TW201038628A - Liquid-crystal alignment material for ink-jet coating, liquid-crystal alignment film, and liquid-crystal display element - Google Patents

Abstract

A silicon-based liquid-crystal alignment film and a liquid-crystal alignment material, the alignment material being suitable for application by ink-jet coating and the alignment film having excellent in-plane evenness and edge straightness. The liquid-crystal alignment material for ink-jet coating is characterized by comprising a polysiloxane (A) having a side chain comprising a C8-30 hydrocarbon group optionally substituted by a fluorine atom, a C2-7 glycol solvent (B), and the following solvent (C) and solvent (D). Solvent (C): a solvent represented by formula (A1) K1O(CH2)wOH (A1) (wherein K1 is a C1-4 alkyl and w is an integer of 1-3). Solvent (D): a solvent selected from a group consisting of: at least one compound selected from a group consisting of compounds of formulae (T1), (T2), and (T3); ketones having 3-6 carbon atoms; and alkyl alcohols having 5-12 carbon atoms. (In the formulae (T1), (T2), and (T3), X1, X3, and X5 are a C1-4 alkyl; X2 and X6 are a hydrogen atom or a C1-4 alkyl; X4 is a C1-4 alkyl; P is a C1-3 alkyl; m, n, j, and k each independently is an integer of 1-3; and h is an integer of 2-3.)

Description

201038628 VI. Description of the Invention: [Technical Field] The present invention relates to a polyoxyalkylene which is mainly obtained by polycondensation of polyoxyalkylene, in particular, alkoxydecane, which can be formed by inkjet coating. A liquid crystal alignment agent which is a more uniform film, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. Q [Prior Art] The liquid crystal display element is generally known in a structure in which two substrates in which a liquid crystal alignment film is provided on a transparent electrode are opposed to each other, and a liquid crystal material is filled in the gap. Recently, as a light source for a commercial use and a liquid crystal projector for a home theater (referred to as a back of a third thin type television, a rear projection TV), a metal toothed lamp having a high irradiation intensity is used. Therefore, high heat resistance and high light resistance are required as characteristics of the liquid crystal alignment film. Q The liquid crystal alignment film material generally used is mainly composed of polyamic acid or polyamidiamine. However, an inorganic liquid crystal alignment film is also proposed. For example, a liquid crystal alignment film is formed by a vapor deposition method (see, for example, Patent Document 1). Further, it is proposed to use a tetraalkyloxydecane, a trialkoxysilane, an alignment agent composition of a reaction product of an alcohol and oxalic acid as a coating-type inorganic liquid crystal alignment film, and it is reported that a vertical alignment is formed on an electrode substrate of a liquid crystal display device. A liquid crystal alignment film excellent in properties, heat resistance, and uniformity (for example, see Patent Document 2). In addition, it is proposed to contain a liquid crystal alignment agent composition of a reaction product of four-epoxy decane, a trialkoxy decane, and water, and a liquid crystal alignment agent of a glycol ether solvent, which can be formed to prevent poor display and remain after being driven for a long time. A liquid crystal alignment film which is excellent in image characteristics, does not reduce the alignment ability of the liquid crystal, and has a small decrease in voltage holding power with respect to light and heat (see, for example, Patent Document 3). In general, a film forming method of a liquid crystal alignment film, such as a spin coating method, a gravure coating method, or the like, is actually mostly used by gravure printing. However, in the gravure printing method, it is necessary to exchange the printing plates depending on the size of the substrate when the liquid crystal alignment film is formed, and it is necessary to perform a pseudo film forming process or the like in order to ensure the film formation step. Therefore, the inkjet coating method is emphasized as a new coating method which does not require the use of a printing plate. The inkjet coating method is a method in which fine droplets are dropped on a substrate, and a film is formed by liquid wetting expansion, so that the printing pattern can be freely set without using a printing plate, so that the liquid crystal display element can be used. The manufacturing steps are simplified. Moreover, since there is no need for false film formation, there is an advantage that the coating liquid is wasted. Therefore, it is expected to reduce the cost of the liquid crystal panel and improve the production efficiency. Under the circumstances, an inorganic liquid crystal alignment film which is excellent in heat resistance and light resistance is required, and a process of forming a liquid crystal alignment film by an inkjet coating method is desired. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION An object of the present invention is to provide a ruthenium-based liquid crystal alignment film which can be formed by an inkjet coating method, and to provide in-plane uniformity of a film formed by the ink-jet coating and excellent straightness to a film end portion Liquid crystal alignment film. In other words, the present invention has the following gist. (1) A liquid crystal alignment agent for inkjet coating characterized by containing polyoxalate (A) having a side chain formed by a hydrocarbon group substituted or unsubstituted with a fluorine atom and having a carbon number of 8 to 3 Å. 'Clycol of 2 to 7 carbons Solvent (B), the following solvent (C) and solvent (〇), solvent (C): Solvent represented by formula (A1) Ί O (CH) 2) w〇H (A 1 ) (wherein K is an alkyl group having 1 to 4 carbon atoms; w is an integer of 1 to 3) Solvent (D): selected from at least one selected from the group consisting of formula (τΐ), a solvent of a group of compounds of the formula (T2) and (T3), a ketone having 3 to 6 carbon atoms, and an alkanol having 5 to 12 carbon atoms, [化1] Χ, Ο-fCH^ CH-^OXa p (T1) Μ x3〇-(ch2^〇x4 (T2) Xs〇<CH 士. 十CH2^〇X6 (Τ3) (where X丨, X3 and X5 are carbon number 1~ 4 垸 ;; X2 and X6 201038628 is a hydrogen atom or an alkyl group having a carbon number of 1 to 4; X4 is an alkyl group having a carbon number of 1 to 3; m, n, j, and k are each a single number; h is (2) The solvent (D) for inkjet coating according to the above (1) is selected from the group consisting of formula (τ丨) to formula (ketone having 3 to 6 carbon atoms) (3) The spray agent of the above (1) or (2) wherein the polyoxyalkylene (A) is obtained by polycondensation of an alkoxy decane containing a broth Poly(R) s ' (〇Rz) 3 (1) (R ! represents a substituted or unsubstituted hydrocarbon group of a fluorine atom; R 2 represents a hydrocarbon group having 1 to 5 carbon atoms). (4) As described in the above (3) In the inkjet coating, the polyalkylene oxide (A) is a polyoxane having an alkoxy group represented by the formula (2) and having an alkoxydecane represented by the following formula (2), (R3) nS i (〇R4)4_„ (2) (a hydrogen atom, a halogen atom, a vinyl group or a group: at this time, any hydrogen atom in the above hydrocarbon group may be an alkyl group of 1 to 4; P 1 to 3; a liquid crystal alignment agent, a compound of T 3 ), a liquid crystal for ink application coating in which an alkanol is grouped, and an alkoxysilane represented by (1), a liquid crystal alignment agent having a carbon number of 8 to 30, and an alkoxylate thereof The hydrocarbon having a carbon number of 1 to 7 is polycondensed with a decane and a decane, and is substituted by a glycidoxy group, a -8 - 201038628 fluorenyl group, a methacryloxy group, a propyleneoxy group, an isocyanate group, an amine group or a urea group. And may have a hetero atom; R4 is a carbon number of 1 (5) The liquid crystal alignment agent for inkjet coating according to the above (3) or (4), wherein the polyoxyalkylene (A) is contained in the formula (3) 1) a polyoxyalkylene obtained by polycondensation of an alkoxydecane shown with an alkoxydecane of an alkoxydecane represented by the following formula (3), si (OR4) 4 (3) (R4 carbon number 1 to 5 hydrocarbon groups). (6) The liquid crystal alignment agent for inkjet coating according to any one of the above-mentioned (1), wherein the glycol solvent (B) is one or more selected from the group consisting of ethylene glycol and diethyl phthalate. Alcohol, dipropylene glycol, 2-methyl-2,4-pentanediol, 1,2-propanediol '1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2.3-butyl Alcohol, 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-hexanediol, 1,6-hexanediol, 2.3- Hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 1,2-heptanediol, 2,3-heptanediol, 3,4-heptane Alcohol, 1,3-heptanediol, 2,4-heptanediol, 3,5-heptanediol, 1,4-heptanediol 2,5-heptanediol, 1,5-heptanediol, A solvent in the group of 2,6-heptanediol, 1,6-heptanediol, and 1,7-heptanediol. (7) The liquid crystal alignment agent for inkjet coating according to any one of the above (1), wherein X2 in the formula (T1) is a hydrogen atom. -9 - 201038628 (8) The liquid crystal alignment agent described in any one of the above (a), wherein the total amount of yttrium in terms of SiO 2 relative to the polysoda (A) is 100 parts by mass. Glycol) The solvent (B) is 20 to 18,000 parts by mass, the solvent is f 17 to 500 parts by mass, and the solvent (D) is 2 to 17, 500 mass (9) as described in any one of the above (1) to (8). In the liquid crystal alignment agent, the total amount of cerium in terms of SiO 2 relative to the polyoxyalkylene (A) is a mass part by weight of the solvent (B): 120 to 17,000 parts by mass, 2 to 16, 800 parts by mass of the solvent. (D) is a liquid crystal alignment agent as described in any one of the above (1) to (9), wherein the viscosity of the aforementioned alignment agent is 1. ϊ 〇 (11 ) as described above (1) The liquid crystal alignment agent for recording according to any one of (1), wherein the surface of the alignment agent is 40 mN/m 1(1 2 ), which is characterized by coating on a spray substrate as described above (1). Any one of the liquid crystal alignment agents for recording in any one of (11), which is obtained by firing. (1 3) A method for forming a liquid crystal alignment film, which is obtained by applying a liquid crystal alignment agent for inkjet coating as described in (1) to (11) above on a substrate. (14) A liquid crystal display element characterized by comprising the liquid crystal alignment film described. The inkjet coated ruthenium atom, ethylene glycol (Qin! I (C) is 2 Η. The inkjet coated ruthenium atom, ethylene glycol (I agent (c) is the amount of the spray. Ink coating! ~1 8 m P a · s The inkjet coating I force is 20~ Ink device, and the inkjet coating in the carrier is used in any of the sprays as described above (1 2 -10- 201038628 〔 Advantageous Effects of Invention The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film having excellent in-plane uniformity of the film and end straightness of the film end portion by the inkjet coating method. The present invention will be described in detail. Ο <Polyoxane A> The polyoxyalkylene (A) used in the present invention has a carbon number of 8 to 30, preferably substituted or unsubstituted with a fluorine atom. a polyoxyalkylene having a side chain (hereinafter referred to as a specific organic group) formed by a hydrocarbon group of 8 to 2 2. The specific organic group 'has an effect of aligning the liquid crystal in one direction' as long as it has such an effect, and Particular limitations. Such as alkyl, fluorinated alkyl, alkenyl, styryl, fluorinated phenylalkyl, anthracenyl The alkyl group, the naphthyl group, etc. are preferred because the alkyl group is easily available. The polyoxyalkylene (A) used in the present invention may have a plurality of specific organic groups. When the oxane (A) is used for the purpose of improving the adhesion to the substrate or the affinity with the liquid crystal molecules, it may have a side chain different from the specific organic group (hereinafter referred to as the effect of the present invention). The second organic group is an organic group having a carbon number of 1 to 7 (preferably 1 to 6, more preferably 1 to 5). The second organic group may be an aliphatic hydrocarbon-11 - 201038628 base; ring structure such as aliphatic ring, aromatic ring, heterocyclic ring; unsaturated bond; hetero atom such as oxygen atom, nitrogen atom or sulfur atom; may also have a branched structure. 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 may be substituted by a glycidoxy group, a decyl group, a methacryloxy group, a propyleneoxy group, an isocyanate group, an amine group or a urea group, or Has a hetero atom. The polyoxyalkylene (A) used in the present invention may also have one or a plurality of second organic The method for producing the above polyoxane (A) is not particularly limited, and is generally obtained by polycondensation of an alkoxydecane. Specifically, ' can be represented by the following formula (1) The alkoxy decane is an essential component of the alkoxy decane polycondensed to obtain a polyoxyalkylene (A) R-^Si (OR2) 3 (1) in the formula (1) 'R, which means a specific organic group The examples are the same as those described for the specific organic group described above. Among them, the alkoxy fluorene of the alkyl group is preferred because it is relatively inexpensive and can be easily taken from a commercial product. R2 represents a carbon number of 1. ～5, preferably a hydrocarbon group of 1 to 4. The following are specific examples of the alkoxydecane represented by the above formula (1), but are not limited thereto. For example, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane, dodecyltrimethoxydecane, dodecyltriethoxydecane, Cetyltrimethoxydecane, hexadecene-12-201038628 alkyltriethoxydecane, heptadecyltrimethoxynonane, heptadecyltriethoxydecane,octadecyltrimethoxydecane , octadecyltriethoxydecane, nonadecyltrimethoxydecane, nonadecyltriethoxydecane, undecyltriethoxydecane 'undecyltrimethoxydecane, 21 -dodecadienyltriethoxydecane, octyltrifluorooctyltrimethoxydecane, trifluorononyltriethoxydecane, heptadecylphosphonium trimethoxydecane, heptafluoride Mercapto triethoxy decane, isooctyl triethoxy decane, phenethyl triethoxy decane, pentafluorophenyl trimethoxy decane, m-vinyl phenyl ethyl trimethoxy decane , P-vinylphenylethyltrimethoxysulfonium, (1-naphthyl)triethoxydecane, (1-naphthyl)trimethoxydecane, susceptibility Ethyl undecyl triethoxy decane, benzyl methoxy propyl trimethoxy decane, 3-(4-methoxyphenoxy) propyl trimethoxy decane, 1-[ (2-tri-B) Oxymethane alkyl)ethyl]cyclohexane_3,4-epoxide, 2-(diphenylphosphino)ethyltriethoxydecane, diethoxymethyloctadecyllithium , 1-methoxymethyl 18 yards, sandstone, ethoxylated eleven-mole methyl decane, dimethoxy dodecylmethyl decane, diethoxy decyl methyl cleavage, Dimethoxydecylmethyl decane, diethoxyoctylmethyl decane, dimethoxyoctylmethyl decane, ethoxy dimethyl octadecyl decane, methyl dimethyl octadecyl Alkyl decane and the like. Among them, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane, dodecyltrimethoxyoxyl, dodecyltriethoxy Basear, cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane, heptadecyltriethoxydecane,octadecyltrimethoxydecane, Octadecyltriethyl-13- 201038628 oxydecane, nonadecyltrimethoxynonane, nonadecylalkane, undecyltriethoxydecane, or undecyltrimethyldiethoxymethyl Preferably, octadecyl decane or diethoxydodecane is preferred. In the present invention, a plurality of decanes of the formula (1) may also be used. The ratio of use of the alkoxydecane represented by the formula (1) to all of the alkoxysilanes used in the polyoxyalkylene (A) is preferably 0.1, since a good liquid crystal alignment property cannot be obtained. More preferably, it is 0.5 mol% or more. Further, if it exceeds, the formed liquid crystal alignment film cannot be sufficiently cured, and it is preferably at most or less. More preferably, it is 22 mol% or less. Another 15% or less. Further, in the present invention, a polyxide furnace obtained by polycondensation of a decane of the formula (1) and an alkoxy decane represented by the following formula (2) is preferred. (R3)nS i (OR4)4_n (2) The halogen atom of the Κ·3 series, the vinyl group or the hydrocarbon having 1 to 7 carbon atoms is a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms. Any of the above hydrocarbon groups may be substituted by a glycidoxy group, a mercapto group, a methacryloxy group, a cyanocyanate group, an amine group or a urea group, or may have a hetero atom of 1 to 5, preferably 1 to 1. 4. More preferably, it is a hydrocarbyl triethoxy methoxy oxalate of 1 to 3, and an alkoxy group represented by a methyl decane, when the ratio is 0.1 mol% or more and 30 mol% or more. The alkoxy alkoxyalkyl group represented by the 30's best is preferably a hydrogen atom alkenyloxy group. R4 is the carbon number. The η system represents 0 - 14 - 201038628 ~ 3 ' is preferably an integer of 0 to 2. Further, when R3 of the formula (2) is a vinyl group or a hydrocarbon group, R3 represents a second organic group as described above. Therefore, the example of Rs at this time is the same as that described for the second organic group. An alkoxydecane represented by the formula (2), such as methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, ethyltrimethoxydecane, ethyltriethoxy Decane, propyltrimethoxydecane, propyltriethoxy decane, butyltrimethoxydecane, butyltriethoxydecane, pentyltrimethoxydecane, pentyltriethoxydecane, hexyltrimethyl Oxydecane, hexyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2(aminoethyl)-3-aminopropyl Triethoxy decane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-(2-aminoethylaminopropyl)trimethoxynonane, 3-( 2-Aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyltrimethoxydecane, 2-(2-aminoethylthioethyl)triethoxy Decane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, 3-ureidopropyltriethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, Allyl triethoxy decane, 3 -Methacryloxypropyltrimethoxydecane, 3-methacryloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxylate Base decane, 3-isocyanate propyl triethoxy decane 'trifluoropropyl trimethoxy decane, propyl triethoxy decane, bromopropyl triethoxy decane, 3 - decyl propyl Acid methoxy decane and the like. In the alkoxy decane of the formula (2), the alkoxy group when r3 is a hydrogen atom • 15 - 201038628 Specific examples of decane, such as trimethoxy decane, triethoxy decane, tripropoxy decane, and tributyl Oxydecane, etc. In the alkoxydecane of the formula (2), the alkoxydecane wherein η is 0 represents a tetraalkoxydecane of the formula (3). s i (0R4) 4 (3) In the formula (3), 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. The tetraalkoxydecane represented by the formula (3) is preferred because it is easily condensed with the alkoxydecane represented by the formula (1) to obtain a polyoxyalkylene (A). Specific examples of the tetraalkoxydecane of the formula (3) include tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane, tetrabutoxydecane and the like. When the alkoxydecane represented by the above formula (2) or (3) is used, one type or plural kinds may be used as needed. When using the alkoxydecane represented by the formula (2) or the formula (3), in the case of all the alkoxydecane used in the preparation of the polyoxyalkylene (A), the formula (2) or the formula (3) The total amount of the alkoxydecane shown is preferably from 70 to 99.7 mol%. The better is 78 to 99.7 mol%. The alkoxy decane represented by the formula (2) or the formula (3) is preferably 85 to 99.7 mol%. The polyoxyalkylene (A) used in the present invention is obtained by condensing an alkoxysilane having an alkoxysilane represented by the above formula (1) as an essential component in an organic solvent. In this case, the alkoxydecane containing the alkoxydecane represented by the formula (1), the formula (2) and the formula (3) is preferred. Usually, polyoxyalkylene (A) is obtained by polycondensing the alkoxydecane to form a solution uniformly dissolved in an organic solvent of -16 - 201038628. The method for condensing the polyoxyalkylene (A) used in the present invention is not particularly limited. For example, a method of hydrolyzing and condensing an alkoxydecane in an alcohol or a glycol (glyc〇1) solvent. In this case, the hydrolysis/condensation reaction may be any of partial hydrolysis and complete hydrolysis. For complete hydrolysis, it is theoretically possible to add 〇.5 moles of water to all of the alkoxy groups in the alkoxy decane, except that a greater amount of excess water than 0.5 moles is usually added. In the present invention, the amount of water used in the above-mentioned reaction may be appropriately selected depending on the necessity. It is usually preferably from 05 to 2.5 times the total amount of the hospitaloxy group in the hospital. Further, 'usually, for the purpose of promoting hydrolysis/condensation reaction, acid, ammonium, methylamine, ethylamine, ethanolamine, triethylamine such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid are used. A catalyst such as an amine or a metal salt such as hydrochloric acid, sulfuric acid or nitric acid. Further, in general, the hydrolysis/condensation reaction is further promoted by heating a solution in which an alkoxysilane is dissolved. 〇 At this time, the heating temperature and the heating time may be appropriately selected depending on the necessity, for example, heating at 50 ° C, stirring for 24 hours, heating under reflux, stirring for 1 hour, or the like. Further, another method is, for example, a method in which a mixture of alkoxydecane, a solvent and oxalic acid is heated and polycondensed. Specifically, a method in which oxalic acid is added to an alcohol to form an alcohol solution of oxalic acid, and then the alkoxylate is mixed in a state where the solution is heated. In this case, the amount of oxalic acid to be used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of the oxirane. The heating of the method can be carried out at a liquid temperature of 50 to 180. (: proceeding, -17-201038628 preferably in the case of causing liquid evaporation, volatilization, etc., for example, in a vessel equipped with a reflux tube, under reflux, for several tens of minutes to several tens of hours. In the case of (A), when a plurality of alkoxy decanes are used, the alkoxy decane may be previously mixed as a mixture, or a plurality of alkoxy decane may be sequentially mixed. The solvent used in the polycondensation of the alkoxy decane ( The term "polymerization solvent" is not particularly limited as long as it can dissolve the alkoxysilane. Moreover, even if the alkoxysilane is not dissolved, the polycondensation reaction of the alkoxy group can be carried out and dissolved. In general, when an alcohol is formed by a polycondensation reaction of an alkoxydecane, an organic solvent having good compatibility with an alcohol, a glycol, a glycol ether or an alcohol is used. Specific examples of the polymerization solvent, such as methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, ethyl carbene Alcohol, butyl carbitol, ethylene glycol , 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 monobutyl Ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N,N-dimethylformamide, hydrazine, hydrazine-dimethyl acetamidine An amine, γ-butyrolactone, dimethyl sulfoxide, tetramethyl urea, hexamethylphosphoric acid triamide, m-cresol, etc. In the present invention, a plurality of the above-mentioned polymerization solvents may be mixed and used. -18- 201038628 The solution obtained by the method is generally 20% by mass or less in terms of concentration of Si〇2 (hereinafter referred to as Si〇2 conversion) of all the oxirane atoms of the oxoxane added as a raw material. The amount is preferably 15% by mass or less. By selecting an arbitrary concentration in the concentration range, gel formation can be suppressed, and a homogeneous one can be obtained. Solution. <Solution of Polyoxane (A)> In the present invention, the solution obtained by the above method can be directly used as a solution of polyoxyalkylene (A), and the obtained method can also be obtained as required. The solution is concentrated and diluted with a solvent or substituted with another solvent to obtain a solution of polyoxane (A). In this case, the solvent to be used (hereinafter also referred to as an additive solvent) can be used in the same manner as in the case of polycondensation. Any solvent may be used as long as it can dissolve the polyoxyalkylene oxide (A) uniformly, and may be arbitrarily selected one or more kinds. Specific examples of the added solvent, such as methanol, may be used. Alcohols such as ethanol, propanol, butanol, diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ethylene glycol, diethylene glycol, propylene glycol, 2-methyl pentane Glycols such as glycols; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether Glycol ethers such as diethylene glycol diethyl ether, diethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; methyl acetate, acetic acid Ethyl ester, ethyl lactate, etc. -19- 201038628 Ester; N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, γ-butane Ester, dimethyl hydrazine, tetramethyl urea, hexamethylphosphoric acid triamide, m-cresol and the like. In the present invention, one or a plurality of solutions of the polysiloxane (A) obtained as described above may be used. <glycol solvent (B) > Ethylene glycol (g 1 y C 〇 1 ) solvent (B) used in the present invention is a carbon number of 2 to 7 (preferably 2 to 5) a glycol solvent, such as, for example, 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-pentane Glycol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol 1,5-hexanediol, 1,6-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 1 , 2-heptanediol, 2,3-heptanediol, 3,4-heptanediol, 1,3-heptanediol, 2,4-heptanediol, 3,5-heptanediol, 1,4 - heptanediol, 2,5-heptanediol, 1,5-heptanediol, 2,6-heptanediol, 1,6-heptanediol, 1,7-heptanediol, and the like. Glycol (B) can also be used in a variety of applications. Among them, 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- Pentylene glycol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexane Alcohol, 1,6-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5--20- 201038628 hexanediol, 3,4-hexanediol, or the like Mixed solvent. The glycol solvent (B) may be used as a polymerization solvent or an addition solvent in which the polyoxyalkylene (A) is condensed in whole or in part, or may be added to a polyoxane synthesized in another solvent. (A). The content of the glycol solvent (B) used in the present invention is 100 parts by mass based on the total amount of ruthenium atoms of the polysiloxane (A) in terms of Si 〇 2 in the liquid crystal alignment agent. The glycol 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 it is less than 20 parts by mass, good coatability cannot be obtained. The ethylene glycol (g 1 y C ο 1 ) solvent (B) used in the present invention is particularly effective in suppressing the liquid expansion at the time of coating, and in particular, a film excellent in end straightness. <Solvent (C) > The solvent (C) used in the present invention is a solvent selected from the group consisting of a solvent represented by the formula (A1).

Kt〇 (CH2) wOH (a 1 ) wherein Κι is a hospital base having a carbon number of 1 to 4; 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 a polymerization solvent or an additive solvent in the polycondensation of all or $#@-21 - 201038628 polyoxyalkylene (A), or may be added to a polyfluorene synthesized in another solvent. Oxytomane (A). The solvent (C) is 2 to 17, 500 parts by mass, based on the total amount of the cerium atom of the polysiloxane (a) in terms of Si 〇 2, which is 10 〇 by mass. Preferably, it is 2 to 16,800 parts by mass, more preferably 2 to 16,0 parts by mass. When it is less than 2 parts by mass, good coatability cannot be obtained. The solvent (C) has an effect of expanding the liquid at the time of coating, and in particular, a film excellent in in-plane uniformity. <Solvent (D) > The solvent (D) used in the present invention is selected from the group consisting of one or more compounds selected from the group consisting of the following formula (T1), formula (T2) and formula (T3), carbon number 3~ A solvent of a group of 6 ketones and an alkanol having 5 to 12 carbon atoms. [Chemical 2]

Xi〇iCH 姑 Ht〇X2 (T1)

P X30-(-CH2)jj0X4 (12)

4-OXe (T3) wherein X!, Χ3 and x5 are alkyl groups having 1 to 4 carbon atoms; Χ2 and Χ6 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms; and Χ4 is an alkyl group having 1 to 4 carbon atoms. base;? It is an alkyl group having 1 to 3 carbon atoms; m, n, j, and k are each an integer of 1 to 3 independently; and 11 is an integer of 2 to 3. -22- 201038628 The solvent (D) used in the present invention is one or more selected from the group consisting of a compound of the formula (T1) to the formula (T3), a ketone having 3 to 6 carbon atoms, and an alkanol having 5 to 12 carbon atoms. Group of solvents. The solvent (D) used in the present invention may, for example, be a compound represented by the above formula (T1), a compound represented by the above formula (T3), a ketone having 3 to 6 carbon atoms, and an alkane having 5 to 12 carbon atoms. A separate solvent for the alcohol. Further, a mixed solvent of the compound represented by the formula (T1) and the compound represented by the formula (T2) may be a compound represented by the formula (τ 1 ) and a carbon number of 5 to 1 2 a mixed solvent of an alkanol. Further, x2 and Χ6 of the above formulae (T1) and (T3) are preferably a hydrogen atom. Specific examples of the compound represented by the formula (Τ 1 ) include 1-methoxy-2-propanol (propylene glycol monomethyl ether), 1-ethoxy-2-propanol (propylene glycol monoethyl ether), and hydrazine. Propoxy-2-propanol (propylene glycol monopropyl ether), 丨-butoxy-2-propanol (propylene glycol monobutyl ether), 1,2-dimethoxypropane (propylene glycol dimethyl ether oxime), i,2-diethoxypropane (propylene glycol diethyl ether), 1,2-dipropoxypropyl (propylene glycol dipropyl ether), 1,2-dibutoxypropane (decanediol dibutyric acid) good. Among them, 1-methoxy-2-propanol, 1-ethoxypropanol, acyloxy-2-propanol or 1-butoxy-2-propanol is more preferred. Specific examples of the compound represented by the formula (T2) include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether and the like. Among them, ethylene glycol dimethyl ether or ethylene glycol dibutyl ether is preferred. Specific examples of the compound represented by the formula (T3), such as diethylene glycol monomethyl®, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether-23-201038628, two Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and the like. Among them, 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 Preferably. Specific examples of the ketone having 3 to 6 carbon atoms of the solvent (D), such as methyl ethyl ketone and methyl isobutyl ketone. Specific examples of the alkanol having a carbon number of 5 to 12 in the solvent (D) include hexanol, heptanol, octanol, nonanol, decyl alcohol, undecyl alcohol, and dodecyl alcohol. Among them, hexanol, heptanol, octanol, nonanol or decyl alcohol is preferred. The solvent (D) used in the present invention may be a polymerization solvent or a solvent added as a whole or a part of polycondensation of polyoxyalkylene (A), or may be added to a polysiloxane (A) synthesized in another solvent. in. The solvent (D) is 2 to 17,500 parts by mass, based on the total amount of the ruthenium atom of the polyoxane (A) in terms of SiO 2 in terms of the total amount of the solvent (D). It is preferably 2 to 16,800 parts by mass, more preferably 2 to 16,000 parts by mass. When it is less than 2 parts by mass, good coatability cannot be obtained. These solvents (D)' have an effect of expanding the liquid at the time of coating, which is particularly excellent in the in-plane uniformity. <Other solvents> In the present invention, a solvent other than the glycol solvent (B), the solvent (C), and the solvent (d) may be used without impairing the effects of the present invention. Specific examples of other solvents such as methanol, ethanol 'propanol, butanol-24-201038628, alcohols such as diacetone alcohol; esters of acetone, methyl acetate, ethyl acetate, ethyl lactate, etc.; N-A Base-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone dimethyl hydrazine, tetramethyl urea, hexamethyl phosphating Tridecylamine, m-cresol, and the like. <Other components> In the present invention, it is also possible to contain 0-polyoxyalkylene oxide (A), glycol (G) solvent (B), solvent (c), and the like without impairing the effects of the present invention. Other components other than the solvent (D), such as inorganic fine particles, methyloxy oxide oligomers, methyloxycarbon polymers, leveling agents, surfactants, and the like. The inorganic fine particles are preferably fine particles such as cerium oxide fine particles, alumina fine particles, titanium oxide fine particles, and magnesium fluoride fine particles, and the colloidal solvent of the inorganic fine particles is more preferable. The colloidal solution may be such that the inorganic fine particle powder is dispersed in a dispersion medium or a colloidal solution of a commercially available product. In the present invention, by containing inorganic fine particles, the surface shape or other functions of the formed hardened film can be imparted. The average particle diameter of the inorganic fine particles is preferably 0.001 to 0.2 μηη, more preferably 0.001 to 0.1 μπι. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed using the prepared coating liquid is lowered. A dispersion medium of inorganic fine particles such as water and an organic solvent. Colloidal solution In terms of the stability of the coating liquid for film formation, pH 値 or PKa 较佳 is preferably adjusted to 1 to 10%. The better is 2 to 7. An organic solvent used in a dispersion medium of a colloidal solution, such as methanol, ethyl-5-201038628 alcohol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, 2_methyl-2,4-pentyl Alcohols such as diol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; Amidoxime such as carbamide, dimethylacetamide or N-methylpyrrolidone; esters of ethyl acetate, butyl acetate, γ-butyrolactone, etc.; tetrahydrofuran, 1,4-dioxane Ethers such as ethers. Among them, alcohols and ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium. The metalloxane oligomer or the metalloxane polymer is a single or composite oxide precursor of ruthenium, titanium, zirconium, aluminum, molybdenum, niobium, tantalum, tin, indium, zinc or the like. The metalloxane oligomer or the metalloxane polymer 'may be a commercially available product' or may be a monomer such as a metal alkylate, a nitrate, a hydrochloride or a carboxylate, by hydrolysis or the like. Law earners. In the present invention, the refractive index of the hardened film can be increased by the presence of the metal oxyalkylene oligomer or the metalloxane polymer, and the photosensitivity can be imparted. When a metal oxyalkylene oligomer or a metal oxyalkylene polymer is used, it may be used at the same time as the synthesis of the polyoxyalkylene (A), or may be added to the polyoxyalkylene (A). Specific examples of commercially available metal oxyalkylene oligomers or metal oxyalkylene polymers, such as Methyl silicate 51, Methyl silicate 53A 'Ethyl silicate 40 ' Ethyl silicate 48 ' EMS-48 5, SS-1, manufactured by Colcoat a oxane oligomer or a siloxane polymer of 0 1 or the like; a titan ox an e oligomer such as a n-butoxytitanium tetramer manufactured by Kanto Chemical Co., Ltd. These may be used alone or in combination of two or more. Further, a leveling agent, a surfactant, and the like can be used, and in particular, -26-201038628 is preferable in that a commercially available product can be easily obtained. Further, the method of mixing the other components in the polyoxyalkylene (A) may be carried out simultaneously with the solution of the polyoxyalkylene (A) and the solvent (B) of the glycol (B). There are no special restrictions. <Preparation of Liquid Crystal Aligning Agent> A method of preparing the liquid crystal alignment agent of the present invention is not particularly limited. 0 is a state in which the polyoxyalkylene (A) and the glycol solvent (B), the solvent (C), and the solvent (D) or other components are uniformly mixed. Usually, the polyoxyalkylene (A) can be obtained in the form of a solution because it is polycondensed in a solvent. Therefore, the method of directly using the polymerization solution of the polyoxane (A) as described above can be used as it is. When the polymerization solvent of the polyoxyalkylene (A) is ethylene glycol (g 1 yc ο 1 ) solvent (B) or solvent (C) or solvent (D), no ethylene glycol can be added afterwards (glyC〇l Solvent (B) or solvent (C) or solvent (D). In addition, when the solution of polyoxyalkylene (A) does not contain a glycol solvent (B) or a solvent (C) or a solvent (D), glycol (glycol) may be added when preparing a liquid crystal alignment agent. Solvent (B) or solvent (C) or solvent (D). When the liquid crystal alignment agent is prepared, the concentration in the SiO 2 conversion in the liquid crystal alignment is preferably from 0.5 to 15% by mass, more preferably from 1 to 6% by mass. When the concentration of the SiO 2 is converted into a range, it is easy to obtain a desired film thickness by one application, and it is easy to obtain a sufficient service life of the solution. Further, at this time, the solvent used for adjusting the concentration of the SiO 2 conversion may be a group of at least one selected from the group consisting of a polymerization solvent selected from polyoxyalkylene (A), an additive solvent, and a -27-201038628 glycol solvent (b). Solvent. The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film excellent in the in-plane uniformity of the film and the end straightness of the film end portion by inkjet coating. <Liquid crystal alignment film and method of forming the same> A method of applying a liquid crystal alignment agent when forming a liquid crystal alignment film, for example, a spin coating method, a printing method, an inkjet coating method, a spray method, a roll coating method, or the like It is expected that an inkjet coating method with improved productivity can be expected. The inkjet coating method is a method of forming a film by dropping fine droplets on a substrate and spreading the droplets wet. The liquid crystal alignment agent of the present invention has good coatability, and can be stably applied by a spray coating method, whereby a liquid crystal alignment film can be obtained by the coating method. Further, by baking after application, a cured film can be formed. In order to form a film more uniformly by using the inkjet coating method, it is necessary to discharge the liquid stably from the nozzle of the ink jet. One of the factors that cause the liquid to be discharged safely is related to the viscosity of the liquid. The liquid viscosity of the liquid crystal alignment agent is different depending on the inkjet coating device to be used. The E-type viscosity meter (for example, the viscosity meter TV-20 manufactured by Toki Sangyo Co., Ltd.) is approximately 1.8 to 18 mPa. s (measurement temperature 2 The range of 5 ° C) is preferred. More preferably, it is 3 to 1 5 m P a . s. In addition, one of the factors causing the droplets to be dripped is greatly affected by the surface tension of the liquid. The surface tension of the liquid of the liquid crystal alignment agent varies depending on the type of material used. The hanging drop method (for example, AUTO DISPENCER AD-3 manufactured by Kyowa Interface Science Co., Ltd., measuring temperature of 25 ° C) is approximately 20 to 40 mN/m. Preferably. -28 - 201038628 The liquid crystal alignment agent of the present invention has a viscosity of 1-8 to 18 mPa·s (measuring temperature of 25 ° C) and a surface tension of 2 〇 to 4 0 mN/m (measurement temperature 25 t:) is more preferable. The drying step after the application of the liquid crystal alignment agent is not necessarily necessary, but it is preferably carried out in the case where the drying step is carried out after the application to the time when the baking is not constant and the substrate is not directly baked after the application. The drying is not particularly limited as long as the solvent is removed without deforming the coating film by transporting the substrate. For example, a method of drying for 5 to 30 minutes (preferably 1 to 5 minutes) is carried out on a hot plate having a temperature of 40 to 150 ton (preferably 60 to 100 ° C). The coating film formed by coating the liquid crystal alignment agent by the above method can be fired to form a cured film. In this case, the firing can be carried out at any temperature of from 1 Torr to 350 ° C, preferably from 14 Torr to 300 MPa. (:, more preferably 150 to 230 ° C, and most preferably 160 to 220 ° C. The polyoxyalkylene (A) in the liquid crystal alignment film is subjected to Q polycondensation treatment in the firing step. In the present invention, it is not necessary to completely perform the polycondensation without impairing the effects of the present invention, but the heat treatment at a temperature higher than 10 ° C higher than that required for curing of the sealant required for the liquid crystal cell manufacturing stroke is performed. The thickness of the cured film can be selected as desired. 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, and more preferably 10 nm or more. When it is 300 00 nm or less, the power consumption of the liquid crystal display element is not extremely large, and it is preferably 150 nm or less. -29- 201038628 The cured film can be directly used as a liquid crystal alignment film, or The cured film is subjected to treatment such as rubbing, irradiation of polarized light, light of a specific wavelength, or the like to form a liquid crystal alignment film. The liquid crystal alignment film of the present invention formed by the above method has good water repellency and can obtain a good liquid crystal vertical. <Liquid crystal display device> The liquid crystal display device of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above-described method, and then forming a liquid crystal cell by a conventional method. In the production example, a pair of substrates on which a liquid crystal alignment film is formed is sandwiched by a spacer, and a sealing agent is fixed, and a liquid crystal is injected and sealed. At this time, the size of the spacer used is 1 to 3 μm, preferably. The method of injecting the liquid crystal is not particularly limited, and for example, a vacuum method in which a liquid crystal cell is produced under reduced pressure, and a liquid crystal is injected; or a dropping method in which a liquid crystal is dropped and sealed, etc. The substrate to be used for the device is not particularly limited as long as it is a substrate having high transparency, and is usually a substrate on which a transparent electrode for driving a liquid crystal is formed on a substrate. Specifically, for example, a glass plate; polycarbonate, poly(A) Acrylate, polyether oxime, polyacrylate, polyurethane, polyfluorene, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (A) base A substrate on which a transparent electrode is formed on a plastic plate such as acrylonitrile, triethylenesulfonyl cellulose, diethyl acetyl cellulose, acetate butyrate cellulose, etc. and high function as a TFT type liquid crystal display element In the device, when -30 - 201038628 is used as a component for forming a transistor such as a transistor between an electrode for driving a liquid crystal and a substrate, a substrate such as the above is generally used, and the reflective liquid crystal display device is only on the substrate. On one side, an opaque substrate such as a silicon wafer may be used. In this case, a material that reflects light, such as aluminum, may be used for the electrode ' formed on the substrate. Q [Embodiment] In the following, More specifically, the present invention is not limited thereto. [Examples] The abbreviations of the compounds used in the examples are as follows: TEOS: tetraethoxydecane C18: octadecyltriethyl Oxydecane Q UP S: 3-ureidopropyltriethoxydecane 110: 2-methyl-2,4-pentanediol BCS: 2-butoxyethanol PB: 1-butoxy-2- Propyl alcohol 1,3-BDO: 1,3-butanediol NMP ·· N-methyl-2-pyrrolidone DEDE: two Glycol diethyl ether EDM: ethylene glycol dimethyl ether MIBK: methyl isobutyl ketone-31 - 201038628 C 8 Ο Η : 1 - octanol < Synthesis Example 1 > 1L four-port reaction with a thermometer 'return tube> Into the flask, 22.6 g of HG, 7_5 g of BCS, 39.6 g of TEOS, and 4.2 g of C18 were charged, and a solution of the monomer of the oxygen sand chamber was prepared. An oxalic acid solution in which HG 11.3 g, BCS 3.8 g, water l.8 g and 0.2 g of oxalic acid as a catalyst were mixed in the solution at room temperature for 30 minutes, at room temperature, at room temperature. Stir for 30 minutes. Then, after heating for 1 hour under reflux, the mixture was allowed to cool, and a polyoxysilane solution (K1) having a solid concentration of 12% by mass in terms of S i02 was obtained. <Synthesis Example 2> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 30.2 g of HG, 39.6 g of TEOS, and 4.2 g of C18 were placed, and a solution of the alkoxy decane monomer was stirred and stirred. An oxalic acid solution in which HG 15.1 §, water 10.8 g, and cerium oxalate 2 g as a catalyst were preliminarily mixed in the solution at room temperature and for a minute was stirred at room temperature for 30 minutes. Then, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxane solution having a solid concentration of 12% by mass in terms of S i Ο 2 (K: 2) ° <Synthesis Example 3> In a 1 L four-neck reaction flask, 'BCS 30.2 g, TE〇s 39.6 g, and C18 4_2 g were charged and stirred to prepare a solution of the oxydecane monomer of 32-201038628. In this solution, at room temperature, 3 hours after the dropwise addition of oxalic acid solution premixed with BCS 15.lg, water 10.8 g, and 0.2 g of oxalic acid as a catalyst, the mixture was dripped at room temperature. Minutes. Then, after heating under reflux for 1 hour, the mixture was allowed to cool to obtain a polyoxane solution (K3) having a solid concentration of 12% by mass in terms of S | 〇 2 . <Synthesis Example 4.> 0 In an iL four-neck reaction flask equipped with a thermometer and a reflux tube, HG 23.0 g' BCS 7.7 g' TEOS 40.4 g and C18 〇.8 g were charged and stirred to prepare an alkoxy decane monomer. Solution. An oxalic acid solution in which 1 g of HG, 3.8 g of BCS, 10.8 g of water, and bismuth oxalate as a catalyst were preliminarily mixed in the solution at room temperature for 30 minutes, and after completion of the dropwise addition, it was carried out at room temperature. Stir for 30 minutes. Then, after heating under reflux for 30 minutes, a mixed solution of a UPS 92% by mass methanol solution of 1.15 g, HG 0.48 g, and BCS 0.16 g was added, and then subjected to superheating under reflux for 30 minutes, and then allowed to cool to obtain Q Si. 〇2 conversion of a solid concentration of 12% by mass of polyoxyalkylene solution (κ4)

Synthesis Example Polyoxane Solution Alkoxydecane (mol) _ Formula (1) Formula (2) - Formula (3) 1 Κ1 C18 (0. 005) TE0S (0.095) 2 Κ 2 C18 (0. 005) TE0S (0.095) 3 Κ3 C18 (0. 005) TE0S (0.095) 4 Κ4 C18 (0. 001) UPS (0. 002) TE0S (0.097) -33- 201038628 <Examples 1 to 7, Comparative Examples 3 and 4> The polyoxazane solution (K 1 ) obtained in Example 1 was mixed with the solvent in the solvent composition shown in Table 1 to obtain a liquid crystal alignment agent having a solid content of SiO 2 of 3% by mass (KL1 to 7, KM3~4). <Example 8> 50 g of the polyoxaxane solution (K4) obtained in Synthesis Example 4 was mixed with each solvent in the solvent composition shown in Table 2 to obtain a solid content concentration of SiO 2 of 3% by mass. Liquid crystal alignment agent (KL8). <Comparative Example 1 > The polysiloxane mixture solution (K2) obtained in Synthesis Example 2 (52 g) and 150 g of HG were mixed and stirred to obtain a liquid crystal alignment agent having a solid concentration of 3 mass% in terms of Si〇2. (KM1). <Comparative Example 2 > 5 μg of the polyoxyalkylene oxide solution (K3) obtained in Synthesis Example 3 and 150 g of BCS were mixed and stirred to obtain a liquid crystal alignment agent having a solid concentration of 3 % by mass in terms of Si 2 . (KM2). -34- 201038628 [Table 2] Liquid crystal alignment agent polyoxyalkylene solution SiOt conversion concentration (wt%-) ethylene glycol (glycol) solvent (B) (wt%) solvent (C) (wt%) solvent (D) (wt%) Other solvent (Wt%) Example 1 KL1 K1 3 HG (435 BCS (9) PB (34) Example 2 KL2 K1 3 HG (26) BCS 0) PB (52) Example 3 KL3 K1 3 HG ( 43) 1,3-BD0 ¢17) BCS (9) PB (17) Example 4 K14 K1 3 HG (43) BCS (9) PB (9) MIBK (26) Example 5 KL5 K1 3 HG (43) BCS (34) C80H (9) Example 6 KL6 K1 3 HG ¢ 43) BCS (9) DEDE (34) Example 7 KLT K1 3 HG (43) BCS (9) PB (17) EDM (17) Example 8 KL8 K4 3 HG (43) BCS (9) PB (34) Comparative Example 1 KM1 K2 3 HG (86) Comparative Example 2 KU2 K3 3 BCS ¢86) Comparative Example 3 KM3 K1 3 HG (26) BCS (60) Comparative Example 4 KU4 K1 3 HG (43) BCS (9) mp (34) The solution viscosity and surface tension of the liquid crystal alignment agents obtained in Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Table 3. Further, the solution viscosity and surface tension were measured by the following methods.

G

[Solid viscosity] The measurement was carried out at a temperature of 25 t using an E-type viscometer (a viscometer TV-20 manufactured by Toki Sangyo Co., Ltd.). [Surface tension] The measurement was carried out using AUTO DISPENCER AD-3 manufactured by Kyowa Interface Science Co., Ltd. -35- 201038628

Liquid crystal alignment agent viscosity (mPa · s) Surface tension (mN/m) Example 1 KL1 7. 5 2 6. 9 Example 2 KL2 5. 4 2 5. 4 Example 3 KL3 14. 6 2 7. 4 Implementation Example 4 KL4 3. 4 2 5 . 7 Example 5 KL5 7. 3 2 7.1 Example 6 KL6 4. 2 2 6. 5 Example 7 KL7 5. 3 2 5. 4 Example 8 KL8 7. 3 2 7 0 Comparative Example 1 KM1 2 1. 3 2 7. 7 Comparative Example 2 KM2 3. 3 2 6. 7 Comparative Example 3 KM3 6. 1 2 6. 8 Comparative Example 4 KM4 6. 5 2 9, 5 [Inkjet Coating] The inkjet coating was carried out under the following apparatus and conditions.

Device name: Hitachi Plant Technologies Co., Ltd., fine pattern coating device HIS-200-1H Coated substrate: lOOxIOOmm ITO substrate coating area: 30>< 40 mm Coating conditions: decomposition capacity 25 μιη 'table speed 50 mm/sec, cycle The number is 1 000 Hz, the pulsation width is 9.6 psec, the liquid amount is 42 pl, the pitch width is 70·5 μη, the pitch length is 125 μm, the applied voltage is 14 to 19 V (the film thickness is adjusted to 1 〇〇 nm), the nozzle slit is 0.5 mm, and the flattening time is 30 sec. Drying temperature: 60 ° C 'drying time 2 min (hot plate) [Coating property] The obtained film was visually observed and observed under a microscope to confirm the coating property. Can it be formed into a film: if there is no defect in the film, it is defective in the film - 36- 201038628 is χ. In-plane uniformity: the uniformity of the surface of the film is 〇, and the plaque or line-like plaque is χ ^ End straightness: those with excellent straightness are 〇, and those lacking straightness are X. [Table 4] Whether the liquid crystal alignment film can be formed into a film, and the in-plane uniformity is straightforward. Example 1 K11 〇〇〇 Example 2 KL2 〇〇〇 Example 3 KL3 〇〇〇 Example 4 KL4 〇〇〇 Example 5 KL5 〇〇〇 Example 6 KL6 〇〇〇 Example 7 KL7 〇〇〇 Example 8 KL8 〇〇〇 Comparative Example 1 KM1 X — A Comparative Example 2 RM2 0 XX Comparative Example 3 KM3 〇〇X Comparative Example 4 KM4 X —

As is clear from Table 4, in Comparative Example 1 and Comparative Example 4, film formation was not possible, and in Examples 1 to 8 as compared with Comparative Examples 2 and 3, in-plane uniformity and end straightness were good, and coatability was improved. [Production of liquid crystal cell] Two glass substrates each having a transparent electrode on which a liquid crystal alignment film is formed are used, and an gg device having a particle diameter of 6 μm is spread on the liquid crystal alignment film surface of one substrate, and is printed by a screen. After applying an epoxy-based adhesive to the outer edge of the substrate, the film is bonded to the liquid crystal alignment film, and after being pressed and melted, it is cured to form an empty cell. After MLC-6608 (trade name) manufactured by Merck Co., Ltd. was injected into the empty cell by a vacuum injection method, the injection hole was sealed with a UV curable resin, and a liquid crystal cell (element) was produced at -37-201038628. At this time, in the examples, the coating film was formed by the method described in the above "Inkjet Coating", and dried on a hot plate at a temperature of 80 ° C for 5 minutes - in a hot air circulation type clean oven at a temperature of 200 ° C. A liquid crystal alignment film having a film thickness of 80 nm obtained by firing for 60 minutes was prepared. Further, in the comparative example, a liquid crystal alignment film having a film thickness of 100 nm obtained by the same method as that of the Example except that the spin coating method was used instead of the inkjet coating method was used. [Liquid crystal alignment] The liquid crystal cell produced by the method of [manufacture of liquid crystal cell] was observed by a polarizing microscope to confirm the alignment state of the liquid crystal. In the liquid crystal cell, the uniform alignment state without defects is 〇, and when there are alignment defects on some liquid crystal cells and when there is no vertical alignment, it is x. The results are shown in Table 5. [Contact angle] A contact angle was measured by dropping a purely 3 μί on the liquid crystal alignment film and using an automatic contact angle meter CA-Z type manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 5. In the examples, a coating film was formed by the method described in the above [Inkjet Coating], and dried on a hot plate at a temperature of 80 ° C for 5 minutes, and then fired in a hot air circulating clean oven at a temperature of 200 ° C. A liquid crystal alignment film having a film thickness of 80 nm obtained in 60 minutes. Further, in the reference example, a liquid crystal alignment film having a film thickness of 100 nm obtained by the same method as that of the Example except that the spin coating method was used instead of the inkjet coating method was used. -38- 201038628 [Table 5] Directional agent KL1 Coating method Inkjet coating method __: Contact angle measurement method of liquid crystal alignment water Ο 89 Reference example KL1 Spin coating method Ο 86 As can be seen from Table 5, The liquid crystal alignment film obtained by the inkjet coating method has the same vertical alignment property as the film obtained by another coating method.产业 [Industrial use price 値] The liquid crystal alignment film obtained by the liquid crystal alignment agent for inkjet coating of the present invention is excellent in the in-plane uniformity of the film and the end straightness of the film end portion, and the liquid crystal display element using the film It is suitable for use as a highly reliable liquid crystal display device. Further, all of the specification, patent application scope and abstract of Japanese Patent Application No. 2008-329123, filed on Jan. 25, 2008, and the Japanese Patent Application No. 2 009-001 The contents are all referred to in the specification and are disclosed and adopted as the specification of the present invention. -39-

Claims (1)

201038628 VII. Patent application scope: 1. A liquid crystal alignment agent for inkjet coating, which is characterized by containing a side chain formed by a hydrocarbon group substituted or unsubstituted with a fluorine atom and having a carbon number of 8 to 3 fluorene. Anthrax (A), ethylene m 2~7 solvent (B), solvent (C) and solvent (〇), solvent (C): solvent represented by formula (A1) CHz) wOH (A 1 ) (wherein 'K, is an alkyl group having a carbon number of 1 to 4; you are an integer of 丨~3) Solvent (D): selected from at least one selected from the formula (τ丨), (Τ2) and a compound of the formula (Τ3), a solvent having a ketone of 3 to 6 carbon atoms and an alkanol having 5 to 12 carbon atoms [Chemical Formula 1] ^HCH^H-fn〇X2 Ρ (T1) x3o-^ch2^ox4 (Τ2) X5〇^CH2Y〇-^CH2j^OX6 (Τ3) (wherein, Xi, Χ3 and Χ5 are alkyl groups having a carbon number of 1 to 4; Χ2 and Χ6 are hydrogen Atom or a carbon number of 1 to 4; X4 is a hospital base having a carbon number of 1 to 4; Ρ is an alkyl group having a carbon number of 1 to 3; m, n, j, and k are each an integer of 1 to 3; h is an integer from 2 to 3). 2. The liquid crystal alignment agent for inkjet coating according to the first aspect of the invention, wherein the solvent (D) is selected from the group consisting of a compound of the formula (τ 1 ) to the formula (τ 3 ), having 3 to 6 carbon atoms. A solvent for a ketone and an alkanol having 5 to 12 carbon atoms. -40 - 201038628 3. Liquid crystal alignment agent for inkjet coating according to item i or item 2 of the patent application, wherein poly (four) yard (A) is an alkoxy decane containing a oxydecane represented by formula (1) Polycondensation obtained by polycondensation, RtS i (〇R2) 3 (1) (I represents a substituted or unsubstituted hydrocarbon group having a carbon number of 8 to 30; R·2 represents a carbon number of 1 to 5 Hydrocarbyl group). 4. The liquid crystal alignment agent for inkjet coating according to Item 3 of the patent application, wherein the polyoxyalkylene (Α) is obtained by containing an alkoxy oxime represented by the formula (1) and having the following formula (2) a polyoxyalkylene obtained by polycondensation of an alkoxydecane of an alkoxydecane, (R3)nS i (〇R4)4_n (2) (K·3 hydrogen atom, halogen atom, vinyl or carbon) a hydrocarbon group of 1 to 7; in this case, any of the hydrogen atoms in the aforementioned hydrocarbon group may be substituted by a glycidoxy group, a thiol group, a methacryloxy group, a propyleneoxy group, an isocyanate group, an amine group or a urea group. And may have a hetero atom; r4 is a hydrocarbon group having 1 to 5 carbon atoms; n is an integer of 0 to 3). 5. The liquid crystal alignment agent for inkjet coating according to the third or fourth aspect of the patent application, wherein the polyoxyalkylene is contained in the alkoxysilane represented by the formula (1) and is represented by the following formula (3) a polyoxyalkylene obtained by polycondensation of an alkoxydecane of an alkoxydecane shown, s '(〇R4)4 (3) (a hydrocarbon group having 1 to 5 carbon atoms). The liquid crystal alignment agent for inkjet coating according to any one of claims 1 to 5, wherein the glycol solvent (B) is one or more -41 - 201038628 is selected from the group consisting of ethylene glycol and Ethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, 1.2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3- Butylene glycol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentane Alcohol, 2,4-pentanediol, 1,2-hexanediol, 1.3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2, 3· hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, ι,2-heptanediol, 2,3-heptanediol, 3,4- Heptanediol, 1,3-heptanediol, 2,4-heptanediol, 3,5-heptanediol, 1,4-heptanediol, 2,5-heptanediol, 1,5-heptane A solvent group of alcohol, 2,6-heptanediol, 1,6-heptanediol, and 1,7-heptanediol. 7. The liquid crystal alignment agent for inkjet coating according to any one of claims 1 to 6, wherein X2 in the above formula (T1) is a hydrogen atom. 8. The liquid crystal alignment agent for inkjet coating according to any one of the first to seventh aspects of the present invention, wherein the total amount of ruthenium in terms of Si 〇 2 with respect to the ruthenium atom of the polysiloxane (A) is In terms of 1 part by mass, the ethylene glycol (solvent) solvent (B) is 20 to 18,000 parts by mass, the solvent (C) is 2 to 17,500 parts by mass, and the solvent (D) is 2 to 17,500 mass. Share. 9. The liquid crystal alignment agent for inkjet coating according to any one of the first to eighth aspects of the invention, wherein the total amount of ruthenium in terms of Si 〇 2 with respect to the ruthenium atom of the polysiloxane (A) is In 100 parts by mass, the ethylene glycol (glycol) solvent (B) is 120 to 1 7,000 parts by mass, the solvent (C) is 2 to 16, 800 parts by mass, and the solvent (D) is 2 to 16,800 parts by mass. 10. The liquid crystal alignment agent for inkjet coating according to any one of claims 1 to 9, wherein the viscosity of the aforementioned alignment agent is 1 · 8 to 18 m P a · s - 42 - 201038628 The liquid crystal alignment agent for inkjet coating according to any one of claims 1 to 3, wherein the surface tension of the alignment agent is 20 to 40 mN/m. 12. A liquid crystal alignment film which is obtained by baking an inkjet coating liquid crystal alignment agent according to any one of claims 1 to 11 by using an ink jet apparatus. A method for forming a liquid crystal alignment film, which is characterized in that the liquid crystal alignment agent for inkjet coating according to any one of claims 1 to 11 is applied onto a substrate by an inkjet apparatus, and is fired. Got it. A liquid crystal display element comprising the liquid crystal alignment film of claim 12 of the patent application. 〇 -43- 201038628 IV. Designated representative map: (1) The designated representative figure of this case is: None (2), the representative symbol of the representative circle is simple Description: None 201038628 V If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none