Classifications

• • 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
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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

Definitions

• the present invention mainly includes a polysiloxane, particularly polysiloxane obtained by polycondensation of alkoxysilane, and a liquid crystal aligning agent capable of forming a uniform film by inkjet coating, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and
• the present invention relates to a liquid crystal display element having the liquid crystal alignment film.
• a liquid crystal display element has a structure in which two substrates each having a liquid crystal alignment film provided on a transparent electrode are arranged to face each other and a liquid crystal material is filled in a gap therebetween.
• a metal halide lamp with high irradiation intensity is used as a light source for a liquid crystal projector for business use and home theater (a rear pro TV referred to as a third thin TV). Therefore, not only high heat resistance but also high light resistance is required as a characteristic of the liquid crystal alignment film.
• liquid crystal alignment film materials are mainly composed of polyamic acid or polyimide, but inorganic liquid crystal alignment films have also been proposed.
• a liquid crystal alignment film is formed by vapor deposition (see, for example, Patent Document 1).
• an alignment agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid is proposed as a coating-type inorganic liquid crystal alignment film, and an electrode substrate for a liquid crystal display element is proposed. It has been reported that a liquid crystal alignment film having excellent vertical alignment properties, heat resistance and uniformity is formed (see, for example, Patent Document 2).
• liquid crystal aligning agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane and water, and a glycol ether solvent has been proposed to prevent display defects and good afterimage characteristics even after long-time driving.
• a liquid crystal alignment film is formed without decreasing the ability to align liquid crystals and with little decrease in voltage holding ratio against light and heat (see, for example, Patent Document 3).
• examples of the method for forming a liquid crystal alignment film include spin coating, dip coating, flexographic printing, and the like, but actually, flexographic printing is often used.
• the printing plate in flexographic printing, the printing plate must be exchanged according to the size of the substrate for forming the liquid crystal alignment film, and provisional film formation must be performed to stabilize the film formation process. It is a problem.
• an inkjet coating method has attracted attention as a new coating method that does not use a printing plate.
• the ink jet coating method is a method in which fine droplets are dropped on a substrate and the film is formed by wetting and spreading the liquid. Not only the printing plate is not used, but also a printing pattern can be freely set. The manufacturing process can be simplified.
• An object of the present invention is to provide a silicon-based liquid crystal aligning agent that can be formed using an ink jet coating method, and to provide liquid crystal excellent in in-plane uniformity of the film and edge straightness of the film edge by ink jet coating.
• An alignment film is provided.
• the present invention has the following gist. (1) a polysiloxane (A) having a side chain comprising a hydrocarbon group having 8 to 30 carbon atoms, substituted or unsubstituted with a fluorine atom, a glycol solvent (B) having 2 to 7 carbon atoms, A liquid crystal aligning agent for inkjet coating, comprising a solvent (C) and a solvent (D).
• a liquid crystal aligning agent for inkjet coating comprising a solvent (C) and a solvent (D).
• Solvent (C) a solvent represented by the formula (A1), K 1 O (CH 2 ) w OH (A1) (Wherein K 1 is an alkyl group having 1 to 4 carbon atoms, and w is an integer of 1 to 3)
• the solvent (D) is a solvent selected from the compounds represented by the formulas (T1) to (T3), ketones having 3 to 6 carbon atoms, and alkyl alcohols having 5 to 12 carbon atoms ( Liquid crystal aligning agent for inkjet coating as described in 1).
• the polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (1) Liquid crystal aligning agent.
• R 1 Si (OR 2 ) 3 (1) R 1 represents a hydrocarbon group having 8 to 30 carbon atoms in which a fluorine atom is substituted or unsubstituted, and R 2 represents a hydrocarbon group having 1 to 5 carbon atoms.
• the polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the following formula (2).
• the liquid crystal aligning agent for inkjet coating as described in said (3).
• R 3 is a hydrogen atom, a halogen atom, a vinyl group or a hydrocarbon group having 1 to 7 carbon atoms.
• an arbitrary hydrogen atom of the hydrocarbon group is a glycidoxy group, a mercapto group, a methacryloxy group, an acryloxy group, It may be substituted with an isocyanate group, amino group or ureido group, and may have a hetero atom, R 4 is a hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 0 to 3 Represents.
• the polysiloxane (A) is a polysiloxane obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the following formula (3).
• Glycol solvent (B) is ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol,
• the liquid crystal aligning agent of the present invention can form a liquid crystal aligning film excellent in in-plane uniformity of the film and edge straightness at the end of the film by inkjet coating.
• the present invention is described in detail below.
• the polysiloxane (A) used in the present invention is a side chain (hereinafter also referred to as a specific organic group) composed of a hydrocarbon group having 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms, substituted or unsubstituted with fluorine atoms. ).
• the specific organic group has an effect of aligning the liquid crystal in one direction, but is not particularly limited as long as it has this effect.
• Examples thereof include an alkyl group, a fluoroalkyl group, an alkenyl group, a phenethyl group, a fluorophenylalkyl group, a styrylalkyl group, and a naphthyl group.
• an alkyl group is preferable because it is easily available.
• the polysiloxane (A) used in the present invention may have a plurality of specific organic groups.
• the polysiloxane (A) used in the present invention is a side chain different from the specific organic group (hereinafter, referred to as “unaffected”) as long as the effect of the present invention is not impaired for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules. It may also have a second organic group).
• the second organic group is an organic group having 1 to 7, preferably 1 to 6, more preferably 1 to 5 carbon atoms.
• the second organic group is an aliphatic hydrocarbon; a ring structure such as an aliphatic ring, an aromatic ring or a hetero ring; an unsaturated bond; a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom; a branched structure It may be.
• the second organic group is a vinyl group or a hydrocarbon group having 1 to 7 carbon atoms, and any hydrogen atom of the hydrocarbon group is a glycidoxy group, a mercapto group, a methacryloxy group, an acryloxy group, an isocyanate group, an amino group It may be substituted with a group or a ureido group, and may have a hetero atom.
• the polysiloxane (A) used in the present invention may have one or more second organic groups.
• polysiloxane (A) is not particularly limited, but is generally obtained by polycondensation of alkoxysilane.
• polysiloxane (A) can be obtained by polycondensation of an alkoxysilane having an alkoxysilane represented by the following formula (1) as an essential component.
• R 1 Si (OR 2 ) 3 (1)
• R 1 represents a specific organic group, and examples thereof are the same as those described as the specific organic group.
• alkoxysilanes in which R 1 is an alkyl group are preferable because they are relatively inexpensive and easily available as commercial products.
• R 2 is a hydrocarbon group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms.
• alkoxysilane represented by the said Formula (1) is not limited to this.
• a plurality of alkoxysilanes represented by the formula (1) can be used in combination.
• the use ratio of the alkoxysilane represented by the formula (1) is less than 0.1 mol% in all alkoxysilanes used for obtaining the polysiloxane (A)
• good liquid crystal alignment is obtained. Since it may not exist, 0.1 mol% or more is preferable. More preferably, it is 0.5 mol% or more.
• it exceeds 30 mol% since the liquid crystal aligning film formed may not fully harden
• polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by following formula (2). . (R 3 ) n Si (OR 4 ) 4-n (2)
• R 3 is a hydrogen atom, a halogen atom, a vinyl group or a hydrocarbon group having 1 to 7 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms. Any hydrogen atom of the hydrocarbon group may be substituted with a glycidoxy group, mercapto group, methacryloxy group, acryloxy group, isocyanate group, amino group or ureido group, and may have a hetero atom.
• R 4 is a hydrocarbon group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and n represents an integer of 0 to 3, preferably 0 to 2.
• R ⁇ 3 > of Formula (2) is a vinyl group or a hydrocarbon group
• R ⁇ 3 > represents the 2nd organic group mentioned above. Therefore, in this case, the example of R 3 is the same as described as the second organic group above.
• the alkoxysilane represented by the formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and butyltrimethoxysilane.
• alkoxysilane of the formula (2) specific examples of the alkoxysilane when R 3 is a hydrogen atom include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane and the like.
• an alkoxysilane in which n is 0 represents a tetraalkoxysilane of the formula (3).
• R 4 is a hydrocarbon group having 1 to 5, preferably 1 to 4, more preferably 1 to 3 carbon atoms.
• the tetraalkoxysilane represented by the formula (3) is preferable for obtaining the polysiloxane (A) because it easily condenses with the alkoxysilane represented by the formula (1).
• tetraalkoxysilane of the formula (3) examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like.
• alkoxysilane represented by the above formula (2) or formula (3) one type or a plurality of types can be used as necessary.
• the alkoxy represented by the formula (2) or the formula (3) in all the alkoxysilanes used for obtaining the polysiloxane (A).
• the total amount of silane used is preferably 70 to 99.7 mol%. More preferably, it is 78 to 99.7 mol%. More preferably, the alkoxysilane represented by the formula (2) or the formula (3) is 85 to 99.7 mol%.
• the polysiloxane (A) used in the present invention is obtained by condensing an alkoxysilane containing an alkoxysilane represented by the above formula (1) as an essential component in an organic solvent.
• the alkoxysilane containing the alkoxysilane represented by Formula (1), Formula (2), and Formula (3) is preferable.
• the polysiloxane (A) is obtained as a solution obtained by polycondensation of such an alkoxysilane and uniformly dissolved in an organic solvent.
• the method for condensing the polysiloxane (A) used in the present invention is not particularly limited, and examples thereof include a method of hydrolyzing and condensing alkoxysilane in an alcohol or glycol solvent.
• the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically 0.5 times mole of water of all alkoxy groups in the alkoxysilane may be added, but usually an excess amount of water is added 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 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, fumaric acid, alkalis such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine Catalysts such as hydrochloric acid, sulfuric acid, nitric acid and other metal salts 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 alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding succinic acid to alcohol in advance to obtain an alcohol solution of succinic acid, alkoxysilane is mixed while the solution is heated. In this case, the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups contained in the alkoxysilane.
• the heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and preferably, for example, several tens of minutes under reflux in a container equipped with a reflux pipe so that the liquid does not evaporate or volatilize. It takes about 10 hours.
• alkoxysilane When using multiple types of alkoxysilane when obtaining polysiloxane (A), alkoxysilane may be mixed as a mixture beforehand, or multiple types of alkoxysilane may be mixed sequentially.
• 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
• an organic solvent having good compatibility with alcohols, glycols, glycol ethers and alcohols is used.
• such a polymerization solvent examples include methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, ethyl carbitol, butyl carbitol, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobut
• the solution obtained after such a method generally has a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO 2 (hereinafter referred to as SiO 2 converted concentration) to 20% by mass or less. Preferably, it is 15 mass% or less. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.
• the solution obtained by the above-described method may be used as it is as the polysiloxane (A) solution.
• the solution obtained by the above-described method may be concentrated or a solvent may be added.
• the solution of polysiloxane (A) may be diluted or replaced with another solvent.
• the solvent to be used hereinafter also referred to as an additive solvent
• This 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 an additive 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, propylene glycol and 2-methyl Glycols such as -2,4-pentanediol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, Diethylene glycol dimethyl ether, diethylene glycol Glycol ethers such as coal diethyl ether, diethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol
• the glycol solvent (B) used in the present invention is a glycol solvent having 2 to 7, preferably 2 to 5 carbon atoms. Specific examples thereof include ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2, 4-pentanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2, -Pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3- Hexanediol, 1,4-hexanediol, 1,5-hexaned
• a plurality of glycol solvents (B) may be used in combination.
• Such a glycol solvent (B) may be used as all or part of a polymerization solvent or an addition solvent when polysiloxane (A) is polycondensed, and is added to polysiloxane (A) synthesized with another solvent. It may be added later.
• the content of the glycol solvent (B) used in the present invention, in the liquid crystal aligning agent, relative to 100 parts by weight of the total amount of the values obtained by converting the silicon atoms in the SiO 2 having polysiloxane (A) is glycol
• the solvent (B) is 20 to 18,000 parts by mass, preferably 120 to 17,000 parts by mass, more preferably 150 to 16,000 parts by mass. When the amount is less than 20 parts by mass, good coatability may not be obtained.
• the glycol solvent (B) used in the present invention has an effect of suppressing the spread of the liquid particularly when applied, and a film having particularly excellent edge straightness can be obtained.
• the solvent (C) used in the present invention is at least one solvent selected from the group consisting of solvents represented by the formula (A1).
• K 1 O (CH 2 ) w OH (A1) In the formula, K 1 is an alkyl group having 1 to 4 carbon atoms, and w is an integer of 1 to 3.
• Specific examples of the solvent (C) include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol and the like.
• the solvent (C) used in the present invention may be used as all or a part of the polymerization solvent or additive solvent for polycondensation of the polysiloxane (A). ) May be added later.
• the content of the solvent (C) is preferably 2 to 17,500 parts by mass of the solvent (C) with respect to 100 parts by mass of the total amount of the silicon atoms of the polysiloxane (A) converted to SiO 2. Is 2 to 16,800 parts by mass, more preferably 2 to 16,000 parts by mass. When the amount is less than 2 parts by mass, good coatability may not be obtained. These solvents (C) have an effect of spreading the liquid when applied, and a film having particularly excellent in-plane uniformity can be obtained.
• the solvent (D) used in the present invention is at least one compound selected from the group consisting of the following formula (T1), formula (T2) and formula (T3), a ketone having 3 to 6 carbon atoms, and carbon.
• X 1 , X 3 and X 5 are alkyl groups having 1 to 4 carbon atoms
• X 2 and X 6 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms
• X 4 is 1 to 4 carbon atoms.
• 4 is an alkyl group
• P is an alkyl group having 1 to 3 carbon atoms
• m, n, j, and k are each independently an integer of 1 to 3
• h is an integer of 2 to 3.
• the solvent (D) used in the present invention is at least one selected from the group consisting of compounds of formula (T1) to formula (T3), ketones having 3 to 6 carbon atoms, and alkyl alcohols having 5 to 12 carbon atoms.
• a solvent is preferred.
• the solvent (D) used in the present invention is, for example, a compound represented by the above formula (T1), a compound represented by the above formula (T3), a ketone having 3 to 6 carbon atoms, or 5 to 5 carbon atoms. It may be a single solvent of 12 alkyl alcohols. Further, it may be a mixed solvent of the compound represented by the formula (T1) and the compound represented by the formula (T2), and further, the compound represented by the formula (T1) and the compound having 5 to 12 carbon atoms. A mixed solvent with an alkyl alcohol may be used. Further, the equation X 2 and X 6 in (T1) and (T3) is preferably a hydrogen atom.
• Specific examples of the compound represented by the formula (T1) include 1-methoxy-2-propanol (propylene glycol monomethyl ether), 1-ethoxy-2-propanol (propylene glycol monoethyl ether), 1-propoxy-2-propanol ( Propylene glycol monopropyl ether), 1-butoxy-2-propanol (propylene glycol monobutyl ether), 1,2-dimethoxypropane (propylene glycol dimethyl ether), 1,2-diethoxypropane (propylene glycol diethyl ether), 1,2 -Dipropoxypropane (propylene glycol dipropyl ether), 1,2-dibutoxypropane (propylene glycol dibutyl ether) are preferred. Of these, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, or 1-butoxy-2-propanol is preferable.
• Specific examples of the compound represented by the formula (T2) include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, and ethylene glycol dibutyl ether. Of these, ethylene glycol dimethyl ether or ethylene glycol dibutyl ether is preferable.
• Specific examples of the compound represented by the formula (T3) include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and the like. .
• diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, or diethylene glycol dibutyl ether are preferable.
• Specific examples of the ketones having 3 to 6 carbon atoms in the solvent (D) include methyl ethyl ketone and methyl isobutyl ketone.
• Specific examples of the alkyl alcohol having 5 to 12 carbon atoms of the solvent (D) include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and the like. Of these, hexanol, heptanol, octanol, nonanol, and decanol are preferable.
• the solvent (D) used in the present invention may be used as all or a part of the polymerization solvent or additive solvent for polycondensation of the polysiloxane (A). ) May be added later.
• the content of the solvent (D) is preferably 2 to 17,500 parts by mass of the solvent (D) with respect to 100 parts by mass of the total amount of the silicon atoms of the polysiloxane (A) converted to SiO 2. Is 2 to 16,800 parts by mass, more preferably 2 to 16,000 parts by mass. When the amount is less than 2 parts by mass, good coatability may not be obtained.
• These solvents (D) have an effect of spreading the liquid when applied, and a film having particularly excellent in-plane uniformity can be obtained.
• a solvent other than the glycol solvent (B), the solvent (C) and the solvent (D) may be used in combination as long as the effects of the present invention are not impaired.
• specific examples of other solvents include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; esters such as acetone, acetic acid methyl ester, acetic acid ethyl ester, and lactate ethyl ester; N-methyl-2-pyrrolidone N, N-dimethylformamide, N, N-dimethylacetamide, ⁇ -butyrolactone, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol and the like.
• inorganic fine particles other components other than polysiloxane (A), glycol solvent (B), solvent (C), and solvent (D), for example, inorganic fine particles, metalloxane oligomers, as long as the effects of the present invention are not impaired.
• a metalloxane polymer, a leveling agent, a surfactant and the like may be contained.
• the inorganic fine particles fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and a colloid solution of these inorganic fine particles is particularly preferable.
• 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.
• the inorganic fine particles preferably have an average particle size of 0.001 to 0.2 ⁇ m, more preferably 0.001 to 0.1 ⁇ m. When the average particle diameter of the inorganic fine particles exceeds 0.2 ⁇ m, the transparency of the cured film formed using the prepared coating liquid may be lowered.
• the dispersion medium for the inorganic fine particles include water and organic solvents.
• the colloidal solution it is preferable that the pH or pKa is adjusted to 1 to 10 from the viewpoint of the stability of the coating solution for forming a film. More preferably, it is 2-7.
• Organic solvents used for the dispersion medium of the colloidal solution include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene glycol, ethylene Alcohols such as glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; ethyl acetate and butyl acetate And esters such as ⁇ -butyrolactone; ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as
• metalloxane oligomer or metalloxane polymer single or composite oxide precursors such as silicon, titanium, zirconium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used.
• the metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from monomers such as metal alkoxides, nitrates, hydrochlorides, and carboxylates by a conventional method such as hydrolysis. .
• a metalloxane oligomer or a metalloxane polymer it is possible to improve the refractive index of the cured film or to impart photosensitivity.
• metalloxane oligomer or a metalloxane polymer When using a metalloxane oligomer or a metalloxane polymer, it may be used simultaneously with the synthesis of the polysiloxane (A) or may be added to the polysiloxane (A) later.
• Specific examples of commercially available metalloxane oligomers or metalloxane polymers include siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat.
• the polymer include titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.
• a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.
• the method of mixing the above-mentioned other components with the polysiloxane (A) may be simultaneous with the solution of the polysiloxane (A) and the glycol solvent (B) or after mixing them, and is not particularly limited. .
• the method for preparing the liquid crystal aligning agent of the present invention is not particularly limited.
• the polysiloxane (A), the glycol solvent (B), the solvent (C), the solvent (D), and other components may be in a uniformly mixed state.
• polysiloxane (A) is polycondensed in a solvent, and thus is obtained in a solution state. Therefore, the method of using the polymerization solution of polysiloxane (A) described above as it is is simple.
• the polymerization solvent for polysiloxane (A) is glycol solvent (B), solvent (C) or solvent (D), glycol solvent (B), solvent (C) or solvent (D) is not added later May be.
• the glycol solvent (B) or the solvent (C) is used when preparing the liquid crystal aligning agent.
• solvent (D) can be added.
• the concentration in terms of SiO 2 in the liquid crystal aligning agent is preferably 0.5 to 15% by mass, and more preferably 1 to 6% by mass. Within such a SiO 2 equivalent concentration range, it is easy to obtain a desired film thickness by a single application, and it is easy to obtain a sufficient pot life of the solution.
• the solvent used for adjusting the SiO2 equivalent concentration may be at least one solvent selected from the group consisting of a polymerization solvent for polysiloxane (A), an addition solvent, and a glycol solvent (B).
• the liquid crystal aligning agent of the present invention can form a liquid crystal aligning film excellent in in-plane uniformity of the film and edge straightness of the film end by inkjet coating.
• liquid crystal aligning agent for forming the liquid crystal alignment film examples include spin coating, printing, ink jet coating, spraying, roll coating, and the like.
• the coating method has attracted attention.
• the ink jet coating method is a method in which fine droplets are dropped on a substrate and a film is formed by wetting and spreading of the liquid.
• the liquid crystal aligning agent of this invention has favorable applicability
• liquid viscosity In order to form a film more uniformly by using an ink jet coating method, it is necessary to stably discharge a liquid from an ink jet nozzle.
• One of the factors for stably discharging the liquid is the liquid viscosity.
• the preferred liquid viscosity of the liquid crystal aligning agent varies depending on the ink jet coating apparatus to be used. 25 ° C.) is preferred. More preferably, it is 3 to 15 mPa ⁇ s.
• the surface tension of the liquid greatly influences one of the causes of the spread of the dropped droplet.
• the surface tension of the liquid crystal aligning agent varies depending on the type of material used, but is approximately 20 to 40 mN / in the hanging drop method (for example, AUTO DISPENSER AD-3, manufactured by Kyowa Interface Science Co., Ltd., measurement temperature 25 ° C.). A range of m is preferred.
• the liquid crystal aligning agent of the present invention preferably has a viscosity of 1.8 to 18 mPa ⁇ s (measurement temperature 25 ° C.) and a surface tension of 20 to 40 mN / m (measurement temperature 25 ° C.).
• the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, a drying process is included. Is preferred.
• the drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like.
• the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
• the calcination temperature can be any temperature of 100 to 350 ° C., preferably 140 to 300 ° C., more preferably 150 to 230 ° C., and further preferably 160 to 220 ° C.
• the polysiloxane (A) in the liquid crystal alignment film undergoes 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 liquid crystal cell production process, such as curing of the sealant.
• the thickness of the cured film can be selected as necessary. When the thickness of the cured film is 5 nm or more, it is preferable because the reliability of the liquid crystal display element can be 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 become extremely large. More preferably, it is 150 nm or less.
• Such a cured film can be used as a liquid crystal alignment film as it is. However, the cured film is rubbed, irradiated with polarized light, light of a specific wavelength, etc. An alignment film can also be used. Since the liquid crystal alignment film of the present invention formed by the above method exhibits high water repellency, good liquid crystal vertical alignment can be obtained.
• 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 manufacturing a liquid crystal cell by a known method.
• a method is generally employed in which a pair of substrates on which a liquid crystal alignment film is formed are fixed with a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed.
• the size of the spacer used is 1 to 30 ⁇ m, preferably 2 to 10 ⁇ m.
• the method for injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting 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, but is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate. Specific examples include glass plates; polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl. Examples thereof include a substrate in which a transparent electrode is formed on a plastic plate such as cellulose, diacetyl cellulose, and acetate butyrate cellulose.
• a high-performance element such as a TFT type liquid crystal display element
• an element in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.
• a transmissive liquid crystal display element it is common to use a substrate as described above.
• an opaque substrate such as a silicon wafer may be used. Is possible.
• a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
• TEOS tetraethoxysilane
• C18 octadecyltriethoxysilane
• UPS 3-ureidopropyltriethoxysilane
• HG 2-methyl-2,4-pentanediol
• BCS 2-butoxyethanol
• PB 1-butoxy-2-propanol
• 1,3 -BDO 1,3-butanediol
• NMP N-methyl-2-pyrrolidone
• DDE diethylene glycol diethyl ether
• EDM ethylene glycol dimethyl ether
• MIBK methyl isobutyl ketone
• C8OH 1-octanol
• Example 8 50 g of the polysiloxane solution (K4) obtained in Synthesis Example 4 and each solvent were mixed so as to have the solvent composition shown in Table 2, and a liquid crystal aligning agent (KL8) having a solid content concentration of 3% by mass as SiO 2 was mixed. Got.
• Table 3 shows the solution viscosity and surface tension of the liquid crystal aligning agents obtained in Examples 1 to 8 and Comparative Examples 1 to 4.
• the solution viscosity and surface tension were measured by the following methods. [Solution viscosity] Using an E-type viscometer (Viscometer TV-20 manufactured by Toki Sangyo Co., Ltd.), the temperature was measured at 25 ° C. [surface tension] It measured using AUTO DISPENCER AD-3 made from Kyowa Interface Science.
• Inkjet coating was performed with the following apparatus and conditions.
• Device name Hitachi Plant Technology
• fine pattern coating device HIS-200-1H Coating substrate 100 ⁇ 100 mm ITO substrate Coating area: 30 ⁇ 40 mm
• Coating conditions resolution 25 ⁇ m, stage speed 50 mm / sec, frequency 1000 Hz, pulse width 9.6 ⁇ sec, appropriate amount 42 pl, pitch width 70.5 ⁇ m, pitch length 125 ⁇ m, applied voltage 14-14 V (adjusted to a film thickness of 100 nm) ), Nozzle gap 0.5 mm, leveling time 30 sec, drying temperature 60 ° C., drying time 2 min (hot plate)
• a coating film is formed by the method described in the above [Inkjet coating], dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and then baked in a hot-air circulating clean oven at a temperature of 200 ° C. for 60 minutes.
• a liquid crystal alignment film with a film thickness of 80 nm was used.
• a liquid crystal alignment film having a film thickness of 100 nm obtained by the same method as in the example except that the spin coating method was used instead of the ink jet coating was used.
• the liquid crystal alignment film obtained by the liquid crystal aligning agent for inkjet coating of the present invention is excellent in the in-plane uniformity of the film and the straightness of the edge of the film end, the liquid crystal display element using this is reliable. It is suitably used as a liquid crystal display device having high properties.

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