TW201235412A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

The object of this invention is to provide a liquid crystal aligning film agent. The liquid crystal aligning film agent can be used for forming a liquid crystal alignment film which can maintain good electric property even driven continuously for a long period in rigorous environments such as those of light stress, heat and humidity, and have excellent rework property when defects are generated. This invention is a liquid crystal aligning agent includes: [A] at least a polymer selected from a group consisted of polyamic acid and polyimides formed by dehydration cyclization of the polyamic acid, [B] an antioxidant, and [C] a compound having epoxy group. The [B] antioxidant prefers having a group represented by the following formula (1) or (2).

Description

201235412^fizuipif VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. [Prior Art] TN (Twisted Nematic) type, STN (Super Twisted Nematic ' type), VA (Vertical Alignment type), and IPS (In-Plane Switching) are known. A liquid crystal display element of a display mode such as a coplanar conversion type or an OCB (Optical Compensated Bend) type. In any of the display modes, the alignment state of the liquid crystal molecules is controlled by the liquid crystal alignment film, and therefore the characteristics of the liquid crystal alignment film and the liquid crystal alignment agent which is a material of the liquid crystal alignment film affect the characteristic performance of the liquid crystal display element. As a material of the liquid crystal alignment agent, a resin material such as polyacrylic acid, polyimine, polyamine or polyester is known, and in particular, a liquid crystal alignment agent containing polyglycolic acid or polyimine is formed. The liquid crystal alignment film is excellent in heat resistance, mechanical strength, affinity with liquid crystal, etc., and is used in a public display device (see Patent Documents 1 to 6). In recent years, with the advancement of studies such as improved display quality and low power consumption, such as high definition of liquid crystal display elements, liquid crystal display elements are particularly prepared for use environments such as Μ and driving time. The use of LCD TVs under the conditions is constantly expanding with the trend of eliminating the cathode ray tube TV. Therefore, a liquid crystal display element having a liquid crystal alignment film formed of a 201235412 alignment agent containing polyacrylic acid or polyimine is subjected to long-term continuous operation under severe environments such as light stress, heat, and moisture. When driving, there is a possibility that the liquid crystal alignment film is deteriorated, and the display quality is remarkably lowered due to deterioration of electrical characteristics of the liquid crystal cell or the like. On the other hand, the substrate in which the pinhole of the coating film produced in the production step of the liquid crystal alignment film or the uniform defect of the cloth* is likely to pass through (4) the coating film (rework) may be re-applied. However, when the liquid crystal alignment agent having an epoxy group is used in the front, the cross-linking reverse side of the epoxy group is likely to have a decrease in reworkability (peelability) of the liquid crystal alignment film. In view of such a situation, it has been desired to develop a liquid crystal alignment agent which can form reworkability in the case where a good electrical property can be maintained even when a long-term continuous driving is performed and defects are generated. Excellent liquid crystal alignment film. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] US Patent No. 5,958,333 [Patent Document 5] Japanese Patent Laid-Open Publication No. SHO 62-165628 [Patent Document 6] Japanese Patent Laid-Open No. 11 2586 No. 5 The present invention is based on the above facts and aims to provide a liquid hydrazine alignment agent which can be formed long in a harsh environment such as light stress, heat, 6201235412 bucket lAHpif shoulder gas. In the case of continuous driving of time, it is also possible to maintain a good electrical property and a liquid crystal alignment film excellent in reworkability in the case of occurrence of defects. The invention for solving the above problems is a liquid crystal alignment agent comprising: [A] at least i selected from the group consisting of polypyridic acid and polyamidene which is dehydrated and closed by the polyamic acid. A polymer (hereinafter also referred to as "Γ" polymer)"; a compound having an epoxy group (hereinafter also referred to as "[c] compound") from the [c] for Vi'iU. Since the liquid crystal alignment agent contains the [A] polymer, the [B] antioxidant, and the [c] compound, it is excellent in light stress, heat, moisture, and the like (4). [B] The antioxidant preferably has the formula (1) or the formula (1) represented by the following formula: R1 X1 R4 X2

N X4 R3 Χ 3 X5-R5

201235412 (In the formula (1), R1 is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an aryl group having 6 to 2 carbon atoms, and an aralkyl group having 7 to 13 carbon atoms; - Dioxobutyl or hydrazine, 4 • dioxobutyl and the group represented by the formula (1) is an alkyl group, an aryl group, an arylalkyl group or a 1,3-dioxobutyl group represented by R1. The base and the oxime, the winter dioxobutyl group is removed from the J hydrogen group to form a divalent group, and a part of the molecular chain can also be formed. RR is independently a thio group having a carbon number of 1 to 、, and the carbon number is 6 〜 The square base or the slave number of 2 is an aromatic alkyl group of 7 to 13. X is a single bond, #厌基, 氺-(CH2)n_〇_, * _〇_, or wood _c〇nh·. * The indicated bond indicates the site to which the acridine ring is bonded. Further, η is an integer of 1 to 4. X to X are independently a single bond, a few groups, * * <氏_〇〇_ or wood* -CHrCH(QH)_. The key represented by the towel '** indicates the part bound to the ring.)

8 201235412 ^ When izuipif R7 is multiple, multiple R7s may be the same or different. Since the [B] antioxidant has a base of the above specific structure, the light resistance and the high temperature and high humidity resistance can be further improved. The [C] compound is preferably a polyorganooxazane-functional epoxy compound containing an epoxy group. When the [C] compound is an epoxy group-containing polyorganosiloxane or a monofunctional epoxy compound, a liquid crystal alignment film having more excellent reworkability can be formed even with a composition having an epoxy group. The polymer [A] is preferably a polymer obtained by reacting a tetra-bis-bis needle with a diamine, the tetracarboxylic dianhydride comprising a solvent selected from the group consisting of 2,3,5-tridecylcyclopentyl acetic acid dianhydride, 1, 3,33,4,5,%-hexahydro-8-fluorenyl-5-(tetrahydro-2,5-dioxo^.f.s.)-naphtho[l,2-c]furan- i,3-dione, -5-(tetrahydro-2,5-dioxo-3-.f-amylnaphthalene and 2,4,6,8-tetra-redentylbicyclo[3.3_0]xin _ At least one of the groups consisting of 2, 4, 6, and 8 is formed by using the specific compound as the acid dianhydride to further improve the light transmittance and the south temperature resistance to southerness. The above diamine preferably contains Selected from ^(4-aminophenyl) 2,3 di-amp; -1,3,3-trimethyl-1 -indole-5-amine and 1-(4-aminophenyl)_2 3-dihydro-13 ^ At least one species of the group consisting of tridecyl-1Η-gang-6-amine. The use of the above specific compound as a diamine can improve the light fastness and high temperature and high thirst resistance. A liquid crystal alignment film formed by the agent and a liquid crystal display element having the liquid crystal alignment film are also suitably included in the present invention. The liquid three= display element can be suitably applied to various devices. For example, 201235412 • ·» wva 2-» ** type game machine, word processor, notebook computer, car navigation system, camera, personal digital assistant, digital camera, mobile phone, various monitors, LCD TV, etc. In the display device of the present invention, the liquid crystal alignment agent of the present invention can be formed by performing continuous driving for a long period of time even under a severe environment such as light stress, heat, and moisture. A liquid crystal alignment film which is excellent in reworkability when a defect is generated, and the liquid crystal display element of the present invention having such a liquid crystal alignment film has less display quality and can be effectively applied. Among various devices, for example, it can be suitably applied to a clock, a portable game machine, a word processor, a notebook computer, a car navigation system, a camcorder, a personal digital assistant, a digital camera, a mobile phone, various displays, and an LCD TV. [Embodiment] &lt;Liquid Crystal Aligning Agent&gt; The liquid crystal alignment agent of the present invention contains [A] polymer, [B] antioxidant The compound and the [C] compound. Since the liquid crystal alignment agent contains the [A] polymer, the [B] antioxidant = and the [C] compound, it is carried out under the harsh ring of the earth, such as light stress, heat and moisture. In the case of continuous driving for a long period of time, it is possible to maintain good electrical characteristics and to exhibit excellent reworkability. Further, the liquid crystal alignment agent may contain other optional components as long as the effect of the present invention is not impaired. Each component is described in detail. <[A] Polymer> [A] The polymer is at least selected from the group consisting of polyglycine and polycarbamide which is obtained by dehydrating ring closure of 201235412 ^ιζυιριί. 1 polymer. The polyamic acid as the [A] polymer can be obtained by reacting a tetracarboxylic dianhydride with a diamine. The following is a detailed description of tetracarboxylic dianhydride and diamine. [Tetracarboxylic acid dianhydride] The tetracarboxylic acid dianhydride may, for example, be an aliphatic tetracarboxylic dianhydride or an alicyclic tetraphosphonium tetracarboxylic dianhydride. These tetracarboxylic dianhydrides can be used singly or in combination of two or more. ;: Two:: The tetracarboxylic dianhydride may, for example, be butane tetracarboxylic dianhydride or the like. The dianhydride: diruthenium pentane dianhydride can be exemplified by 3, cyclobutane tetradecanoic acid W tetracyclic guanidinoacetic acid hexahydroindole, phenyl)-naphtho[1,2 inch, shout, &amp; methyl Μtetrahydro-2,5·dioxo_3_°furandi- 6-spirotetrahydrogen. Furan = ketone, 3_oxabicyclo[3.2. Π辛院-2,4-furyl)-3-methyl 3 „ ^2,5_二_), 5-(2,5-dioxo) Tetrahydro-3-carboxyindenylnorbornane 2埤'1,2-diphthalic anhydride, 3,5,6-tricarboxy-2-[3.3.0]octane_2,4,6,=2 · : 6-dianhydride, 2,4 6,8·tetracarboxybicyclo-3,5,8,1〇_tetrathene, etc.. One anhydride, 4,9-dioxatricyclo[5 3丨〇2 (6) Undecyl ruthenium ruthenium acid and other tetracarboxylic acid hydrides, for example, pyromellitic acid dianhydride, etc. 铋 = 日本 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举 列举Anhydrides are superior. Anhydrides. Moreover, it is more preferred to scavenge cycloaliphatic tetracarboxylic dianhydrides of tetracarboxylic acid hexahydrate to S 2,3,5·tricarboxycyclopentyl acetic acid dianhydride, methyl-5-(tetrahydrogen) ·2,5-dioxo-3-furanyl)- 201235412 ~Γ X ^\J Apli ”, U,3a,4,5,9b_hexahydro·5_(tetrahydro-2,5-ylbicyclo[ 3.3.G]幡2,4 from 喃2二_,2,4,6,8-four rebellion preferably contains Yin^tailiuyi hydrogen^four performances^ further special^ (tetrahydro-2,5_diox代·3_furan-5-(tetrakis-2,5--wei_3_biting base)_naphthalene dimer, 2,4, Μ·reading double ring [3.3. 料料4,6,8_ Di-anhydride of four Wei two needles. By using The specific compounds are improved in terms of properties and high temperature and high humidity resistance. ^ η文]兀

1,3,33Λ5?%--Α-2,5-^-Α -8- ψ Κ-^( h2^]Ok^-l^--m ' l,3,3a54,559b-AA -1 3 -2, oxo-anthracene) _naphtho[1,2_C] ° verbose with two (four) two two four county double ring [3.3. °] simmer _2,4,6,8_ two needles === is preferably η or more in all tetra-dianhydrides, more preferably 20 mol% to 9 〇m〇i〇/〇. [Diamine] Amine, an aliphatic diamine, an alicyclic diamine, or a mixture of two or more aromatic groups i. These diamines may be used singly or as a 2-butylamine, a ketone, and a ketone diamine, for example, a p-diamine, a 4,4, diaminodiphenyl 12 201235412 41201 pif decane, 4, 4'-di Aminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2,-dimercapto-4,4,diaminobiphenyl, 4,4'-diamino-2,2'-bis(tri-I Indole, 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 2,2-bis[4_(4-aminophenoxy)phenyl]propane, 9,9- Bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexapropanol, 2,2-bis(4-aminophenyl)hexafluoropropane , 4,4'-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(meta-diphenylidene)diphenylamine, bis(4-aminophenoxy) Benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-di-amino 0-bite, 3,4-one-based bite, 2,4-diaminodine, 3,6 _Diaminoα丫°, 3,6--cut 1 base 11 squat,]^-mercapto-3,6-diamino"1 get 0 sit,]^_ethyl_3,6_ one gas base °嗤,嗤-phenyl-3,6-diaminoπ, saliva, ν,1ST-bis(4-aminophenyl)-benzidine, anthracene, Ν'-bis(4-aminophenyl)-N , N'c methylbenzidine, 1,4_bis-(4-aminophenyl)-pyridazine, 1-(4-aminophenyl)_2,3-dihydrotridecyl·1Η·节-5-amine, 1-(4-aminobenzene -2,3_Dihydro-1,3,3-tridecyl_1H_ 茚-6.amine, 3,5-diaminobenzoic acid, cholyloxy-3-3,5-diamino Benzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy 2,4-diaminobenzene, cholestyloxy-2,4-diamino stupid, 3,5 -cholinyl diaminobenzoate, cholestyl 3,5-diaminobenzoate, lanyl alkyl 3,5-diaminobenzoic acid, 3,6-bis(4-amino Phenyloxy)cholane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5 -diaminobenzoate, 4·(4'-trifluorodecyl benzhydryloxy)cyclohexyl-3,5-diaminobenzoate, ((aminophenyl)decyl)phenylhydrazine -butylcyclohexene, 1,1-bis(4-((aminophenyl)indenyl)phenylheptylcyclohexane, 1,1-bis(4.((aminophenoxy)methyl)) Phenyl) hollyheptyl ring ^, U-bis(4_((aminophenyl)methyl)phenyl)_4_(4-heptylcyclohexyl)cyclohexane 13 201235412 Τ 1 LV 1 ριχ alkane, 2, 4 -diamino-N,N-di Propyl aniline, 4-amino benzene Yue amine compound represented by Yue amine and 3-amino benzene following formula (3). [Formula 3] H2N ^

C(jH2d+1 ( 3 ) In the above formula (3), R 8 is an alkyl group having a carbon number of 1 to 3, *-Ο-, *_COO_ or *_OCO_ 〇 wherein * is a diaminophenyl bond The site of the knot. b is 0 or 1. c is an integer of 0 to 2. d is an integer of 1 to 20. It is preferred that two amino groups in the diaminophenyl group are bonded to the 2, 4 or 3, 5 positions. In addition, it is preferable that a and b are not 0. The compound represented by the following formula (3) is, for example, a compound represented by the following formula.

Nh2 14 201235412 412Ulpif = amino organic #氧(四)如可县1,3_双(3_aminopropyl)_tetramethyl-#oxygen, etc. Other diamines can be exemplified by the diamines and the like described in Japanese Patent Application No. 2971〇_97188. The monoamine preferably comprises a diamine of an aromatic diamine. Further, more preferably from -1·(4-aminophenyl)_23_dihydro·(1)·trimethyl-ih _5-amine and =4-aminophenyl)_2,3-dihydrom-trimethyl• The amine consists of a group of two, and one of the two. Light resistance and high temperature and high humidity resistance can be further improved by using the above specific compound as $'. As a commercial item of the above-mentioned = compound, TMDA (Nippon Pure Medicine ^) can be mentioned, for example. TMDA is H4_aminophenyl)_23_diaza_U3trimethyl_ih_=s-amine and phenylaminophenyl)-2,3_dihydro-1,3,3-trimethyl.茚_6_ a mixture of amines. The ratio of use of the above-mentioned preferred aromatic diamine is preferably 30% by weight or more, more preferably 5% by mass or more, and preferably 8 Gm% or more, based on all of the amine. Further, as the above-mentioned more preferred one selected from the group consisting of phenylphenyl--hydrogen-(3)-when methyl-methyl orbital and ice-based, 2,3-dihydro-U,3·trimethyl-1Ή|6-amine The ratio of the constituent group to the one type is preferably 5% or more with respect to all diamines, and more preferably 20% by mole to 9 Å (10)%. Moreover, the two selections used in the synthesis of the poly-branched acid in the VA type alignment film include 12% or more of the 12 alkoxy 2 as a pre-division of 5 g or more of all the diamines. 4·Diamine, cut alkoxy group from diamine=本, 十魏氧_2,4_二氨丝,六十六魏基_2,4·diamino 18-epoxy-2,4- Diaminobenzene, dodecyloxy 2,5-diamino stupid, 15 201235412 ~ri tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, Hexadecane oxy-2,5-diaminobenzene, octadecyloxy-2,5·diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy _ 3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, choline alkenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestene Base ester, 3,5-diaminobenzoic acid, lanoleyl ester, 3,6-bis(4-aminophenylhydrazolyl) cholane, 3, bis(4-aminophenoxy) cholate Decane, 4-(4'-trifluorodecyloxybenzoyloxy)cyclohexyl_3,5-diaminobenzoate, 4-(4'-trifluoromethylphenyloxy) Cyclohexyl_3,5-diaminobenzoate, 1,1_bis(4-(aminophenylfluorenyl) )4_butylcyclohexene, 1,1-bis(4-(aminophenylindenyl)phenyl)-4-heptylcyclohexene, 1, 丨-bis(4-(aminophenoxy) Mercapto)phenyl)-4-heptylcyclohexene, 1,1-bis(4-(aminophenylmethyl)phenyl M-(4-heptylcyclohexyl)cyclohexyl, above formula (3) More preferably, the compound or the like is contained in an amount of 10 mol%. [Synthesis Method of Polylysine] The poly-proline in the liquid crystal alignment agent can be obtained by reacting the above tetra-baric acid dianhydride with a diamine. The use ratio of the tetracarboxylic dianhydride to the synthesis reaction of the poly-proline is preferably 0.2 equivalent to 2 equivalents, more preferably 1 equivalent to 2 equivalents based on 1 equivalent of the amino group contained in the diamine. The reaction reaction of the poly-proline is preferably carried out in an organic solvent, and the reaction temperature is preferably -20 Torr to 15 (TC, more preferably 0 〇C 〜1 〇〇. (: The reaction time is preferably From 0.1 hour to 24 hours, more preferably from 5 hours to 12 hours. Examples of the organic solvent include an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, and the like. 412 Ulpif The above aprotic polar solvent may, for example, be N-mercapto-2-pyrrolidone, hydrazine, fluorenyl-dimercaptoacetamide, hydrazine, hydrazine-dimercaptoamine, dimethyl sulfoxide, γ-butyl Lactone, tetradecylurea, hexamethylenephosphonium triamide, etc. Examples of the phenol derivative include m-nonylphenol, dinonylphenol, and halogenated phenol. Examples of the alcohol include decyl alcohol, ethanol, and isopropanol. , cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monoterpene ether, and the like. Examples of the ketone include acetone, mercaptoethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the above esters include ethyl lactate, butyl lactate, decyl acetate, ethyl acetate, butyl acetate, decyloxy propionate, ethyl ethoxypropionate, diethyl oxalate, and propylene. Diethyl acid and the like. Examples of the ether include diethyl ether, ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, and ethylene glycol dioxime. Ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monoterpene ether acetate , diethylene glycol monoethyl ether acetate, tetrahydrofuran, and the like. Examples of the i-generation hydrocarbons include dichlorosilane, 1,2-dioxaethane, 1,4-di-butane, tri-ethane, chlorobenzene, ortho-benzene. Examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, diphenylbenzene, isoamyl propionate, isoamyl isobutyrate, and diisoamyl ether. Among these organic solvents, it is preferred to use a group selected from an aprotic polar solvent, a phenol and a derivative thereof (the first group of organic solvents) 17 201235412 Examples of the solvent are, for example, relative to the first group and the second group: have a denier, ° °, and 5 are preferably 50% by mass or less, more preferably 4 〇 里 / 〇 or less, and particularly preferably 30 mas. %the following. The amount of the organic solvent to be used is preferably 〇·1 mass °/ with respect to 5 measurements of tetradextrin and diamine. ~ 50% by mass. A reaction solution obtained by dissolving polyamic acid was obtained as described above. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be prepared by isolating the polylysine contained in the reaction solution to the liquid crystal alignment agent, or purifying the isolated polyamic acid to the liquid crystal. Modulation of the alignment agent. When the poly-aracine is dehydrated and closed to form a polyimine, the above reaction solution may be directly supplied to the dehydration ring-closure reaction, or the polylysine contained in the reaction solution may be isolated and supplied to the dehydration ring. The reaction or the isolated polylysine is purified and supplied to a dehydration ring closure reaction. The isolation and purification of polylysine can be carried out in accordance with a known method. [Synthesis method of polyimine] The polyimine which can be contained in the liquid crystal alignment agent can be obtained by imidating the above-mentioned polyamic acid by dehydration ring closure. The tetracarboxylic dianhydride and the diamine used in the synthesis of the polyimine may be the same compounds as the four ortho-neuric acid and the diamine used in the synthesis of the polystyrene. The type and use ratio of the preferred tetracarboxylic dianhydride and diamine are also the same as in the case of the synthesis of polyglycine. 18 201235412 4UUipif The above polybendimimine may be a complete ruthenium imide formed by dehydration and ring closure of the chiral acid structure of polylysine as a raw material, or may be a part of the structure of the tyrosine acid dehydration ring closure, 醯A partial quinone imide of an amine acid structure coexisting with a quinone ring structure. The ruthenium iodide ratio of the polyanilin in the liquid crystal alignment agent is preferably 30% or more, more preferably 50% to 99%, and particularly preferably 65% to 99%. The above ruthenium amination ratio is a percentage of the total number of quinone imine ring structures of the polyimine relative to the total number of guanamine structures and the number of quinone ring structures. At this time, a part of the quinone ring may also be an isoindole ring. The ruthenium amination rate is known by the 1 h_nmr of the polyimine. In addition, the ruthenium amide ratio in the present specification is obtained by dissolving the polyiminimide in a reduced pressure at room temperature, and then dissolving it in deuterated dimethyl sulfoxide and using tetramethyl decane as a reference material. The lH_NMR measured at the temperature was determined by the following mathematical formula (3). (3) 醯 imidization rate (%) = {1_ (eight 1 / 八 2) χ α} χ 1 〇〇 in the above formula (3), A1 is present in the chemical shift 1 〇, near the NH-based The peak area of the proton, human 2 is the peak area derived from other protons, and α is the ratio of the number of protons of the other protons to the NH group in the poly(imide) of i polyimine. The dehydration ring closure of the polyamic acid for synthesizing the above polyimine can be carried out by heating the polyamido I or by dissolving the poly-aracine in the organic solution. Agent and dehydration ring closure 19 201235412 -Γ Jl ^\JL · The agent is heated according to the need, the watch, 隹 y y ..., W Wan go and enter. The latter method is preferred. The dehydrating agent may, for example, be an acid such as acetic acid, propionic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably 0.01 mol to 20 mol with respect to the structural unit of the polyglycolic acid. Examples of the dehydration ring-closure catalyst include secondary amines such as dentate, trimethyl nitrene, dimethyl hydrazine, and diethylamine. The amount of use as the dehydration ring-closure catalyst is preferably from 0 01 mol to 1 mol per mol of the dehydrating agent used. The organic solvent to be used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as the organic solvent used in the synthesis of the polystyrene. The reaction temperature of the dehydration ring closure reaction is preferably 〇 ° C 〜 , more preferably 1 〇. 〇 ~ 150 C. The reaction time is preferably from 1 to 12 hours, more preferably from 2 to 30 hours. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or can be prepared by removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and can be supplied to the liquid crystal alignment agent, and can also be supplied to the liquid crystal alignment agent after segregation of the polyimine. Modulation' or purification of the isolated polyimine to a liquid crystal alignment agent. In order to remove the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution, for example, a solvent replacement method or the like can be applied. The isolation and purification of the polyimine can be carried out in accordance with a known method. The polyphthalic acid or polyimine which may be contained in the liquid crystal alignment agent may also be a terminally modified polymer having a molecular weight adjusted. By using the terminal-modified polymer 'the coating property and the like of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. Such a terminally modified polymer can be carried out by adding a molecular weight modifier to a polymerization reaction system when synthesizing polyamic acid. 201235412 412Ulpif The molecular weight modifier may, for example, be an acid monoanhydride, a monoamine compound or a monoisocyanate compound. Examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinate, and n-hexadecane amber. Anhydride, etc. Examples of the above monoamine compound include strepamine, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-decylamine, and positive ten Dialkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, positive twenty Alkylamine and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less based on the total mass parts of the tetraphthalic acid dianhydride and the diamine used in the synthesis of the polyamic acid. The polyamic acid or polyimine obtained as described above is preferably a solution viscosity of 20 mPa·s to 800 mPa·s when it is made into a solution having a concentration of 10% by mass, more preferably 30 mPa·s~ Solution viscosity of 500 mPa · s. In addition, the solution viscosity (mPa·s) of the polymer in the present specification is a polymer solution having a concentration of 1% by mass prepared by using a predetermined solvent, and is measured at 25 〇c using an E-type rotational viscometer. . &lt;[B]Antioxidant&gt; [B] An antioxidant is a peroxy radical and a hydroperoxide which can be generated by decomposing or decomposing energy such as ultraviolet rays or heat, and inhibits oxidative degradation of a substance. UV or heat, etc., is free in the [A] polymer. The free form is based on the base to generate new or peroxide (the peroxide is further produced (4) by the radical-inactivated free radicals. Knot = oxidation of the raw material of the knife to suppress its deterioration. 8. [B] The antioxidant preferably has an upper group. Since the [B] antioxidant has the optical properties and high temperature and high humidity resistance represented by the above formula (7) - Step up. ,. , * ‘ Therefore, in the case of A(1), Rl is a hydrogen atom, a carbon number of 1 to 20, an aryl group having a slave number of ό20, and a magnetic

Dioxobutyl or 1,4-dioxobuty. a, ~3 of the Fangyuan base, H is the filament represented by R1, the formula represented by the formula (1), 1,4 dioxobutane removal soil, quaternary alkyl, hydrazine, 3 dioxodine Base and v soil, oxygen atoms become 2 valence, Xuan Ke Zai / # molecular chain - part. R, R5 points: 丄卞 can also form 2 aryl groups or carbon number == diyl: bond, several groups, *-(CH2)n-〇-, = square wire. The key represented by x is expressed as the bond bond 3 0NH_. Where ' * is an integer. X2 to X5 are each a single j and a part of the *-ch2-ch(oh)-〇5 ^ *&quot;CH2-C〇-^* junction, in the above formula (7), the 鐽 indicates the money Among the ring bonds, the above hydrocarbon group may also be a ketone group having a carbon skeleton of 4 to 16. For 〇~3 integers. R7 is a hydrogen atom or a sulfur atom. a , 7 , the number of rabbits is 1 to 16 of the move A. Ganzhong, in the case of R, more than one, multiple == the same base 22 201235412 Ηίζ, νιριΐ 癸 base, decyl, pentyl, hexyl, heptyl, octyl, decyl, earth elata A group, a tridecyl group, a tetradecene, a +77 alkyl group, a hexadecyl group, a heptadecane, a earthy iiL R1 - decyl octadecyl group, a nonadecyl group, and the like. Examples of the aryl group of the above ~2G include a phenyl group, a benzyl group, a propyl group, a 4-n-butylbenzene-based earthy soil, a 4-phenyl-4-indenyl group, a 2-phenyl-4-indolyl group, and 2_( 4, _ = grade = phenyl), 啥 啥 基, 2 _ (four) phenyl), 喧 喧 基 。. Examples of the alkyl group having a carbon number of 1 to 6 as described above include a methyl group, a ethyl group, a butyl group, a pentyl group, a hexyl group and the like. The aromatic filaments having a carbon number of from 5 to 13 in the above-mentioned r1 to r5 are, for example, a separable base or a phenethyl group. Examples of the aryl group having 6 to 12 carbon atoms represented by the above R 2 and R 56 include a phenyl group and the like. The carbon skeleton chain represented by the above R6 may have a hydrocarbon group having an oxygen atom or a sulfur atom and having a carbon number of 4 to 16, and examples thereof include a tertiary butyl group, a hydrazine-decylpentadecyl group, an octylthiomethyl group, and ten. Examples of the hydrocarbon group having 1 to 16 carbon atoms represented by the dithiomethyl group include a methyl group, a tertiary butyl group, a fluorenyl decyl group, and an octylthio group. As the antioxidant, a commercially available product can be used, and examples thereof include a phenolic antioxidant, an amine antioxidant, a phosphorus antioxidant, a sulfur antioxidant, and a blending compound thereof. These [B] antioxidants may be used singly or in combination of two or more.

Commercial products of phenolic antioxidants include, for example, ADEKASTAB.

AO-20, ADEKASTAB AO-30, ADEKASTAB AO-40, ADEKASTAB AO-50, ADEKASTAB AO-60, ADEKASTAB 23 201235412 AO-80, ADEKASTAB AO-330 (above by Adico), IRGANOX1010, IRGANOX1035, IRGANOX1076 , IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX1726, IRGANOX1425, IRGANOX1520, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX3790, IRGANOX5057, IRGANOX565, IRGAMOD295 (above manufactured by BASF Corporation). Commercial products of the amine-based antioxidants include, for example, ADEKASTAB LA-52, LA-57, LA-63, LA-68, LA-72, LA-77, LA-81, LA-82, LA-87, LA- 402, LA-502 (above manufactured by AIDCO), CHIMASSORB119, CHIMAS SORB2020, CHIMASSORB944, TINUVIN622, TINUVIN123, TINUVIN144, TINUVIN765, TINUVIN770, TINUVIN11, TINUVIN783, TINUVIN791 (above, manufactured by BASF Japan). Commercial products of phosphorus-based antioxidants include, for example, ADEKASTAB PEP-4C 'ADEKASTAB PEP-8 'ADEKASTAB PEP-36 &gt; HP-10, 2112 (above manufactured by Adico), IRGAFOS168, GSY-P101 (' Manufactured by 堺Chemical Industries, Inc., IRGAFOS168, IRGAFOS12, IRGAFOS126, IRGAFOS38, IRGAFOS P-EPQ (above, manufactured by BASF Japan). Commercial products of the sulfur-based antioxidants include, for example, ADEKASTAB AO-412, ADEKASTAB AO-503 (above manufactured by AIDCO), IRGANOX PS 800, and IRGANOX PS 802 (above manufactured by Bath 24 201235412 41201pif )Wait.

Commercial products of blended antioxidants include, for example, ADEKASTAB A-611, ADEKASTAB A-612, ADEKASTAB A-613, ADEKASTAB AO-37' ADEKASTAB AO-15 'ADEKASTAB AO-18, 328 (above by Adico) Manufacturing), TINUVIN111, TINUVIN783, TINUVIN791 (above, manufactured by BASF Japan). Among these commercial products, a phenol-based antioxidant or an amine-based antioxidant is preferable. The content ratio of the [B] antioxidant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 0'1 part by mass to 3 parts by mass based on 1 part by mass of the [A] polymer. The following. <[C] Compound&gt; The compound [C] is a compound having an epoxy group. The epoxy group in the present specification means a group containing an ethylene oxide and an epoxy propyl green. The compound [C] is not particularly limited as long as it has one or more epoxy groups in the fraction t, and examples thereof include ethyl alcohol-glycidyl diol, polyethylene glycol diglycidyl diol, and propylene glycol condensed oligosaccharide/two-two. Propyl diglycidyl diglycidyl ether, polypropylene glycol diglycidide with i bride wide-glycidyl-, 1,6-hexanediol diglycidyl ether, glycerol = glycidyl ether, triterpene-based tri-glycoside (four), 2 2二油(四)卿,, shrinking water ^ four beginnings, Ν• diglycidylamino fluorenyl) cyclohexane, hydrazine, hydrazine, hydrido glyceryl diaminobis stupidyl carbaryl, ν with diminishing Glyceryl benzoylamine, hydrazine-bi- fluorination, hydrazine, hydrazine _ diglycidyl heart H gas based thiol hexyl hexyl dressing, glycidyloxy hydrazino triterpenes 2012 20121212 base stone sulphur, glycidol Oxymethyldimethyl bis-ethyl trimethoxy pour, 2- methoxy wei, 2 · glycidoxy oxy, 3 _ glycidoxy propyl oxyethyl triethoxy oxa propyl triethoxy Wei, 3, kewei, 3_glycidoxymethylene)) bis (3·ethyl epoxide, diyl bis(oxymethoxy)methyl] ethene, U• [(3, and [(3_ethyl·3·Lv propyl)]propane, ethylene glycol bis (3 ethane^: carbyl propyl methoxy) methyl bis (3. Base-3. Epoxy (propylmethyl^^yl), bicycloindoleoxypropylmethyl), tetraethanol bis (3. ethyl sulphate trimethyl ketone: (3•B A 3 soil _3_% oxypropylmethyl) acid, di- propyl propyl methyl ether, 1,4-bis(3_ethyl L ) butyl, u-bis (3-ethyl-3-ring Oxypropyl propyl gas storm) hexa, pentaerythritol three (3- 匕 its q ^ alcohol four α-ethyl - 3-epoxy _ two: = two, season: two Qin two seasons 戍 tetraol 51 one = two Pentaerythritol tetrakis (3_ethyl_3·epoxypropylmethyl), di-trimethylolpropionate tetras(3-ethyl-3-epoxypropylmethyl, hydrazine double {[ (3·Ethyl·3_epoxypropyl)methoxy]methyl}benzene, bis[2-(3-epoxypropyl)butyl, ~10 pairs [Ρ-ethyl epoxiconazole-3· ψ) ψoxy]benzene, u·bis[(3ethyl epoxypropyl)methoxy]benzene, 1&gt;2-bis[(3_ethyl propylene propylene _3_ yl) A Oxy]benzene, 4,4'-bis[(3-ethylglyoxime_3_yl)methoxy]biphenyl, 2,2,_bis[(3-ethyl-3-epoxy) Propyl)methoxy]biphenyl, 3,3·,5,5 Im_tetramethyl[4,4,_bis(3-ethylepoxypropan-3-yl)methoxy]biphenyl, 2,7-bis[(3-ethylepoxypropan-3-yl) )methoxy]naphthalene, anthracene, 6-bis[(3-ethyl propylene oxide _3 yl) decyloxy]-2,2,3,3,4,4,5,5-octafluorohexan , 3(4),8(9)-bis[(1-ethyl_3_epoxy 26 201235412 412Ulpif propyl) decyloxymethyl]-tricyclo[5.2 J 02,6]decane, seven hearts Bis(1)ethyl_3_epoxypropyl)indenyl]thiodiphenyl sulfide, 2,3·bis[(3-ethylepoxypropan-3-yl)nonyloxy]norbornane, 2 -ethyl-2-[(3-ethylepoxypropan-3-yl)methoxyindolyl]-1,3-0-bis[(1-ethyl-3-cyclopropyl)methyl ]_propane-1,3-diol, 2,2-dimethyl-1,3-indole-bis[(3-ethyl propylene oxide·3_yl)indenyl]-propanone-1,3 -diol, 2 · butyl 2 - ethyl ethyl epoxy _ 3 _ yl) fluorenyl] - propyl sulphur-1, 3 diol, l, 4 〇 〇 [ [ 3- Propylene oxide-3-yl)indenyl]-butane-1,4-diol, 2,4,6-0-tris[(3-ethylepoxypropan-3-yl)indenyl] Etherification of polycyanic acid, bisphenol A with 3-ethyl-3-chloroindolyl propylene oxide, etherification of bisphenol F and 3-ethyl-3-yl ketone propylene oxide , ethers of phenolic novolacs with 3-ethyl-3-methylmethyl propylene oxide, phenolic phenol varnish and 3-ethyl-3-chloroindenyl propylene acrylate bond, propylene oxide A sesquioxane salt of a sesquiterpene alkane, a 3-ethyl-3-hydroxymethyl propylene oxide, or the like.

Further, as a commercial item of the '[C] compound, for example, DENACOL EX611, DENACOL EX612, DENACOL EX614, DENACOL can be cited.

EX622, DENACOL EX512, DENACOL EX62 卜 DENACOL

EX411 ' DENACOL EX421' DENACOL EX313 &gt; DENACOL

EX32 Bu DENACOL EX201, DENACOL EX211, DENACOL

EX212, DENACOL EX252, DENACOL EX91 卜 DENACOL

EX941, DENACOL EX920, DENACOL EX93 卜 DENACOL

EX111, DENACOL EX121, DENACOL EX141, DENACOL

EX 142, DENACOL EX 146, DENACOL EX 192, DENACOL

EX721, DENACOL EX203, DENACOL EX71 卜 DENACOL

EX 147, DENACOL EX22, DENACOL EX 150, DYNAREX 27 201235412

R45EPT, DYNAREX ΕΧ810, DYNAREX ΕΧ811, DYNAREX EX850, DYNAREX EX851, DYNAREX

EX821, DYNAREX EX830, DYNAREX EX832, DYNAREX EX841, DYNAREX EX861, DYNAREX EX 145, DYNAREX EXM7 (above), ARONE OXETANE OXT-121 (XDO), ARONE OXETANE 221 (DOX), HQOX, RSOX, CTOX, 4, 4, -BPOX, 2, 2, -BPOX, TM-BPOX, 2,7-NpDOX, OFH-DOX, NDMOX, TMPTOX, NPGOX, BisAOX, BisFOX, PNOX, CNOX, OX-SQ, ΟΧ- SC (above, manufactured by Toagosei Co., Ltd.), ETARNACOLL OXBP (manufactured by Ube Industries, Ltd.), etc. As the other [C] compound, an epoxy group-containing polyorganosiloxane may be used as described in WO2009/096598. The [C] compound in these is preferably an epoxy group-containing polyorganosiloxane or a monofunctional epoxy compound. When the compound [c] is an epoxy group-containing polyorganosiloxane or a monofunctional epoxy compound, a liquid crystal alignment film having more excellent reworkability can be formed even with a composition having an epoxy group. a polyorgano group having an epoxy group; a method for synthesizing anoxetane can be synthesized by: preferably a decane compound having an epoxy group or a cerium compound having an epoxy group and another hetero compound (tetra), Hydrolysis or hydrolysis and condensation are preferably carried out in the presence of a suitable diorganogluten, water and a catalyst. Examples of the Wei compound having an epoxy group include, for example, 3 glycidyl oxodioxanthracene, 3 g-glycidoxypropyltriethoxy ruthenium, and a di-glycolate Dimethoxy-Wei, 3'----------------------------------------------------- Oxypropyl propyl decyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy Decane and so on. These compounds may be used singly or in combination of two or more. Examples of the other cerium compound include tetrachloro decane, tetradecyl decane 'tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and four or more. Butoxy decane, trichloro decane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane, di-n-butoxy decane, tri- or 2-butoxy decane, Fluorine trioxane, trimethoxydecane, fluorotriethoxydecane, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy decane, fluorotri-n-butoxylate Burning, methyl trigas sulphate, decyl trimethoxy sulphur, methyl triethoxy decane, methyl tri-n-propoxy decane, decyl triisopropoxy decane, methyl di-n-butoxy Base decane, methyl tri- or 2-butoxybutane, 2-(trifluoromethyl)ethyl chloroform, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoromethyl) Ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriisopropoxydecane, 2 (trifluoromethyl)ethane Tri-n-butoxy decane, 2-(trifluoromethyl)ethyl tri-n-butoxy decane, 2-(perfluoro-n-hexyl)ethyltrichloromethane, 2-(perfluoro-n-hexyl)ethyltrimethoxy Baseline, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2 (perfluoro-n-hexyl)ethyldi-n-propoxylate, 2-(perfluoro-n-hexyl)ethyl-terminated Methan, 2-(perfluoro-n-hexyl)ethyltri-n-butoxydecane, 2_(J; fluoro-n-yl)ethyltri-n-butoxypropane, 2-(perfluoro-n-octyl)ethyltri Chloroquinone 29 201235412 H(perfluoro-n-octyl)ethyltrimethoxydecane, L (all-gas n-octyl)ethyldiethoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-propoxy Baseline, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2_(perfluoro-n-octyl)ethlyltri-n-butoxyoxane, 2_(perfluoro-n-octyl)ethyl-tert-butyl Grade butoxy oxane, hydroxydecyl trioxane, hydroxydecyltrimethoxy decane, hydroxyethyl decyloxydecane, hydroxydecyl tri-n-propoxy decane, hydroxymethyl triisopropoxy Decane, hydroxymethyl tri-n-butoxy decane, hydroxydecyl tri- or two-butoxy Decane, 3-(indenyl)propenyloxypropyl trioxane, 3-(indenyl)propenyloxypropyltrimethoxyoxydecane, 3-(indenyl)propenyloxypropyltriethoxylate基石夕烧, 3-(indenyl) propylene oxypropyl tri-n-propoxy calcination, comparable to propylene methoxypropyl triisopropoxy decane, 3-(fluorenyl) propylene oxime Propyl tri-n-butoxy decane, 3-(indenyl) propylene oxypropyl tri-n-butylbutane decane, 3-mercaptopropyl trichloro decane, 3-mercaptopropyltrimethoxy decane, 3 - mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxyoxydecane, 3-sulfopropyldiisopropoxylate, 3-sulfopropyltri-n-butoxy-oxane, 3-mercaptopropyl tri- or two-butoxybutane, mercaptomethyltrimethoxy oxime, sulfhydrylmethyldiethoxy pulverization, ethylene-trivalent gas-fired, ethylene-trimethoxy sulphur Burning, Ethylene-triethoxy zebra, Ethyl-tri-n-propoxy oxylate, Ethyl-diisopropoxy oxyphyllin, Ethyl-tri-n-butoxy-command, Ethyl-based Grade butoxylate, allyl triphos, sulphur Trimethoxy fever, propylene diethoxy fever, propyl tri-n-propoxy calcination, allyl triisopropoxy zebra, propyl propyl tri-n-butoxy sho Propyl bis-butoxy ketone, ketone gas, phenyl trimethoxy phenoxy, phenyl triethoxy decane, phenyl tri-n-propoxy decane, phenyl triisopropoxy 30 201235412 41201pif The base of three-n-butoxy-oxan, phenyl tri-n-butoxy-Xiyuan, ^一乱魏, methyl dimethoxy-Wei, methyl di-ethoxy Wei, thiol-n-propoxy Base decane, methyl diisopropoxy decane, methyl-n-butoxy = leu- 1 dimethyl dibutoxy dimethyl, dimethyl dimethyl J = - methoxy Wei, dimethyl diethoxy Wei, dimethyl di-n-propan-one earth-stone burning, one-part diisopropoxy oxime, dimethyl di-n-butoxy decane, ^ methyl di- or two-butoxy sylvestre, (曱基) [2_(perfluoro-n-octyl)ethyl]digas, (methyl)[2_(perfluoro-n-octyl)ethyl]dimethoxy shixi, (methyl)[2-(perfluoro-positive Octyl)ethyl]diethoxydecane, (methyl)indole_(perfluoro-n-octyl)-B, Di-n-propoxy decane, (methyl) [2 (perfluoro-n-octyl) ethyl] diisopropoxy zebra, (methyl) [2_(perfluoro-n------- Ethyl]diyloxy]yl J-oxy(methyl)(3-sulfopropyl)-dichlorite, (methyl)(3-disylpropyl)dimethoxydecane, Methyl)(3-sulfopropyl)diethoxylate, (f-)(3·weilpropyl)di-n-propoxydecane, (methyl)(3-mercaptopropyl)di Propoxy decane, (methyl) (3 benzyl propyl) di-n-butoxy oxalate, (methyl g-propyl propyl) di- or 2-butoxy decane, (methyl) (vinyl) Gas decane, (meth) (vinyl) dimethoxy decane, (fluorenyl) (vinyl) diethoxy decane, (methyl) (vinyl) di-n-propoxy decane, (methyl) (Vinyl) diisopropoxy decane, (methyl) (vinyl) di-n-butoxy decane, (decyl X vinyl) di-2-butoxy decane, divinyl dichloro decane, diethylene Dimethoxy decane, divinyl diethoxy decane, divinyl di-n-propoxy decane, divinyl diisopropoxy Alkane, divinyldi-n-butoxydecane, divinyldi-n-butoxybutane, diphenyldichlorodecane, diphenyldimethylene 31 201235412 —τ λ. ^\j λ. a a. Oxygen Base decane, diphenyldiethoxy decane, diphenyldi-n-propoxy oxazepine, mono-n-isopropoxy oxalate, diphenyldi-n-butoxy-stone, diphenyl-- - Grade butoxy calcination, gas-methyl shirt, methoxy dimercapto, burn, ethoxy, monomethyl calcination, dimethyl gas fragmentation, trimethyl desert, triterpenoid Base smoldering, methoxy trimethyl decane, ethoxy trimethyl decane, n-propoxy trimethyl sulphate, isopropoxy trimethyl sulphur, n-butoxy trimethyl sylvestre, first-grade Oxy-dimethyl dimethyl sulphur, third-grade butoxy sulphate, (gas) (ethylene) dimethyl sulphur, (methoxy) (ethlyl) dimethyl sulphur Calcined, (ethoxy) (ethlyl) dimethyl sulphur, (gas) (methyl) diphenyl sulphur, (decyloxy) (fluorenyl) diphenyl decane, (ethoxy) (曱基) Diphenyl oxime, etc. Things and so on. These compounds may be used singly or in combination of two or more. The epoxy equivalent of the polyorganosiloxane having an epoxy group is preferably 5 〇g/mol 〜1 〇, and more preferably _ g/m 〇 刚 〜 〜 〜 〜 _ _ _ _ _ _ , , , , 100g/m〇l~l,000g/m〇 Therefore, when synthesizing polyorgano oxysulfonate having an epoxy group, the ratio of the use of the epoxy group-containing compound and the other compound is preferably The epoxy equivalent of the obtained polyorganococcal oxide was set to the above range. The epoxy equivalent 疋 of the present specification means a value measured by the hydrochloric acid-butyroside method described in JIS C2l〇5. In the case of synthesizing the polyorganococene having an epoxy group, examples of the organic solvent which can be used include a hydrocarbon compound, a ketone compound, a brewing compound, a compound, an alcohol compound and the like. These compounds may be used singly or in combination. Examples of the smoking compound include methyl bromide, xylene, and the like. Ketone compounds such as 32 201235412 41201pif include methyl ethyl ketone and decyl isobutyl ketone.

« m T Lane n-decyl ketone, - L ketone, cyclohexanone and so on. Examples of the vinegar compound include ethyl acetate, ethyl &amp; n-butyl vinegar, acetic acid, propylene glycol monoterpene, acetic acid _3_methoxy butyl, and ethyl oleate. Examples of the ether compound include ethylene glycol diterpene ether (IV), and two-co-alcoholization products: such as argon-cyclohexanediol mono-n-top, propylene glycol monomethyldipropanediol monoethyl hydrazine, propylene glycol mono-n-propyl epoxide, and the like. The amount of use of the solvent is '1' is preferably 1 () part by mass to 1 G, _ 5 parts by mass to 1 part by mass, relative to all of the Wei compound. The more excellent k is the use of water in the synthesis of polyorgano-oxo hospitals having an epoxy group. It is preferably 倍5 times the molars to 1 〇〇 莫 摩尔 relative to all the ceramsite compounds. More preferably, it is 1 time mole to 3 times mole. The hydrolysis or hydrolysis and the a-reduction reaction in the synthesis of the polyorganophosphorus having an epoxy group are preferably carried out by transferring a Wei compound having a Wei group and another Wei compound as desired to the organic solvent, and The solution is mixed with water and water, and is heated, for example, by an oil bath. The heating temperature in the hydrolysis and condensation reaction is preferably 13 (rc or less, more preferably thief to 10 (TC). The heating time is preferably 〇5 hours to 12 hours, more preferably H, hour to 8 hours. The mixed solution may be stirred or placed under reflux. Preferably, after the reaction is completed, the organic solvent layer separated from the reaction liquid is washed with water. In the case of washing, it is easy to clean from the viewpoint of cleaning operation 33 201235412 - Γ Λ ,Select, water containing a small amount of salt, for example, about 02% by mass of aqueous solution, etc., can be cleaned. The cleaning can be carried out until the water layer after washing becomes neutral, and the rear view = dry with inorganic sulfur, molecular sieve, etc. After the organic solvent layer is dried, the solvent is removed to obtain a polyorganosiloxane having an epoxy group. A commercially available product can also be used as the polyorganosiloxane having an epoxy group. DMS-E01, DMS-E12, DMS-E2, EMS-32 (manufactured by Chisso Co., Ltd.), etc. Polystyrene determined by gel permeation chromatography of polyorganosiloxane having epoxy group Converted weight average The amount (Mw) is preferably 5 Å to 100,000 Å, more preferably 1, 〇〇〇 〜 1 〇, 〇〇〇 &lt; 5 In addition, in the description, Mw is a gel permeation chromatograph using the following specifications The measured value of poly(ethylene) was measured. Column: manufactured by Tosoh Corporation, TSK-GEL solvent: tetrahydrofuran column temperature: 40 ° C pressure: 80 kgf/cm 2 as the content ratio of [C] compound, relative to [a] The amount of the polymer is preferably 40 parts by mass or less, more preferably 丄 part by mass to 3% by mass or less. <Optional component> The liquid crystal alignment agent is other than [A] polymer, [B] In addition to the oxidizing agent and the compound [c], an optional component such as a polymer other than the [A] polymer or a functional decane compound may be contained in a range that does not impair the effects of the present invention. These 34 201235412 41201pif These may be used in combination of two or more kinds. Hereinafter, each component will be described in detail. [Other Polymers] Other polymers may be used to improve solution properties and electrical properties. Other polymers may, for example, be polyamidates. Polyester, polyamine, polyoxyalkylene, fiber a derivative, a polyfurfural, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(indenyl)acrylate, etc. Moreover, the content of other polymers may be according to the purpose thereof. [Functional decane compound] The functional ceramsite compound may be contained from the viewpoint of further improving the printability of the liquid crystal alignment agent. Examples of the functional ishixiyuan compound include 3-aminopropyltrimethyl Oxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxysulfene, 2-aminopropyltriethoxysulfate, n-(2-aminoethyl)-3 -aminopropyltrimethoxy decane, ν-(2.aminoethyl)-3-aminopropyl decyldimethoxy sylvestre, 3-glycamyl propyl sulfoxide, 3-urea Propyl triethoxy oxalate, N-ethoxymethyl-3-aminopropyltrimethoxy oxysulfate, N-ethoxymethyl-3-aminopropyltriethoxy , N-triethoxydecyl propyl triethylidene triamine, N-trimethoxy phthalocyanine propyl triethylidene triamine, 10-trimethoxy decyl _i, 4, 7•triaza Alkane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxyxanthene-3,6-diazaindolyl acetate, 9-triethyl Oxyl sulphate _3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxy oxalate, N-nodal-3-aminopropyltriethoxylate Xishou, N-phenyl-3-aminopropyltrimethoxy oxycarbazide, N-phenyl-3-aminopropyltriethoxy fluorene,]Si-bis (oxyethyl sulphate 35 201235412 ke)- 3-aminopropyltrimethoxy decane, N-bis(oxyethylidene)-3-aminopropyltriethoxydecane, and the like. The use ratio of the functional decane compound is preferably 2 parts by mass or less, more preferably 0.1 part by mass to 1 part by mass, per 100 parts by mass of the [A] polymer. &lt;Preparation method of liquid crystal alignment agent&gt; The liquid crystal alignment agent is prepared so that the above [A] polymer, [B] antioxidant, and [C] compound, and optionally any optional component are preferably dissolved in an organic solvent. Solution-like composition. Examples of the organic solvent include N-fluorenyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, hydrazine, hydrazine, hydrazide, hydrazine, hydrazine, hydrazine, hydrazine Amine, 4_hydroxy-4-methyl-2-pentanone, butyl lactate, butyl acetate, decyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monoterpene ether, ethylene glycol single Ether, ethyl alcohol mono-n-propyl ether, ethyl alcohol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl > gluten), ethylene glycol dioxime ether, ethylene glycol ethyl ether acetate, diethyl Glycol dioxime ether, diethylene glycol diethyl ether, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monoterpene ether acetate, diethylene glycol monoethyl ether acetate, two Isobutyl ketone, isoamyl propionate, isoamyl isoamyl, diisoamyl ether, ethylene carbonate, propylene carbonate and the like. These money solvents may be used singly or in combination of two or more. The solid content concentration of the liquid crystal alignment agent (the ratio of the total mass of the liquid crystal alignment agent other than the organic component to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of purity, volatility, and the like. Preferably, it is 1 mass/〇~10 mass/. . By applying the liquid crystal alignment agent to the surface of the substrate, the organic solvent is removed. When the coating film of the liquid crystal alignment film is not more than 1% by mass in the case of the solid material 36 201235412 412 UIpif, the film thickness of the coating film is too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the concentration of the material is more than 10% by mass, the film thickness of the coating film may become too large, and it may be difficult to obtain a favorable liquid crystal alignment film in the same manner, and the viscosity of the liquid crystal alignment agent may increase. Large, resulting in poor coating properties. A more preferable range of the solid content varies depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, in the case of using the spin coating method, a range of from 1 to 5 mass% to 4.5 mass 〇 / 〇 is preferable. In the case of using the printing method, it is preferably in the range of 3% by mass to 9% by mass, and the solution viscosity is preferably in the range of 12 mPa*s to 50 mPa·s. In the case of using the inkjet method, it is preferably in the range of 1% by mass to 5% by mass, and the solution viscosity is preferably in the range of 3 mPa·s to 15 mPa·s. The temperature at which the liquid crystal alignment agent is prepared is preferably 1 (rc to 50 ° C, more preferably 20 ° C to 30 ° C. <Method for Forming Liquid Crystal Alignment Film and Method for Producing Liquid Crystal Display Element> From the Liquid Crystal Alignment A liquid crystal alignment film formed by the agent and a liquid crystal display element having the liquid crystal alignment film are also suitably included in the present invention. The liquid crystal display element can be suitably applied to various devices, for example, for a clock, a portable game machine, In a display device of a word processor, a notebook computer, a car navigation system, a camcorder, a personal digital assistant, a digital camera, a mobile phone, various displays, a liquid crystal television, etc. The liquid crystal alignment film of the present invention can pass the liquid crystal alignment agent It is applied to the substrate. Secondly, the coated surface is heated to be formed on the substrate. Further, this method is used to describe the liquid crystal. The following is the description of the liquid crystal. The manufacturing method is detailed (M). When manufacturing TN type and STM opening I]·+, two pieces are provided with a pattern printing method, a spin coating method or an inkjet printing 22: 2: Each transparent guide 2: = The coated surface is heated, whereby the Dan people break the glass for each glass, nano glass, etc.; and include a floating method, a diced vinegar 'poly _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Shrug, Li Riyi, Jiugui, Gongsi Plastic (Sn〇2) ^2lZT^T^m 5 ^ 脔栌, u匕u (PPG manufactured, registered t-pattern transparent conductive film: rr:== method In order to prevent the liquid from escaping, etc., it is preferable to apply the functional Wei compound and the functionalizing solution a day alignment agent to the surface of the substrate before the coating of the liquid crystal. Red preheating (pre-culture). The pre-culture temperature is preferably 耽~2赃, more preferably 〜15叱, particularly preferably thief~boots. The pre-culture time is preferably 0.25 minutes~l〇 minutes between 2012 and 35,354. More preferably, it is 〇5 minutes to 5 minutes. Next, 'the solvent is completely removed' and, if necessary, calcination (post-baking) is carried out for the purpose of heat-imidization of poly-proline. The post-baking temperature is preferably 80C. 〜300C, more preferably i2〇°C~250° C. The post-baking time is preferably 5 minutes to 2 minutes, more preferably 1 minute. The film thickness of the coating film to be formed is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm. (1-2) In the case of manufacturing an IPS type liquid crystal display device, it is preferable to use an offset plate. The liquid crystal alignment agent of the present invention is applied to the conductive film forming surface of the translucent electric circuit substrate of the comb-shaped type, and the conductive film is not provided by the P brush method, the smear coating method or the inkjet printing method. On one surface of the counter substrate, the coated surface is heated to form a coating film. The material of the US plate and the transparent conductive film used at this time, the patterning method of the transparent conductive film, and the pretreatment of the substrate And a heating method after applying a liquid crystal alignment agent, which is the same as (id) above. The thickness of the formed coating film is preferably the same as that of the above (1_n/. (2) When the liquid crystal display element produced by the method of the present invention is a va type liquid crystal display element, the coating layer formed as described above can be formed. The film can be directly used as a liquid crystal alignment film'. After the rubbing treatment as described later, it can be used for use. On the other hand, when the liquid crystal display other than the VA type is used, the pass condition is as described above. The formed coating film is subjected to a rubbing treatment to form a liquid crystal alignment film. ": The rubbing treatment can be carried out by using a cloth wound with a fiber such as a nylon, a rayon, or a cotton, for example, in a directional orientation. For example, 39 201235412 I Λ V Λ ^ΛΛ- The rubbing surface which was opened as described above is rubbed, thereby imparting the alignment ability of the liquid crystal molecules to the coating film, thereby becoming a liquid crystal alignment film. The formed liquid crystal alignment film is subjected to irradiation of ultraviolet rays to a portion of the liquid crystal alignment film, as shown in, for example, Japanese Patent Laid-Open Publication No. Hei. After the treatment of the change in the pretilt angle or the formation of the photoresist film on a part of the surface of the liquid crystal alignment film shown in Japanese Patent Laid-Open No. Hei 5:107544, the friction is performed in a direction different from the previous rubbing treatment, and then By removing the photoresist film, the field-of-sight characteristics of the liquid crystal display element obtained by different liquid crystal alignment capabilities in each region of the liquid crystal alignment film can be improved. (3) Two substrates on which the liquid crystal alignment film is formed are prepared. A liquid crystal cell is produced by disposing liquid crystal between two substrates arranged in the opposite direction. When the coating film is subjected to a rubbing treatment, the two substrates are at a predetermined angle to each other in the rubbing direction of each of the coating films. For example, in the case of manufacturing a liquid crystal cell, the following two methods are exemplified. The first method is a method known from the prior art. First, the liquid crystal alignment film is opposed to each other. By arranging two substrates in a gap (cell gap), the peripheral portions of the two substrates are bonded to each other using a sealant, and the surface of the substrate is densely bonded. After filling the liquid crystal into the cell gap divided by the agent, the liquid crystal cell is fabricated by sealing the injection port. The first method is a method called ODF (One Drop Fill) method to form a liquid crystal alignment. For example, one of the two substrates of the film is coated with a UV curable sealant at a predetermined position on the substrate, and further liquid crystal is added to a predetermined number of portions on the liquid crystal alignment film surface, and then the liquid alignment film is relatively opposed. In the case of using a method, it is preferable to use a liquid crystal cell by irradiating ultraviolet light to the entire surface of the substrate to cure the sealing agent. The liquid crystal unit manufactured as described above is heated in a stepwise manner until the liquid crystal used becomes an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow at the time of liquid crystal injection. Next, the liquid crystal display element is obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. The agent may, for example, contain oxygen globules as a spacer and hardened lipids. Examples of the liquid crystal include a nematic liquid crystal, a smectic liquid, and the like. Among these, a nematic liquid crystal is preferable. In the case of a VA type liquid crystal cell, a nematic Weiri day with (iv) dielectric anisotropy is preferred. Such a liquid 曰曰 1 = dicyanid paper 3, azine-based liquid crystal, Schiff test liquid 糸 liquid crystal, ligated liquid crystal, phenyl ring-fired liquid crystal, and the like. In the case of a positive human STN twin unit, a nematic liquid crystal having an anisotropy is preferable. Examples of such a liquid crystal include a phenyl group-di-t-cyclohexene-fired liquid crystal, a vinegar-based liquid crystal, a terphenyl-based liquid crystal, and a octyl crystal. The liquid crystal, the diwei liquid crystal, the double 瓖, the boat, the W曰曰 cubic burning liquid crystal, and the like. Further, in the above liquid crystal, an acid such as guanidinated cholesteryl alcohol, cholesteryl phthalate, or cholesteric carbon is used as a patterned liquid crystal (manufactured by Merck, CM5, CB-"), and a chiral agent 'p-oxobenzene. Methylene, p-amino, 2, p, butyl sulphide 201235412 cinnamic acid material, ferroelectric liquid crystal, etc. Λ , as a polarizing plate attached to the outer surface of the liquid crystal cell, the holding of the protective film of the vistasin is called " A polarizing film made of a polarizing film of the η film (the above-mentioned (4) 疋&gt; surface of the polyvinyl alcohol is stretched and absorbed by one side), or a polarizing plate composed of the ruthenium film itself. [Examples] The present invention is described in detail below based on examples, but the present invention is not limited by the description of the examples. &lt;[Α] Synthesis of Polymer&gt; [Synthesis Example 1] 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic dianhydride 22, 4 g (〇.l mole) And as a diamine p-phenylenediamine (PDA) 2.6g (〇.〇2mol), 3,5-diaminobenzoic acid cholesteryl ester (HCDA) l〇.4g (〇.〇 2 mol) and 3,5-diaminobenzoic acid (DAB) 9.1 g (0.06 mol) dissolved in N-mercapto-2-pyrrolidone (NMP) 176 g, and reacted at 60 ° C for 6 hours. A solution containing 1% by mass of polylysine was obtained. The solution viscosity of the obtained polyaminic acid solution was 102 mpa.s. Next, 410 g of NMP was added to the obtained polyamic acid solution, and 7.9 g of pyridine and 10.2 g of acetic anhydride were added to carry out a dehydration ring-closing reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP (the pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to the outside of the system), thereby obtaining 15% by mass of ruthenium iodide. A solution of about 47% polyethylenimine (A-1). A small amount of the obtained poly-imine solution was added, and NMP was added to prepare a solution having a polyimine concentration of 10% by mass. The viscosity of the solution was 56 mPa·s as measured by 201203412 41201pif solution. [Synthesis Example 2] TCA 22.3 g (〇·ι Moule) as a tetracarboxylic dianhydride, and 4,4·-diaminodiphenyl fluorene (DDM) as a monoamine 3.9 g (0.02 mol) Ear), HCDA5.2g (0.01 mol), cholesteryloxy 2,4-diamino (HCODA) 4.9 g (0.01 mol) and DAB 9.1 g (〇.〇6 molar) dissolved in In NMP 182 g, the reaction was carried out at 60 ° C for 6 hours to obtain a solution containing 10% by mass of poly-proline. The resulting polyaminic acid solution had a solution viscosity of 117 mPa·s. Next, 423 g of NMP was added to the obtained polyamic acid solution, and 10.2 g of pyridine and 13 2 g of acetic anhydride were added to carry out a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, thereby obtaining a solution of the polyimine (a-2) having a ruthenium iodide ratio of about 67% containing 15 mil A. . A small amount of the obtained polyimine solution was added, and a solution having a concentration of 10% by mass of NMp was added to obtain a solution viscosity of 7 μmPa·s ° [Synthesis Example 3] TCA 17·9 g (0.08 mol) and l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[ 1,24] bite ° Nan-1,3-diketone (Ding 0 8) 6. (^ (〇.〇2 Moer), and as a diamine 0 into 2.2§ (〇.〇2 Moer) , 11〇) 八1〇4§(〇〇2莫耳) and 0入6 9.18(〇.〇6莫耳) dissolved in ^^11)182§, at 6〇. (: 6 hours of reaction was carried out' to obtain a solution containing 1% by mass of polylysine. The solution viscosity of the obtained polyaminic acid solution was 99 mPa·s. Next, 43 201235412 μιη to the obtained polyamine NMP 423 g was added to the acid solution, and 7.9 g of pyridyl bromide and 10.2 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out for 4 hours at ll 〇 ° C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP solvent. Thus, a solution containing 15% by mass of a polyamidimide (A-3) having a ruthenium iodide ratio of about 51% was obtained. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a polyazide. The solution viscosity of the solution having an amine concentration of 1% by mass was 55 mPa·s. [Synthesis Example 4] TCA 18.0 g (〇.〇8 mol) and 1,3,3a as tetracarboxylic dianhydride ,4,5,9b-hexahydro-8-f-yl-5-(tetrahydro-2,5-dioxo-3-indolyl)-naphtho[l,2-c]吱--1 3-D (MTDA) 6.3 g (〇.〇2 Mo), and PDA 2.2 g (〇.〇2 Mo) as HCII, HCDA 10.5 g (0.02 Mo) and DAB 9.2 g (0.06 Mo Ear) dissolved in NMP 185 g, at 60 ° C A 6-hour reaction was carried out to obtain a solution containing 1% by mass of poly-proline. The solution viscosity of the obtained poly-proline solution was 92 mPa·s. Secondly, NMP 429 g was added to the obtained poly-proline solution. Adding β ratio, setting 8.0 g and acetic acid liver 10.3 g to 11 〇. The dehydration ring closure reaction was carried out for 4 hours under the sputum. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP solvent. A solution containing 15% by mass of a polyamidiamine (A-4) having a ruthenium iodide ratio of about 48% was obtained. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a polyimine concentration of 1 The solution viscosity measured by the 〇 mass % solution was 50 mPa · s. [Synthesis Example 5] TCA l8.〇g (〇.〇8mole) and 2,4,6,8- as tetracarboxylic dianhydride were used. 44 201235412 41201pif Tetradecylbicyclo[3.3.〇]cincinary _2,4,6,8-dianhydride (3〇£&gt;8)5〇8(〇〇2 molar), and PDA as diamine 2.2 g (0.02 mol), HCDA1 〇5 g (0.02 mol) and dab 9.2 g (0.06 mol) were dissolved in nmp 179 g, and reacted at 6 〇t for 6 hours to obtain 1% by mass. a solution of polylysine. The solution viscosity of the obtained polyaminic acid solution is 81 mPa·s. Secondly, NMp4i6g is added to the obtained polyamic acid solution, and 7.9 g of bite and 10.2 g of acetic anhydride are added. Ll (4 hours of dehydration and closed coat reaction under TC). After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new Nmp, whereby a solution containing 15% by mass of a polyamidimide (A-5) having a ruthenium amination ratio of about 50% was obtained. A solution of a small amount of the obtained polyimine solution was added, and a solution having a polyethylenimine concentration of 1 〇% by weight was added to prepare a solution viscosity of 42 mPa·s. [Synthesis Example 6] 22.5 g (0.1 mol) of TCA as tetracarboxylic dianhydride, and 1-(4-aminophenyl)-2,3-dihydro-l,3,3- as diamine &amp; Kun of tridecyl-lH-indole-5-amine and l-(4-aminophenyl)-2,3-dihydro-1,3,3-tridecyl-lH-indole-6-amine Compound (TMDA) 10.7 g (0.04 mol), HCDA 10.5 g (0.02 mol) and DAB 6.1 g (0.04 mol) were dissolved in NMP 199 g, and reacted at 6 〇t: for 6 hours. A solution containing 1% by mass of polylysine. The resulting polyamic acid solution had a solution viscosity of 80 mPa·s. Next, NMP 462 g was added to the obtained polyaminic acid solution, and a ° ratio was added. The 7.9 g and acetic anhydride iijg were subjected to a dehydration ring closure reaction for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, thereby obtaining a polyimine containing 15% by mass of ruthenium 45 201235412 ~r Α V# Λ rate of about 44%. Solution of (A-6). A small amount of the obtained polyimine solution was added, and a solution having a concentration of 10% by mass of NMP was added to obtain a solution viscosity of 66 mPa·s. [Synthesis Example 7] TCA 18.0 g (〇·〇8 mol) and TDA 6·〇g (0.02 mol) as tetracarboxylic dianhydride, and TMDA 5.3 g (0.02 mol) as a diamine, HCDA 10.5 g (0.02 mol) and DAB 9.2 g (0.06 mol) dissolved in NMP 196 g 'at 60. (: The reaction was carried out for 6 hours to obtain a solution containing 10% by mass of poly-proline. The solution viscosity of the obtained polyaminic acid solution was 84 mPa·s. Secondly, it was added to the obtained poly-proline solution. NMP455 g, adding 7.9 g of pyridine and 10.2 g of acetic anhydride, and performing a dehydration ring-closure reaction at 11 (TC) for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP solvent to obtain a solvent. U mass % of hydrazine imidization is a solution of polyimine (A-7) of about 49 °. A small amount of the obtained polyimine solution is added, and NMp is added to make a polyimine concentration of 10 The solution viscosity measured by the mass % solution was 52 mPa·s. [Synthesis Example 8] TCA 17.9 g (0.08 mol) and MTDA 6*3 g (〇.〇2 mol) which are tetracarboxylic dianhydrides. And TMDA5 3 g 〇2 mol) as diamine, HCDA 10.4 g (0.02 mol) and DAB9_lg (〇.〇6 Moer) = solution in NMP196g, ό hour reaction at 60. A solution containing 10% by mass of polyamic acid was obtained. The solution viscosity of the obtained polyaminic acid solution was 75 mPa·s. In a poly-proline solution 46 201235412 412Ulpif Add NMP455 g, add pyridine 7.9 g and acetic anhydride 1 〇 2 g and carry out a dehydration ring closure reaction at 11 ° C for 4 hours. After dehydration ring closure reaction, use new NMP is used to replace the solvent in the system with a solvent, thereby obtaining a solution containing 15% by mass of polyimine (α·8) having a ruthenium iodide ratio of about 47%. The solution viscosity of the imine solution, which was prepared by adding Njyjp to a solution having a concentration of acrylamide of ίο% by mass, was 49 mPa·s ° [Synthesis Example 9] TCA 四·8 g as tetracarboxylic dianhydride (〇 .08 mol) and b〇da 5-〇g (0.02 mol), and as the top of the diamine ^^^ (〇〇2 mol), HCDA 10.4 g (〇·〇2 moor) and DAB 9 g ( 〇〇6 摩尔,) = solution in NMP 190 g, 6 hours at 60t: to obtain a solution of two polyphosphamides with a mass of 10%. The obtained polyaminic acid solution The viscosity of the solution is 85 mPa · s. Secondly, NMP 442 g is added to the obtained (four) lysine solution, and 7.9 g of t is added and 1 G 2 g of acetic anhydride is added at 11 〇. After the dehydration ring-closure reaction, a new NMP was used to disperse the solution, thereby obtaining a solution containing a U mass% of a polyamidimide (A-9) having a ruthenium iodide ratio of about 56%. Take 3: the Wei imine solution of 彳f, the solution viscosity of the solution obtained by adding NMp to a concentration of 10% by mass of polyimine is 5 〇 mPa·s. &lt;Synthesis of [C] compound&gt; [Synthesis Example 10] 2-(3) was loaded in the counter 201235412 ~r ± λ. ^/ι a reactor with a machine, a thermometer, a dropping funnel and a reflux condenser , 4-epoxycyclohexyl)ethyltrimethoxysulfide 345 g, 34.5 g of decyl isobutyl ketone and 3.45 g of triethylamine were mixed at room temperature. Next, deionized water (27 6 ) was added dropwise thereto over 30 minutes using a dropping funnel, and the mixture was stirred at reflux for 8 Torr. The armpit was allowed to react for 6 hours. After completion of the reaction, the organic layer was taken out and washed with a 2% by mass aqueous solution of ammonium tartaric acid until the water after washing became neutral, and then the solvent and water were removed under reduced pressure to obtain a thick layer. Organic poly-stone oxygen burning solution. 1H-NMR analysis of the organopolyoxane showed that a peak based on the epoxy group was obtained as the theoretical shift in the vicinity of the chemical shift (σ) = 3.2 ppm, and a side reaction which did not produce an epoxy group in the reaction was confirmed. . The polyorganooxane had a Mw of 3,000, an epoxy equivalent of 185 g/m, and a 200 mL three-necked flask was charged with the obtained polyorganooxime 7.3 g, and methyl isobutyl ketone as a solvent 41.6. g, 4-octyloxybenzoic acid 3 〇g and 0.7 g of tetrabutylammonium bromide as a catalyst, reacted at rc for 8 hours. After the reaction, in the reaction mixture The solution obtained by adding ethyl acetate was washed with water three times, and the organic layer was dried over magnesium sulfate, and then the solvent was evaporated to obtain 10.1 g of an epoxy group-containing polyorganooxane C-4. Mw was 8,000. [Synthesis Example 11] In Synthesis Example 10, 'the above polyorganosiloxane was set to 7/7 g, and 4'-pentyl-ι, ι'-bicyclohexyl harylic acid 3.5 g was used instead. In the same manner as in Synthesis Example 10 except that tetrakis-butylammonium bromide as a catalyst was used as the catalyst, 100.9 g of an epoxy group-containing polyorganooxane was obtained. C-7. Mw of C-7 is 8,500. 48 201235412 41201pif &lt;Preparation of liquid crystal alignment agent&gt; [B] antioxidant used in preparation of each liquid crystal alignment agent His [C] compound is as follows: &lt;[B]Antioxidant&gt; B-1 : IRGANOX1010FF (phenolic antioxidant) B-2 : ADEKASTABLA-72 (amine antioxidant) B-3 : TINUVIN622LD (amine Antioxidant) B-4 : IRGAFOS12 (phosphorus antioxidant) B-5 : IRGANOXPS 800FL (sulfur anti-deuteration agent) B_6 : ADEKASTAB AO-40 (phenolic antioxidant) &lt; [C] compound &gt; C -1 : Ν,Ν,Ν',Ν'-tetraglycidyl-isophthalamide C-2: manufactured by Changchun Chemical Co., Ltd., EX-142 C-3 : &gt;^^-tetraglycidyl- 4,4'-diaminodiphenyl fluorene c'5 : ARONE OXETANE OXT-121 C-6: dipentaerythritol tetrakis(3-ethyl-3-epoxypropyl fluorenyl [Example 1] contained as [ A] Polyimine (A-1) of the polymer 100 parts by mass of a solution is added with NMP and ethylene glycol mono-n-butyl ether, and added as the [B] antioxidant, the above (Bl) 3 parts by mass and as [c The above (cl) parts by mass of the compound was sufficiently stirred to prepare a solvent having a solvent composition of NMp: ethylene glycol, n-butyl ether, 60:40 (mass ratio), and a solid concentration of 3.0% by mass. The solution for the 丨μιη screening program Line filter, thereby to prepare a liquid crystal alignment agent. 49 201235412 A dmt \ J Λ. ^ ΛΛ.

[Example 2 to Example 39 and Comparative Example i to Comparative Example 12] Each of the liquid crystal alignment agents was adjusted in the same manner as in Example 将 except that the type and content of the components to be formulated were each as the type and content in the surface. Further, in Table 1, the corresponding components are not used. &lt;Formation of Liquid Crystal Alignment Film&gt; The liquid electrode alignment agent was applied to a transparent electrode surface of a glass substrate having a transparent electrode composed of an IT0 film having a thickness of 1 mm, and was coated on a hot plate by a spinner. Prebaking was performed at 80 ° C for 1 minute, followed by post-baking for 3 minutes, whereby a liquid crystal alignment film having a film thickness of about 8 μm was formed. &lt;Production of Liquid Crystal Display Element&gt; The formation of the liquid crystal alignment film was repeated to obtain a pair of (two) substrates having a liquid crystal alignment film. Next, an epoxy resin adhesive having a diameter of 5.5 μm is applied to an outer edge of any one of the pair of substrates having a liquid crystal alignment film, and then the liquid crystal alignment film faces are opposed to each other. The crimping is performed to harden the adhesive. Next, a nematic liquid crystal (manufactured by Merck & Co., Ltd., MLC-6608) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal. unit. Further, this operation is repeated to manufacture another pair of liquid crystal cells. &lt;Evaluation&gt; The liquid crystal alignment film formed above and the liquid crystal display element produced were evaluated as follows. The results are shown together in Table 1. 50 201235412 Hizuipif [Light resistance] With respect to the pair of liquid crystal cells manufactured as described above, a voltage of 5 v was applied for a few seconds of application time and a span of 167 milliseconds, and then the application was released using VH]M_made by Dongyang Technology Co., Ltd. Voltage retention after 167 milliseconds. The value is taken as the initial voltage holding ratio (νΗι) (%). Next, the liquid crystal cell after the initial voltage holding ratio was measured by using a carbon button as a photo-nano testing machine was subjected to 8, (8) Μ, _ light irradiation. For the liquid crystal cell after light irradiation, the voltage holding ratio was measured again by the method of _ and Shang Lang #. The value was taken as the voltage holding ratio (VH2) (8) after light irradiation. The amount of decrease in voltage holding ratio ΔVHR (%) was obtained from the following equation as a property. ΔVHR (%) = VHrVH2 When the ΔνΗΐΙ is less than 2.5%, the light resistance is judged to be excellent, and when the AVHR is 25% or more and less than 5%, the light resistance is judged to be good, and the AVIJR is 5.0% or more. In the case of the case, the light resistance is judged to be bad. [High Temperature and High Moisture Resistance] The other pair of liquid crystal cells manufactured above were applied with a voltage of 5 V at a load time of 6 〇 microseconds and a span of 167 milliseconds at 7 ° C, and then manufactured by Dongyang Technology Co., Ltd. The VHR-1 was measured and the voltage holding ratio after 167 milliseconds of application was released. The value is taken as the initial voltage holding ratio (VH3) (%). Next, the liquid crystal cell after the liquid crystal cell whose initial voltage holding ratio was measured was stored in an oven set to 51 201235412 6〇C and a humidity of 9 G% for 5 GG hours, and the voltage holding ratio was measured again in the same manner as described above. The value is the voltage holding rate (VH4) (%) after the general surface is wet. According to the following; find the reduction of the voltage holding rate, (%), as the high temperature resistance △VHR' (%) = vh3-vh4 in M ^ R, less than 30% of the case will be high temperature and high humidity 2 = When △Qing is above and insufficient, it is judged to be good, and when ΔVHR is 5.0% or more, it is judged that the temperature is not bad. , sub-reworkability; | ITO =: transparent conductive film on one surface of a glass substrate having a thickness of 1 mm, coated with the above-mentioned prepared liquid by a spinner = ' on a hot plate, 100 t A pre-baking was performed for 90 seconds to form a film; it was a coating film of 80 nm. This operation was repeated to prepare a substrate for the film. Secondly, the obtained 2 animal substrates are placed under a nitrogen atmosphere, 2

Keep it in a safe place. After 12 hours from the start of storage, 72 hours later, the knife was removed from the dark room, and was placed in a beaker of 4 (rc NMp). After 2 minutes, the substrate was taken out from the beaker, and ultrapure was used. After several times of cleaning, the water droplets were removed by blasting, and the substrate was observed by an optical microscope to observe whether or not the coating film remained. It was judged that the residue of the coating film was not observed after the collapse. P 52 201235412 412Ulpif (A), the residue of the coating film was observed on the substrate after 72 hours, but the case where the residue of the coating film was not observed on the substrate taken out from the dark room after 12 hours was judged to be good (B), The case where the residue of the coating film was observed on the substrate taken out from the dark room after 12 hours was judged to be defective (C). 53 201235412 [Table i]

Composition evaluation of liquid crystal alignment agent [A] Polymer [B] - Antimony oxidizing agent [C] Compound VH! (%) Visibility (%) Chonan temperature and humidity (%) Reprocessing type content (mass parts) Species content (parts by mass) Species content (parts by mass) Example 1 A-1 100 B-1 3 C-1 2 99.2 4.2 3.1 B Example 2 A-1 100 B-2 3 C-1 2 99.4 4.1 3,3 B Example 3 A-1 100 B-3 3 C-1 2 99.3 3.9 3.9 B Example 4 A-1 100 B-4 3 C-1 2 99.3 4.9 4.0 B Example 5 A-1 100 B-5 3 C-1 2 99.0 4.8 4.4 B Example 6 A-1 100 B-6 3 C-1 2 99.1 4.0 3.3 B Example 7 A-1 100 B-1 0.1 C-1 2 99.1 4.9 3.8 B Example 8 A-1 100 B-1 10 C-1 2 99.2 3.0 4.8 B Example 9 A-1 100 B-6 5 C-1 2 99.0 4.1 3.4 B Example 10 A-1 100 B-1 3 C-2 5 99.4 3.9 4.4 A Example 11 A-1 100 B-1 3 C-3 30 99.4 3.1 3.1 B Example 12 A-1 100 B-1 3 C-4 5 99.2 2.9 2.9 A Example 13 A-1 100 B-1 3 C-5 5 99.1 4.0 4.6 A Example 14 A-1 100 B-1 3 C-6 5 99.2 4.2 4.9 A Example 15 A-1 100 B-1 3 C-7 5 99.4 4.5 4.5 A Example 16 A-1 100 B-3 1 C-4 5 99.1 2.2 2.7 A Example 17 A-1 100 B-3 1 C-5 5 99.2 4.1 4.1 A Example 1 8 A-2 100 B-1 3 C-1 2 99.1 3.7 2.5 B Example 19 A-2 100 B-2 3 C-1 2 99.3 3.5 3.5 B Example 20 A-2 100 B-2 3 C-2 5 99.4 2.8 3.4 A Example 21 A-3 100 B-1 3 C-1 2 99.6 3.8 2.0 B Example 22 A-4 100 B-1 3 C-1 2 99.5 3.9 1.9 B Example 23 A-5 100 B-1 3 C -1 2 99.3 3.2 1.3 B Example 24 A-6 100 B-1 3 C-1 2 99.6 2.4 1.7 B Example 25 A-7 100 B-1 3 C-1 2 99.1 2.1 1.0 B Example 26 A-8 100 B -1 3 C-1 2 99.3 2.2 0.8 B Example 27 A-9 100 B-1 3 C-1 2 99.1 2.1 0.8 B Example 28 A-3 100 B-2 3 C-2 5 99.1 2.1 1.7 A Example 29 A -4 100 B-2 3 C-2 5 99.0 2.5 2.0 A Example 30 A-5 100 B-2 3 C-2 5 99.2 2.6 1.4 A Example 31 A-6 100 B-2 3 C-2 5 99.3 2.3 1.6 A Example 32 A-7 100 B-2 3 C-2 5 99.0 2.0 0.9 A Example 33 A-8 100 B-2 3 C-2 5 99.4 1,0 1.1 A Example 34 A-9 100 B-2 3 C -2 5 99.2 1.9 1.1 A Example 35 A-3 100 B-4 3 C-5 5 99.1 3.0 1.7 A Example 36 A-6 100 B-3 1 C-7 5 99.1 2.2 1.4 A Example 37 A-8 100 B -3 1 C-4 5 99.7 1.8 1.4 A Example 38 A-8 100 B-3 1 C-7 5 99.4 1.5 1.1 A Example 39 A-8 100 B-4 3 C-5 5 99.4 3.1 1.0 A 54 201235412 41ZUl Pif

In the case where the liquid crystal alignment agent of the present invention can be formed, excellent electrical characteristics can be maintained, and an excellent liquid crystal alignment film can be read in the event of a defect. [Industrial Applicability] The liquid crystal alignment agent of the present invention can form a good electrical property even when it is continuously driven for a long period of time under a severe environment such as light stress or heat = gas. In the case of a defect, the T-crystal alignment film is reprocessed. Therefore, the plug of the present invention having the liquid crystal alignment film has a small reduction in display quality and can be effectively applied to each of the substrates, and can be suitably applied to, for example, a clock, a portable game machine, a text processor, or a processor. Notebooks, car navigation systems, camcorders, digital assistants, digital cameras, mobile phones, various displays, LCD TV temple display devices. [Simple description of the diagram] None. [Main component symbol description] &lt;,,, 55

Claims (1)

201235412 一一r " VII, the scope of application for patents: 1. A liquid crystal alignment agent, which contains: [A] selected from the group of poly-proline and dehydration ring closure of the polyamid At least one of the polymers; [B] an antioxidant; and [C] a liquid crystal alignment agent according to claim 1, wherein the above [B] antioxidant has a lower a group represented by the formula (1) or the formula (2), [Chemical 1] (In the formula (1), ^ is a hydrogen atom, an alkyl group having a carbon number of 1 to 20, a carboxyl group having a carbon number of ό 20, an aralkyl group having a carbon number of 7 to 13, ruthenium, 3 - 2 Oxobutyl or hydrazine, 4-dioxo=yl, and the group represented by the formula (1) is an alkyl group, an arylalkyl group, a dioxobutyl group and a 1,4-dioxobutyl group represented by R1. 】 】 虱 成为 成为 成为 成为 成为 成为 成为 成为 成为 成为 2 2 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; * -Ο-, or 氺-CONH-; t-junction; and, e early key, several bases, 氺* _CH2_C〇- or * * ** represents the bond with the p melon bite ring R7)a (2), ., 匕 (7) In the formula (7), r6 is a hydrocarbon group having a carbon number of 4 to 16; wherein, the upper group may have an oxygen atom or a sulfur atom in the carbon skeleton chain; and the ?3 hydrogen atom or carbon number is The hydrocarbon group of the group 16; wherein, in the case of ^, the plurality of R? may be the same or different). The liquid crystal alignment described in the first or second aspect of the patent application is "'," and the above [C] compound is more concentrated than the thiol-containing or early g-energy epoxy compound containing a Wei group. 4. The liquid crystal alignment I according to Item 1 or 2 of the patent scope, wherein the above [A] polymer is a polymer obtained by reacting tetradecanoic dianhydride with a diamine. The anhydride comprises an agent selected from the group consisting of 2,3,5·trisylcyclopentanyl 57 201235412-based acetic acid dianhydride, 1,3,3&amp;, 4,5,%-hexahydro_8-methyl_5_(tetrahydro-2, 5_Dioxo-3-furanyl)-naphtho[l,2-c]furan-ls diketone, ^,^,7^Exohexahydro-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthoquino-pAc]furan], 3-dione and 2,4,6,8-tetracarboxybicyclo[3.3.〇]octane-2,4,6,8-dianhydride At least one of the groups. 5. The liquid crystal alignment agent according to claim 4, wherein the diamine comprises a compound selected from the group consisting of 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl- At least one group consisting of 1H-knot-5-amine and 1-(4-aminophenyl)_2,3-dihydro-1,3,3-trimethyl-old 茚-6-amine . A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 1 to 5. A liquid crystal display element comprising a liquid crystal alignment film according to claim 6 of the patent application. ' 58 201235412 ---- IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: