrate is only on one side. It is possible to use. At that time, a material such as aluminum which reflects light can be used for the electrode formed on the substrate.
• the liquid crystal alignment film obtained by using the liquid crystal aligning agent of the present invention has the characteristics that the liquid crystal alignment is good and the voltage holding ratio is high in device driving at low frequency under high temperature. It is possible to provide a liquid crystal display element having the same.
• HG51.3 g, BCS15.6 g and T 69.4 g of EOS was added and stirred to prepare an alkoxysilane monomer solution.
• oxalic acid solution containing HG25.6g, BCS7.8g, / X30. Og and 0.3g of oxalic acid as a hornworm medium was added dropwise at room temperature. Stir. Thereafter, the solution was heated at a solution temperature of 70 ° C. for 1 hour and then allowed to cool to obtain a solution (Z1).
• HG: BCS: NMP 30:50:20 and the SiO equivalent concentration is 3.5% by mass.
• 126 g of water and 4.25 g of ammonia water (concentration: 28% by mass) were added and stirred at 40 ° C. for 4 days to prepare a particle-containing solution.
• a silica particle-containing solution (Y1) was prepared by adding 435 g of HG to 500 g of the prepared silica particle-containing solution and concentrating it to 300 g.
• the particle diameter was measured by a dynamic light scattering method. This method for measuring the particle diameter is described in Journal of Chemical Physics, Journal of Chemical Physics, 57-11 (December 1972), page 4814. In the present invention, Otsuka Electronics Co., Ltd. Measurements were made using a DLS-7000 made by the manufacturer. As a result, the particle size of the silica particle-containing solution (Y1) was 20 nm.
• the polysiloxane solutions (P2, P5 and P8) and the polysiloxane solution (P1) were mixed at room temperature to obtain liquid crystal aligning agents (L1 to L8).
• the polysiloxane solution (P2), the polysiloxane solution (P1), and the silica particle-containing solution (Q1) were mixed at room temperature to obtain a liquid crystal aligning agent (L9).
• a liquid crystal cell (element) was prepared using the liquid crystal aligning agents (L1 to L9), and the liquid crystal alignment and voltage holding ratio were measured. The results are shown in Table 3.
• a film was formed on a glass substrate with a transparent electrode by a spin coating method using a liquid crystal aligning agent filtered under pressure with a membrane filter having a pore diameter of 0.5 / .m.
• This substrate was dried on a hot plate at 80 ° C for 5 minutes and then baked in a hot air circulation oven at 180 ° C for 60 minutes to form a liquid crystal alignment film having a film thickness of lOOnm.
• a liquid crystal cell obtained by the same method as in [Preparation of liquid crystal cell] was observed with a polarizing microscope using Merck MLC-7021-100 as the liquid crystal, and the alignment state of the liquid crystal was visually confirmed.
• a liquid crystal cell obtained using Merck MLC-6608 as the liquid crystal in the same manner as described above in [Creation of liquid crystal cell] was applied to Toyo Technicaneto VHR-1 and 4V voltage was applied.
• the voltage holding ratio (Voltage Holding Ratio: VHR) after 1667ms was measured in a constant temperature bath at 80 ° C.
• Liquid crystal alignment agents L5 and P2 were pressure filtered through a membrane filter with a pore size of 0.5 / im, spin-coated on a silicon substrate [(100) surface], and placed on an 80 ° C hot plate and dried for 5 minutes. did. Thereafter, it was baked for 60 minutes in a 180 ° C hot air circulating oven to obtain a coating film having a film thickness of lOOnm.
• ESCA-3200 manufactured by Shimadzu Corporation was used to analyze the element distribution from the surface of the film to the substrate. The results are shown in Figs.
• the coating film obtained using P2 has a uniform carbon concentration in the film, whereas the liquid crystal alignment film obtained from the liquid crystal aligning agent (L5) of the present invention is near the surface layer. It was confirmed that the carbon concentration was high and the layer was present.
• the liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film having a good alignment property and a high voltage holding ratio in driving an element at a low frequency at a high temperature, and also has a highly reliable liquid crystal display.
• An element can be provided.
• the liquid crystal alignment film of the present invention can be suitably used in various liquid crystal display elements, particularly in the vertical alignment type (VA).
• VA vertical alignment type
• it can be used in polarizing films, retardation films, and alignment films for wide viewing angle films.

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