TW201206998A - Liquid crystal alignment agent, liquid crystal display element and method for producing liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal alignment agent which can provide a liquid crystal alignment film with excellent vertical alignment property and UV resistant. The liquid crystal alignment agent is characterized by containing organic polyorganosiloxane with a group comprising a polymerizable carbon-carbon double bond represented by following formula (A) (In formula (A), R is hydrogen or methyl; XI and XII respectively represent 1, 4-phenylene, methylene, 1, 2-ethylene, 1, 2-propylene or 1, 3-propylene; a, b, c and d respectively represent 0 or 1; when c is 0 and d is 1, XII is 1, 4-phenylene; when b is 0, d is 0.)

Description

201206998 DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a liquid crystal alignment agent and a method for producing a Luoqi θ element. More specifically, liquid; = element: and liquid crystal display excellent and at the same time has a high UV edge σ to provide a vertical alignment crystal alignment agent. (4) Liquid of external linear liquid crystal alignment film [Prior Art] As a liquid crystal display element, in addition to 佶STN (^ M a, ^ A in TN (twisted nematic) type, v, shift steering column) type is representative of column liquid crystal The liquid level positive of the standard alignment mode:: the direction of the opposite sex is known to have a negative dielectric anisotropy. There are also 35? ^ liquid vertical (vertical alignment) VA (vertical alignment) type Liquid crystal display element. Alignment: The liquid crystal display element has a liquid crystal alignment film having a liquid crystal molecule in a predetermined direction. As the material, polyamines are known, such as the material of the liquid crystal alignment film, etc., especially... Polyamine, polyester, poly-aligned film, due to 1 w amine or polyimine The liquid crystal field of the composition is preferably used in the heat resistance and the kinetic properties of the liquid crystal molecules, and has been used for the affinity of the liquid crystal molecules (Patent Document M). Further, in Patent Document 4, the energy can be hydrolyzed, and the mixture of the a' compounds can be formed into a liquid crystal alignment agent in the presence of oxalic acid and an alcohol. A liquid crystal alignment agent of decane, and is different from the above. Liquid M alignment film vertical alignment and heat resistance Excellent liquid crystal display elements in recent years and high-speed animation responsiveness is excellent... Sperm. Should not, homogenous I display, in addition to TV sets, -4 - 201206998 It is widely used in car-mounted display racks, game consoles, portable animation players, and the like. In addition, with the display of high luminance, the liquid crystal display element of the above 4 is used outdoors during the daytime, and thus the liquid crystal display element and the liquid crystal alignment film having the same are exposed for a long time. In high-intensity ultraviolet rays that have not been considered in the conventional use state. Therefore, the conventional liquid crystal alignment film material does not have ultraviolet light resistance which can be adapted to the current state of use, and the ultraviolet light resistance of the liquid crystal alignment film needs to be improved. In recent years, Yu Yu proposed a liquid-phase display component in the PSA (Polymer Continuous Alignment) mode. The PSA mode is in a gap between a pair of substrates composed of a substrate having a patterned conductive film and a substrate having a patterned conductive film, or a gap between a pair of substrates composed of two substrates having a patterned conductive film. In the liquid crystal composition containing a polymerizable compound, a liquid crystal is irradiated with a voltage applied between the conductive films to polymerize the polymerizable compound, thereby achieving a technique of exhibiting a pretilt angle characteristic and controlling the alignment direction of the liquid crystal region. According to this technique, the conductive film can have a specific configuration, and the viewing angle can be increased and the response of the liquid crystal molecules can be increased. This eliminates the problem of insufficient transmittance and contrast in the MVA type panel. In the PSA mode, in order to carry out the polymerization of the above polymerizable compound, it is necessary to irradiate a large amount of ultraviolet rays of, for example, 1 (), 000 j/m 2 or more. Therefore, it is understood that there is a possibility that the liquid crystal alignment film is deteriorated in the ultraviolet irradiation step. In order to replace the PSA mode described above, a technique for a new display mode has recently been proposed (Patent Document 5). The intent of this technology is to use a non-polarized ultraviolet ray to illuminate the polystyrene 201206998 imipenoid containing a photofunctional cinnamate structure, which is expected to cause the liquid purple pressure to remain as new, and the newness is improved. In the domain, the specified part is combined with the sealing liquid, which can be too medium, such as unevenness of the element. The desired pretilt angle is presented. Among them, in order to impart pretilt angle visibility, it is necessary to irradiate a considerable amount of ultraviolet rays, the working time during the production of the crystal display element becomes long, or the electrical characteristics of the liquid crystal alignment film formed due to the strong external line, particularly the electric power rate is impaired. Disadvantages. As described above, with the development of the liquid crystal display device, the development of the page display mode has become stronger, and the demand for ultraviolet rays in the liquid crystal alignment film material has become strong. Aspects In recent years, the manufacturing process of liquid crystal display elements has taken steps. In particular, a technique such as a large-sized substrate and a liquid crystal dropping method (the 〇ne Dr〇p method, which is referred to as "ODF method" in the present technology) used for increasing the size of the substrate has attracted attention. In the 〇DF method, a necessary amount of liquid crystal is added to a plurality of droplets on a substrate on which a liquid crystal alignment film is formed, and the liquid crystal is pressed and spread on the entire surface of the substrate by vacuuming the other substrate by 8 inches. The crystal sealing agent is UV-cured, so that the liquid crystal method on the entire surface of the panel is a technique of shortening the operation time of the liquid crystal filling step as compared with the conventional vacuum injection method. As a result, in the conventional VA type liquid crystal display having a liquid crystal alignment film, the 〇DF method is employed, which may cause a problem of display unevenness called "〇df. It is believed that this phenomenon is due to the film. This is because there is a need for a liquid crystal display element which is required to provide a liquid crystal alignment film which does not cause the above-mentioned unevenness and which is excellent in liquid crystal display elements, which does not impair the liquid crystal alignment agent. 201206998 CITATION LIST Patent Literature Patent Literature 1: Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. . Phys. 48 rolls 1783 (1977) Non-Patent Document 2: F. Nakano et al., JPN. J. Appl. Phys. 19, 2013 (1980) [Problem to be Solved] The present invention has been made in view of the above circumstances. The object of the present invention is to provide a liquid crystal alignment agent which can provide a liquid crystal alignment film which is excellent in vertical alignment property and has high ultraviolet resistance at the same time. [Means for Solving the Problem] According to the present invention, the above problem of the present invention can be Liquid crystal alignment by polyorganosiloxane containing a group having a polymerizable carbon-carbon double bond

-7 - S 201206998 to solve. In addition, the polyorganosiloxane is a substance having one or more ring structures selected from a cyclohexane ring and a benzene ring in a side chain, or a compound represented by the following formula (1) and the following formula (2) The polyoxyalkylene obtained by polycondensation of the alkoxysilane of the compound shown. RASi(ORB)3 (1)

RcSi(ORD)3 (2) (In the formula (1), Ra is a hydrocarbon group having a carbon number of V substituted by a fluorine atom, and Rb is an alkyl group having 1 to 5 carbon atoms; in the formula (2), Rc is A graft substituted with an acryloyl or fluorenyl fluorenyl group, RD is an alkyl group having 1 to 5 carbon atoms). [Effects of the Invention] The liquid crystal alignment agent of the present invention can provide a liquid crystal alignment film which is excellent in vertical alignment and has high ultraviolet resistance. Therefore, the liquid crystal alignment agent of the present invention is not applicable to a liquid crystal display element of a PSA mode or an update display mode which requires strong ultraviolet irradiation in its manufacturing step, except for being applicable to a conventionally known VA type liquid crystal display element. The deterioration of the liquid crystal alignment film in the manufacturing step occurs, and the desired display quality can be achieved. Since the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention has high ultraviolet resistance, the liquid crystal display element including the liquid crystal alignment film can be used for a long time even under strong ultraviolet irradiation conditions, for example, during the daytime outdoors. Quality will not deteriorate. Further, according to a preferred embodiment of the present invention, if the liquid crystal alignment agent of the present invention is used for the production of a VA liquid crystal display device, even in the liquid crystal filling step, the liquid crystal dropping method (ODF method) is employed, and 201206998 The excellent vertical alignment binding force can reliably form a liquid crystal alignment film which does not cause ODF unevenness, and thus is extremely advantageous in terms of product yield. [Embodiment] As described above, the liquid crystal alignment agent of the present invention contains a polyorganosiloxane (hereinafter also referred to as "polyorganosiloxane (A)") having a group containing a polymerizable carbon double bond. . σ, public organic oxime (A) > The polyorganosiloxane (A) contained in the liquid crystal alignment agent of the present invention has a group of 3 polymerizable carbon-carbon double bonds. As a polyorganofluorene gas (VIII), in addition to the group of a polymerizable carbon-carbon double bond, it may have a group which plays a role in θ, β < It is at least one group selected from the group consisting of "liquid crystal alignment group" and 1 methoxy group. 矽; organic oxime (Α) preferably has a side chain selected from cyclohexane Φ. A substance having more than one ring structure. • The content of these ring structures in the 9-mer organic oxo:: is more preferably more than 2 mmol/g, and is 0.3 to 6 mmol/g. The polymerizable group of the compound (4) may, for example, be CH2=C-(c〇〇) broadly χΙΙ^(a) of the following formula (A) (in the formula (A), R is a hydrogen atom or a Base '1 phenylene, yakiqishi Shishan shield machine Λ 〇 and χ 别 1,4- 1,4- 1,4- 1,4- 1,4- 或 或 或 或 或 或 1,4- 1,4- 1,4- 1,4- 1,4- 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 4 ΟΓΠ VJL Φ r * J The alkyl group, Z is the oxygen atom, a, b, (where the bond with "on the 妒-side", b, c and d are 0 or i, respectively, where r λ side)' χ·* Λ , , c is 〇 and d is 1, Stretch stupid group, b is square, dg〇, Q is not a group table and the like. 201206998 Specific examples of the group represented by the above formula (A) include, for example, an ethylene group, an allyl group, a p-styryl group, a (fluorenyl) propylene fluorenyl fluorenyl group, and a 2-((meth) propylene group. Ethyloxy)ethyl, 3-((indenyl)propenyloxy)propyl, 4-((meth)acryloxy)butyl '5-((meth)acryloxy)pentyl, 6-((indenyl)propenyloxy)hexyl, 7-((indenyl)propenyloxy)heptyl, 8-((indolyl)propenyloxy)octyl, 9-((meth)propene醯oxy) fluorenyl, 1 〇-((meth)acryloxy) fluorenyl, 4_(2_((indolyl)propenyloxy)ethyl)phenyl, 2-((4-(曱) Base) acryloxy)phenyl)ethyl, 4-((meth)acryloxycarbonyl)phenyl, 4-(meth)propenyloxyphenylmethyl, 4-(3-( (Meth) propylene oxime) propyl) phenyl, 3-(4 _(indenyl) propylene aryl group) propyl, 4-((methyl) propylene oxide methoxy methoxy) benzene Base, core (2-((indenyl) propylene oxime)ethoxy)phenyl, 4-(3-((methyl) propylene oxy)propoxy)phenyl, (methyl) Propylene oxime oxime oxymethyl, 2-((indenyl) propylene methoxy methoxy) ethyl, methyl) propylene oxime) ethoxy) ethyl, 2 _ (2 _ (2 _ (( Methyl)propenyloxy)ethoxy)ethoxy)ethyl, 3-(3-((indolyl)propenyloxy)propoxy)propyl, acryloxymethyl, 6- { [6-(Propyloxy)hexyl]oxyxanyl and the like. Among these groups, a vinyl group, an allyl group, a p-styryl group, a (fluorenyl) propylene methoxymethyl group, a 2-((meth) acryloxy) ethyl group, a 3-((methyl) group) Acryloxy)propyl and 6-{[6-(acryloxy)hexyloxy]hexyl) are preferred groups. The base group Z in the above formula (A) is preferably an oxygen atom. The polyorganoanthracene (A) 'polymerizable carbon-carbon double bond-containing group contained in the liquid crystal alignment agent of the present invention is preferably a group represented by the above formula (A). More preferably, it is selected from the above-exemplified examples. One or more of the specific groups of the -10-201206998 group is preferably in a ratio of 0.01 to 60.60 m〇i relative to the im〇i group contained in the polyorganosiloxane (A). Preferably, the ratio of 〇〇-5〇mol is further preferably 〇〇2~〇3〇m〇i. With respect to the polyorgano-oxyalkane (A), as the liquid-permeable group which may be optionally contained, for example, the following formula (D,) (D,) (Formula (D,)_, R1 is a carbon atom number 1 a fluoro group of ～40, a fluoroalkyl group of a carbonogen of 1 to 4 fluorene, a cyano group or a fluorine atom, or a hydrocarbon group having a steroid bone number of 17 to 5 1; z1 is a single bond, 〇-, *-C00 · or 〇c〇 (where 'the connection key is on the R1 side'), RU is a cyclohexyl group or a stupid base, wherein the exocyclic hexyl group or extension may be a gas group, an I atom, a trimethyl group or The substitution of carbon number b is 1, or 2, wherein when nl is 2, two Rn may be different in phase, n2 is 〇 or 1; Z is a single bond, *_〇, *_c〇〇* - or -OCO- (wherein the phenyl group with a ruthenium 02~ ratio of the crystal gametes is also a linkage bond at R1:3, an integer of 〇~2' Π4 is a group represented by 1 or 1} and = is a number of carbon atoms in the above formula (1), and is represented by a compound; for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a decyl group, a decyl group, and a hexadecane group. , side group, pentyl group e -11- 201206998 as carbon The fluoroalkyl group having a subnumber of 1 to 40, specifically, for example, trifluoromethylpropyl, trifluoromethylbutyl, trifluoromethylhexyl, trifluoromethylindolyl, pentafluoroethylpropyl , pentafluoroethylbutyl, pentafluoroethyloctyl, 3,3,4,4,5,5,5-heptafluoropentyl, 3,3,4,4,5,5,6,6, 7,7,8,8,8-tridecafluorooctyl, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- Heptadecyl fluorenyl group or the like; as the above-mentioned hydrocarbon group of 17 to 51 having a steroid skeleton, for example, 3-cholesteryl group, 3-cholestyl group, 3-lanyl group, 3-bromo-alkyl group can be exemplified. , 3-pregnant alkyl group, 3-androst-alkyl group, 3-anhydro-alkyl group, etc. The extension of R11 in the above formula (D '), cyclohexyl group and phenylene group are preferably 1,4-stretch, respectively. Cyclohexyl and 1,4-phenylene are the divalent groups represented by -(R1)! in the above formula (D'), and when n1 is 1, for example, 1,4 _ phenylene is exemplified. And a 1,4-cyclohexylene group or the like is preferable. When n1 is 2, for example, 4,4′-biphenylene group, 4,4′-subdicyclohexyl group, and the following formula may be mentioned.

(In the above formula, a group represented by a "*" linkage bond on the R1 side) is preferably a group. N3 in the above formula (D') is preferably 2. Preferably, n2 in the above formula (D') is 1, or n2 is 0 and R1 is a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton. Since the polyorganosiloxane (A) has such a group represented by the above formula (D'), a film formed of a liquid crystal alignment agent containing the same exhibits good liquid crystal alignment ability'. -12- 201206998 Example, the existence of the liquid crystal base in the spectroscopy (A) is higher than that of the 丨:, the organic atom (4) contained in the atomic atom, which is better than the ratio of 〇.7mol or less. (M~0.5mol ratio. The ratio of the lower one, its ΐ! 'Because of the epoxy group in the polyorganosiloxane (4), the film formed by the diaster has strong mechanical properties, heat resistance, t forequality, etc. It is preferred that various properties are excellent. The ratio of the presence of the polyoxygen-epoxy group is lower than that of the following: (A) contains #lm() 1 second original +, preferably 0.7 m〇1 = Example 'better ratio of 4〇.5mol or less, (K5mol ratio β ~ υ· _ι overpolymerization 7^^! Oxygen_), weight average molecular weight determined by gel permeation chromatography and converted by human olefin Preferably, it is 5~I'ooo'ooo, more preferably 1〇〇〇~1〇〇, _佳〜50,000. 〆文仏 is 1,000 <Polymer = machine oxane (A) manufacturing method> As a feature of such a polyorgano port, it can be produced by any method as described above, and among them, an alkoxy group which is preferably a compound represented by the following A#2-2 compound and the following formula (2) is preferable. A polyoxane obtained by argon polymerization. RASi(0RB)3 (1) RCsi(〇RD)3 (2) (In the formula (1), the number of carbon atoms in which the RA-Phase group is substituted by a fluorine atom 8~30', a subunit of 1 to 5; in the formula (2), Rc θ, an alkyl group substituted by an acryl fluorenyl group or a methacryl fluorenyl group, and an inverse number of R vermiculite is 5 5 -13-201206998 The polyorgano oxy-oxygen in the present invention, if a oxy-stone is used, the compound containing the compound of the above formula (2) and the compound represented by the above formula (2) is used. In the production of VA liquid crystal display elements, the ODF unevenness occurs when the ODF method is used, which is not preferable. Therefore, the reason is not good. It is clear that it is presumed that the liquid crystal alignment film formed by the above method has insufficient affinity with liquid crystal molecules, and thus the specific component in the liquid crystal mixture is not uniform in the unit memory. For example, a decane compound having a group containing a polymerizable carbon-carbon double bond and an alkoxy group (hereinafter referred to as "decane compound U1"), Hair alkyl compounds (Al) and other alkoxy Silane compound (hereinafter referred to as "burning stone Xi compound (a2)") was produced in the polycondensation step (Production Method 1). Here, 'in addition to the hard-burning compound (a), a decane compound (a2) is used, and a decane compound having an epoxy group and an alkoxy group (hereinafter the following is a "decane compound (a2-l)") is used as a decane. In the compound (a2), first, a polyorganosiloxane having a group containing a polymerizable carbon-carbon double bond and an alkoxy group (hereinafter referred to as "precursor polyorganosiloxane (A)" is produced. Then, by reacting with a slow acid containing a compound having a liquid crystal aligning group and a carboxyl group (hereinafter referred to as "salt acid (丨-D)), a group having a polymerizable carbon-carbon double bond can be obtained. a polyorganooxy oxane (manufacturing method 2) of both a group and a liquid crystal alignment group. Further, polycondensation of a decane compound (al) or a decane compound (al) and a decane compound (a2) and a mixture is first carried out. Production of a polyorganosiloxane having a group containing a polymerizable carbon-carbon double bond (hereinafter referred to as "precursor poly-14-201206998 organic zephyr (A11)")" and then selecting it from an amine and At least one nucleophilic compound of a thiol (wherein the nucleophilic compound package A nucleophilic compound having a liquid crystal alignment group (hereinafter referred to as "nucleophilic compound (1)")) can be reacted to obtain a group having a polymerizable carbon-carbon double bond and a liquid crystal alignment group. Polyorganosiloxane (A) (Production Method 3). Polyorganosiloxane (A) can also be obtained from a decane compound (a2_i) or a sulphur compound (a2-l) and other decane compounds thereof. Polycondensation of a mixture of (a2) (hereinafter referred to as "Shixia compound (a2-2)"), first producing a polyorganosiloxane having a % oxygen group (hereinafter referred to as an r precursor polyorganosiloxane (AU1) Then, the step of reacting with a carboxylic acid containing a group containing a polymerizable carbon-carbon double bond and a carboxyl group (hereinafter referred to as "carboxylic acid (1_2)) is produced. Here, as a carboxylic acid, by using a combination of a few acids (1 _2) and a carboxylic acid (1-1), a liquid crystal alignment group can be obtained in addition to a group containing a polymerizable carbon-carbon double bond. Polyorganosite (A) (manufacturing method 5). Or 'precursor polyorganoquinone as described above After calcination (A111) ', it is then reacted with a carboxylic acid containing a carboxylic acid (1-2), and then reacted with a nucleophilic compound (1), whereby a group other than a polymerizable carbon-carbon double bond can also be obtained. A polyorganosiloxane (A) having a liquid crystal alignment group in addition to the group (Production Method 6). In either case, the decane compound (a2) may be used in combination with the decane compound (a2-l). a decane compound (hereinafter referred to as "decane compound (a2_2)") which is a decane compound (& 2) and does not have a hydrocarbon group having 8 to 30 carbon atoms and a fluorinated hydrocarbon group. The manufacturing method is summarized as 'can be sorted into the following table. -15- 201206998 The second stage reaction of the smelting compound used in the polycondensation of the manufacturing method The third stage reaction polyoxane (A) contains c=c contains an epoxy group other c=c liquid crystal aligning group 1 Optionally, there is no M. 2 must have a carboxylic acid optionally containing a liquid crystal aligning group. There are 3 nucleophilic compounds which optionally contain a liquid crystal aligning group, and there are 4 It is necessary to optionally contain c=c or not. 5 Do not necessarily contain a carboxylic acid containing c=c + a tickic acid containing a liquid crystal aligning group. 6 No carboxylic acid containing c=c optionally The nucleophilic compound of the liquid crystal aligning group is a <decane compound> containing a c-c: a decane compound having a group having a carbon-carbon double bond and an alkoxy group (a dream compound (a 1)) Epoxy group: a decane compound having an epoxy group and an alkoxy group (decane compound (a2-l)) Other: alkoxydecane compound (a2-2) other than the above <carboxylic acid> Containing a liquid crystal alignment group Carboxylic acid: having a liquid crystal aligning group and a compound of a group (carboxylic acid (1-1)) A carboxylic acid containing c=c: a compound having a group containing a polymerizable carbon-carbon double bond and a carboxyl group (carboxylic acid (1-2)) <nucleophilicity Compound > Nucleophilic compound having a liquid crystal aligning group: a nucleophilic compound having a liquid crystal aligning group (nucleophilic compound (1)) Hereinafter, the above production methods 1 to 6 will be described in order. [The decane compound to be used as a raw material] The decane compound (a 1 ) may, for example, be represented by the following formula (a 1) -16 - 201206998

R CH2 C^(co〇)r-(Χ^-((Ζ)—(in the formula (al), R, χ1, χ„, z II. :Si(〇R1)4-e (a1) b , , Δ , ^ C and d are the same as the above, and R1 is an alkyl group having 1 to 12 carbon atoms or an aryl group 'e having an alkyl group having 6 to 12 is an integer of 1 to 3). The alkyl group having 1 to 4 carbon atoms of R1 in the above formula (al) is preferably a carbon atom; i AU, ^ Ji-^ an alkyl group having 1 to 4 moles, as a specific example thereof, For example, exemplified by methyl, ethyl-^^.^hexyl-n-propyl, n-butyl, secondary butyl, tertiary butyl, etc., are preferably sulfhydryl, ethyl or n-propyl, particularly preferably Examples of the aryl group having 6 to 12 carbon atoms include a stupid group, a fluorene group, and the like. e e in the above formula (a 1) is preferably 1 or 2, particularly preferably i. Specific examples of the compound (a丨) include, for example, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tripropoxy decane, vinyl triisopropoxy decane, and vinyl. Tri-n-butoxy decane, vinyl triisobutoxy decane, vinyl tri-tertiary butoxy fluorene Home, propyl tridecyl decane, allyl triethoxy decane, propyl tripropoxy decane, allyl triisopropoxy decane, allyl tri-n-butoxy decane, olefin Propyl triisobutoxy decane, allyl tris-butoxy decane, p-styryl trimethoxy decane, p-styryl triethoxy decane, p-styryl tripropoxy decane Styryl triisopropoxy decane, p-styryl tri-n-butoxy decane, p-vinyl diisobutoxy decane, p-styryl tris-butoxy decane '(fluorenyl) propylene Oxymethyltrimethoxydecane, (meth)propenyloxymethyl

S -17- 201206998 Triethoxy decane, (meth) propylene decyl decyl tri-n-propoxy decane L (mercapto) propylene methoxymethyl triisopropoxy decane, (fluorenyl) propylene醯 甲基 甲基 甲基 正 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基, 2-(methyl) propylene oxiranyloxyethyl triethoxy decane, methyl) propylene oxyethyl tri-n-propoxy alcohol, 2-(methyl) propylene oxirane ethyl triisopropyl Oxydecane, 2-(methyl)propenyloxyethyltri-n-butoxyoxane, 2-(indenyl)propenylethylpropyltri-n-butoxypropane, fluorenylmethyl)propene醯oxypropyltrimethoxydecane, 3-(methyl) propylene methoxypropyltriethoxydecane, 3-(methyl)propenyloxypropyltri-n-propoxy decane, 3- (Meth) propylene methoxy propyl triisopropoxy decane, 3-(indenyl) propylene oxypropyl tri-n-butoxy decane, 3-(indenyl) propylene oxypropyl three-second Butoxy decane, 4_(meth) propylene oxy butyl Trimethoxy decane, 4 (meth) propylene oxy butyl triethoxy decane, 4 - (meth) propylene oxy butyl tri - n-propoxy decane, 4- (meth) propylene decyloxy Butyl triisopropoxide, 4-(fluorenyl) propylene oxybutyl tri-n-butoxy decane, 4 曱(曱" )) propylene methoxy butyl propyl tri-n-butoxy decane , 5-(indenyl)propenyloxypentyltrimethoxy decane, 5-(methyl)propenyloxypentyltriethoxydecane, 5-(methyl)propenyloxypentyl tri-n-butyl Propoxy decane, 5-(indenyl)propenyloxypentyltriisopropoxydecane, 5-(meth)propenyloxypentyltri-n-butoxyoxane, 5-(indenyl)propene oxime Pentyl propyl tri-n-butoxy decane, 6-(f-) propylene decyloxy hexyl methoxy fluorene, 6-(methyl) propylene decyloxy hexyl triethoxy sylvestre, & (Meth) oxyhexyl tri-n-propoxy oxime, 6-(fluorenyl) propylene oxiranyl -18 - 201206998 triisopropoxy decane ' 6-(methyl) propylene decyl hexyl tri-n- Butoxy decane, 6-(fluorenyl) propylene oxime The propyl group three-stage butoxy decane, propylene methoxymethyl trimethoxy decane, etc., are preferably used by selecting one or more of these. More preferably selected from the group consisting of vinyl trimethoxy decane, vinyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, p-styryl trimethoxy decane, and benzene Vinyl triethoxy decane, (fluorenyl) propylene methoxymethyl trimethoxy decane, 2-(methyl) propylene methoxyethyl trimethoxy decane and 3-(mercapto) propylene oxime More than one substance of propyltrimethoxy decane. The above decane compound (a2-1) is a decane compound having an epoxy group and an alkoxy group, and preferably has the following formula (a2-l) (R5)h(R6)iSi(OR7)4-hi (a2-l (In the formula (a2-l), R5 is a monovalent group having an epoxy group, R6 is an alkyl group having 1 to 3 carbon atoms, and R7 is an alkyl group having 1 to 12 carbon atoms or a carbon number. 6 to 1 2 of an aryl group, h is an integer of 1 to 3, and i is an integer of 0 to 2, wherein h+i$3) is a compound. Examples of R5 in the formula (a2-l) include 3-glycidoxypropyl group, 2-(3,4-epoxycyclohexyl)ethyl group and the like. As R6, a mercapto group is preferred. Regarding R7, it is the same as the above case regarding R1 in the above formula (al). Preferably, h is 1 and i is 0 or 1. Specific examples of the decane compound (a2-1) include, for example, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycoloxypropoxide. Propyl decyl dimethoxy decane, 3-glycidoxypropyl decyl diethoxy decane, 3-glycidoxypropyl-19-201206998 dimethyl methoxy decane, 3 -glycidoxypropyl decyl ethoxy oxime, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2_(3 epoxy hexyl)ethyltriethoxy It is possible to select one or more of these substances by base-burning or the like. The above-mentioned calcined compound (a2_2) is a stone of a cerium compound (a2) other than a decane compound (a2-i), which is a hydrocarbon group having no carbon atoms of 8 to 3 Å and a ruthenium group in a fluorine-bearing soil. Burning compound at night. For example, in the following formula (a2-2) (a2.2) (, 2-2), r8 is a carbon atom number? A compound represented by an alkyl group or a phenyl group, an alkyl group having an inverse number of 1 to 12 or an aryl group having a carbon number of ό~1 2 , and J is an integer of 0 to 3. The above is the same as the above case regarding R1 in the above formula (4). Specific examples of the compound (a2·2): a compound of the formula: i, for example, tetramethoxy ['tetraethoxy]tetradecane, tetraisopropenyl, oxoxane, tetra-d-butyl In the case of a poorly-derived lactyl decane, tetra-n-butyl pentane, a first-order butoxy oxane, etc.; a compound wherein j is 1 may be exemplified by a group of triethoxy (tetra), a methyl group: a methyl group... A A = n-butyl \ its propoxy zexi-sinter, sulfhydryl triisopropoxy fluorene lanes, a butoxide, a sulphur, a _ methyl sulphate, a di-butoxy decane, Τ Φ - n-pentyl decane二— ^ S «. soil---butoxy decane, A two-milk base stone, methyl tri-p-methylmethyl-decane, B-A abundance decyl, ethyl tridecyloxy G-based decyl decane, _ =^ # ^ ethyl di-n-propoxy decane, ethyl..., propyl I sulphate, ethyl tri-n-salt hydrogen, its square ka soil 'machine', two storms Butadiene, Ethyl tri-n-oxo-oxyfluorenyl decane, Ethyl tri-n-butoxy fluorene-20-201206998 Alkane, Ethyl tri-octyloxydecane, Ethyl tri-p-nonylphenoxy矽, n-propyl trimethoxy shi Hyun, n-propyl triethoxy sulphur, n-propyl tri-n-propoxy decane, n-propyl triisopropoxy decane, n-propyl tri-n-butoxy decane, n-propyl tri-n-butoxy Base decane, n-propyl tri-n-pentyloxy decane, n-propyl tri-n-butoxy decane, n-propyl triphenoxy decane, n-propyl tri-p-methyl phenoxy decane, phenyl trimethoxy Decane, phenyl diethoxy oxalate, phenyl tri-n-propoxy zephyr, stupid triisopropoxy zephyr, base di-n-butoxy sinter, phenyl tri-n-butoxylate Burned, n-butyl trimethoxy decane, n-butyl triethoxy decane, n-butyl tri-n-propoxy decane, n-butyl triisopropoxy decane, n-butyl tri-n-butane sulphur 'n-butyl di- or two-butoxybutanthine, n-butyl tri-n-pentyloxy decane, n-butyl tri-n-butoxy decane, n-butyl triphenoxy decane, n-diyl tri-p-nonyl benzene Oxydecane, n-pentyltrimethoxy decane, n-pentyl triethoxy decane, n-pentyl tri-n-propoxy decane, n-pentyl triisopropoxy oxacyclohexane, n-pentyl tri-n-butyl Oxydecane, n-pentyl tri-n-butoxy decane, n-pentyl tri-n-pentyloxy decane, n-pentyl tri- or two-butoxy oxanthene, n-pentyl tri-octyloxy sulphur, n-pentyl Tri-p-methylbenzene=yl...hexyltrimethoxy-l-hexyltrioxane, heptyl-methoxydecane, heptyldiethoxydecane, etc.; the compound may, for example, be dimethyldimethoxy Xiyuan, monoethyl dimethoxy zebra, di-n-propyl dimethoxy zeoxi, diisopropyl dimethoxy money, dimethyl diethoxy shi xia, diethyl diethyl milk Base stone simmering, di-n-propyldiethoxy sulphur, diisopropyldiethoxy sulphur, dimethyl-diisopropoxy sulphide, bis-isopropoxy zebra, di-n-propyl Base-diisopropoxy oxazepine, isopropyl-diisopropyloxy

S * 21 - 201206998 Gerazol, dimethyl-di- or 2-butoxybutane, diethyl-di- or 2-butoxybutane, di-n-propyl-di- butoxybutane, diisopropyl - a two-stage butoxy oxane or the like; a compound wherein j is 3, for example, tridecyl methoxy oxime triethyl methoxy oxime, tri-n-propyl methoxy oxime, triisopropyl曱 石 夕 、, trimethyl ethoxy decane, triethyl ethoxy decane, tri-n-propyl ethoxy decane, triisopropyl ethoxy decane, tridecyl - n-propoxy oxylate , triethyl-n-propoxy decane, tri-n-propyl-n-propoxy decane, diisopropyl-n-propoxy decane, tridecyl-isopropoxy oxime, diethyl _ Propoxy decane, tri-n-propyl-isopropoxy decane, triisopropyl-isopropoxy decane, tridecyl-secondary butoxy decane, triethyl _ methoxybutane, three positive For propyl-secondary butoxy decane, triisopropyl-based butoxide, or the like, one or more of these may be used, and 0 + is used as R8 in the formula (a2-2), preferably a carbon number.丨~3 alkyl or benzene As the decane compound (a2 2), it is more preferred to use a compound wherein J is ruthenium or 1 in the above formula (a2 2), more preferably ethyl ruthenium hydride, ethyl diethoxy decane or ruthenium. In the group consisting of trimethoxy decane, decyl triethoxy sulphur, tetramethoxy sinter, and tetraethoxy sulphur, the selected one or more substances are used, and it is particularly preferable to use the above formula ( A" is a material for the production of a material, and it is preferred to use one or more selected from the group consisting of tetramethoxy zephyr and tetraethyl ketone: alkane. The right manufacturing method 1 produces a polyorganite contained in the liquid crystal alignment agent of the present invention. In the case of oxane (A), as a sulfonium compound used in the original pot

Yu Quan. The decane compound A is preferably 3, as described above, the zephyr compound -22-.201206998 (a 1) 1 mo 1% or more, more preferably i~6〇m〇丨%, further preferably contains 2~50mol%, especially good for containing 2~3〇m〇1%. In the production method i, it is preferred to use a decane compound (a2_2) in addition to the above decane compound. The proportion of use thereof is preferably 60 mol% or less, more preferably 〇 4 4 〇 m 〇 1%, and particularly preferably 〇 2 2 〇 m 〇 1% with respect to the entire decane compound. When the polyorganosiloxane (a) is produced by the production method 2, the decane compound used as a raw material thereof is preferably 3 as described above for the cerium compound (al)im〇i More preferably, it is contained in an amount of 1 to 60 mol%, more preferably 2 to 50 m〇1%, particularly preferably 2 to 30 mol%, when the polyorganosiloxane (A) is produced by the production method 2 The decane compound (a2-l) is used in addition to the above decane compound (al). The ratio of use of the decane compound (&2_υ is preferably 10% by mole or more, more preferably 2% to 90% by mole, particularly preferably 30 to 60% by mole based on the total of the decane compound. 3 When the polyorganosiloxane (A) is produced, the precursor ♦ organic oxirane (a part of the carbon-carbon double bond of A' is consumed by the reaction with the nucleophilic compound (1), and thus is used as a raw material. The ratio of the use of the decane compound to be used should be set in consideration of the consumed portion. From the viewpoint of =, the decane compound used as the raw material in the production method 3 preferably contains 1 〇m 〇 1% or more as the total decane compound. The decane compound (al) is more preferably contained in an amount of from 1 to 8 〇m 〇 1%, particularly preferably from 20 to 70% by mol. When the polyorganosiloxane (A) is produced by the production method 4, The decane compound to be used as a raw material preferably contains 2 〇 mol% or more of the decane compound (a2i) as described above, more preferably 4 〇 mol%. -23- 201206998 Manufacturing method 5, when manufacturing polyorganosiloxane, precursor The epoxy group of the organic siloxane (A!) is supplied to both the reaction with the carboxylic acid (1_υ 仃 and the reaction with the carboxylic acid (1-2). Therefore, the production method 5 is used as a raw material. The ratio of the use of the decane compound is set in consideration of the consumption portion. From the viewpoint of the decane compound used as the raw material in the production method 5, it is preferred to contain 20 mol% or more of the decane compound as described above with respect to all the broth compounds. More preferably, it contains 40 mol%. When the polyorganismite (a) is produced by the inner method 6, the decane compound used as a raw material is preferably contained with respect to all the decane compound. 20 mol% or more of the decane compound (at", more preferably 40 mol%. In the production methods 2 to 6, it is preferred not to use the decane compound (a2_2). [Polycondensation of a decane compound] In the above production method 1 a polyorganosiloxane (A), a precursor polyorganosiloxane (A1) in Process 2, a precursor polyorganodecane (A11) in Process 3, or Process 4 to 6 Precursor polyorganooxane (eight It can be produced by subjecting a decane compound (or a mixture thereof) as described above to polycondensation. The polycondensation of a decane compound can be carried out by reacting a zephyr compound as described above, for example, in the presence of a dicarboxylic acid and an alcohol. The method (polycondensation method 1), hydrolysis, condensation method (polycondensation method 2), and the like are separately produced. Hereinafter, the polycondensation method 1 and the polycondensation method 2 will be described in order. [Polycondensation method 1] The polycondensation method 1 is as described above. The method for reacting a decane compound in the presence of a di-lowering acid and an alcohol. -24- 201206998 As the diterpene acid used herein, it may be a oxalic acid having a number of atoms of 2 to 4 and a propionic acid, a carbonaceous substance, and a benzene. Two slow acid and so on. Specific two V, a slow base formed by the formation of acid, succinic acid, glutaric acid, hex: to: for example, oxalic acid, malonic acid, terephthalic acid, etc., = o-dicarboxylic acid, bismuth Use it on. Particularly preferred is grass: for the purpose of selecting a kind of these materials for the use of the di-bumonic acid, it is preferred to use the alkane compound to have an alkane, as a raw material to make an amount of ~2.0 mol, more preferably A. 1 lm 〇 1 , the amount of the slow base reaches and the amount of the carboxyl group reaches 〇 5 〜 as the above alcohol, preferably used. For example, methanol can be cited as its specific example alcohol, isobutanol, dipropylene glycol, isopropanol, n-butan-2-methylbutanol, tertiary pentanol, 3-methoxyl-pentane® Pentanol, pentanol, 2-ethylbutanol, heptyl-n-hexanol '2-methyl^ggzhi-3, n-octanol, 2-ethyl alcohol, 2,6-dimethylheptanol_4, Benzyl alcohol, 3,3,5_trimethyl ring: two kinds of yeast, methyl ring, sputum, yeast, glycerol A preferred alcohol is preferably used in the order of carbon number ". Here, it is preferred to select from methanol, ethanol, isoamyl alcohol ester: group-terminated alcohol, more preferably tertiary butanol, and more than one or more species, particularly preferably selected from methanol and ethanol. The above substances are used.

The ratio of % used in the _ & I in the polycondensation method 1 is preferably such that the ratio of the decane compound and the dicarboxylic acid to the total amount of the reaction solution is 3 to 8 % by weight, more preferably 25 to 7 〇. The percentage by weight. The reaction temperature is i 1 , and 仏 is 1 toloot', more preferably 15 to 801. The reaction time is preferably from 0.5 to 2 4 f ntt for 24 hours, more preferably from 1 to 8 hours. -25- 1 201206998 The other and the second generation of the product are the 0.5, which is used as the hydrazine, and the triethyl group. The ratio or the like is preferably a solvent other than the above-described alcohol in the polycondensation method. With respect to the polycondensation method i as described above, it is presumed that an intermediate formed by the reaction of a decane compound carboxylic acid reacts with an alcohol to form a polyorganosiloxane which is a condensate of a decane compound (al), or as a decane. Co-condensation of a compound (al) and a decane compound (a2) with a polyorganosiloxane. σ [Polycondensation method 2] The polycondensation method 2 is a method in which a decane compound as described above is subjected to a hydrolysis condensation method. The hydrolysis condensation reaction can be carried out by reacting a decane compound and water in the presence of a optimizing agent, preferably in a suitable organic solvent. ^ The amount of the water used herein is preferably "2.5 mol °" as the total amount of the alkoxy group which the decane compound has as a raw material, and the acid, the alkali metal compound is mentioned. Wait. Specific examples of such a catalyst include, for example, salt sulfonium, nitrate, acetic acid, citric acid, oxalic acid, maleic acid and the like. As the base, any of an inorganic base and an organic base can be used, and examples of the inorganic test include ammonia water 'sodium hydroxide' potassium hydroxide, 'sodium ethoxide, potassium ethoxide, and the like; and examples of the organic base include amine-n-propyl An organic tertiary amine such as a base amine, tri-n-butylamine, pyridine or 4-dimethylamine; tetramethylphosphoric acid. The ruthenium compound is, for example, a titanium compound or a zirconium compound -26-201206998. The ratio of use of the catalyst is preferably 10 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the decane compound used as a raw material. 0.001 to 10 parts by weight, still more preferably 0.001 to 1 part by weight. Examples of the organic solvent include alcohols, ketones, decylamines, esters, and other aprotic compounds. As the above alcohol, any of an alcohol having one hydroxyl group, an alcohol having a plurality of hydroxyl groups, and a partial ester of an alcohol having a plurality of hydroxyl groups can be used. As the ketone, a monoketone and a β-diketone can be preferably used. As a specific example of such an organic solvent, an alcohol having one hydroxyl group may, for example, be decyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentane Alcohol, isoamyl alcohol, 2-mercaptobutanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, 2-mercaptopentanol, 2-ethylbutanol, heptanol-3, n-octyl Alcohol, 2-ethylhexanol 'n-decyl alcohol, 2,6-dimercaptoheptanol-4, n-nonanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethyl Cyclohexanol, benzyl alcohol, diacetone alcohol, etc.; an alcohol having a plurality of hydroxyl groups may, for example, be ethylene glycol, 1,2-propanediol, 1,3-butanediol, pentanediol-2,4,2- Methyl pentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol And tripropylene glycol and the like; a partial ester of an alcohol having a plurality of hydroxyl groups, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and B Glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, diethylene glycol Mercapto ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol -27- 201206998 monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monodecyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, etc.; monoketone can be, for example, acetone, methyl ethyl Ketone, mercapto-n-propyl ketone, decyl-n-butyl ketone, diethyl ketone, decyl-isobutyl ketone, decyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl- n-Hexyl ketone, diisobutyl ketone, triterpene fluorenone, cyclohexanone, 2-hexanone, nonylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, anthrone, etc. The above β-diketone may, for example, be acetamidine, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octyl Diketone, 2,4-decanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetradecyl-3,5-heptane Ketone, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, etc.; the guanamine may, for example, be decylamine, fluorenyl-mercaptomethylamine, hydrazine, hydrazine-di Methyl decylamine, hydrazine-ethylformamide, hydrazine, hydrazine-diethylformamide, acetamamine Ν-mercaptoacetamide, hydrazine, hydrazine-dimercaptoacetamide, hydrazine- Ethyl acetamide, hydrazine, hydrazine-diethyl acetamide, hydrazine-methyl propyl hydrazide, hydrazine-hydrazinopyrrolidone, fluorenyl-methyl hydrazino, hydrazine-hydrazinopiperidine, hydrazine - mercapto pyrrolidine, hydrazine-ethinyl porphyrin, hydrazine-ethinylpiperidine, hydrazine-ethenyl pyrrolidine, etc.; esters may, for example, be diethyl carbonate, ethyl carbonate, and carbonic acid S, acid-breaking diethyl vinegar, acetic acid methyl vinegar, acetic acid, gamma-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate , n-butyl acetate, n-amyl acetate, diethyl amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, acetic acid Benzyl ester, cyclohexyl acetate, decylcyclohexyl acetate, n-decyl acetate, acetoacetic acid vinegar, ethyl acetate, ethylene glycol monodecyl ether, ethylene glycol monoethyl ether, Diacetate acetate - 28,069,069 Alcohol monodecyl _, acetic acid diacetate Monoethyl _, vinegar, ethylene glycol mono-n-butyl _, propylene glycol monomethyl ether acetate, propylene glycol monoethyl sulphate, propylene glycol monopropyl (tetra), acetic acid propylene: alcohol monobutyl ether, acetic acid dipropylene Drunken early methyl ether, dipropylene glycol monoethyl ether acetate, diacetic acid glycol 8 vinegar 酉夂 methoxy diethylene glycol 、 、, propionic acid vinegar, propionate n-butyl vinegar, propionate isoprene , oxalic acid, oxalic acid, di-n-butyl vinegar, lactic acid, vinegar, vinegar, butyl vinegar, lactic acid, n-butyl sulphate Diethyl phthalate and the like; other aprotic solvents include, for example, acetonitrile, dimethyl sub: nn, n', n, ethyl sulfonamide, trimethylamine hexamethyl phosphate, hail-flavored鲷, N-methyl ° ° °, N-ethyl heart, N-methyl-... than methyl mother... ethyl mother bite, heart dimethyl terminal N_ methyl n, N-methyl _4_ trip. Determination of 嗣, N_methyl·2_[ ketone, n-methyl 2" Bilou 嗣, 17 - Tianfa, 3 · monomethyl-2-imidazolidinone, 1,3-dimercaptotetrahydro . If it is equal, it is possible to select one or more of these substances. 2 The ratio of use of the organic solvent is preferably such that the ratio of the total weight of the components in the reaction solution to the total amount of the reaction solution is ::. The ratio of 9% by weight is better to reach ~7. The specific gravity of % by weight can be added to the organic fucible compound or the compound to be dissolved in the organic brightening compound or the liquid mixture is continuously or continuously added. The shi shi huahua person is previously added to the dream burning compound as a raw material or may be dissolved in a solution formed in an organic solvent, or may be dissolved or dispersed in the added water. -29- 201206998 The reaction temperature is preferably 1 toloot, more preferably 15 to 80 «^^ anti-deer time is preferably 〇 5 to 24 hours, more preferably 1 to 8 hours. As a method for producing the polyorganosiloxane (A), a polyorganosiloxane (A) can be obtained in the above manner by a production process. As a method for producing the polyorganosiloxane (A), when the production method 2 is employed, the precursor polyorganosiloxane (aI) obtained in the above manner is further mixed with a carboxylic acid containing a carboxylic acid (1-1). The reaction is carried out to obtain a polyorganosiloxane (A). When the production method 3 is employed as the method for producing the polyorganosiloxane (A), the precursor polyorganosiloxane (aI) obtained as described above can be reacted with the nucleophilic compound (1). A polyorganosiloxane (A) is obtained. As a method for producing the polyorganosiloxane (A), when the production method 4 is employed, the precursor polyorganooxane (αΙΠ) obtained in the above manner is further mixed with a carboxylic acid containing a tickic acid (1-2). The reaction is carried out to obtain a polyorgano oxane. As a method for producing a polyorganooxane, when the production method 5 is employed, the precursor polyorganosiloxane (AlII) obtained in the above manner is further mixed with the m acid (1-1) and the carboxylic acid. (1_2) The carboxylic acid of both is reacted to obtain a polyorganosiloxane (A). As a method for producing the polyorganosiloxane (A), when the production method 6 is employed, 'the precursor obtained by the above-mentioned method is polyorgano-oxygen (A! u) and contains tannic acid (1 - 2). The reaction of the carboxylic acid is carried out. First, the precursor polyorgano-oxygen (AIV) is obtained, and then reacted with the nucleophilic compound (1) to obtain a polyorganosiloxane. -30- 201206998 Also, as a precursor polyorganodecane (AII), in addition to products manufactured by the above method, commercially available products such as AC-SQ TA-100 (manufactured by East Asia Synthetic Co., Ltd.) may also be used. product. [Carboxylic Acid] The carboxylic acid (丨_丨) used in the above Production Methods 2 and 5 is a compound having a liquid crystal alignment group and a carboxyl group. The liquid crystal alignment group which the carboxylic acid (1_1} has is the same as the case where the liquid crystal alignment group which can be arbitrarily possessed for the polyorganosiloxane (A) is the same as described above. The carboxylic acid used in the production method 3 (丨_丨), preferably a carboxylic acid having a group represented by the above formula (D'), more preferably a formula (b21) D, -COOH (b2-l) (in the formula (b2-l) 'D, a compound represented by the above formula (D)). Examples of such a slow acid (1 · 1 ) include a long-chain fatty acid, a benzoic acid derivative having a long-chain alkyl group, and a long a benzoic acid derivative of an alkoxy group, a benzoic acid derivative having a steroid skeleton, another carboxylic acid having a steroid skeleton, a benzoic acid derivative having a polycyclic structure, another carboxylic acid having a polycyclic structure, or a fluoroalkyl group-containing carboxylic acid, etc. As specific examples thereof, examples of the long-chain fatty acid include hexanoic acid, n-octanoic acid, n-decene, n-dodecanoic acid, n-hexadecanoic acid, stearic acid, and the like; The benzoic acid derivative having a long-chain alkyl group may, for example, be 4·n-hexyl Formic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-undecylbenzoic acid, 4-n-hexadecylbenzoic acid, 4-bromobenzoic acid, etc.; -31- 201206998 The benzoic acid derivative having a long-chain alkoxy group may, for example, be 4-n-hexyloxycartanoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid or 4-n- 12 Alkoxybenzoic acid, 4-n-hexadecyloxybenzoic acid, 4-stearyloxybenzoic acid, etc.; as a benzoic acid derivative having a steroid skeleton, for example, biliary alkoxybenzoic acid, gall bladder Arendyloxybenzoic acid, wool alkoxybenzoic acid, cholestyloxycarbonylbenzoic acid, cholestyloxycarbonylbenzoic acid, wool alkoxycarbonylphthalic acid, succinic acid-5ξ-cholane -3-_, succinic acid-5ξ-cholestene-3-brew, succinic acid-5ξ-lanyl alkane-3-S, etc.; as another carboxylic acid having a steroid skeleton, for example, the following formula ( 1) or (2) a compound or the like respectively indicated;

As the benzoic acid derivative having a polycyclic structure, for example, 4-(4-pentyl-cyclohexyl)benzoic acid, 4-(4-hexyl-cyclohexyl)benzoic acid, -32-201206998 4- (4-Heptyl-cyclohexyl)benzoic acid, 4,-pentyl-dicyclohexyl-4-carboxyl 4 hexyl-bicyclohexyl-4-hypoacid, 4,-heptyl-dicyclohexyl-4-carboxylic acid 4 Pentyl-biphenyl-4-carboxylic acid, 4,-hexyl-biphenyl-4-carboxylic acid, 4'-heptyl-4-carboxylic acid, 4-(4,-pentyl-bicyclohexyl-cardyl group Benzoic acid, 4-(4'-hexyl-dicyclohexyl-4-yl)benzoic acid, 4_(4,-heptyl-dicyclohexyl-4-yl)benzoic acid, etc.; as other polycyclic structures Examples of the acid include, for example, 6 (a gas-based biphenyl-4-fluorenyl) hexanoic acid, a 3-hydroxyl group, and the like. Examples of the acid having a fluoroalkyl group include the following formulas (b2-ll) and (b2). -l-2) CF3~(〇F2)k—(CH2)n-C00H rb2-1-1 ) CF3-(CF2)k—(CH2)n

(b2-1-2) (in the formulas (b2-ll) and (b2-l-2), each of k is an integer of 〇~2, each of which is an integer of 3 to 18), and a compound etc. One or more of a substance is used for use. The carboxylic acid (1-1) used in the production methods 2 and 5 is preferably selected from the group consisting of a succinic acid derivative having a polycyclic structure, a benzoic acid derivative having a steroid skeleton, and another carboxylic acid having a steroid skeleton. More than one 'quality. The tickic acid (1-2) used in the above production methods 4 to 6 is a compound having a group containing a t-bonded carbon-carbon double bond and a slow group, and preferably has a group represented by the above formula (A). The carboxylic acid is particularly preferably a carboxylic acid having a carboxyl group directly bonded to the group represented by the above formula (A) (that is, the following formula (b2-2)

S • 33 - 201206998 A-COOH (b2-2) (In the formula (b2-2), A is a group represented by the above formula (A)) Table $' compound). Specific examples of such a carboxylic acid (Bu 2) include (methacrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid n-butylacrylic acid, maleic acid, fumaric acid, and lemon. Kang acid, mesaconic acid, benic acid, 6-{[6-(acryloxy)hexanyl]oxyindole, sub- & linolenic acid, cinnamic acid, etc., can be selected from these substances One or more of them are used. In the above production method 2, only the carboxylic acid (1-1) as described above may be used; in the production methods 4 and 6, only the carboxylic acid (1-2) as described above may be used; In the production method 5, only the acid (1-1) and the acid retardation (1-2) ' as described above may be used, or in addition to these carboxylic acids, a carboxylic acid (Bu 1) and a slow acid (1-1) may be used in combination. 2) a carboxylic acid (hereinafter referred to as "carboxylic acid (2)"). The carboxylic acid (2) is a citric acid which does not have any of a polymerizable carbon-carbon double bond and a liquid crystal aligning group. For example, citric acid, acetic acid, propionic acid, 蒽醌_2_carboxylic acid, 2-(4-diethylamino-2-hydroxy-methane)-benzoic acid, and the like can be cited, and these materials can be selected. More than one The use ratio of the carboxylic acid (丨_丨) in the production method 2 is preferably 〇1 to 0.9m〇l with respect to the epoxy group of the precursor polyorganosiloxane (Α1). More preferably, it is 〜2~0.8m〇1, and further preferably 〇~ 〇.7 5m〇l. Here, when carboxy hydrazine (1-1) and carboxylic acid (2) are used together, it is preferable to make it slow. The total use ratio of (1 -1) and (2) is higher than that of the precursor -34-201206998. The epoxy group (A1) has an epoxy group of 1 mol, preferably 〇·ΐ~〇.9 mol, more preferably It is 0.1 to 〇·6 m 〇1, and the ratio of use of the carboxylic acid (1 _ 1) to the total of the carboxylic acids (丨_i) and (2) is preferably 6 〇 m 〇 1% or more, more preferably 7〇mol% or more and less than i〇〇m〇i%. The ratio of use of the carboxylic acid (1-2) in the production method 4 is relative to the epoxy group imol of the precursor polyorganosiloxane (Am). It is preferably 〇"~ 〇.9 mol, more preferably 0.2 〇.6 mol. Here, when the carboxylic acid (1-2) and the carboxylic acid (2) are used together, it is preferred to use the carboxylic acid (1_2) and 2) The total use ratio is relative to the epoxy group of the precursor polyorganosiloxane (Απι) 1 is preferably 0.1 to 0.9 mol, more preferably 〇.1 to 〇6 m〇i, and the ratio of use of the tickic acid (ι_2) to the total of the slow acid (1-2) and (2) is preferably 5 〇. Ιη以上% or more, more preferably 60 to 95 mol%. The use ratio of the acid retardation in the production method 5 is as follows. The total use ratio of the carboxylic acid: 1 mol of the epoxy group having respect to the precursor polyorganosiloxane (A111) Preferably, it is from 1 to 〇9 mol, more preferably from 0.2 to 0.7 mol', further preferably from 〇.3 to 〇5m〇1. The acid (1-1): is preferably 5% or less, more preferably 1 to 30% by mole, still more preferably 5 to 10% by mole based on the total of the carboxylic acid. The acid retardation (1-2) is preferably 5 〇 m 〇 1% or more, more preferably 70 m % or more, and still more preferably 9 〇 m 〇丨 % or more, based on the total carboxylic acid. The carboxylic acid (2): is preferably 5 〇 m 〇 1% or less, more preferably 30 % by mole or less, and still more preferably 1 〇 m 〇 1% or less based on the total carboxylic acid. In the manufacturing methods 4 and 5, it is most preferable not to use the slow acid (2). In the production method 6, since a part of the carboxylic acid (1_2) to be used is required to be used for the subsequent reaction with the nucleophilic compound (1), it is necessary to set the carboxylic acid (i-2) from the side of the 201206998 side. The proportion of use. In this regard, the ratio of use of the carboxylic acid (1-2) in the production method 6 is preferably from 1 to 0.9 mol per 1 mol of the epoxy group of the precursor polyorganosiloxane (A111). More preferably 0.2 to 0.6 mol. Here, when the acid (1-2) and the acid retardation (2) are used together, it is preferred to use the total ratio of the carboxylic acids (1-2) and (2) to the precursor polyorganosiloxane (A111). The epoxy group having 1 mol of the epoxy group is preferably 0.1 to 9.9 mol, more preferably 0.1 to 0.6 mol, and the use ratio of citric acid (ι_ι) to the total of the carboxylic acids (1-2) and (2) is preferably used. It is 50 m〇1% or more 'more preferably 60 to 95 mol%. [Preaction of polyorganooxy oxane (A1) or (A111) and carboxylic acid] Precursor polyorganooxane (A1) or (A111) (hereinafter referred to as Θ 物 聚 聚 聚 聚 聚 聚 聚 聚The reaction with oxo acid is preferably carried out in the presence of a suitable catalyst and a suitable organic solvent. The η agent, the oxidized catalytic organic amine as an organic substance, and the fourth grade is the latent type latent temperature dissociation of the above type, except for the aptamer and the acid agent. For the above-mentioned test, the graded squama salt, the gold latent sclerosing hardening type of the hot material, the organic oxime smoldering and the slow acid reaction are used, such as organic testing, and can also be used for promotion. The hardening accelerator for the reaction of the ring needle may be, for example, a primary or secondary tertiary amine or an organic quaternary amine salt as the above-mentioned organic base in the reaction; and a hardening accelerator' may, for example, be a tertiary amine. Except for tertiary amines, imidazole derivatives, organophosphorus compounds, diazabicycloalkenes, organometallic compounds, halo-based compounds, latent curing accelerators, and the like. Examples of the curing accelerator and the like include a high melting point dispersion accelerator (e.g., an amine addition accelerator), a microcapsule accelerator, an amine salt type latent curing agent accelerator, and a high cationic polymerization type latent curing accelerator. -36-201206998 As a specific example of the catalyst, the above-mentioned primary or secondary organic amine may, for example, be ethylamine, diethylamine, σ bottom, or mother. And π ratio σ each bite 'pyrrole or the like; the above organic tertiary amine may, for example, be triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo The undecene or the like; the above-mentioned quaternary organic amine salt may, for example, be tetramethylammonium hydroxide or the like; and the above tertiary amine (excluding the organic tertiary amine as an organic base) may, for example, be benzyldidecylamine, 2, 4,6-gin(didecylaminoindenyl)phenol, cyclohexyldidecylamine, triethanolamine, etc.; the above imidazole derivatives may, for example, be 2-methylimidazole, 2-n-heptyl imidazole, 2-negative Undecylimidazole, 2-phenylimidazole, 2-phenyl-4-mercaptoimidazole, 1-benzyl-2-mercaptoimidazole, 1-benzyl-2-phenylimidazole, 1,2-di Mercaptoimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2-n-undecyl Imidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-mercaptoimidazole, 2-phenyl-4-methyl -5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2-phenyl-4,5-double [(2'-Cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazole trimellitate, 1-(2-cyanoethyl) -2-phenylimidazolium stearate, 1-(2-cyanoethyl)-2-ethyl-4-mercaptoimidazole trimellitate, 2,4-diamino-6- [2'-nonyl imidazolyl-(fluorene)]ethyl-s-tripper, 2,4-diamino-6-(2-n-undecylimidazolyl)ethyl-s-triad, 2 , 4-diamino-6-[2'-ethyl-4'-mercaptoimidazolyl-(indenyl)]ethyl-s-trisole, 2-mercaptoimidazole isocyanurate 5^-37- 201206998 Acid adduct, isocyanuric acid addition of 2-phenylimidazole, 2,4-diamino-6-[2'-methyl meth. And the isocyanuric acid addition product of the ethyl-(1')]ethyl-s-triazine, and the organic filler compound may, for example, be diphenylphosphine, triphenylphosphine or triphenylphosphite; The quaternary scale salt may, for example, be a benzyltriphenyl gasification scale, a tetra-n-butyl bromine scale, a methyltriphenyl bromine scale, or an ethyltriphenyl bromide-n-butyldiphenyl bromide. Scale, tetraphenyl desertification town, ethyl triphenyl moth town, ethyl trisyl acetate lock 'tetra-n-butyl fluorene, 〇 _ diethyl dithiolate, tetra-n-butyl scale a benzotriazole salt, a tetra-n-butyl quaternary tetrafluoroborate, a tetra-n-butyl quaternary tetraphenyl borate, a tetraphenylphosphonium tetraphenylborate or the like; and the above-mentioned diazabicyclo smog may, for example, be 1, 8 -diazabicyclo[5·4·0]undecene-7, an organic acid salt thereof or the like; and the above organometallic compound may, for example, be octanoic acid, tin octylate, orthofluorene, and the like; The quaternary ammonium salt may, for example, be tetraethylammonium bromide, tetra-n-butyl bromide, tetraethyl chloride, tetra-n-butyl sulphate or the like; and the above metal halogen compound may, for example, be three a compound such as boron fluoride or diphenyl borate; zinc sulfide, tin chloride, etc.; and the above-mentioned south melting point dispersion type latent hardening accelerator, for example, an addition product of dicyandiamide or an amine and an epoxy resin, etc. The above-mentioned microcapsule-type latent curing accelerator may, for example, be a latent curing accelerator formed by coating a surface of a hardening accelerator such as the above-described imidazole derivative, organophosphorus compound or quaternary phosphonium salt with a polymer; 201206998 The thermal-cationic polymerization type latent hardening promotion of the above-mentioned temperature-dissociating type is exemplified by, for example, a Lewis acid salt or a Bronsted acid salt, and one or more of these may be used. In these materials, it is preferred to use an organic quaternary ammonium salt or a halogenated quaternary ammonium. * The ratio of use of the catalyst is preferably from 1 to 100 parts by weight, more preferably from 1 to 20 parts by weight, per 100 parts by weight of the precursor. The organic solvent used in the reaction of the precursor polyorganisms and the carboxylic acid may, for example, be a ketone, an ether, an acid, a decylamine, an alcohol or the like. Specific examples of the organic solvent include the following: exemplified by methyl group, methyl isobutyl net, methyl n-pentyl network, diethyl or the like. Glycol __ γ T emulsifiable ether, tetrahydrofuran, bismuth, etc.; the above ester may, for example, be isoamyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, etc.; ethyl ester, n-butyl acetate, vinegar 3 -曱 butyl butyl acetic acid, acid amide can be turmeric, 叱Ν _ ~ methyl carbamide, Ν - ethyl decylamine, χ 酼 酼 Ν, Ν - diethyl hydrazine Indoleamine, B ▲ month female, Ν-methyl acetamide, ν, Ν-dimethyl -7, 7-mercaptoacetamide, N-ethyl acetamidine*, hydrazine, hydrazine-diethyl acetamide, Ν-甲其 a * 8Π Τ丞 醯 醯 Ν Ν Ν 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 听 听 听 听 听 听 疋 疋 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 己 己 己 己 己 己 己 己 己 己- 6 St base <j bottom bite, Ν-乙醯基°Bilo bite, etc.;

S -39- 201206998 The above guanamine can be listed, m, cattle such as guanamine, N_mercaptoamine, dimethyl carbamide, N-ethyl sulphate, snail, N, N-diethylformamide

Indoleamine, N-methylacetamide, N,N-methylethylamine, N-ethylamine, N,N-diethylacetamide, methylpropanamine, N-methylpyridinium

Ketone, N-methyl decyl porphyrin, N-methyl hydrazino piperidine, N-methyl hydrazinopyrrole N-ethyl ketone, N-ethyl ketone oxime piperidine, N-acetylpyrrolidine Examples of the above alcohols include, for example, 1-hexanol, 4-methyl-2-nonanol, alcohol monomethyl ether, ethylene glycol, 7 Α μ _ ^ 〇〇 early ethyl ether, ethylene glycol mono- N-propyl ether-alcohol early • n-butyl sulphate, propyl succinyl ether, propylene glycol monoethyl propylene glycol mono-n-propyl ether, etc., 4 ” used in a selection of some of the substances. The ratio of use of the organic solvent to the ratio of the total weight of the components other than the solvent of the reaction solution to the total amount of the reaction solution is preferably 0.1 to 50% by weight, more preferably 5 to 5 〇. . The reaction of the precursor polyorganosiloxane and the carboxylic acid is preferably carried out at 200 ° C, more preferably at a temperature of 50 to 150 ° C, more preferably for 5 to 20 hours. In the production methods 2, 4 and 5, the polyoxyalkylene (A) can be obtained in the above manner. In the production method 6, the precursor polyoxo-oxygen (AlV) can be obtained in the above manner, and by reacting with the nucleophilic compound (1), the organic monoxide (A) can be collected. [nucleophilic compound] Ν, Ν-, 乙乙醯 醯 啶 、 、 、 、 、 、 乙 、 、 、 、 、 以上 以上 以上 以上 以上 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 -40 The nucleophilic compound (丨) used in Λm to 6 is a nucleophilic compound derived from at least one of the amine and the thiol, wherein the nucleophilic compound has a liquid-phase alignment Sex group. Such a nucleophilic compound (1) is preferably a nucleophilic compound having a group represented by the above formula. The nucleophilic compound (1) & s) is an amine having a group represented by the above formula (D,) (when the stalk is "compound (c 1 , X j. (c1)")" as the above formula ( The Ri in the D,) is preferably a fluoroalkyl group having a carbon number of 4 to 2 Å, and a fluoroalkyl group having a number of 4 to 20 atoms. As the compound (cl), it is preferred to use a primary amine. Or a secondary amine. As the compound (cl) which is a primary amine, for example, octylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, decylamine, undecylamine, dodecylamine, and the like may be mentioned. Indoleamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, pentadecaneamine, 4-(4-pentylcyclohexyl)aniline, 4-octyloxy Aniline or the like; ι as a compound (c丨) belonging to a secondary amine, for example, dibutylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, diamine, diamine, double eleven Alkylamine, dodecylamine, bistridecylamine, bistetradecylamine, dipentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine , di-nonadecylamine, etc., can It is preferred to use one or more of these materials. R1 in the formula (D,) in the compound (cl) is preferably an alkyl group having 4 to 12 carbon atoms or a fluoroalkyl group having 4 to 12 carbon atoms. In the above compound (cl), it is preferable to use a compound belonging to a secondary amine from the viewpoint of easiness of gelation and ease of synthesis when reacting with a polyorganosiloxane having a (meth) propylene group ( c 1) 2 -41- 201206998 As a ratio of use of the compound (C 1 ), the compound (c 1) has a polymerizable carbon-carbon double bond with respect to the precursor polyorganooxanes (A11) or (AIV). The molar ratio is preferably 1 mol% or more and less than 100 mol%, more preferably 3 to 5 μm〇1%, still more preferably 5 to 30 mol%. As an amine belonging to the nucleophilic compound in the present invention, The compound (c 1) as described above may be used together with other amines other than the amines. Examples of such other amines include, for example, decylamine, diamine, diethylamine, dipropylamine, strepamine, etc. At least one of them is preferably 40 mol% or less based on the total of the amine. In the present invention, as the amine, it is preferred to use only the compound (cl) as described above. The nucleophilic compound (1) is a thiol having a group represented by the above formula (D,) ( When it is hereinafter referred to as "compound (c2)"), it is preferably an alkyl group having 4 to 20 carbon atoms or a fluoroalkyl group having 4 to 20 carbon atoms, or a true carbon atom, in the above formula (D). a substituted alkyl group of 2 to 2 or a substituted fluoroalkyl group having 2 to 12 carbon atoms, or a fluoroalkyl group having an alkyl group having 2 to 5 carbon atoms or a carbon atom of 2 to 12 A group having a polycyclic structure. Examples of the polycyclic structure include a bicyclohexyl structure, a biphenyl structure, and a cyclohexylphenyl structure. As the compound (C2), for example, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, mercapto mercaptan, mercapto mercaptan, undecyl mercaptan, Dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan 'hexadecyl mercaptan, heptadecyl mercaptan, octadecyl mercaptan, nonadecane Mercaptan, 4-butyl thiol, 4-pentyl phenyl thiol, 4-hexyl thiol thiol, 4 -heptyl phenyl thiol, 4 - -42 - 201206998 octyl phenyl thiol, 4-nonylphenyl thiol, 4-nonylphenyl thiol, 4. Η alkyl thiol thiol, 4 - dodecyl phenyl thiol, 4-trimethyl phenyl thiol, 4 - tetradecylphenylthiol, 4_pentadecylphenylthiol, hexadecane basic thiol, 4 to 17 decyl thiol, 4 to 18 phenyl thiol , 4-nonadecylphenylthiol, 4-butoxyphenylthiol, 4-pentyloxyphenylthiol, 4-hexyloxyphenylthiol 4-heptyloxyphenylthiol , 4-octyloxyphenylthiol, 4-methoxyphenylthiol, 4-methoxyphenylthiol, 4-dodecyloxyphenylthiol, 4-10 Alkoxyphenylthiol, 4-dodecyloxyphenylthiol, 4-(4,-butylcyclohexyl)phenylthiol, 4-(4-pentylcyclohexyl)phenylthiol, 4 -(4,-hexylcyclohexyl)phenylthiol, 4-(4-heptylcyclohexyl)phenylthiol, 4-(4-octylcyclohexyl)phenylthiol, etc., preferably from these substances Choose one or more to use. The ratio of the molar ratio of the polymerizable carbon-carbon double bond which the compound (c2) has as a compound (c2) to the precursor polyorganosiloxane (A11) or (A1V) is preferably 1 m ο 1 % or more and less than 1 0 0 m ο 1 %, more preferably 3 to 50 m ο 1 % » further preferably 5 to 30 mol%. As the thiol which is a nucleophilic compound in the present invention, the compound (c 2) as described above can be used together with other thiols other than the above. Examples of the other thiol include methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan. Any one of these may be selected, and it is preferably 4 in terms of the total of the mercaptan. 0 m ο 1 % or less is used. In the present invention, as the mercaptan, it is preferred to use only the compound (c2) as described above. -43- 201206998 [Precursor polyorganooxane (A1) or (A111) and nucleophilic reaction] °About the precursor polyorganooxane (Αι) or (AnI) (hereinafter referred to as ~ total) The precursor polyorganosiloxane" and the nucleophilic compound = should be divided into the case where the nucleophilic compound is an amine containing the compound (c?) = the case of the thiol containing the compound (c2), which will be described in order. In the case where the nucleophilic compound is an amine containing the compound (c丨)} When the nucleophilic compound is an amine containing the compound (cl), the reaction of the polyorganosiloxane can be preferably made organic Solution: The reaction is carried out in the presence of an optional catalyst in the presence of a catalyst. As the organic solvent which can be used in the reaction of the precursor polyorganosiloxane and the amine, a polar compound can be preferably used, and for example, a nitrile, a sulfoxide, an ether, an ester, an alcohol or the like can be used. Specific examples of the nitrile include, for example, acetonitrile; and the above-mentioned sub-grinding may, for example, be a 2-base mill or the like; and the ether may, for example, be diethyl ether or dipropyl ether; and the ester may, for example, be ethyl acetate. Butyl acetate or the like; the alcohol port is exemplified by, for example, trifluoroethanol, hexafluoroethanol or the like. When Y is preferable or subhard in these materials, it is preferable from the viewpoint of reaction stability. In view of the reaction rate, it is preferred to use a ratio of the solid refrigerant (the ratio of the total weight of the components other than the solvent in the reaction solution to the solution: =: : ratio) is 40% by weight or more, more preferably For use: It is used in a ratio of 50 to 90% by weight. As the precursor polyorganosiloxane and the amine, and the catalyst which can be optionally used in the reaction, for example, aluminum chloride, citric acid or the like can be mentioned. The reaction temperature is preferably 10 to 10 (TC, more preferably 6 Torr to 1 Torr. The time is preferably 0.5 to 8 hours, more preferably 丨 to 6 hours. -44-201206998 {nucleophilic compound蛊A 士 is a compound having a compound (C2) thiol. The nucleophilic compound is a compound containing ruthenium, and the sulphur red which has a ruthenium with the precursor is carried out in the presence of an organic solvent and a catalyst, preferably m Μ The reaction is carried out. As an organic solvent for the reaction of the precursor, the organic oxime and the thiol can be preferably used, for example, a polar compound can be used, for example, Nitrile, subhard, m, etc. are given as 具体J. 作为 曰 曰 。 。 。 。 。 。 。 举 举 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈 腈Wind, etc.; the above 趟 can be 丨丨 ML ML soil to enumerate, for example, diethyl _, dipropyl fluorination, etc. § θ can be exemplified by, for example, # brewed 曰 酗, butyl acetate, etc. For the solvent,

The car father is in accordance with the ratio of the solids, the basket g &amp; A / Chen (the ratio of the S in the reaction solution, that is, the S meter to the solution of the solution | | the ratio of the weight to the weight) is 40% by weight or more For use, it is better to use: ag #甘&amp; c 仏 仏 杈 杈 Make it to be used in a ratio of 5〇~90% by weight. As a catalyst which is preferably used in the reaction of a polyorganosiloxane and a mercaptan, a catalyst is used, for example, an organic base or the like. More specifically, a tertiary amine, specifically trimethylamine 'diethylmethyl group, may be mentioned. Amine, ethyl dimethylamine: triethylamine, tripropylamine, and the like. The use ratio of the catalyst is preferably 5 parts by weight or less, more preferably 1 to 30 parts by weight, per 1 part by weight of the thiol. The reaction temperature is preferably 10 to 10 (rc, more preferably 4 to 8 Torr. 〇. The reaction time is preferably 〇 5 to 8 hours, more preferably i to 6 hours. It is preferably by the above The polyorganosiloxane (A) of the present invention is produced by any one of the methods 1 to 6. 201206998 <Other components> The liquid crystal alignment agent produced by:::: is preferably produced as described above. A (A) is an essential component, as long as the effect of the present invention is not lowered. If necessary, it may contain the right one.. 5, and other components. As the other components, polyorganic oxygenation &amp; Polymer other than () (hereinafter referred to as "other polymer"), polymerizable unsaturated, ^ ^ , compound, photopolymerization initiator, radical scavenger, intramolecular Γ ^ 尺, male eve - An epoxy group-based compound (the following is a "oxygen compound"), an official, a sb compound, a surfactant, a latent hardener, etc., and one or more of the above substances are selected. [Other polymers] The other polymers mentioned above can be ^ _ The solution characteristics of the obtained liquid daily alignment agent, the electrical characteristics of the liquid crystal alignment film formed by the number of liquid crystals, and the liquid crystal alignment property are used. Yu, +, # use the other polymer as described above. For example, the polyorgano-oxygen/hole (other than "polyoxymethane"), which is a polyorgano-oxygen-fired (A), may be used as the compound of the octopus of the arsenic (A). , poly ugly acid, poly ugly arsenic 16, poly phthalic acid vinegar, polydecylamine, polyoxyalkylene, cellulose derivatives, polyacetal, poly cumin &quot; He bio, poly (styrene-phenyl A maleic acid imide derivative, a polyacrylic acid vinegar, etc., and one or more of these may be selected as a base) Ben! When other polymers are used in the description, it is preferred to use one of the other polyorganooxane, polyamic acid and polyimine.樘 樘 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ And the ring &quot; ° may optionally have at least one group selected from the group consisting of liquid crystals. y "when there is a liquid crystal aligning group, the polyorgano oxo protected water of the organic cericoxane, as a ratio of the presence of the porphyrin-containing group, preferably 1 mol of the ruthenium atom relative to the presence of the porphyrin-containing group. The ratio of the ratio of 卞@〇.2m〇l or more contained in the organic oxime is particularly good as 〇4~〇7〗 &lt; 〇·3~〇.8mol. 〇·7m〇1 ratio ❶ About Other polyorganic ^ ... B conversion weight two hunters by the reaction chromatography to determine ^ 000,000, more preferably!, _ 2000 knife 00: t good 500 ~ ~ 50,000. 〇 '000 into - step better 1 , 000 as such other polyorganosiloxane, = compound (four) and peak 2), except that the compound of 2:: (): is not used as a raw material for the production of polyoxo-oxygen (A) It is preferable to use other polyorganosiloxane to obtain a decane compound (: 2 2), or a smelting compound (a2_2), and a decane compound having a liquid crystal aligning group and an alkoxy group. (hereinafter referred to as "decane compound (a3)"), a method of performing polycondensation (manufacturing method 7), and manufacturing Alternatively, by using the decane compound (a2_丨) as at least a part of the raw material compound in the above method, first, a polyorganooxime having an epoxy group is produced and then reacted with the above-mentioned retarded acid (1 - The method of producing a reaction (manufacturing method 8) of a slow acid (in which the slow acid does not contain a carboxylic acid (1-2)) is produced. The above-mentioned compound (a3) can be exemplified by the following formula (a3-l) -47 - 201206998 (R2)f(R3)gSi(OR4)4.fg (a3-l) (formula (a3-l) In the above, R2 is a fluoroalkyl group having 8 to 30 carbon atoms having 8 to 30 carbon atoms, or a hydrocarbon group having 5 1 carbon atoms having a steroid skeleton, and R3 is an alkyl group having 1 to 3 carbon atoms, and R4 is 1 to 12; An alkyl group or an aryl group having 6 to 12 carbon atoms, fj number, and g is an integer of 0 to 2, wherein f+g$3) represents the following formula (a3-2) R^ZHR11)n1)n2-(' zIHcH2-)^rSi-(OR10)3 (a3-2) (In the formula (a3-2), R1, R11, Z1, Z11, and nl have the same meanings as in the above formula (D'), and n2 is 1 , ii is a compound represented by the number 1 to 3 of the alkyl group. As the compound represented by the above formula (a 3 -1), an alkyltrimethoxy decane, n-octyltriethoxydecane, n-oxydecane, n-octyltriisopropoxydecane, n-octyldecane may be used. , n-octyl tri- or two-butoxy decane, n-octyl trioxane, n-octyl tri- or two-butoxy decane, n-octyltriphenyl-n-octyl tri-p-nonyl phenoxy decane, n-decyl曱 癸 三 triethoxy decane, n-decyl tri-n-propoxy decane isopropoxy decane, n-decyl tri-n-butoxy decane, n-butoxy decane, n-decyl tri-n-pentyloxy decane , n-decyloxydecane, n-decyltriphenoxydecane, n-decyltridecane, n-dodecyltrimethoxydecane, n-dodecyl sulphate, n-dome-based tri-n-propoxylate Xishao, Zhengshiji, dish atomic number 1 7~ is a whole compound of carbon number 1.1~3, n3 and n4, .1() is a carbon atom, for example, n-octyl-n-n------- Butoxy-n-pentoxide-oxyxanthene, sulphate, n-n-decyltridecyltrioderytriodet-butyl-p-methylphenoxyalkyltriethoxydioxane Triiso-48- 201206998 propoxy decane, n-dodecyl tri-n-butoxy decane, n-dodecyl tri-n-butoxy decane, n-dodecyl tri-n-pentyloxy decane, positive ten Dialkyltris-butoxybutane, n-dodecyltriphenoxydecane, n-dodecyltris-p-nonylphenoxydecane, n-octadecyltrimethoxydecane, n-octadecane Triethoxy decane, n-octadecyl tri-n-propoxy decane, n-octadecyl triisopropoxy decane, n-octadecyl tri-n-butoxy decane, n-octadecyl tris Butoxy decane, n-octadecyltri-n-pentyloxydecane, n-octadecyltri-n-butoxy decane, n-octadecyltriphenoxynonane, n-octadecyltrisium Phenoxy decane, 2-(perfluoro-n-hexyl)ethyltrimethoxy decane, 2-(perfluoro-n-hexyl)ethyltriethoxy decane, 2-(perfluoro-n-hexyl)ethyl Tri-n-propoxy decane, 2-(perfluoro-n-hexyl)ethyltriisopropoxy decane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxy decane, 2-(perfluoro-positive Ethyl tri- or 2-butoxy decane, 2-(perfluoro-n-octyl)ethyltrimethoxy decane, 2-(perfluoro-n-octyl)ethyltriethoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-butyl Propoxy decane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-butoxy decane, 2-(perfluoro-positive Octyl) ethyl tri- or 2-butoxybutane, 3-cholesteryltrimethoxydecane, 3-cholesteryltriethoxydecane, 3-cholesteryltri-n-propoxy decane, 3 - Cholesteryl triisopropoxy decane, 3-cholesteryl tri-n-butoxy decane, 3-cholesteryl tri- or 2-butoxy decane, 3-cholesteryl trimethoxy decane , 3 - biliary alkenyl triethoxy decane, 3- bilisalkenyl tri-n-propoxy decane, 3-cholestenyl triisopropoxy decane, 3-cholesteryl tri-n-butoxy a decane, a 3-cholestyl group, a tri-n-butoxybutane, or the like; -49-201206998, as a compound represented by the above formula (a3-2), for example, pentyloxy phenyl dimethoxy decane, pentane Oxyphenyl triethoxydecane, 4-hexyloxyphenyl trimethoxy decane, 4-hexyloxyphenyl triethoxy Alkane, 4-octyloxyphenyl trimethoxy decane, cardinyloxyphenyl triethoxy decane, 4 · dodecyloxy benzyl tridecyloxy decane, 4 - dodecyloxybenzene Triethoxy decane and the like. The ratio of use of the decane compound (a3) in the above production method 7 is preferably 7 〇m 〇 1% or less, more preferably 5 to 70 ο 1 / 〇, relative to the total amount of the raw material decane compound. It is 5~5 〇m 〇1%. The polycondensation in the production method 7 can be carried out by the same operation as the polycondensation in the production of the polyorganocaline (A), except that the decane compound as described above is used as a raw material. When the polyorganosiloxane having an epoxy group is synthesized in the above production method 8, the ratio of the use of the compound (4) is preferably 20 mol% or more, more preferably 20 mol% or more. ^ ^ _ 1 1 bandit 30 ~ 70mol%, 乂 better 4 0~6 0 m ο 1 %. For 劁#, this s 1 γ # ^ is the polycondensation in the method of the method 8, except that the decane compound as described above is used as the raw material, and the 女 ^ 由 由 由 由 ♦ organic oxane (A) The same operation of polycondensation - 1 butyl package 0 In the production method 8, by obtaining the polyorganosiloxane of the soil obtained in the above manner, followed by the carboxylic acid (1_丨)瑗) of citric acid (wherein the 3 carboxylic acid (1 - 2)) is reacted to form a liquid crystal alignment of the group ♦ organic &gt; Here, as the carboxylic acid, the acid (κη, 斗, Γ Γ uses only the carboxy group; or the carboxylic acid (1 丨 丨) and the upper hydrazine may be used together as the A 4 m and the carboxylic acid (2). The ratio of use of the acid (1 _ 1) is relative to that of the organic 矽 4 P * * 聚 碇 具有 碇 碇 碇 碇 碇 碇 碇 碇 碇 碇 碇 碇 l l l l l l l l l l l l - l - - l l l l :~.·8_, step-by-step is better. 25~.7 竣夂ί) When using slow acid (7), it is better to make the total use ratio of several acids (1)) and ^ relative to the ring... Lm. &quot;Good for the better, better ~ Bu and make the acid (1)) relative to the slow acid (11: the use ratio is better "--, more preferably 70mol% to:: Ten manufacturing method 8 has a ring The polyorgano group of the oxy group can be carried out in the same manner as the reaction of the precursor organic compound oxo oxo acid in 2 and 4 to 6 in accordance with the method of 盥劁i 〇» 4 r ^ /. When the liquid crystal alignment agent contains another polyorganosiloxane, the content thereof is preferably 8 parts by weight or less per part by weight based on 1 part by weight of the polyorganosiloxane (A), more preferably 5 parts by weight or less. - Polyamino phthalic acid and polydiamine, for example, the tetracarboxylic dianhydride and the diamine described in Patent Document 9 (Japanese Patent Laid-Open Publication No. Hei 20 10-97188), These are produced by reacting them according to a known method. 1 Sa imine can be produced by subjecting the above polyamic acid to dehydration ring closure by a known method. The liquid crystal alignment agent of the present invention contains a polyphosphonic acid selected from polyamines. And the poly-imine type of the above polymer when 'for its content ratio, relative to the polyorganic oxy-combustion (A) 1 00 weight The total amount of the poly' amide and the polyimine is preferably 60 parts by weight or less, more preferably 3 parts by weight or less. [Polymerizable unsaturated compound] The polymerizable property optionally used in the present invention is not Preferably, the saturated compound has at least one of the following formulas (BI) -51 - 201206998 - Χ '- Υ ^ Χ 2- (Β-Ι) (wherein X1 and X2 are each independently 1,4-phenylene or 1,4-cyclohexylene, Υ1 is a single bond, a divalent hydrocarbon group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom or -COO-, wherein the above X1 and X2 can be one a divalent group represented by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom or a cyano group, and at least two of the following formulas (Β-ΙΙ) ί ΟΗ2-C—0' 丫3—(Β-ΙΙ) (In the formula (Β-II), R is a hydrogen atom or a fluorenyl group, and Υ2 and Υ3 are each independently an oxygen atom or a sulfur atom) An unsaturated compound of the compound (hereinafter referred to as "compound (Β -1 )"). As the unsaturated compound, only the compound (Β -1 ) may be used, or the compound (Β -1 ) and other unsaturated groups may be used in combination. Chemical The number of the monovalent groups represented by the above formula (Β-ΙΙ) in the compound (Β-1) is preferably two. The divalent hydrocarbon group having 1 to 4 carbon atoms in the above formula (Β-I) For example, a methylene group, a dimethylmethylene group, etc. may be mentioned. The divalent group represented by the above formula (Β-Ι) may, for example, be represented by the following formula (Β-Ι-1)~(Β-Ι- 6) -52- 201206998

(B-I-1)

(B-I-2)

Represented groups, etc. The benzene ring and the cyclohexane ring in the above formulas (BI-1) to (BI-6) may each be an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom or cyanogen. Substituted. Y2 in the above formula (B-II) is preferably an oxygen atom. The compound (B-1) used in the present invention may, for example, be a di(meth)acrylate having a biphenyl structure (the divalent group represented by the above formula (BI) is represented by the above formula (B-1-1)) a group in which each of Y2 and Y3 in the above formula (B-II) is an oxygen atom) and a bis(indenyl)acrylate having a phenyl-cyclohexyl structure (the divalent group represented by the above formula (BI) is a group represented by the above formula (BI-2), each of Y2 and Y3 in the above formula (B-II) is an oxygen atom), -53-201206998 a di(indenyl) group having a 2,2-diphenylpropane structure The acrylate (the divalent group represented by the above formula (BI) is a group represented by the above formula (BI-3), and each of Y2 and Y3 in the above formula (B-II) is an oxygen atom), and has a diphenylanthracene. The di(meth) acrylate having an alkane structure (the divalent group represented by the above formula (BI) is a group represented by the above formula (BI-4), and each of Y2 and Y3 in the above formula (B-II) is oxygen. (Atom), a dithio(meth)acrylate having a diphenyl sulfide structure (the divalent group represented by the above formula (BI) is a group represented by the above formula (BI-5), and the above formula (B- Y2 in II) An oxygen atom, Y3 is a sulfur atom) and other compounds (B-1). As a specific example of these, a di(indenyl) acrylate having a biphenyl structure may, for example, be 4'-acryloxy-biphenyl-4-yl-acrylate or 4'-methylpropenyloxy- Biphenyl-4-yl-methacrylate, 2-[4'-(2-propanyloxy-ethoxy)-biphenyl-4-oxy]-ethyl acrylate, 2-[ 4'-(2-Mercaptopropenyloxy-ethoxy)-biphenyl-4-oxy]-ethyl decyl acrylate, bishydroxyethoxybiphenyl diacrylate, bishydroxyethoxy Biphenyl dimercapto acrylate, 2-(2-.{ 4'-[2-(2-propenyloxy-ethoxy)-ethoxy]-biphenyl-4-oxy}-ethoxy Ethyl acrylate, 2-(2-{ 4'-[2-(2-mercaptopropenyloxy-ethoxy)-ethoxy]-biphenyl-4-oxy}-B Oxy)-ethylmercapto acrylate, diacrylate of ethylene oxide adduct of biphenyl, dimethacrylate of ethylene oxide adduct of -54-201206998 biphenyl, biphenyl Diacrylate of propylene oxide adduct, dimethacrylate of propylene oxide adduct of biphenyl, 2 - ( 4 '-propionyl SE-based-linked 4-oxo -ethylpropionic acid, 2-(4'-mercaptopropenyloxy-biphenyl-4-oxy)-ethyl methacrylate, etc.; phenyl having a phenyl-cyclohexyl structure Examples of the methyl acrylate include 4-(4-acryloxy-phenyl)-cyclohexyl acrylate and 4-(4-methylpropenyloxy-phenyl)-cyclohexyl decyl acrylate. 2-{4-[4-(2-Propyloxy-ethoxy)-phenyl]-cyclohexyloxy}-ethyl acrylate, 2-{4-[4-(2-曱Acryloxy-ethoxy)-phenyl]-cyclohexyloxy}-ethyl methacrylate, 2-[2-(4-{4-[2-(2-propenyloxy)- Ethoxy)-ethoxy]-phenyl}-cyclohexyloxy)-ethoxy]-ethyl acrylate, 2-[2-(4-{ 4-[2-(2- fluorenyl propylene)醯oxy-ethoxy)-ethoxy]-phenyl}-cyclohexyloxy)-ethoxy]-ethyl decyl acrylate or the like; two having a 2,2-diphenylpropane structure The methyl acrylate may, for example, be 4-[1-(4-acryloxy-phenyl)-1-indenyl-ethyl]-phenylpropionic acid, 4-[1-(4- Methyl propylene methoxy-phenyl)-1-fluorenyl-ethyl]-phenyl decyl acrylate, 2-(4- ·{ 1- [4-(2-Propyloxy-ethoxy)-phenyl]-1-indenyl-ethyl}-phenoxy)-ethyl acrylate, -55- 201206998 2-(4- { l -[4-(2-Methylpropenyloxy-ethoxy)-phenyl]-1-indenyl-ethyl}-phenoxy)-ethyl decyl acrylate, bishydroxyethoxy- Bisphenol A diacrylate, bishydroxyethoxy-bisphenol A dimercapto acrylate, 2- { 2-[4-(l - { 4-[2-(2-propenyloxy-ethoxy) )-Ethoxy]-phenyl} -1 -fluorenyl-ethyl)-phenoxy]-ethylidene oxime-ethylpropanuric acid, 2-{2-[4-(1- { 4-[2-(2-Methylpropenyloxy-ethoxy)-ethoxy]-phenyl}-1-methyl-ethyl)-phenoxy]-ethylidyl}-ethyl Methylpropionic acid, diacrylate of ethylene oxide adduct of bisphenol A, dimethacrylate of ethylene oxide adduct of bisphenol A, epoxy propylene of A. The diacrylate acid of the adduct, the dimethacrylate of the propylene oxide adduct of bisphenol A, 2-(4-{1-[4-(2-propenyloxy-propoxy) )-Phenyl]-l-fluorenyl-ethyl}-phenyllacyl)-1-indolyl-ethylpropanic acid, 2-(4-{ 1-[4-(2-methylpropene) Oxyloxy- Oxy)-phenyl]-1-indenyl-ethyl}-phenoxy)-lF-ethyl methacrylate, 2-{ 2-[4-(1-{ 4-[2-( 2-Acetoxy-propoxy)-propoxy]-phenyl}-1-indolyl-1-ethyl)-phenoxy]-1-indenyl-ethoxy}-1-indenyl -ethyl acrylate S, 2- { 2-[4-(l- { 4-[2-(2-methylpropane; fcijj acid-propoxy)-propoxy]-phenyl} - 1-methyl-1-ethyl)-phenoxy]-1-methyl-ethoxy}-1-methyl-ethyl decyl acrylate, 3-{4-[l-(3- { 1-[4-(3-propionyl lactyl-2-alkyl-propoxy)-phenyl]-1-methyl-ethyl}-phenyl)-1-methyl-ethylphenoxy Benzyl-2-hydroxy-propyl acrylate acid, -56- 201206998 3- { 4-[l-(3- { l-[4-(3 - decyl propylene oxy-2-hydroxy- propyl Oxy)-phenyl]-1-methyl-ethyl}-phenyl)-1-methyl-ethylphenoxy-2-hydroxy-propyl decyl acrylate, 3-(4- { 1 -[4-(3-propionyloxy-2-startyl-propoxy)-3-desfyl-phenyl]-1-indenyl-ethyl}-2-cyclohexyl-phenoxy) 2-hydroxy-2-propylpropionic acid S, 3-(4-{ 1-[4-(3-methylpropenyloxy-2-hydroxy-propoxy)-3-diacyl- Phenyl]_1_mercapto- Ethyl}-2-3⁄4-hexyl-phenyllactyl)-2-carbamic-2-propylmethacrylate, 3-(5-{1-[6-(3-propionic acid lactyl-2-)基-propyl-propyl)-biphenyl-3·yl]-1-indolyl-ethyl}-biphenyl-2-oxy)-2-hydroxy-propyl acrylate, 3-(5- { 1 -[6-(3-methylpropanecarbo!-yl-2-yl-propyl-propoxy-yl-3-phenyl-3-yl]-1-methyl-ethylhydrazine-biphenyl-2-oxo 2-hydroxy-propylmercaptoacrylic acid S, 3-{4-[1-(4-丨1-[4-(3-propenyloxy-2-hydroxy-propoxy)-3 -mercapto-phenyl]-1-indenyl-ethyl}-phenyl)-1-indolyl-ethyl]-2-indolyl-phenoxy}-2-hydroxy-propyl acrylate, 3 - { 4-[l-(4- { 1-[4-(3 -Mercaptopropenyloxy-2-hydroxy-propoxy)-3-indolyl-phenyl]-1-indenyl-B }}-phenyl)-1-methyl-ethyl]-2_indolyl-phenoxy}-2-carbyl-propylmercaptopropionic acid S, 3-(4-{ 1-[4 -(3-propenyloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl}-indolyl)-2-hydroxy-propyl acrylate, 3-(4- { 1-[4-(3-Methylpropanoloxy-2-yl-propyl-propyl)-phenyl]_ 1 曱-yl-ethyl}-phenylyl)_2_light-propyl Methyl propyl fine acid @, e -57- 2 01206998 3-[4-(l- { 4-[3-(4- { 1-[4-(3·Acetyloxy-2-hydroxy-propoxy)-phenyl]-1-methyl- Ethyl}-phenyllacyl)-2-yl-propyl-propyl]-phenyl}-1-methyl-ethyl)-phenyllactyl]-2-trans-propylpropionic acid S 3-[4-(Bu{4-[3-(4 - { 1-[4-(3-methylpropenyloxy-2-hydroxy-propoxy)-phenyl]-1-methyl- Ethyl hydrazino-phenoxy)-2-hydroxy-propoxy]-phenyl}-1-methyl-ethyl)-p-oxy]-2-yl-propylmercaptopropionate, 3- { 4-[1-(4- { 3-[4-(1- { 4-[3-(4- { 1-[4-(3-Propyloxy-2-hydroxy-propoxy) )-Phenyl]-1-methyl-ethyl}-phenoxy)-2-hydroxy-propyllacyl]-phenyl}-1-indolyl-ethyl)-phenoxy]-2- -propoxy]-phenyl}-1-methyl-ethyl)-indolyl} - 2 -yl-propylpropionic acid vinegar, 3- { 4-[1-(4- { 3 -[4-(1- { 4-[3-(4- { 1-[4-(3-Mercaptopropenyloxy-2-alkyl-propoxy)-phenyl]-1-methyl) -ethyl}-phenoxy)-2 _ phenyl-propoxy]-phenyl}-1-methyl-ethyl)-phenyllacyl]-2-yl-propoxy]-phenyl }-1-fluorenyl-ethyl)-phenyllactyl}-2-yl-propylmercaptopropionic acid S, 1- (2- { 4 -[1-(4- { 2-[2-]-based 3-(1-indenyl-finepropoxy)-propyllacyl]-propoxy}-phenyl)-1-methyl- Ethyl]-lacyl}·-1-indolyl_ethoxy)-3-(1-methylene-allyloxy)-propan-2-ol; The mercapto acrylate may, for example, be 4-(4-oxapropenyloxy-benzyl)-phenylacrylate, 4-(4-mercaptopropenyloxy-benzyl)-phenylmercaptoacrylate, 2-{4-[4-(2-Propyloxy-ethoxy)-benzyl]-phenyl}-ethyl acrylate, 2-{4-[4-(2-methylpropene oxime) Ethyl-ethoxy)-benzyl]-phenyl}-ethyl methacrylate, -58- 201206998 Ethylene oxide adduct of diphenol F, diacrylate, ethylene oxide of bisphenol F Dimercapto acrylate of adduct, diacrylate of propylene oxide adduct of bisphenol F, dimercapto acrylate of propylene oxide adduct of bisphenol F, 2_[2_(4-{ 4 -[2-(2-Acetoxy-ethoxy)-ethoxy]-benzyl}-phenoxy)-ethoxy]-ethyl acrylate, 2-[2-(4-{ 4 -[2-(2-Methylpropenyloxy-ethoxy)-ethoxy]-benzyl}-phenoxy)-B Oxy]-ethyl methacrylate, 2-{4-[4-(2-propenyloxy-propoxy)-benzyl-phenoxyindole-1-methyl-ethyl acrylate, 2-{4-[4-(2-Mercaptopropenyloxy-propoxy)-benzyl-phenoxy}-1-indolyl-ethyl methacrylate, 2-[2-(4 - { 4-[2-(2-Propyloxy-propoxy)-propoxy]-benzyl}-phenoxy)-1-indenyl-ethoxy]-1-methyl-B Ethyl acrylate, 2-[2-(4-丨4-[2-(2-methylpropionyloxy-propoxy)-propoxyphenyl]}-phenylyl)-1 -Methyl-ethyllacyl]-1-mercapto-ethylethyl decyl acrylate or the like; a dithio(indenyl) acrylate having a diphenyl sulfide structure, for example, 4-(4-sulfuric acid) Acetylene thiol-phenylthio)-phenyldithioacrylic acid S, 4-(4-thiodecyl propylene sulfenyl-phenylthio)-phenyldithio methacrylate Bis(4-mercaptopropenylthiophenyl) sulfide; etc.; other compound (B-1) may, for example, be 2,5-bis{4-(3-propenyloxy-propoxy)-benzene Tannic acid} benzene and so on. -59-201206998 The compound (Β-υ, which is synthesized by a conventional method in which organic chemistry is appropriately combined, can also be obtained as a commercially available product. As a commercially available product of the compound (Β-1), for example, Bis-ethoxyethoxy oxime diacrylate, bishydroxyethoxy Bis_A diacrylate (manufactured by Honshu Chemical Industry Co., Ltd.); ARONIX M-208 'M-210 (East Asia Synthetic Co., Ltd.) SR-601, SR-602 (manufactured by Sartomer); KAYARAD R-712, R-551 (manufactured by Sakamoto Chemical Co., Ltd.); NK Ester BPE-100, NK Ester BPE-200, NK Ester ΒΡΕ.500, NK Ester BPE- 1 300, NK Ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Actilane 420 (manufactured by Siber Hegner Co., Ltd.);

Light Ester BP-2EM, Light Acrylate BP-4EA, Light

Acrylate BP-4PA, Epoxy Ester 3000M, Epoxy Ester 3000A (Kyoeisha Chemical Co., Ltd.); V#540, V#700 (Osaka Organic Chemical Industry Co., Ltd.); FA-3 21M (Hitachi Chemical Industry Co., Ltd. ( Stock system); MPSMA (Sumitomo Refinery Co., Ltd.);

RipoxyVR-77 (Showa Polymer Co., Ltd.) and the like. The compound (Β-1)' used in the present invention is preferably used by selecting at least one of the compounds exemplified above. The above-mentioned other unsaturated compound may be included in the liquid crystal alignment agent of the present invention for the purpose of achieving a pretilt angle closer to 90°, thereby more effectively achieving the intended effects of the present application. The other unsaturated compound is preferably a compound having one carbon-carbon double bond, more preferably -60-201206998. It has a carbon-refinery, a reverse bond and a liquid crystal as described above. An ortho-based compound. Examples of such other unsaturated compounds include, for example, urethane U-3- group, propylene terpene 4 (4-phenyl, dicyclohexyl-4-yl) phenyl ester, methacrylic acid. 4-octyloxybenzene, 4-(4-pentylcyclohexyl)benzophenone methacrylate. The use ratio of the polymerizable unsaturated compound in the liquid crystal alignment agent of the present invention is preferably 10 parts by weight, more preferably 1 part by weight, based on 100 parts by weight of the polyorganosiloxane and other polymers. 5~^ 乍 is a polymerizable unsaturated compound, and when a compound (called a blood-saturated compound) is used in combination, the ratio of use thereof is: 5 parts by weight or less of the total amount of the unsaturated compound, and Λ is the weight of the phase or less For the *fresh compound of the pot, it is possible to achieve its intended effect by using 5 parts by weight of its milk with respect to the total amount of the polymerizable unsaturated compound in π. [Photopolymerization Initiator] The photopolymerization initiator may be exemplified by the examples of α-), oxalate, acetoin, benzophenone, acetophenone, anthraquinone, quinone Specific examples of the compound, the fluorenylphosphine oxide, the organic peroxide, and the like, and the α-diketone may, for example, be a sulfhydryl group or a tererene. For example, benzoin may be mentioned, for example, benzoin or the like; List for example Ether, benzoin ethyl ether, benzoin isopropyl ether, etc.; quinone benzophenone compound may, for example, thioxanthone, 24 thioxanthone, thioxanthone-4-sulfonic acid, diphenyl hydrazine Ketone, 44, decyl ethyl, _ (dimethylamine-61-201206998-based) benzophenone, 4,4'-bis(diethylamino)benzophenone, phenyl·(4_pair Benzylthio-phenyl)-methanone or the like; examples of the acetophenone compound include acetophenone, p-didecylaminoacetophenone, 4-(α,α,-dimethoxyethenyloxy group Diphenyl fluorenone, 2,2,-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-2 _ sylylene-methylthiophenyl) 1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, etc.; the quinone compound can be exemplified by, for example, brewing, 1, 4 - naphthalene and the like; the halogen compound may, for example, be acetophenone benzene, tribromomethyl phenyl base, ginseng (trichloromethyl)-s-three tillage, etc.; fluorenyl phosphine oxide may, for example, be 2, 4, 6- Trisyl alum-based diphenylphosphine oxide, bis(2,6-dimethoxyphenylhydrazino)-2,4,4-tridecylpentylphosphine oxide, (2,4,6-trimethylbenzene Yue acyl) phenylphosphine oxide and the like; organic peroxides include, for example, tert.butyl peroxide and the like, may be selected for use from one or more of these substances. Commercially available products of the photopolymerization initiator include, for example, IRGACURE-124, homo-149, homo-184, homo-369, homo-500, homo-651, homo-819, homo-907, homo-1000, and the like. -1700, the same -1800, the same -1 850, the same -2959, Darocur-1116, the same -1173, the same -1 664, the same -2959, the same -4043 (above, Ciba · Specialty · Chemicals); KAYACURE- BMS, homo-DETX, homo-MBP, homo-DMBI, same-EPA 'same ΟΑ (above, Sakamoto Chemical Co., Ltd.); LUCIRIN TPO (manufactured by BASF); VICURE-10, same-55 ( Above, STAUFFER company); -62 - 201206998 TRIGONALPl (made by AKZO); SANDORAY 1000 (made by SANDOZ); DEAP (made by APJOHN); QUANTACURE-PDO, same-ITX, same as _EpD (above, Ward BLEKINSOP) System) and so on. As the photopolymerization initiator, it is preferred to use a benzophenone compound from the viewpoint of high thermal stability. When the ratio of use of the photopolymerization initiator in the liquid crystal alignment agent of the present invention is such that no polymerizable unsaturated compound is present in the liquid crystal alignment agent, the polyorganosiloxane (A) is preferably used in an amount of 1 part by weight. 3 parts by weight or less, more preferably 0.5 to 30 parts by weight, particularly preferably 1 to 2 parts by weight. In the case where a polymerizable unsaturated compound is present in the liquid crystal alignment agent, the use ratio of the t polymerization initiator is preferably 1 part by weight based on the total of the polyorganosiloxane (a) and the polymerizable unsaturated compound. It is more preferably 0.5 to 30 parts by weight, and particularly preferably 1 to 2 parts by weight, based on the parts by weight. [Radical Scavenger] The liquid crystal alignment of the present invention can be avoided by the heating. Therefore, when the above-mentioned radical scavenger of the present invention is applied as a coating film on a substrate, it is preferably heated to produce a polymerizable carbon-carbon double. The bond is not preferred, and is contained in the 'night crystal alignment agent. Alcohol as a specific example of such a radical scavenger, for example, quaternary tetraeththene: [3-(3,5-di-tri-butyl-4-yl-hydroxyphenyl)propionate [3-(3,5_二三级基基基基phenyl)propionic acid vinegar], 18 炫_土2'3' (3,5_二三级丁·4·经基基基Propionic acid _, 1,3,5-trimethyl, 4,6-parade (3,5-di-tributyl butyl benzyl) benzene, hydrazine, hydrazine, -hexane g -63 - 201206998 -1 ,6-diylbis[3-(3,5-ditributyl-4-hydroxyphenylpropanamide), 3,3',3'',5',5''-six-three Butyl _01, 〇1', 〇1"-(homotriphenylene-2,4,6-triyl)trisylphenol, 4,6-bis(octylthioindenyl)-o-cresol , 4,6_bis(dodecanylthiocarbenyl)-o-fluorene, hexyl bis(oxyethyl)bis[3_(5-tris-butyl-4-trans-tolyl)propane Acid g, hexamethylene bis[3_(3,5-ditributyl-4-hydroxyphenyl)propionate], 1,3,5-paran (3,5-di-tertiary butyl- 4-Phenylbenzyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione, 1,3,5-tri[[4-tert-butyl-3 -hydroxy-2,6-xylene)methyl]-1,3,5-tri-trap-2, 4,6(1H,3H,5H)-trione, 2,6-di-tributyl-4-(4,6-bis(octylthio)-1,3,5-trioxan-2- Alkylamine, phenylhydrazine, etc., may be selected from one or more of these materials. As a commercially available product of these materials, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO- manufactured by ADEKA can be cited. 40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 &gt; ADK STAB AO-80 &gt; ADK STAB AO-330; Sumitizer GM, sumilizer GS, sumilizerMDP-S 'SumilizerBBM manufactured by Sumitomo Chemical Co., Ltd. -S, sumilizerWX-R, sumilizerGA-80 »

Manufactured by Ciba Japan, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1 135, IRGANOX 1 330, IRGANOX1 726, IRGANOX1425WL, IRGANOX1520L, IRGANOX245, IRGANOX259, IRGANOX31 14 , IRGANOX565, IRGAMOD295 ; -64 - 201206998 (share) API Corporation Yoshinox ΒΗΤ, Yoshinox BB ' Yoshinox 2246G ' Yoshinox 425 ' Yoshinox 250, Yoshinox 93〇, Y〇shinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314, etc. The use ratio of the radical scavenger in the liquid crystal alignment agent of the present invention 'in the case where no polymerizable unsaturated compound is present in the liquid crystal alignment agent' is preferably 1 part by mass relative to the polyorganosiloxane (A). It is less than 1 〇 mass damage, more preferably 〇丨 5 parts by mass. Further, when a poly σ I·saturated compound is present in the liquid crystal alignment agent, the use ratio of the radical scavenger is preferably 100 parts by weight based on 100 parts by weight of the polyorganosiloxane and the polymerizable unsaturated compound. It is preferably 10 parts by mass or less, more preferably 〇. L oxime compound] The above epoxy compound has at least one compound in the molecule, wherein in! _, f is taken from the lacquer base. The above is the case where the above t-organooxane (A) and other alkane have an epoxy group. K organic oxime as the epoxy compound, in addition to, for example, ether, polyethylene glycol diglycidyl propylene, propylene glycol di-glycerol propylene glycol condensed water ..., polypropylene glycol two: water: water glycerin shout, triol diglycidyl ether,丨,6_hexane II I' oxime ether, neopentyl glycol monoglycerol gyfr glycerol ether, trimethylol..., glycerol condensed c _ —-&amp; glyceryl ether, 2 〇--and- In addition to glycidol, etc., it is also possible to list, as a compound, a neopentyl glycerylamino group. And hydrazine-di-condensed water as the compound of (4) oxidized (9) hydroglycosylamino group in the present invention, 仫 has Ν, Ν-distriction as a specific example thereof, and may be exemplified by -65-5 201206998, Ν, Ν, Ν',Ν'-tetraglycidyl-m-diphenylene diamine, 1,3-bis(indole, Ν-diglycidylaminomethyl)cyclohexane, hydrazine, hydrazine, hydrazine Ν, Ν' -tetraglycidyl-4,4'-diaminodiphenyl decane, hydrazine, hydrazine-diglycidyl-benzylamine, hydrazine, hydrazine-diglycidyl-aminomethyl ί And hydrazine, hydrazine-diglycidyl-cyclohexylamine, and the like, and one or more of these may be used. The blending ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 30 parts by weight or less based on 100 parts by weight of the polyorganosiloxane. [Functional decane compound] Examples of the functional decane compound include 3-aminopropyltrimethoxyxanthene, 3-aminopropyltriethoxysulfate, and 2-aminopropyltrimethoxysilane. Erythroxy, 2-aminopropyltriethoxy oxalate, Ν-(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3 -Aminopropylmethyldimethoxyoxydecane, 3-ureidopropyltrimethoxyoxydecane, 3-ureidopropyltriethoxydecane, oxime-ethoxycarbonyl-3-aminopropyltrimethyl Oxime, Ν-ethoxyxo-3-aminopropyl triethoxy pulverization, Ν-triethoxy decyl propyl triethylidene triamine, Ν-trisethoxy oxime矽alkylpropyltrisethyltriamine, 10-trimethoxymethoxymethylidene-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-tri Azadecane, 9-trimethoxydecylalkyl-3,6-diazadecyl acetate, 9-trimethoxycarbamido-3,6-diazadecyl acetate, 9- Triethoxydecyl-3,6-diazadecyl acetate, 9-trimethoxydecyl-3,6-diazepine decyl ester, 9-three曱矽 曱矽 -3 -3 -3 -3 Ν Ν Ν Ν Ν Ν Ν 卞 卞 卞 卞 卞 卞 卞 卞 卞 Ν Ν Ν Ν Ν 卞 卞 卞 卞 卞 卞 卞 卞 卞 卞 卞 卞 卞 卞 卞201206998 base triethoxy dream, N_ stupyl I aminopropyl trimethoxy money, benzyl-3-aminopropyl triethoxy money, ring "oxymethyl ketone", epoxy Propyloxymethyltriethoxy...2_epoxy = ethyltrimethoxytin, 2_glycidoxyethyltriethoxylated 3-glycidoxypropyltrimethoxyindole ^ ethoxylate eve 6f. lactopropyl propyl:: is a blend of two functional ... ... ... qing "0. The parts by weight ' is preferably 2 parts by weight or less, more preferably 0.2 parts by weight or less. Further, [surfactant] As the above-mentioned surfactant, the anionic surfactant Ν-oxy group can be exemplified by, for example, a nonionic boundary cationic surfactant, two ^ ^ , , . . . Agent, two, agent, 矽顚1 surfactant, poly JS y, field preparation, clothing oxygen, hospital surfactant, surfactant, etc.. μ When the liquid crystal alignment agent of the present invention contains a surfactant, as an example 'Comparative to the total liquid crystal alignment, 〇〇 by weight, preferably less than 1 part by weight, more preferably 1 part by weight or less. [Latent hardener] The above-mentioned latent hardener is a change in the storage of the liquid crystal alignment agent. A component in which a liquid crystal alignment agent is applied and a function of hardening property is obtained by heating. By allowing the liquid I agent of the present invention to contain such a latent cured product, heat resistance and excellentness can be formed. The liquid crystal alignment film simultaneously has excellent storage stability and is preferable.

S-67-(C-1) CH2)m1 (C-2) 201206998 As the latent curing agent in the present invention, it is preferred to have two or more acetal ester structures selected from carboxylic acids in the molecule, 嗣s A compound having at least one structure of a structure, a decanoic acid-based structure, and a tickate structure. The latent hardening has a combination of the same structure of two or more of these structures to have a different structure of two or more of these structures as a group forming the acetal structure of the above carboxylic acid, and the following formula (C- 1) and (C-2) &gt;α —~jj—〇—CH—〇—Ο r~v( (Formula (Cl)t, R« and RP are each 2 carbon atoms, 3 to 1 carbon atoms) a group represented by an alicyclic group of 0, a aryl group of a carbon atom or an aralkyl group having 7 to 〇, a formula (C-2), an integer of 1 )). Here, as (4) of = a group, preferably a methyl group; as an alicyclic hexyl group, as an aryl group, + benzyl is preferably a group; as an aralkyl fluorenyl group, as an alkyl group, it is a weight of an atomic number I~ as an alicyclic ring a group of groups, preferably ® ^ Λ v: soil is thicker than a few ό~1 〇, or 23⁄4 of its 7·Μ· 'soil, as a matter of appearance," fly 2 cumyl, as (2) The ml, preferably the shoulder, may be a compound or a compound, for example, a condensed tertiary butyl reagent such as a carboxylic acid. It is exemplified that /20 of 6 to 10 ml is 2 [formula (C-1)' is preferably ' Preferred is a decyl group; : benzyl or 4. -68-201206998 The group represented by the above formula (C-1), for example, 1-methoxyethoxycarbonyl, 1-ethoxyethoxycarbonyl, 1-n-propoxy Ethoxycarbonyl, 1-isopropoxyethoxycarbonyl, 1-n-butoxyethoxycarbonyl, 1-isobutoxyethoxycarbonyl, 2-butoxyethoxycarbonyl, 1-tertiary Oxyethoxycarbonyl, 1-cyclopentyloxyethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 1-norbornoxyethoxycarbonyl, 1-decyloxyethoxycarbonyl, 1-phenoxy Ethyloxycarbonyl, 1-(1-naphthalenyloxy)ethoxycarbonyl, 1-benzyloxyethoxycarbonyl, 1-phenylethoxyethoxycarbonyl, (cyclohexyl)(methoxy)methoxycarbonyl, (cyclohexyl)(ethoxy)methoxycarbonyl, (cyclohexyl)(n-propoxy)oximeoxycarbonyl, (cyclohexyl)(isopropoxy)oximeoxycarbonyl, (cyclohexyl)(cyclohexyloxy) Anthraceneoxycarbonyl, (cyclohexyl)(phenoxy)methoxycarbonyl, (cyclohexyl)(benzyloxy)methoxycarbonyl, (phenyl)(decyloxy)methoxycarbonyl, (phenyl) (B) Oxy) methoxycarbonyl, (phenyl) (n-propoxy)曱Oxycarbonyl, (phenyl)(isopropoxy)oximecarbonyl, (phenyl)(cyclohexyloxy)oximeoxycarbonyl, (phenyl)(phenoxy)oximeoxycarbonyl, (phenyl) (benzyloxy)methoxycarbonyl, (benzyl)(decyloxy)oximeoxycarbonyl, (benzyl)(ethoxy)oximeoxycarbonyl, (benzyl)(n-propoxy)oximeoxycarbonyl, Benzyl)(isopropoxy)methoxycarbonyl, (benzyl)(cyclohexyloxy)methoxycarbonyl, (benzyl)(phenoxy)methoxycarbonyl, (benzyl)(benzyloxy)methyl An oxycarbonyl group or the like; examples of the group represented by the above formula (C-2) include a 2-tetrahydrofuranoxycarbonyl group and a 2-tetrahydropyranyloxycarbonyl group. Among these groups, preferred is 1-ethoxyethoxymethyl, 1-n-propoxyethoxyphenyl, 1-cyclohexyloxyethoxy, 2-tetrahydropyrene Base, 2-tetrahydro-pyrano-oxyl group, and the like. Examples of the group forming the ketal ester structure of the above carboxylic acid include the following formula (C-3) to (C-5) - 69 - 201206998 (C-3) (C-4) - C - 〇 —C—0—Re

II I 〇 Λδ

(CH2)m2 O o )m3 (C-5) (In the formula (C-3), RY is an alkyl group having a carbon number, ... and γ are each an alkyl group having 1 to 12 carbon atoms, and 3 carbon atoms; An aliphatic group of -20, an aryl group having 6 to 20 carbon atoms or an aryl group having 7 to 2 carbon atoms in the formula (C-4), and R is an alkyl group having 1 to 12 carbon atoms, m2 In the formula (C-5), the group represented by the formula (C-5) is a group of a carbon atom number of 12 and an alkyl group of 2 to 8). Here, the alkyl group of RY as (C-3) is preferably a methyl group, and the alkyl group as R is more preferably a methyl group, and the alicyclic group is preferably a phenyl group. As the aryl group, the second is: A, as a square group, a carbon==6 alkyl group; as an alicyclic group, preferably an alicyclic group having a slave atom number of 6 to 10 is relatively simple. The aryl group is preferably a benzyl group or a group; preferably a phenyl group; a decyl group of 〜, preferably a methyl group; As the burning group of W in the formula (") as the core, the car is preferably 3 or 4, preferably 3 or 4. It is a methyl group; as m3, it is -70. 201206998 as the above formula ( The group represented by C-3) may, for example, be 1-indolyl-1-decyloxyethyl thiol, 1-mercapto-1-ethoxyethoxy methoxy, 1-methyl-1-positive Propyloxyethyl decyl, 1-methyl-1-isopropyllactyloxymethyl, 1-methyl-1-n-butoxyethoxycarbonyl, 1-methyl-1-isobutoxy Oxycarbonyl, 1-mercapto-b-butylbutoxyethoxycarbonyl, 1-mercapto-1-triethoxybutoxycarbonyl, 1-methyl-1-cyclopentyloxycarbonyl, 1 -Methyl-1 -cyclohexyloxyethoxycarbonyl, 1-decyl-1-norpodenyloxyethoxycarbonyl ' 1-indolyl-1-decyloxyethoxycarbonyl, 1-methyl-1 -phenoxyethoxycarbonyl, 1-mercapto-1-(1-naphthalenyloxy)ethoxycarbonyl, 1-methyl-1-benzyloxyethoxycarbonyl, 1-methyl-1-phenylethoxy Ethyloxy group, succinyl-1-anthracene ethoxymethyl group, 1-oxalyl-1-ethoxyethoxymethyl group, 1-3⁄4 hexyl-1-n-propyl propyl ethoxylate, 1-3⁄4 hexyl-1-isopropyloxy-1-ylethoxy group, 1-3⁄4 hexyl_1_cyclohexyloxy Carbonyl, 1-cyclohexyl-1 -phenoxyethoxycarbonyl, 1-cyclohexyl-1-ethoxyethylacetate, 1-phenyl-1-decyloxyethoxy, 1-phenyl- 1-ethoxyethoxycarbonyl, 1-phenyl-1-n-propoxyethoxycarbonyl, 1-phenyl-1-isopropyllactyloxymethyl, 1-phenyl-l- 哀Lactoethoxymethyl, 1-phenyl-1-phenoxyethoxycarbonyl, 1-phenyl-1-benzyloxyethoxycarbonyl, 1-benzyl-1-decyloxyethoxycarbonyl, 1 -benzyl-1-ethoxyethoxycarbonyl, 1-benzyl-1-n-propoxyethoxycarbonyl, 1-benzyl-1-isopropoxyethoxycarbonyl, 1-benzyl-1- Cyclohexyloxyethoxycarbonyl, 1-benzyl-1-phenoxyethoxycarbonyl, 1-benzyl-1-benzyloxyethoxycarbonyl, etc.; as a group represented by the above formula (C-4), For example, 2-(2-mercaptotetrahydrofuranyl)oxycarbonyl, 2-(2-mercaptotetrahydrotetrapyranyloxycarbonyl), and the like; -71-201206998, which is a group represented by the above formula (C-5) For example, a methoxymethoxycyclopentyloxycarbonyl group, a 1-decyloxycyclohexyloxycarbonyl group, etc. may be mentioned. Among these groups, a 1-methyl-1-methoxyethoxymethyl group, 1- Mercapto-1-cyclohexyloxyethoxycarbonyl As the group which forms the structure of the 1-alkylcycloalkyl ester of the above carboxylic acid, for example, the following formula (C-6) _f &quot;~ lean~〇-C-(CH2)m4 (C- 6)

0 CH (in the formula (C-6), 'RK is a group having a carbon number of 1 to 12, and is an integer of -8). Here, 'the base group of C in the above formula' is preferably an alkyl group having 1 to 10 carbon atoms. The group represented by the above formula (C-6) includes, for example, anthracene-methylidene propyloxycarbonyl 'fluorenyl-fluorenylcyclobutoxycarbonyl group, 1-methylcyclopentyloxycarbonyl-t-methylcyclohexyloxycarbonyl group, Base ring heptyloxycarbonyl, ^methylcyclooctane carbonyl 1·methylcycloindole oxycarbonyl, 1-methylcyclodeoxycarbonyl, ethyl ring==rebel, 1-ethylcyclobutoxycarbonyl, 丨_ Ethylcyclopentyloxycarbonyl, 丨_乙旯hexyloxycarbonyl, 1-ethylcycloheptyloxycarbonyl, oxime-ethylcyclooctyloxycarbonyl^ethylcycloindoleoxycarbonyl, 丨_ethylcyclodecyloxycarbonyl i (iso)propyl ==%, 1 (iso)propylcyclobutoxycarbonyl, 丨-(iso)propylcyclopentyloxycarbonyl, 丨^)propylcyclohexyloxycarbonyl ' 1_( Isopropylcycloheptyloxycarbonyl, 1 (iso) VIII: oxime oxo aryl, 1_(iso)propylcyclophosphocarbonyl, 丨-(iso)propyl ring, 1 (iso) butyl Alkyl propyloxycarbonyl, b (iso)butyl ring T oxycarbonyl &quot;(〆,)butylpentyloxy, 1-(iso)butylcyclohexyloxy, 1-(iso)-72- 201206998 Butylcycloheptyloxycarbonyl, 丨_( 壬 几 、, !. (iso) butyl 2 Cyclooctyloxy, isobutyl butyl, 1-(display) pentyl butyl / Hexacarbyl group, 1_(iso)indolylcyclopropoxycarbonyl...butoxyl group, Η))), ethoxycarbonyl, t U)pentylcycloheptyloxycarbonyl ' I· (iso) amyl linkal ruthenium, (iso)pentyl ring, thiol, y-(iso)pentyl oxime oxycarbonyl]-(iso)hexyl propyloxycarbonyl, !-( Iso)hexylcyclopentyloxy, (ex) fluorenyl / butoxymethyl, hexylcycloheptyloxy, hexyl: hexyloxy, "(iso) oxiranyl, (Li)衣衣辛虱非基,〗 〖-(Iso)hexyl ring, W-heteroheptyl ring T-oxygen group, WJ^A =) heptyl-oxy-oxy-heptylcyclohexyloxy, and (/, Heptyl 戍 戍 oxycarbonyl, 〗 〖(()) octyloxy, ^ (a) Geng 壬 壬 heptoxy group, W )) heptyl ring group, W )) Xin Shang soil: Μ base, )) Heptylcyclodecyloxy, '〒 Lane% propylene rolled, b (Li, octyl octylcyclopentyloxy, r (iso)octyl ring = butyl U, W) heptoxycarbonyl, f 4 β Benzyl tetamine, 丨-(iso)octylcyclo-1 (iso)octyl octyl oxycarbonyl, 1-(yl, 丄-(iso)octylcyclononanyl M, etc. (iso)octyl Oxygen Three-butoxy-butoxycarbonyl-called form the carboxylic acid. A ,, said. Configuration of a group refers to three as in the present invention is hard latent

BlmR (C) is preferably the following formula (C) (in the formula (C), Bi is an integer of the above formula (^ a group or a three-stage butoxy drum group, and m is a single number = 1-10) R is a compound derived from a carbon number of 3 to 1 Å, a group obtained by removing 2 m-valent hydrogen, or a compound having a carbon number of K and a substance of 5. The m is preferably a hydrocarbon group. ) -73· 201206998 As a specific example of the above formula 'f \ + 举 single bond, when m is 2, it can be listed, -phenylene 1,3 - # ^ A soil 2,6 - anthranyl, 5 - Sodium sulfonate ^ ''tetrabutyl sulfenyl-1,3_phenylene, etc.; when m is 3', the following formula Ο C2H4' &gt;r /C2H4-

, N

The chain type of the group is better than the straight line.

The base is expressed as a base such as 0, and the use of the latent hardener in the liquid crystal alignment agent is preferably 4 to 4 knives per part by weight of the polyorganosiloxane (a). , Fei Mu to c, λ ^ and 1 soil is 5 to 20 parts by weight. Maximum: Ϊ : When the oxane (4) has an epoxy group, the latent hardener can exert its intended effect to the limit. In this case, it is preferred to use a reducing agent such as an epoxy having an epoxy group, and a acetal ester having a latent hardener of S夂. The structure, the ketal ester of a carboxylic acid, the dialkyl ester structure, and the group of 1-alkyl-species-tertiary ester structures of #萨苒carboxyquinone are up to "~4m〇It Omoi ratio" Preferably, the ratio of the compound represented by the above formula (6) is as follows: when the compound represented by the above formula (6) is used as the curing agent of the formula (6), the ratio of the compound represented by the above formula (c) is compared. The ratio of the epoxy group im〇i to the polyorganic oxygen plant (4) is 0.1/mmol 〜10/mmo, preferably 〇4/mm〇l~4/mm 进一步 进一步 further preferably 1.5/mmol~ 2/mm. In the above, m盥μ bucket, π, θ ^^ /, the above formula (C) 疋 has the same meaning. &lt;Liquid crystal alignment agent&gt; The liquid crystal alignment of the present invention is Nanxun County & 疋 疋 疋 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水The organic compound for use in the liquid crystal alignment agent for the X-ray day of the wooden road can be exemplified by, for example, N-methyl-2_ another machine, and each of the ingredients, γ-butyrolactone, γ-butanide , Ν, Ν-dimercaptomethylamine, γ γ butyl ketone methyl-2-pentanone, ethylene glycol monodiyl 4- 4- Ψ A ® ^ early methyl hydrazine, butyl lactate, vinegar T-methyl-lactyl propionate, B-%, oxy-propionic acid vinegar, ethylene glycol single φ u shout, ethylene glycol monoethyl ether, and early methyl ethyl alcohol early-n-propyl ether, B _ isopropyl ether, ethylene glycol mono-n-alcohol. A I butyl ether (butyl cyproterone), B-age methyl ether, ethylene glycol two technology ^ one alcohol two _ ^ 00 soil Bismuth, ethylene glycol monodecyl ether vinegar, succinyl alcohol ethyl acetate, _7_i 曰, ethyl p, «· , Α monoethylene glycol didecyl ether, diethyl ethyl hydrazine, diethylene Alcohol-stone#—alcohol dipropyl ether, diethylene glycol dibutyl hydrazine, alcohol monomethyl singer, diethylene glycol monoethyl ethane-work, shouting, diethylene glycol mono-ethylene glycol Butyl ether, di-negyl group, St.. wu monoglycol monomethyl ether acetate, -7 is called early ethyl ether acetate, ^—乙二醢。 — Monool monopropyl ether acetate, and butyl ether acetate, di I-ethane, St-Bing Butyl, isoamyl propionate, Sibutate isobutyrate , diisoamyl^isopentyl^, decanoic acid ethyl ester, carbonic acid stretched methanol, ethanol, propanol, butanol, diester propylene-alcohol, acetone, methyl ethyl-75- 201206998 ketone, fluorenyl Butyl ketone, monoethylene glycol, diethylene glycol, monopropylene glycol, monohexanediol, propylene glycol monodecyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, methyl acetate, ethyl acetate, lactate B The ester, dimethyl sulphate, tetramethyl urea, hexamethylphosphoric acid triamide, m-nonyl phenol, etc., are preferably used by selecting one or more of these solvents. In the liquid crystal alignment agent of the present invention, the solid content concentration (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected from the viewpoints of viscosity, volatility, and the like. It is preferably in the range of 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described later, and it is preferred to form a coating film as a liquid crystal alignment film by heating. When the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small. On the other hand, if the solid content concentration exceeds 1% by weight, the film thickness of the coating film is too large, and a good liquid crystal alignment film cannot be obtained. The range of the particularly preferable solid content varies depending on the method used for coating the liquid crystal alignment agent on the substrate. For example, when the spin coater method is used, the solid content is preferably in the range of 丨5 to 7.5% by weight. When the printing method is employed, it is particularly preferable that the solid matter concentration is in the range of 6 to 5% by weight, and thus the solution viscosity is in the range of 8 to 50 mPa.s. In the case of the ink jet method, it is particularly preferred that the solid matter concentration is in the range of 3 to 丨〇% by weight, so that the solution viscosity is in the range of 3 to 15 mPa·s. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably ～50 ° C ', more preferably 2 CTC to 30 ° C. <Method for Producing Liquid Crystal Display Element> The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. -76-201206998 The liquid crystal display element of the present invention can be produced by any of the following methods, for example. It has been known that the liquid crystal display element of the operation mode can be manufactured by the following steps (1) to (3) (Process 1 of the liquid crystal display element). (1) forming a coating step on a substrate using the liquid crystal alignment agent of the present invention, (2) applying a polishing treatment to the surface of the coating film as needed, and (3) forming a liquid crystal cell by holding liquid crystal between the substrates The liquid crystal display element can be manufactured by the light distribution plate on both surfaces of the liquid crystal cell obtained as described above. Further, the liquid crystal display of the new display mode instead of the PSA mode can be manufactured by, for example, the following steps (1') to (3') (Manufacturing Method 2 of Liquid Crystal Display). (1') a step of forming a coating film by dispersing the liquid crystal alignment agent of the present invention on the conductive film of a pair of substrates having a conductive film, and (2') arranging a pair of substrates on which the coating film is formed in the middle The step of aligning the coating film so as to face each other to form a liquid crystal cell, and (3') a step of irradiating the liquid crystal cell with a voltage applied between the conductive films of the pair of substrates. The liquid crystal display element can be manufactured by the liquid crystal cell double-sided polarizing plate after the light obtained in the above manner. Hereinafter, each of the above production methods will be sequentially described. [Manufacturing Method 1 of Liquid Crystal Display Element] An example of a method for forming a square film. The component (1) in the manufacturing method 1 of the liquid crystal display device differs depending on the expected operation mode. Steps (2) and (3) are common to each mode of operation. (1) First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then a coating film is formed on the substrate by heating the coated surface. (1-1) When a TN-type, STN-type or VA-type liquid crystal display element is manufactured, two substrates on which a patterned transparent conductive film is provided are provided as a pair, and it is preferable to use a substrate on each of the transparent conductive films. The liquid crystal alignment agent of the present invention is applied by an offset printing method, a spin coating method or an inkjet printing method, respectively, and then a coating film is formed by heating each coated surface. Here, as the substrate, for example, glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyfluorene; 6 wind, polycarbonate, and poly (fat) can be used. A transparent substrate formed of a plastic such as a cyclic olefin. As the transparent conductive film provided on one surface of the substrate, a NESA film formed of tin oxide (Sn〇2) (registered trademark of PPG, USA), an ITO film formed of indium oxide-tin oxide (IhOrSnO2), or the like can be used. In order to obtain a patterned transparent conductive film ′, for example, a method of forming a pattern by forming a transparent conductive film without a pattern, a method of forming a pattern using a photomask having a desired pattern when forming a transparent conductive film, or the like can be employed. When the liquid crystal alignment agent is applied, in order to make the surface of the substrate and the transparent conductive film and the coating film more excellent, it is also possible to apply a preselected coating functional decane compound or a functional titanium compound on the surface of the substrate surface on which the inner coating film should be formed. Pre-processing. After the application of the liquid crystal alignment agent, in order to prevent liquid dripping of the applied alignment agent, preheating (prebaking) is preferred. The pre-baking temperature is preferably ^ 30 to 200 ° C, more preferably 40 to 150 ° ", the last name is more than 1 Tuma 4U ◦, especially preferably 40 to 100. (:. Pre-baking -78-201206998 baking time It is preferably 〇25 to 10 minutes, more preferably 〇5 to 5 minutes. Thereafter, the solvent is completely removed, and in the case of the production method 1 in which the production of the polyorganismite (8) is removed, The lack of A ^ Gou's monocarboxylic acid 'the firing (post-baking) step. The firing (post-baking) has a warm production (Man). The skill / dish is preferably 80 to 300 ° c, The soil is 120~250 C, the post-baking time is better than 5 in 5 to 200 minutes, and the branch is 10 to 100 minutes. In this way, the film thickness of the film is preferably 1. 〇〇1~;^111, more preferably 〇.〇〇5~〇50111. (1-2) On the other hand, when the IPS type is manufactured, the 7-piece piece is not transparent, and the transparent pattern forming the comb pattern is set. The conductive film surface of the substrate of the conductive film and the opposite substrate on which the conductive film is not provided are coated with a liquid crystal alignment agent, and then heated by each coated surface: at this time of The material of the substrate and the transparent conductive film, the method of applying the transparent lead-side alignment agent and the heating method after coating, and the thickness of the coating are preferably the film (1-1) (2) When the liquid crystal display element manufactured by the method of the present invention is a VA type liquid crystal display element, the coating film formed in the above manner can be directly used as a night crystal alignment film, wherein the following can also be performed as expected. In the case of manufacturing a liquid crystal display element other than VA蜇, it is possible to apply a polishing treatment to the coating film formed as described above to form a liquid crystal alignment film. The polishing treatment can be performed by pressing The coating film surface formed in the above manner is a 5-blade 9-201206998 stick crystal entangled with a cloth formed of fibers such as nylon, rayon, cotton, etc., and the non-liquid crystal improving panel is made of a flat surface of the opposite film. Each of the unit cells is coated in parallel with each liquid phase, and the liquid crystal method 0 is rubbed in a certain direction. Thereby, the alignment ability of the liquid crystal can be imparted to the coating film to form a liquid crystal alignment film. The liquid crystal alignment film which is formed in the above-mentioned manner, as disclosed in the patent document 6 (Japanese Patent Application Laid-Open No. Hei No. Hei 6-222366) and the Japanese Patent Publication No. Hei. A part of the liquid crystal alignment film is irradiated with ultraviolet rays to perform a process of changing the pretilt angle of a part of the liquid crystal alignment, and a photoresist is formed on a part of the liquid crystal alignment film surface as disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. Thereafter, the same polishing treatment as in the previous polishing treatment is performed, and then the treatment of the photoresist film is removed, and each field of the alignment film has a different liquid crystal alignment capability, and the visual field characteristics of the obtained liquid crystal display element are obtained. . (3) Two sheets in which the liquid crystal alignment film was formed as described above were prepared. Waves were formed by disposing liquid crystal between the two substrates arranged in the opposite direction. Here, when the coating film is polished, the two substrates are aligned so that the rubbing directions on the film are at a predetermined angle to each other, for example, orthogonally. For the production of the liquid crystal cell, for example, the following two methods are exemplified. The first method is a method that has been known for a long time. First, two sheets of the substrate are placed in the middle of the film in the middle of the alignment film (the interstitial space), and the peripheral portion of the two substrates is bonded to the cell gap formed by the surface of the substrate and the sealant with a sealant. The liquid crystal cell can be fabricated by injecting and filling the 'closed injection hole'. The first method is a method called an ODF (Dean Drop Fill) method in which a portion such as -80 - 201206998 is coated on one of the two substrates on which the liquid crystal alignment film is formed, for example, an ultraviolet curable sealing material is applied to the crucible. The liquid crystal is dropped on the surface, and then the liquid crystal cell can be manufactured by hardening the liquid helium to the liquid Ha, and then hardening the sealing agent on the substrate. "When the crystal alignment agent contains the liquid oxygen alkane (VIII) invented by the manufacturing methods 2, 3, and II, even in the manufacture of the polyorganisms 叶 方 Fang Fang, manufactured by νΑ &amp; I 6 , In the formula, there is no ODF unevenness, and it is suitable for this method. b. The liquid crystal alignment agent is used here as a sealant to make 5 a β I as a spacer, such as a hardener and a zero oxide. Epoxy resin of the ball, etc. As the liquid crystal, a liquid crystal or the like can be used, and in the case of a white crystal liquid or a smectic crystal of the stalk of the mountain, the scorpion is used in the VA type liquid crystal cell. For example, the nematic liquid crystal of "11" may be, for example, dicyanobenzene liquid crystal, germanium well crystal, oxidized azo liquid crystal, biphenyl plum, 曰', ... Schiff test. In the case where the sputum liquid has a positive liquid crystal cell or an STN type liquid crystal cell, it is preferably an electric anisotropic nematic liquid crystal, J1 liquid. For example, you can use, for example, Lian Bianlian's clumsy system liquid crystal, 酉 系 液晶 liquid crystal, bistriphenyl liquid crystal, octane system', lanthanide liquid 曰曰, 啶 系 liquid crystal, 噚 山 11 mountain liquid crystal, double ring one step Liquid 3 曰, cuba-based liquid crystal, and the like. It is also possible to introduce vinegar and the like in these liquid crystals, such as chlorinated cholesteryl, cholesteric citrate, and cholesteryl carbonate, which are sold under the b. B_15 (manufactured by Merck). Benzyl-to-amino-2-methylbutyl laurate dielectric liquid crystal or the like is used. e -81- 201206998 Regardless of which box, table, stack 4·h, 樘 method, the liquid crystal cell manufactured in the above manner is preferably reheated to the temperature of the liquid crystal used to take the isotropic phase, and then slowly Cooling to room temperature' to eliminate flow alignment during liquid crystal filling. Thus, a liquid crystal display element can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Examples of the polarizing plate include a polarizing plate obtained by stretching and aligning polyvinyl alcohol, and a polarizing film of the (four)-shaped "H film" is lost in a cellulose acetate protective film, or consisting of a ruthenium film itself. Polarizer. [Manufacturing Method 2 of Liquid Crystal Display Element] 0') First, the liquid crystal alignment agent of the present invention is applied to a pair of substrates having a conductive film to form a coating film. The coating film of: can be directly supplied to the following step (2,). It is also possible to apply a polishing treatment such as the step (2) in the production method 1. (2') The pair of substrates on which the coating film is formed are formed into liquid crystal cells in accordance with a layer of mesogenic molecules and the coating film is liquid-phased. 'In the opposite direction, these steps can be carried out in the same way as in the manufacturing method. The helmets LL () to (3) are the liquid crystal molecules used here, and the negligence of the negative dielectric anisotropy is preferably a liquid crystal of the gate type, and it is possible to use, for example, a liquid crystal, Tallon liquid crystal, Schiff system liquid crystal, oxidation: atmosphere biphenyl liquid crystal, phenyl Jf hex p » 'liquid crystal, the degree is preferably 丨 ~ one. It has been burned to the LCD Temple. The thickness of the layer of the liquid crystal molecules is irradiated to the liquid crystal cell in a state in which the conductive film of the counter substrate is applied. For example, -82-201206998 as the irradiated light can be used, for example, ultraviolet light of a long light and visible light, and ultraviolet light of a light of a longer wavelength. For irradiation, a mercury lamp, a high-pressure mercury lamp, a reverberating lamp, a xenon lamp, an excimer laser, or the like, which contains a light source of 150 to 800 nm, preferably containing 300 to 400 nm of light, may be, for example, a low-hydrogen lamp metal toothed lamp or argon. The above-mentioned ultraviolet light preferably in the wavelength region can be obtained by a means for simultaneously using the above-mentioned light source with, for example, a filter, a diffraction grating or the like. The irradiation amount of light is preferably 1,500 J/m2 or more and less than 100,000 J/m2, more preferably ι, 〇〇〇 to 50,000 J/m2. In the manufacture of a PSA mode liquid crystal display element which has been known for a long time, it is necessary to irradiate light of a degree of about 100,000 J/m2, wherein in the method of the present invention, even if the amount of light irradiation is 5 〇, 〇〇〇J / m 2 or less, even when it is 10,000 J/m2 or less, a desired liquid crystal display element can be obtained, and in addition to contributing to reduction in manufacturing cost of a liquid crystal display element, it is possible to avoid deterioration of electrical characteristics due to strong light irradiation, Long-term reliability is low. The liquid crystal display element can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell to which the above-described treatment is applied. As the polarizing plate, the same polarizing plate as in the manufacturing method 1 can be used. EXAMPLES Hereinafter, the present invention will be further specifically described by examples, but the present invention is not limited by these examples. In the following, the weight average molecular weight of the polyorganophosphorus polymer was evaluated by the following method. [Weight average molecular weight] The weight average molecular weight of the polyorganosiloxane polymer was determined by the conversion of -83 to 201206998 using the following apparatus under the following conditions. . Four ethyls. After cold, it contains liquid. The sub-quantity is a polystyrene value using monodisperse polystyrene as a standard substance. Measuring device: Tosoh system model '8120-GPC, column. Tosoh (stock) system, "TSKgelGRCXLII" Solvent: tetrahydrofuran 5 model farming degree: 5 wt% sample injection amount: 1 〇〇μ]: column temperature : 40 ° C Column pressure: 68 kgf / cm 2 &lt;Synthesis of polyorgano-oxane (A) (丨)&gt; Synthesis Example A -1 In: A stirrer, thermometer, dropping funnel and reflux condenser 2 In the Valley M, 13 9 g of oxalic acid and 19 ^ ethanol were poured into the mixture, and the mixture was stirred. Then, the solution was heated to 'under a nitrogen atmosphere, and then a mixture of the mixture of decane compound # 15.lg oxydecane and 1.6e7 oxime-glycidyl diethoxy decane was added dropwise thereto. , kept at 7 〇, UC for 6 hours, then to 2 5 °C, then, 4, „ ^ Add 4〇.〇g butyl 赛 璐, thus made as a polyorgano , &amp; β milk said (Α) polyorganooxane (Α 丨 的) in the δ 亥 海 bath containing the shovel ancient land ^ 1 organic oxiranane (A_i) weight average score Mw is ι2, 00合成. Synthesis Example A - 2 to A -1 〇 In the above Synthesis Example A - 1 τ + &gt; 'The type and amount of Shi Xixuan compound used as a raw material are set by β and the amounts of oxalic acid and ethanol used, respectively. ~ 84 - 201206998 As described in the first step of Table 1, except that the polyorgano-oxygenated gas (A) containing polyorganosiloxane (A) was separately prepared in the same manner as in the above Synthesis Example ( 1 -2) a solution of ~(A_l〇). In Synthesis Examples A-7 and A-8, two kinds of each compound (a2_3) are used. The weight average molecular weight Mw of polyorganisms is shown in Table 1 1 t 'Synthesis Examples A-9 and A-10 are reference synthesis examples. &lt;Synthesis of other polyorganosiloxanes (1) &gt; Synthesis Examples B-1 and B-2 In the above Synthesis Example A-1, the type and amount of the smelting compound used as a raw material, and the amounts of oxalic acid and ethanol used were respectively determined as 1 in Table 1. In the same manner as in the above Synthesis Example A-1, a solution containing polyorganosiloxane (B-1) and (B-2) as other polyorganosiloxanes was prepared in the same manner as described above. The average molecular weight The weight Mw of each polyorganosiloxane contained in each solution is shown in Table 1 and 1. Synthesis Example D -1

The type and amount of 矽A used in the disaster of the small bamboo, and the oxalic acid and ethanol used are as described in Table 1 and 1, in addition to the same method of A-1, the preparation of the bamboo A From the solution of the above synthetic example organic stone sorcerer]). We use two kinds of poly (a2-3) of this. °例巾's sand burning compound

The weight of the polyorganosiloxane contained in the solution I

Mw — is shown in the form of a watch. 9 Knife -85- 201206998 Table 1 of 1 Synthesis of polyorganosiloxane (1) Raw material compound polyorganooxane decane compound oxalic acid (g) Ethanol (g) Name Weight average molecular weight Mw Shixi burning compound (al)矽 化合物 ( ( a a 化合物3.0 TEOS 13.0 - 0.0 13.1 20.9 A-2 11,000 Synthesis Example A-3 VTES 4.3 TEOS 11.1 - 0.0 12.4 22.2 A-3 9,000 Synthesis Example A-4 STMS 1.6 TEOS 13.5 - 0.0 12.4 22.6 A-4 10,000 Synthesis Example A-5 ATES 1.6 TEOS 14.8 - 0.0 13.6 20.0 A-5 13,000 Synthesis Example A-6 MPTMS 1.7 TEOS 13.0 - 0.0 12.0 23.3 A-6 9,000 Synthesis Example A-7 VTES 0.8 TEOS 15.3 - 0.0 14.0 19.2 A-7 13,000 MTES 0.7 Synthesis Example A-8 VTES 0.7 TEOS 14.5 - 0.0 13.3 20.5 A-8 9,000 PTES 0.9 Synthesis Example A-9 (Reference Synthesis Example) APTMS 4.5 TEOS 10.2 ODES 2.5 12.1 21.3 A-9 10,000 Synthesis Example A-10 (Reference Synthesis Example) MPTMS 4.0 TEOS 10.4 DDES 2.2 12.0 20.7 A-10 10,000 Synthesis Example B-1 - 0.0 TEOS 11.1 ODES 2.5 10.2 26.3 B-1 6,000 Synthesis Example B-2 - 0.0 TEOS 12.3 ODES 2.2 11.3 24.2 B-2 9,000 Synthesis Example D-1 - 0.0 TEOS 11.8 - 0.0 11.5 23.1 D-1 9,000 PTES 2.5 The decane compound in Table 1 The abbreviations are as follows. [decane compound (a 1)] VTES : vinyl triethoxy decane STMS : styryl trimethoxy decane ATES · fine propyl diethoxy sec- mp MPTSS : 3-mercapto propylene methoxy propyl Trimethoxydecane APTMS: 3-propenyloxypropyltrimethoxysulfonium [decane compound (a2-l)] TEOS: tetraethoxydecane MTES: methyltriethoxydecane-86-201206998 PTES: Stupyl triethoxy decane [other decane compounds (decane compounds (ahi))] ODES: octadecyl triethoxy sylvestre DDES: 12 decyl triethoxy zebra burned in Table 1 In the compound of Shi Xitong, "_" means that the raw material is not used in this column. &lt;Synthesis of Other Polyorganooxanes (2) &gt; Synthesis Example C-1 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 99 g of 2_(3) as a decane compound was added. 4-Epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone as a solvent and triethylamine as a catalyst were mixed at room temperature. Then, 1 〇〇g of deionized water was added dropwise by means of a dropping funnel over 30 minutes, and the reaction was carried out after the bran continued to disturb 6 在 under reflux of 80 t:. Reaction: After the bundle, 'take out the organic layer 1 0.2% by weight of the ammonium aqueous solution to wash the strip until the washed water is neutral'. The solvent and water are distilled off under reduced pressure to obtain an epoxy group as a viscous transparent liquid. Polyorganosiloxane. For the polyorganic oxime with epoxy group, a &quot;1h_nmr analysis: 'Achieved at a chemical shift of 3 · 2 ppm near the theoretical intensity phase::: peak at the thiol group, it was confirmed that no epoxy group occurred in the reaction. The auxiliary hydrogen aid is also obtained from the organic ash-fired ketone-based ketone-based organic oxalate, 3Gg as a solvent for methyl isobutyl hydrazine, and 3 gram as a carboxylic acid 4-octyloxybenzoic acid. A ring made of (comparative &quot;polyalkyl group of epoxy group; for: 30 mol% of the above soil) and -87- § 201206998 0.10 g as a catalyst for the manufacture of UCAT 18X (trade name, San_Apr〇) Oxygen compound hardening accelerator), the reaction was carried out for 4 hours under 1 〇〇. After the completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with water three times, dried over magnesium sulfate, and the solvent was evaporated to give a polyorganooxane as another polyorganooxane ( C-1)» For the polyorganosiloxane ((&gt;1), the weight average Mw of the polystyrene by gel permeation chromatography is &lt; synthesis of 汆organooxane (A) 2)&gt; In the synthesis of the examples A-ll to A_i6, in the case of C], the combination of the cinnamic acid used as the raw material and the type and amount of the carboxylic acid to be used are respectively set to be 2 or 2 As described above, in the same manner as in the above-mentioned synthesis example cl, the separation of the gas osmosis (AU) ~ (A l6 ^ t polyorganisms oxynphos (A) by gel permeation chromatography Polystyrene B: Drag these poly(oxygen) by 2_ together with the weight average molecular weight Mw in the synthesis example A·14~A]6, two acids are used respectively. 201206998 Table 1 of 2 Synthesis of polyorganosiloxanes (2) Raw material compounds Polyorganosiloxanes, sulfonium compounds Decane Compound Carboxylic Acid Weight Average (al) (a2-l) (1-1 ) (1-2' Name Molecular Weight Species Type Species Type Species Mw (g) (g) (g) (g) Synthesis Example C-1 - 0.0 ECETS 99.0 OCTBA 30.0 - 0 C-1 7,200 Synthesis Example Α-11 MPTMS 24.8 ECETS 73.9 OCTBA 30.0 - 0 Α-11 7,100 Synthesis Example Α-12 MPTMS 93.7 ECETS 147.8 PCHBA 41.2 - 0 A-12 7,600 Synthesis Example MP-13 MPTMS 124.2 ECETS 123.2 SACE 48.9 - 0 Α-13 7,600 Synthesis Example MP-14 MPTMS 123.0 ECETS 117.0 SACE 49.0 AQCA 0.15 Α-14 7,200 Synthesis Example MP-15 MPTMS 123.0 ECETS 117.0 SACE 49.0 AQCA 0.15 Α-15 7,200 Synthesis Example Α-16 MPTMS 99.0 ECETS 148.0 OCTBA 75.0 DAHBBA 16.0 Α-16 7,3 简称 The abbreviations of decane compounds and carboxylic acids in Table 1 bis are as follows: [decane compound (al)] MPTMS : 3 - mercapto propylene methoxy propyl trimethoxy decane [decane compound (a2-l)] ECETS : 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane [carboxylic acid (1-1 )] OCTBA: 4-n-octyloxybenzoic acid PCHBA: 4-(4-n-pentyl-cyclohexyl)benzoic acid SACE: succinic acid - 5ξ-cholreane-3- [Carboxylic acid (2)] AQCA: anthraquinone-2-carboxylic acid DAHBBA: 2- (4- diethylamino-2-hydroxy - phenyl Yue acyl) - benzoic

In the column of the Shixia compound and the tartrate column of Table 1 and 2, "_" indicates that the material is not used in the barrier. -89- 201206998 &lt;Synthesis of Polyorganooxane (A) (3)&gt; Synthesis Example A -1 7 In the reaction vessel equipped with an ifurerator, thermometer, dropping funnel and reflux condenser As a decane compound, $124.2g 3-methylpropenyloxypropyldimethoxyl 11 (MPTMS) and 12.2g 2. (3,4-cyclo-cyclohexyl)ethyltrimethoxy zebra (ECETS) 50 gg of decyl isobutyl ketone &amp; i 0 0 g of triethylamine as a solvent was mixed at room temperature. Then, deionized water hydrazine g was added dropwise thereto through a dropping funnel over 30 minutes, and then mixed under reflux, and reacted at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out, washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing was neutral, and the solvent and water were distilled off under reduced pressure to obtain an epoxy group-containing polymer as a viscous transparent liquid. Organic oxirane. For the polyorgano oxy-oxygen with epoxy group, when the iH_NMR analysis was performed, an epoxy group-based peak having the same theoretical strength was obtained near the chemical shift (δ) = 3.2 ppm, and it was confirmed that no epoxy occurred in the reaction. The side reaction of the base. Then, in a 20 mL three-necked flask, the above-obtained polyorganooxime having an epoxy group, 30 g of methyl isobutyl ketone as a solvent, and 42.1 g of 4-n-decyl-4 as a reductive acid were added. Bicyclohexyl group (PBCHCA) (corresponding to 60 mol% of the epoxy group of the above-mentioned polyorganosite having an epoxy group) and 0.10 g of uc AT 18X as a catalyst (trade name 'San-Apro' The hardening accelerator of the produced epoxy compound was stirred at 100 ° C for 48 hours to carry out a reaction. After the completion of the reaction, ethyl acetate was added to the reaction mixture. The obtained organic layer was washed with water three times, dried over magnesium sulfate, and the solvent was removed to obtain a poly-polyoxane (A) as -90·201206998. Organooxane (A-1 7). With respect to the polyorganosiloxane (A-1 7), the polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography was 4,500. Synthesis Example A-18 to A-23 In the above Synthesis Example A-1, the type and amount of the decane compound used as the raw material, and the type and amount of the carboxylic acid to be used are respectively set as shown in Table 3 In the same manner as in the above Synthesis Example A-1, a polyorganosiloxane (A-18) to (A-23) as a polyorganosiloxane (A) was obtained in the same manner. For these polyorganosiloxanes, the polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography is shown in Table 3 of Table 1. In Synthesis Examples A-22 to A-23, two kinds of carboxylic acids were used. Table 1 3 Synthesis of polyorganosiloxane (3) Raw material compound Polyorganooxime calcined stone compound compound carboxylic acid name Weight average molecular weight Mw decane (a): decane compound (a2-l) decane compound (a2-2) Carboxylic acid (1-1) Carboxylic acid (1-2) Species (g) Species (g) Species (g) Species (g) Species (g) Synthesis Example A-17 MPTMS 124.2 ECETS 123.2 - 0 PBCHA 42.1 - 0 A-17 4,500 Synthesis Example A-18 APTMS 117.2 ECETS 123.2 - 0 OCTBA 37.5 - 0 A-18 4,900 Synthesis Example A-19 APTMS 117.2 ECETS 123.2 - 0 PCHBA 41.2 - 0 A-19 5,300 Synthesis Example A-20 APTMS 117.2 ECETS 123.2 - 0 SACE 73.3 - 0 A-20 4,200 Synthesis Example A-21 APTMS 100.2 ECETS 105.3 TEOS 44.7 SACE 41.7 - 0 A-21 4,500 Synthesis Example A-22 - 0 ECETS 123.2 - 0 PCHBA 27.4 ACDHA 75.1 A-22 4,200 Synthesis Example A-23 MPTMS 62.1 ECETS 184.8 - 0 PCHBA 27.4 - 0 A-23 4,500 CNPPA 44.0 -91- 201206998 The abbreviations for decane compounds and carboxylic acids in Table 1 of 3 are as follows: . [decane compound (al)] MPTMS : 3-mercapto propylene methoxy propyl trimethoxy decane APTMS . 3- propylene helium propyl tridecyloxy decane [Shi Xi burning compound (a 2 -1) ECETS : 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane [Shi Xizhuo Compound (a2-2)] TEOS: Tetraethoxy oxime [carboxylic acid (1-1)] PBCHA. 4-n-pentylcarboxybicyclohexyl OCTBA : 4_n-octyloxybenzoic acid PCHBA : 4-(4-n-pentyl-cyclohexyl)benzoic acid SACE : succinic acid · 5 ξ · cholestane _3_ CNPPA I 2Ε-3(4-(((3-cyanophenyl))) oxy)phenyl)propan-2-enoic acid [carboxylic acid (1-2)] ACDHA: 6-{[6·( Synthesis of propylene decyloxy) hexyl hydrazide] oxonium hexanoic acid <Polyorgano oxoxane (A) &gt; Synthesis Example A-24 equipped with a stirrer, thermometer, dropping funnel and reflux condenser Into the reaction vessel, 67 g of 3-propenyloxypropyltrimethoxydecane (APTMS) as a decane compound, 125 g of mercaptoisobutylphosphonium as a solvent, and 2.5 g of triethylamine were added and mixed at room temperature. Then, 25 g of deionized water was added dropwise by means of a dropping funnel over a period of 30 minutes, and then mixed at -92 to 201206998 under reflux, and reacted at 80 C for 6 hours. After the anti-corridor hits you Han Ying,··°, the 'organic layer is taken out, and the mixture is washed with 0. 2% by weight of ammonium nitrate, vine, and soil V* + , and β dy The water is neutral. The solvent and water are distilled off under reduced pressure to give a polyorganosiloxane having a carbon-carbon double bond as a viscous transparent liquid.

Then, in a 200 mL three-necked flask, the above-obtained polyorganisms having a carbon-carbon double bond, B. No. 4 as a solvent, and MW as a nucleophilic compound of a thiol 3 # w4 base bile were added. Acetone (CH〇sh) and 6.68 g of triethylamine as a catalyst were stirred and stirred at 50 C for 90 minutes to carry out a reaction. After the reaction is completed, add T-based isobutyl ketone i, 〇〇〇g, and then remove the solvent and catalyst under the reduced sputum, and you can pay for it as a polyorgano oxime (A). Polyorganosiloxane (A_24). For the polyorganosiloxane (A-24), the polystyrene had a molecular weight Mw of 4,100 as determined by gel permeation chromatography. Synthesis Example A-25 In the above Synthesis Example A-24, 67 g of 3-propenyloxypropyltrimethoxy decane (ΑρτΜ(9) and μ% tetraethoxy ruthenium (Τ) were used as a mixture of decane compounds, Otherwise, polyorganooxime (Α-25) as a polyorganooxazepine (4) was obtained in the same manner as in the above Synthesis Example Α24. For the polyorganosiloxane, by gel permeation chromatography The measured polystyrene-equivalent weight average molecular weight PCT was 4,8 〇〇^ &lt;Synthesis of other polyorganooxanes (4) &gt; Synthesis Examples Ε-1 and Ε-2 In the above Synthesis Example Α-24 In the above, the type and amount of the decane compound used as the raw material, and the type and amount of the thiol to be used are each as described in Table 1 and 4, except for the above-mentioned synthesis-93-201206998 Example A. Polyorganosiloxane (E-1) and (E-2), which are other polyorganosiloxanes, are obtained in the same manner as in -24. For these polyorganosiloxanes, they are determined by gel permeation chromatography. The polystyrene-equivalent weight average molecular weight Mw is shown in Table 1 and 4. Table 1 4 Synthesis of polyorganosiloxane (4) Raw material compound polyorganooxazepine compound nucleophilic compound name weight average molecular weight Mw decane 彳t (a) compound decane compound (a2-2) thiol species amount (g) species amount ( g) Species (g) Synthesis Example A-24 APTMS 67 - 0 CHOSH 34.7 A-24 4,500 Synthesis Example A-25 APTMS 67 TEOS 14.9 CHOSH 34.7 A-25 4,900 Synthesis Example E-1 APTMS 67 - 0 TGA 13.2 E- 1 5,300 Synthesis Example E-2 APTMS 67 - 0 MPA 15.2 E-2 4,200 The abbreviations of the decane compound and the thiol in Table 1 are the following meanings: [decane compound (al)] APTMS: 3-propenyloxy group Propyltrimethoxy oxime [decane compound (a2-3)] TEOS: tetraethoxy decane [thiol] CHOSH : 3-mercapto cholesteric TGA: thioglycolic acid MPA: 3-mercaptopropionic acid Example 1 &lt;Preparation of Liquid Crystal Aligning Agent&gt; Addition of a butyl group to a solution containing the polyorganooxyl (A-1) obtained in the above Synthesis Example A-1 as a polyorganosiloxane (A) Road stepping, shape -94- 201206998 The concentration of solids is 5 weights 0 / dip w, 6 ^ υ ^ 里 / 〇, 谷液. Using a screening program with a pore size of 1 μιη This solution is used to prepare a liquid crystal alignment agent. <Manufacture and Evaluation of VA Type Liquid Crystal Display Element> [Manufacture of VA Type Liquid Crystal Display Element] A liquid crystal alignment agent which is coated with a spin coater and coated with a spin coater It is coated on a transparent electrode surface of a glass substrate with a transparent film and a bead formed by a ruthenium film, and prebaked at 80 ° C for 1 minute, and then produced. 隹 - 7 - $ After baking in a nitrogen-substituted oven at 200 ° C for 1 hour, you can take the p, p factory. i f 攸 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 Repeat 兮SS, Jt}c 1.' Η. The 疋 疋 刼 ’ ’ 制成 制成 制成 制成 制成 制成 制成 。 。 。 。 一对 一对 一对 一对 一对 一对 一对 一对 一对 一对 一对 一对On the outer periphery of the surface of the one of the substrates having the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5 alumina balls is applied by screen printing, and then the liquid crystal alignment film faces of the pair of substrates are relatively opposed. The mixture was heated and pressed, and heated at i 50 ° C for 2 Torr to thermally harden the adhesive. Then, a negative liquid crystal (manufactured by Merck Co., Ltd., ΜΙΧ·6608) was filled from the liquid crystal injection port to the gap between the substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive to remove the flow alignment during liquid crystal injection. Heat at 50 °C for 1 〇 minutes, then slowly cool to room temperature. Further, a polarizing plate was bonded to the two outer surfaces of the substrate so that the polarization directions thereof were orthogonal to each other, thereby manufacturing a VA liquid crystal display element. [Evaluation of V A type liquid crystal display element] The VA type liquid crystal display element manufactured as described above was evaluated in the following manner. The evaluation results are shown in Table 2. (1) Evaluation of liquid crystal alignment property When the voltage of 5 V was ON.OFF (applied and removed) on the liquid crystal display element manufactured as described above, it was visually observed whether or not there was an abnormality in the change in brightness and darkness. 201206998 At this time, no light leakage was observed when the electric dust was turned off, and the driving area was white when the voltage was applied. 'When the light leakage is not present in other areas, the liquid crystal alignment is regarded as "good", and when the light leakage is observed, it is regarded as liquid crystal. Orientation is "bad". TM (2) Evaluation of ultraviolet ray resistance The iv voltage was applied to the liquid crystal display element manufactured above in accordance with the application time of 6 〇 microseconds and the span of 16.67 msec, and the measurement was performed after the release voltage was 16.67 msec. Voltage holding ratio (initial voltage holding ratio vhrbi). The measuring device used "VHR-1" manufactured by Toyo Technica Co., Ltd. For the liquid crystal display element after the initial electric power retention rate measurement, the 卤, 〇〇〇J/m2 ultraviolet light was irradiated with a metal halide lamp having an illuminance of 800 W/m 2 and then allowed to stand at room temperature and naturally cooled to room temperature. . Next, the voltage holding ratio (voltage holding after irradiation + VHRM) was measured again in the same manner as described above. By the following mathematical formula (1)

VHRB1~VHRAI rate of change (%) = XI 〇〇(1) VHRbi calculates the rate of change of the voltage holding ratio at this time. When the value is 95% or more, the ultraviolet resistance is evaluated as "excellent", and is 90% or more and less than 95. In the case of %, the ultraviolet resistance was evaluated as "good", and when it was less than 9%, the ultraviolet resistance was evaluated as "poor". Examples 2 to 8, 11 and 12, and Comparative Examples 1 and 2 The types and amounts of the polyorganosiloxane (A) to be used were respectively set as described in '2', and the above examples were also used. 1 phase-96-201206998 In the same manner, a liquid crystal alignment agent was prepared and a liquid crystal display element was produced. Further, "one" in the table indicates that the evaluation results in this column are not used in Table 2. Further, 'Examples 1 1 and 12 are reference examples. Example 9 In a solution containing the polyorgano-oxygen (A-1) obtained by the above synthesis as a polyorganosiloxane (A), the weight of the above-mentioned polyorgano-oxygen (Al) 100 wt. To the mixture, a compound (C-1) obtained in the above Synthesis Example C-1 was added in an amount of 5 parts by weight, and a solution of a solid concentration of % was formed by adding butyl cyanidin. The solution was filtered using a screening procedure with a pore size of 1 μηι to prepare a liquid crystal alignment agent. Using the liquid crystal alignment agent, a liquid crystal display element was produced in accordance with the above-described first embodiment and evaluated. "The evaluation results are shown in Table 10, and the types of polyorganosiloxanes and other polyorganisms to be used and The liquid crystal display element liquid crystal display element was prepared and evaluated in the same manner as in the above-described Example 9, except that the amounts were respectively set as described in Table 2. The evaluation results are shown in Table 2, in Example 13, in a solution containing polyorganosiloxane (D-1) obtained from the above D 1 ^ 作为 as another polyorganosiloxane, in the &amp; Polyorganosiloxane (0-1) 90 parts by weight of a polyheterocarbon (A-1 1 ) obtained by the above Synthesis Example A-1 1 added with a 10-heavy polyglycol oxime (Α), and then Add butyl celecoxime to form a solid concentrate for the evaluation Α-1 solution for other machine 矽 oxygen 5 weight, and thus the same square.珍 Oxygen-fired, Manufactured by 〇 Synthesis Example The above solvent was used as a solution having an organic stone concentration of 5 201206998% by weight. The solution was filtered using a screening procedure of a pore size of 1 μm to prepare a liquid crystal alignment agent. Using this liquid crystal alignment agent, a liquid crystal display element was produced and evaluated in the same manner as in the above Example 1. The evaluation results are shown in Table 2. Example 1 4 to 1 8 The amount of the other polyorganosiloxane used and the type and amount of the polyorganooxane were set as described in Table 2, and the above was carried out in addition to the above. In the same manner as in Example 13, a liquid crystal alignment agent was prepared, and a liquid crystal display element was produced and evaluated. The evaluation results are shown in Table 2, Example 1 9 in a solution containing polyorganooxynonane (Α-6) obtained as the polyorganohydrogenated oxime (上述), which is obtained by the above Synthesis Example Α-6, with respect to the above 100 parts by weight of the polyorganococcal oxime (Α-6) in the solution, 8 parts by weight of a compound represented by the following formula (Β-1 -1) which is another additive and which is a polymerizable unsaturated compound, and a butyl group is added. The sputum formed a solution having a solid concentration of 5% by weight. The solution was filtered using a screening procedure of a pore size of 1 μm to prepare a liquid crystal alignment agent. Using this liquid crystal alignment agent, a liquid crystal display element was produced and evaluated in the same manner as in the above Example 1. The evaluation results are shown in Table 2. Example 20 to 23 A liquid crystal alignment agent was prepared and evaluated in the same manner as in the above Example 19 except that the type and amount of the other additives to be used were set as described in Table 2, respectively. . Two other additives were used in each of these examples. -98- 201206998 The results of the evaluation are shown in Table 2. Example 24 The polyorganosiloxane (A-1 7) obtained in the above Synthesis Example A-1 7 as a polyorganosiloxane (A) was dissolved in butyl siatone to form a solid concentration of 5 % by weight solution. The liquid crystal alignment agent was prepared by filtering the solution using a screening method of a pore size of 1 μηη. Using this liquid crystal alignment agent, a liquid crystal display element was produced and evaluated in the same manner as in the above Example 1. The evaluation results are shown in Table 2. Examples 25 to 32 A liquid crystal alignment agent was prepared in the same manner as in the above Example 24, except that the type and amount of the polyorganosiloxane used were set to those described in Table 2, and A liquid crystal display element was produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2, Examples 33 and 34, and a solution containing the polyorganosiloxane (Α-12) obtained in the above Synthesis Example A-1 2 as a polyorganosiloxane (Α) (equivalent to 10 parts by weight of the polyorganosiloxane (Α-12) in an amount of 90 parts by weight, 10 parts by weight of the polyorganosiloxane (Fl) obtained in the above Synthesis Example F-1 as another polyorganosiloxane. Example 33) or polyorganosiloxane (F-2) (Example 34), followed by the addition of butyl quercetin to form a solution having a solids concentration of 5% by weight. The solution was filtered using a screening procedure with a pore size of 1 μηι to prepare a liquid crystal alignment agent. Using this liquid crystal alignment agent, a liquid crystal display element was produced and evaluated in the same manner as in the above Example 1. The evaluation results are shown in Table 2. -99-201206998 Example 3 5 A solution containing a polyorganosiloxane (A-12) obtained from the above Synthesis Example A-1 2 as a polyorganosiloxane (A) (corresponding to polyorganosiloxane) (A-12) 100 parts by weight), 10 parts by weight of ginxyl (1 -butoxyethyl)benzene-1,3,5-tricarboxylic acid which is a latent hardener added as another additive Further, butyl siatone was added to form a solution having a solid concentration of 5% by weight. The solution was filtered using a screening procedure of a pore size of 1 μm to prepare a liquid crystal alignment agent. Using this liquid crystal alignment agent, a liquid crystal display element was produced and evaluated in the same manner as in the above Example 1. The evaluation results are shown in Table 2. -100- 201206998 Table 2 Liquid crystal alignment agent and evaluation results (1) Liquid crystal alignment agent Liquid crystal display element Polyorganosiloxane other additives Liquid crystal alignment initial voltage retention ratio (%) UV resistance polyglycol Other polyorganooxane type (parts by weight) Type (parts by weight) Type of seed (parts by weight) Example 1 A-1 100 - 0 - - - Good 99 Excellent Example 2 A-2 100 - 0 - - - Good 98 Excellent Example 3 A-3 100 - 0 - - - Good 97 Good Example 4 A-4 100 - 0 - - - Good 99 Excellent Example 5 A-5 100 - 0 - - - Good 98 Excellent Example 6 A-6 100 - 0 - - - Good 98 Excellent Example 7 A-7 100 - 0 - - - Good 98 Excellent Example 8 A-8 100 - 0 - - - Good 98 Excellent Example 9 A-1 100 C-1 5 - - - Good 98 Excellent Example 10 A-6 100 C-1 5 - - - Good 98 Excellent Example 11 (Reference Example) A-9 100 - 0 - - - Good 98 Excellent Example 12 (Reference example) A-10 100 - 0 - - - Good 98 Excellent Example 13 A-11 10 D-1 90 - - - Good 98 Excellent Example 14 A-12 5 D-1 95 - - - Good 98 Excellent Example 15 A-13 8 D- 1 92 - - - Good 98 Excellent Example 16 A-14 8 D-1 92 - - - Good 98 Excellent Example 17 A-15 10 D-1 90 - - - Good 98 Excellent Example 18 A-16 20 D -1 80 α Α-ΒΡ-2ΕΟ 8 Good 98 Excellent Example 19 A-6 100 - 0 α PBCHPM 10 Good 98 Excellent Example 20 A-6 100 - 0 α M-211B 10 Good 98 Excellent (2nd table Continued) -101 - 201206998 Table 2 Liquid Crystal Aligning Agents and Evaluation Results (1) (Continued) Liquid Crystal Aligning Agent Liquid Crystal Display Element Polyorganooxane Polyorganooxane Other Polyorganic Other Additives Liquid Crystal Initial Electrical Resistance Purple (8) 矽Oxygenation pressure maintaining external line type (parts by weight) Type (parts by weight) Type of seed (parts by weight) Property rate (%) · Example 21 Α-6 100 0 α MACE 10 Good QO Excellent α A-BP -2EO 10 Example 22 Α-6 100 0 α A-BP-2EO 10 Good 99 Excellent β K-BMS 0.1 Example 23 Α-6 100 0 α M-211B 8 Good 98 Excellent Ί GA-80 1 Example 24 Α-17 100 - 0 - - - Good 99 Excellent Example 25 Α-18 100 - 0 * - - Liang 97 Excellent Example 26 Α-19 100 - 0 - - - Liang 97 Excellent Example 27 Α-20 100 - 0 - - - Liang 97 Excellent Example 28 Α-21 100 - 0 - - - Liang 97 Excellent Example 29 Α-22 100 - 0 - - - Liang 97 Excellent Example 30 Α-23 100 - 0 - - - Liang 97 Excellent Example 31 Α-24 100 Ink 0 - - - Liang 97 Excellent Example 32 Α-25 100 - 0 - - - Liang 97 Excellent Example 33 Α-12 90 Ε-1 10 - - - Liang 97 Excellent Example 34 Α-12 90 Ε-2 10 - - - Liang 97 Excellent Example 35 Α-12 100 - 0 δ TBEBC 10 Good 99 Excellent Comparative Example 1 - 0 Β-1 100 Ink - Good 99 Poor Comparative Example 2 0 Β-2 100 - - Good 99 Poor (End of Table 2) The abbreviations of the components in Table 2 are as follows. [Other Additives] Species α: Polymerizable unsaturated compound Α-ΒΡ-2ΕΟ : Compound Μ-211Β represented by the following formula (Μ-1-1): η is 2 in the following formula (Μ-1-2) Mixture of ～4 compounds MACE: mercapto acrylate-5ξ-cholalkan-3-yl PBCHPM: 4-(4,-n-pentyl-dicyclohexyl-4-yl)phenyl acrylate-102- 201206998

K-BMS : KAYACURE BMS(Ciba Speciality

Chemicals company) γ: Free radical scavenger GA-80 : Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) Species δ: latent hardener TBEBC: ginseng (1 - butoxyethyl) benzene _135_ three Carboxylic acid Example 3 6 &lt;Production of liquid crystal cell&gt; Using the liquid crystal alignment agent prepared in the above Example 2, the pattern (three types) of the transparent electrode and the ultraviolet irradiation amount (three levels) were changed to produce a total of nine The liquid crystal display element ' was evaluated in the following manner. [Production of Liquid Crystal Cell Having a Patternless Transparent Electrode] The liquid crystal alignment agent prepared in the above Example 2 was applied to a transparent electrode having a ruthenium film by using a liquid crystal alignment film printer (manufactured by Nippon Photographic Co., Ltd.). The transparent substrate of the glass substrate is at 8 〇. The solvent was removed by heating (prebaking) on a hot plate for 1 minute, and then heated (post-baking) on a hot plate of i5 (rc) for 1 minute to form a coating film having an average film thickness of 6 Å. The film was polished by a polishing machine having a parent-child wrapped with rayon cloth at a speed of 4 rpm, a platform moving speed of 3 cm/sec, and a velvet-103-201206998 hair-injection length of 0.1 mm. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a 1 〇〇 &lt;^ cleaning oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair ( Two sheets of the substrate having the liquid crystal alignment film. The polishing treatment is a weak polishing treatment for controlling the tilting of the liquid crystal and performing the alignment division by a simple method. Then, for one of the pair of substrates, An epoxy resin adhesive to which an alumina ball having a diameter of 5 μm is applied is coated on the outer edge of the surface of the liquid crystal alignment film, and then the pair of substrates are overlapped and pressed so that the liquid crystal alignment film faces are opposed to each other, so that Then, a liquid crystal cell is produced by filling a liquid crystal injection port between a pair of substrates by nematic liquid crystal (MLC-6608, manufactured by Merck) and then sealing the liquid crystal injection port with an acrylic photocurable adhesive. Three liquid crystal cells having a pattern-free transparent electrode were produced, one of which was directly used for the pretilt angle evaluation described later. For the other two liquid crystal cells, light was applied by applying a voltage between the conductive films by the following methods, respectively. After that, it is used for the pretilt angle and the voltage holding ratio ^ ^ valence. β For the two liquid crystal cells obtained above, a voltage of 60 Hz is applied between the electrodes, and a voltage of 60 Hz is applied to the liquid crystal. The ultraviolet irradiation device as a light source irradiates ultraviolet rays at an irradiation dose of p 10,000 J/m 2 or 100,000 J/m 2 , and the irradiation amount is a value determined by using a light amount leaf having a wavelength of 3 65 nm as a measurement standard. 201206998 [Evaluation of Pretilt Angle] For each of the liquid crystal cells manufactured as described above, according to Non-Patent Document 1 (TJ Scheffer et. al., J. Appl. Phys. νο1·48, pl 783 (1 977)) and Non-Patent Document 2 (F. Nakano et. al., JPN. J. Appl. Phys. ν〇1·19, P20 13 (1 980)), by using He The value of the inclination angle of the liquid crystal molecules to the substrate surface measured by the crystal rotation method of -Ne laser is used as the pretilt angle. The liquid crystal cell which is not irradiated, the irradiation amount is 1 〇, the liquid crystal cell of 〇〇〇J/m2 and the irradiation amount The respective pretilt angles of the liquid crystal cells of 100,000 J/m 2 are shown in Table 3. [Production of Liquid Crystal Cell (1) Having Patterned Transparent Electrode] The liquid crystal alignment agent prepared in the above Example 2 was patterned into a slit shape as shown in Fig. 1, and each had an IT 〇 electrode divided into a plurality of regions. The glass substrate Α and each electrode surface of the crucible were coated with a liquid crystal alignment film printer (manufactured by 曰本写真印刷), and heated (prebaked) on a hot plate of 8 〇 for 丨 minutes to remove the solvent. It was heated (post-baked) on a hot plate of ruthenium for 1 , to form a coating film having an average film thickness of 6 〇〇. Ultra-sonic cleaning for ultra-pure water for i minutes in ultra-pure water, followed by drying in a cleaning oven of TC for 1 minute to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair. (two sheets) a substrate having a liquid crystal alignment crucible. Then, for one of the pair of substrates, an epoxy resin adhesive to which an alumina sphere having a diameter of 5 5 mm is applied is coated on the outer edge of the surface having the liquid crystal alignment film ' Then, the substrate is superposed and pressed in such a manner that the liquid crystal alignment film faces are opposed to each other to harden the adhesive. Then, a nematic liquid crystal is filled between the pair of substrates from the liquid crystal-105-201206998 injection inlet (Merck) Company MLC-6608), and then used acrylic light-curing adhesive to seal the liquid inlet to manufacture liquid crystal cells. Repeat the above operation to manufacture three liquid crystal cells with patterned transparency. One of them is directly used for the evaluation of response speed described later. For the remaining two liquid crystal cells, by applying the voltage state between the conductive turns in the same manner as the above-described method of manufacturing the unpatterned transparent liquid crystal cell, according to 10,000 J/m 2 or 100 The irradiation amount of 000 J/m 2 was used for evaluation of response speed after shooting. Also, the electrode pattern used here is the same pattern as that of the pattern in the PSA mode. [Evaluation of response speed] Configured to be orthogonally polarized The two polarizing plates in the state sandwich the liquid crystal cells described above, and then first irradiate the light lamp without applying a voltage. The luminance of the light transmitted through the liquid crystal cell is measured by a light multimeter, and the relative transmittance is 〇%. In the same manner as described above, the transmittance sH value when the AC voltage of 60 V was applied between the electrodes of the cells was measured as the relative transmittance of 1 〇〇%. When 6 〇v AC voltage was applied to each liquid crystal cell at this time. The time when the transmittance was shifted from 10% to 9〇% was measured, and this time was defined as the speed. The liquid crystal cell which was not irradiated, the 肊 of the irradiation amount of 10,000 J/m2, and the sensitization 1 were 1 〇〇, 〇 The respective responses of the liquid crystal cells of 〇〇J/m2 are shown in Table 3. The electrode of the crystal is injected. The electrode of the illuminating electrode is visible in the liquid, which will respond to the liquid crystal velocity -106-.201206998 [with Patterned transparent electrode Production of Liquid Crystal Cell (2) Using the liquid crystal alignment agent prepared in the above Example 2, glass substrates A and B each having an ITO electrode patterned into a fishbone shape as shown in Fig. 2 were used, except Further, a liquid crystal cell having an unilluminated liquid crystal cell, an irradiation amount of 10,000 J/m 2 , and an irradiation amount of 1,100,000 J/m 2 were produced in the same manner as in the production of the liquid crystal cell (1) having the above-described patterned transparent electrode. The liquid crystal cell was used for the evaluation of the response speed in the same manner as described above. The evaluation results are shown in Table 3. Example 3 7 to 6 7 and Comparative Examples 3 to 5 As the liquid crystal alignment agent, Table 3 was used, respectively. A total of nine liquid crystal display elements were produced and evaluated in the same manner as in the above-described Example 23 except for the liquid crystal alignment agents prepared in the examples or the comparative examples. The evaluation results are shown in Table 3. -107-201206998 Table 3 Evaluation results (2) Example No. and Comparative No. of the liquid crystal alignment agent were evaluated. Liquid crystal cells having a patterned electrode having liquid crystal cells without pattern electrodes (1) Liquid crystal cells having patterned electrodes (1) 2) Pretilt angle 〇 response speed (msec) Response speed (msec) Ultraviolet radiation (J/m2) Purple ray exposure (J/m2) Purple ray exposure (J/m2) 0 10,000 100,000 0 10,000 100,000 0 10,000 100,000 Example 36 Example 2 89.8 89.4 89.1 54 52 47 53 49 40 Example 37 Example 3 89.7 89.3 89.0 54 51 45 53 46 37 Example 38 Example 4 89.8 89.4 89.1 54 52 49 54 49 45 Implementation Example 39 Example 5 89.8 89.3 89.0 54 50 46 53 46 37 Example 40 Example 6 89.8 89.3 89.0 54 50 46 53 46 36 Example 41 Example 9 89.8 89.4 89.1 54 52 47 53 31 26 Example 42 Example 10 89.8 89.5 89.2 54 52 48 51 33 27 Example 43 (Reference example) Example 11 (Reference example) 89.9 89.2 88.1 52 43 38 52 36 27 Example 44 (Reference example) Example 12 (Reference example) 89.9 89.0 88.3 52 40 35 51 33 24 Example 45 Implementation 13 89.9 89.2 88.8 52 48 38 51 39 32 Example 46 Example 14 89.9 89.2 88.8 53 48 38 51 39 32 Example 47 Example 15 89.8 89.2 88.8 52 48 38 51 40 33 Example 48 Example 16 89.9 88.5 88.2 52 41 34 51 30 25 Example 49 Example 17 89.9 88.4 88.1 52 38 33 51 29 24 Example 50 Example 18 89.9 88.3 88.0 52 37 31 51 28 23 Example 51 Example 19 89.9 88.6 80.5 52 38 26 51 32 19 Example 52 Example 20 89.9 88.8 82.4 52 42 34 51 33 21 Example 53 Example 21 89.8 88.2 79.3 53 36 24 51 30 18 (Table 3 to be continued) -108- 201206998 Table 3 Evaluation results (2) (Continued Example No. and Comparative Example No. Evaluation Results of Liquid Crystal Aligning Agent Liquid Crystal Cell with Patterned Electrode (1) Liquid Crystal Cell with Patterned Electrode (2) Pretilt Angle Response Velocity (msec) Response speed (msec) Ultraviolet exposure (J/m2) Ultraviolet illumination = 1 Bu amount (J/m2) Ultraviolet illumination * Amount (J/m2) 0 10,000 100,000 0 10,000 100,000 0 10,000 100,000 Example 54 Example 22 89.8 88.4 79.8 54 37 25 52 31 18 Example 55 Example 23 89.9 89.1 86.2 51 44 35 51 34 22 Example 56 Example 24 89.9 89.2 88.9 54 44 41 52 43 37 Example 57 Example 25 89.8 89.0 88.5 54 40 46 52 38 29 Example 58 Example 26 89.8 89.3 88.8 54 43 37 51 42 34 Example 59 Example 27 89.9 89.5 89.0 55 52 49 51 44 37 Example 60 Example 28 89.8 89.6 89.0 54 53 49 51 43 36 Example 61 Example 29 89.9 89.1 88.4 54 43 37 53 38 30 Example 62 Example 30 89.8 89.2 88.6 55 44 37 53 39 31 Example 63 Example 31 89.8 89.4 89.0 55 51 46 53 44 36 Example 64 Example 32 89.8 89.3 89.1 55 53 48 52 43 37 Example 65 Example 33 89.9 89.1 88.4 54 43 39 53 39 29 Example 66 Example 34 89.9 89.3 88.6 54 42 37 51 38 32 Example 67 Example 35 89.8 89.2 88.7 54 42 37 51 37 30 Comparative Example 3 Comparative Example 1 89.8 89.8 89.8 54 54 54 52 52 52 Comparative Example 4 Comparative Example 2 89.8 89.8 89.8 54 54 54 52 52 52 Comparative Example 5 Comparative Example 3 89.9 89.6 89.5 55 54 54 52 50 48 (End of Table 3) For Example 6 below 8 to 8 5 and Comparative Examples 6 and 7 were used for confirmation The liquid crystal alignment agent of the present invention has an excellent vertical alignment constraint. As a too severe test for the perpendicular alignment, the vertical alignment of the formed liquid crystal alignment film was evaluated using a TN liquid crystal which originally had a tendency to be aligned. Example 68 As the liquid crystal alignment agent, the liquid crystal alignment agent prepared in the above Example 13 was used, and as the liquid crystal, the TN liquid crystal "ZLI-508 1" manufactured by Merck Co., Ltd. was used, and the above Example 1 was used. The VA liquid crystal display element was produced in the same manner as in the "manufacture of the VA liquid crystal display element", and the same evaluation as "(1) Evaluation of liquid crystal alignment property" was performed. -109-201206998 As a result, when the voltage of 5 V is turned ON/OFF (applied/released) on the liquid crystal display element described above, no light leakage is observed when the voltage is OFF, and the drive area is white when the voltage is applied, and no other area is generated. Light leakage, liquid crystal alignment is "good." Example 6 9 to 8 5 and Comparative Examples 6 and 7 As the liquid crystal alignment agent, the liquid crystal alignment agents prepared in the examples or reference examples listed in Table 4 were used, respectively, and the above-mentioned Example 6 8 was used. A VA type liquid crystal display element was produced in the same manner, and the liquid crystal alignment property was evaluated. The evaluation results are shown in Table 4. Table 4 Evaluation of Vertical Alignment Binding Force Example No. and Comparative Example No. Vertical Alignment Formulation of Liquid Crystal Aligning Agent Example 68 Example 13 Good Example 69 Example 14 Good Example 70 Example 15 Good Example 71 Example 16 good embodiment 72 embodiment 17 good embodiment 73 embodiment 18 good example 74 embodiment 24 good example 75 embodiment 25 good example 76 embodiment 26 good example 77 example 27 good example 78 Example 79 Example 29 Good Example 80 Example 30 Good Example 81 Example 31 Good Example 82 Example 32 Good Example 83 Example 33 Good Example 84 Example 34 Good Example 85 Example 35 Good Comparative Example 6 Example 11 (Reference Example) Defective Comparative Example 7 Example 12 (Reference Example) Defective -110-201206998 From Table 4, it is understood that the liquid crystal alignment film of the liquid crystal of the present invention uses TN liquid crystal as a liquid. Excellent vertical alignment binding. The liquid crystal alignment film which empirically shows such a result does not cause ODF to be poured even in the liquid crystal filling liquid crystal dropping method (ODF method). [Simple description of the drawing] Fig. 1 shows a transparent conductive film having a pattern. BRIEF DESCRIPTION OF THE EMBODIMENT AND COMPARATIVE EXAMPLE FIG. 2 is an explanatory view showing a bright conductive film pattern having a patterned transparent conductive film, which is formed by an embodiment and a comparative example [main element symbol description]. Crystal 'is also not shown, as unevenness is used in the display step. The liquid crystal cell is made through. The liquid crystal cell is made through. A glass substrate B glass substrate 1 ITO electrode 2 slit portion 3 light shielding film -111

Claims (1)

201206998 VII. Patent application scope: 1 · A liquid crystal alignment agent' is characterized in that it contains a polyorganosiloxane, and the polyorganosiloxane has a group containing a polymerizable carbon-carbon double bond, wherein 'the Except for the polyoxosiloxane obtained by polycondensation of the compound represented by the formula (II) and the alkoxydecane of the compound represented by the following formula (2), RASi(〇RB)3 (!) RCSi(〇RD)3 (2) (1) wherein 'rA is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted by a fluorine atom' rb is an alkyl group having 1 to 5 carbon atoms; in the formula (2), Rc is an acryloyl group or a methacryl group A thiol-substituted alkyl group, RD is a thio group having 1 to 5 carbon atoms. (2) The liquid crystal alignment agent according to the first aspect of the invention, wherein the polymerizable carbon-carbon double bond-containing group is a group represented by the following formula (A), "CH2~c- (A)" In (A), R is a hydrogen atom or a methyl group, and χ1 and χ11 are respectively i, 4_ a phenyl group, a fluorenylene group or an alkylene group having 2 to 8 carbon atoms, and Z is an oxygen atom, -COO- or - 0C0- 'where the connection key with "*" is on the X11 side - a, b, c and d are 0 or 1, respectively, where c is 〇 and d is 1 'X11 is ι, 4- benzene Base, when b is 0, d is 〇. The liquid crystal alignment agent according to the second aspect of the invention, wherein the polyorganooxacin is obtained by a step of polycondensation of a rhododendron compound containing a compound represented by the following formula (al), -112 - 201206998 R II· •Si(〇Ri) 4**e (a1 ) and d are respectively with an alkyl group of up to 12, in the formula (al), R, X1, Xn, Z, a, b, and The meaning in A) is the same, and Ri is an integer having a carbon number e of 1 to 3. The liquid crystal compound described in the above formula (a) includes the compound represented by the above formula (al) and the compound shown, (R5)h(R6). iSi(OR7)4.hi (a2-2) Formula (a2-2) X, R5 is a valence group having an epoxy group, Μ is an alkyl group having 1 to 3 carbon atoms, and R7 is a carbon atom number ~ ... Mountain U's base or stone anti-atomic number 6~12 aryl, h is an integer from 1 to 3. Λ 默, 1 is an integer of 〇~2, where h+i$3, and 'the above poly organic The oxane is obtained by a step of polycondensation of an upper blocking compound and then reacting with a carboxylic acid, wherein the carboxylic acid comprises a carboxylic acid having a group represented by the following formula (D,), R1+Zl (D, &gt; In the formula (D), 'R1 is a group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, a cyano group or a fluorine atom, or a carbon atom number thereof having a steroid skeleton a hydrocarbon group of 7 to 5 1; Z1 is a single bond '*_〇_, *_c〇〇- or 〇CO-, wherein a bond having 1' is on the R1 side, and R11 is a cyclohexylene group or a benzene extension. a base in which the cyclohexyl group or a phenyl group is It is substituted by a cyano group, a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms, and -113-201206998 nl is a formula 9 wherein, when nl is 2, two R丨丨 can also be It can be different from 'n2' or 1; "* is a single key, -〇·, *-C〇〇- or *-oco-, where," the connection key is on the Ri side, and 113 is an integer from 0 to 2. , n4 is 〇 or i. 5. If applying for the patent age map, ^ the liquid crystal alignment agent described in 3 items, the above-mentioned oxoxane is subjected to polycondensation by the above decane compound, and then k is composed of an amine and an alcohol a nucleophilic compound obtained by the step of at least one nucleophilic reaction in the group, wherein the nucleophilic compound comprises a nucleophilic compound of the group represented by the above formula (D'). In the liquid crystal alignment agent according to the above aspect, the above-described machine gas oxygenation is obtained by a step of calcining a compound represented by the above formula (a2_2) to carry out polycondensation and then reacting with a carboxylic acid, and the method comprises the above formula ( A) a slow acid of the group indicated. * The liquid crystal alignment agent according to item 6 of the patent application scope, the above one A carboxylic acid comprising a group represented by the above formula (〇'). The liquid crystal aligning agent according to claim 6, wherein the oxime is subjected to polycondensation by the above decane compound, followed by carboxylic acid reaction. And then obtained by a step of reacting with at least one compound selected from the group consisting of an amine and a thiol, wherein the nucleophilic substance comprises a nucleophilic compound having the group represented by the above formula (D,). The liquid crystal agent according to any one of the items 1 to 8, which is a vertical alignment type. The liquid crystal display element is characterized in that the liquid crystal alignment agent according to any one of claims 1 to 8 is formed to form a crystal alignment film. A liquid-114-201206998 11 method for producing a liquid crystal display element, wherein the carboxylic acid is condensed with a nucleophilic compound. Passing: a liquid crystal alignment agent according to any one of claims 1 to 8 is applied to the conductive film of a pair of substrates having a conductive film, thereby forming a coating film to form the coating film. The pair of substrates are disposed such that the liquid crystal molecules are interposed therebetween and the coating film is opposed to each other to form a liquid crystal cell. The liquid crystal cell is applied to a state in which a voltage is applied between the conductive films of the pair of substrates. The step of lighting. -115-