JP5866897B2 - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element - Google Patents

Description

The present invention relates a liquid crystal aligning agent, a liquid crystal alignment film, the production how the liquid crystal display element and a liquid crystal display device.

  Conventionally known liquid crystal display elements include horizontal alignment types such as TN mode, IPS mode, and FFS mode, and vertical alignment types such as VA mode. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. Conventionally, polyamic acid, polyimide, polyester, polyorganosiloxane and the like are known as materials constituting the liquid crystal alignment film. For example, Patent Document 1 discloses a liquid crystal aligning agent containing a polyorganosiloxane obtained by reacting a mixture of trifunctional and tetrafunctional hydrolyzable silane compounds in the presence of oxalic acid and alcohol.

  In recent years, as a new technique for expressing the pretilt angle characteristics, a polymerizable component that is polymerized by light is mixed in the liquid crystal, and a voltage is applied to the liquid crystal so that the liquid crystal molecules are tilted and aligned. The PSA (Polymer Sustained Alignment) technology that controls the molecular orientation of the liquid crystal by polymerizing the polymerizable component by irradiating light in the inclined state, and the polymer thin film having a photofunctional group such as a cinnamoyl group Alternatively, a photo-alignment technique for imparting anisotropy to a film by irradiating non-polarized radiation has been proposed (for example, see Patent Documents 2 and 3).

JP-A-9-281502 JP 2003-149647 A JP 2009-36966 A

  By the way, in the manufacturing process of a liquid crystal aligning film, defects, such as a pinhole and a coating film nonuniformity, may arise in the coating film formed on the board | substrate using the liquid crystal aligning agent. In this case, the coating film may be peeled off from the substrate and the substrate may be reused. In such rework, it is required that the peeling property of the coating film on the substrate is good. In addition, in order to improve the liquid crystal alignment film, it is required to improve the peelability of the coating film and to improve the electrical characteristics such as voltage holding ratio and responsiveness to voltage change.

The present invention has been made in view of the above problems, and is formed using a liquid crystal aligning agent that can provide a liquid crystal aligning film that exhibits good electrical characteristics and has excellent peelability from a substrate, and the liquid crystal aligning agent. by liquid crystal alignment film and a liquid crystal display device, and a main object thereof is to provide a manufacturing how the liquid crystal display device.

  The present invention employs the following means to achieve the above object.

The liquid crystal aligning agent of the present invention is at least selected from the group consisting of a carboxyl group, a hydroxyalkyl group, —NHR ¹ (where R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and a mercapto group. It contains a specific group-containing polyorganosiloxane (S1) having one specific group.

  By including the specific group-containing polyorganosiloxane (S1), the liquid crystal aligning agent of the present invention can be easily peeled off from the substrate in rework when a coating film applied on the substrate has a defect. A liquid crystal alignment film can be formed. In addition, a liquid crystal alignment film having favorable electrical characteristics such as a voltage holding ratio and a response speed to a voltage change can be formed.

Moreover, when forming a liquid crystal display element by PSA technique or a photo-alignment technique, the process includes irradiating a coating film formed on a substrate with a liquid crystal aligning agent, for example, radiation such as ultraviolet rays. Therefore, there is a possibility that inconveniences such as deterioration of electrical characteristics of the formed liquid crystal alignment film may occur due to the irradiated radiation. In particular, in the PSA technique, a large amount of radiation of, for example, 10,000 J / m ² or more may be irradiated for polymerization of the polymerizable component, and electrical characteristics are likely to deteriorate due to the irradiation of radiation. In that respect, according to the liquid crystal aligning agent of this invention, the liquid crystal aligning film which can endure such a large amount of radiation irradiation (it was excellent in radiation resistance) can be obtained.

As said specific group containing polyorganosiloxane (S1), what contains the said specific group 7 * 10 < ^-6 > ^-4 * 10 < ^-4 > [mol / g] per solid content weight of this specific group containing polyorganosiloxane. preferable. By including such a specific group-containing polyorganosiloxane (S1), a liquid crystal alignment film that can be easily peeled off from the substrate during reworking while improving liquid crystal alignment and responsiveness to voltage changes is formed. Can do.

（式（Ｓ１−１）〜式（Ｓ１−４）中、Ｚ^１は、単結合、炭素数１〜６のアルカンジイル基、又は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−若しくは−ＮＲ^２−（但し、Ｒ^２は、水素原子又は炭素数１〜６のアルキル基である。）よりなる群から選ばれる少なくとも一種を含む炭素数１〜２０の２価の有機基である。「＊」は、珪素原子との結合手であることを示す。） Moreover, as said specific group containing polyorganosiloxane (S1), what has a structure represented by either of following formula (S1-1)-a formula (S1-4) is preferable.

(In Formula (S1-1) to Formula (S1-4), Z ¹ represents a single bond, an alkanediyl group having 1 to 6 carbon atoms, or —O—, —S—, —COO—, —OCO— or -NR ² - (where, ^{R 2} is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) is a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of. “*” Indicates a bond with a silicon atom.)

（式（Ｓ１−４ａ）及び式（Ｓ１―４ｂ）中、Ｒ^３及びＲ^５は、それぞれ独立に炭素数１〜６のアルカンジイル基であり、Ｒ^４は、水素原子又は炭素数１〜３のアルカンジイル基であり、Ｒ^７は、炭素数２〜６のアルカンジイル基である。Ｚ^２は、硫黄原子又は−ＮＲ^２−（但し、Ｒ^２は、水素原子又は炭素数１〜６のアルキル基である。）である。「＊」は、珪素原子との結合手であることを示す。）

（式（Ｓ１−１ａ）〜式（Ｓ１−３ａ）中、Ｒ^６は、単結合又は炭素数１〜６のアルカンジイル基である。Ｒ^８は、炭素数１〜３のアルカンジイル基であり、Ｒ^９は、単結合又は炭素数１〜６のアルカンジイル基であり、Ｙは、単結合又は酸素原子である。但し、Ｒ^９が単結合の場合、Ｙは単結合である。「＊」は、珪素原子との結合手であることを示す。） The specific group-containing polyorganosiloxane (S1) has a structure represented by the following formula (S1-4a) or formula (S1-4b) as the structure represented by the formula (S1-4). Those having the structures represented by the following formulas (S1-1a) to (S1-3a) as the structures represented by any of the above formulas (S1-1) to (S1-3) Is preferred.

(In Formula (S1-4a) and Formula (S1-4b), R ³ and R ⁵ are each independently an alkanediyl group having 1 to 6 carbon atoms, and R ⁴ is a hydrogen atom or 1 to 3 carbon atoms. R ⁷ is an alkanediyl group having 2 to 6 carbon atoms, Z ² is a sulfur atom or —NR ² — (wherein R ² is a hydrogen atom or having 1 to 6 carbon atoms. (It is an alkyl group.) “*” Indicates a bond with a silicon atom.)

(In Formula (S1-1a) to Formula (S1-3a), R ⁶ is a single bond or an alkanediyl group having 1 to 6 carbon atoms. R ⁸ is an alkanediyl group having 1 to 3 carbon atoms. , R ⁹ is a single bond or an alkanediyl group having 1 to 6 carbon atoms, and Y is a single bond or an oxygen atom, provided that when R ⁹ is a single bond, Y is a single bond. "Indicates a bond with a silicon atom.)

The liquid crystal aligning agent of the present invention, further, the specific group-containing polyorganosiloxane (S1) other polyorganosiloxane (S2) to including non. By further including such a polyorganosiloxane, the adjustment of the content of the specific group with respect to the whole polyorganosiloxane contained in the liquid crystal aligning agent and the addition of functions other than the function derived from the specific group are compared. Can be done easily.

  It is preferable that the liquid crystal aligning agent in this invention contains an epoxy group containing polyorganosiloxane (S2a) as said other polyorganosiloxane (S2). By containing the polyorganosiloxane (S2a) having an epoxy group, the electrical characteristics of the formed liquid crystal alignment film, for example, the response speed to a voltage change can be further improved.

（式（Ｘ２−１）中、Ａは、酸素原子又は単結合であり、ｈは、１〜３の整数であり、ｉは、０〜６の整数である。但し、ｉが０の場合、Ａは単結合である。式（Ｘ２−２）中、ｊは、１〜６の整数である。「＊」は珪素原子との結合手であることを示す。） As said epoxy group containing polyorganosiloxane (S2a), what has group represented by a following formula (X2-1) or a formula (X2-2) is preferable.

(In Formula (X2-1), A is an oxygen atom or a single bond, h is an integer of 1 to 3, and i is an integer of 0 to 6. However, when i is 0, (A is a single bond. In formula (X2-2), j is an integer of 1 to 6. “*” represents a bond to a silicon atom.)

  The liquid crystal display element of this invention comprises the liquid crystal aligning film formed with the said liquid crystal aligning agent. Therefore, the liquid crystal alignment film can be easily peeled from the substrate during reworking, and a liquid crystal display element with good electrical characteristics can be obtained.

  In the method for producing a liquid crystal display element of the present invention, a coating film is formed by applying the liquid crystal aligning agent on the conductive film of a pair of substrates having a conductive film, and the pair of substrates on which the coating film is formed. A step of forming a liquid crystal cell having a configuration in which the coating film is opposed to each other with a liquid crystal layer interposed therebetween, and irradiating the liquid crystal cell with light in a state where a voltage is applied between the conductive films of the pair of substrates. It is characterized by that.

  The liquid crystal alignment film formed from the liquid crystal aligning agent of this invention is excellent in radiation resistance. Therefore, the liquid crystal display device manufactured by the method of the present invention can exhibit good electrical characteristics even after the light irradiation step.

The top view which shows the pattern of the transparent electrode patterned by slit shape. The top view which shows the pattern of the transparent electrode patterned by fishbone shape.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention contains a polyorganosiloxane as a polymer component, and in particular, a carboxyl group, a hydroxyalkyl group, —NHR ¹ (where R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and It contains a polyorganosiloxane having at least one specific group selected from the group consisting of mercapto groups (specific group-containing polyorganosiloxane (S1)). In addition to the specific group-containing polyorganosiloxane (S1), the polyorganosiloxane contained in the liquid crystal aligning agent of the present invention may contain other polyorganosiloxanes other than the specific group-containing polyorganosiloxane (S1) as necessary. Organosiloxane (S2) may be included. Hereinafter, the polyorganosiloxane contained in the liquid crystal aligning agent of the present invention will be described in detail.

<Specific group-containing polyorganosiloxane (S1)>
Particular groups containing polyorganosiloxane in the present invention (S1), the side chain of the polyorganosiloxane backbone, a carboxyl group, a hydroxyalkyl group, -NHR ¹ (where, ^{R 1} represents a hydrogen atom or 1 to 6 carbon atoms The structure is not particularly limited as long as at least one specific group selected from the group consisting of an alkyl group and a mercapto group is introduced. As the specific group, a carboxyl group or a hydroxyalkyl group is particularly preferable.

The content of the specific group in the specific group-containing polyorganosiloxane (S1) is specified from the viewpoint of improving the releasability of the coating film in the rework while improving the liquid crystal orientation and the response to the voltage change It is preferably 7 × 10 ⁻⁶ to 4 × 10 ⁻⁴ [mol / g] per weight of solid content of the group-containing polyorganosiloxane (S1). More preferably, it is 1 * 10 < ^-5 > -3.5 * 10 < ^-4 > [mol / g], More preferably, it is 3 * 10 < ^-5 > -2.5 * 10 < ^-4 > [mol / g].

（式（Ｓ１−１）〜式（Ｓ１−４）中、Ｚ^１は、単結合、炭素数１〜６のアルカンジイル基、又は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−若しくは−ＮＲ^２−（但し、Ｒ^２は、水素原子又は炭素数１〜６のアルキル基である。）よりなる群から選ばれる少なくとも一種を含む炭素数１〜２０の２価の有機基である。「＊」は、珪素原子との結合手であることを示す。） Specifically, the specific group-containing polyorganosiloxane (S1) has the specific group by having a structure represented by any of the following formulas (S1-1) to (S1-4) in the side chain. Can be.

(In Formula (S1-1) to Formula (S1-4), Z ¹ represents a single bond, an alkanediyl group having 1 to 6 carbon atoms, or —O—, —S—, —COO—, —OCO— or -NR ² - (where, ^{R 2} is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) is a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of. “*” Indicates a bond with a silicon atom.)

The alkanediyl group having 1 to 6 carbon atoms in Z ¹ in the above formulas (S1-1) to (S1-4) may be linear or branched. For example, a methylene group or ethylene Group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-diyl group and the like.
Examples of the divalent organic group having 1 to 20 carbon atoms in ^{Z 1, -O -, - S} -, - COO -, - OCO- or ^-NR 2 - ^{(R 2} is an alkyl group having 1 to 6 carbon atoms ) As long as it has at least one selected from the group consisting of 1 to 10 carbon atoms. The divalent organic group may contain a cyclic structure, but preferably has only a chain structure.

Hereinafter, about the detail of specific group containing polyorganosiloxane (S1), when it has a structure represented by Formula (S1-1)-Formula (S1-3), and a structure represented by Formula (S1-4) The explanation will be made sequentially in the case of having it. First, the case where it has a structure represented by Formula (S1-4) is demonstrated.
[When having a structure represented by the formula (S1-4)]
When the specific group is introduced into the side chain of the polyorganosiloxane skeleton by the structure represented by (S1-4), the production method is not particularly limited.
(1) A carboxylic acid having a mercapto group or —NHR ² (wherein R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) on the polyorganosiloxane (S3) having a (meth) acryl group. A method of Michael addition of the compound (1-4A),
(2) A polyorganosiloxane having a mercapto group or —NHR ² (wherein R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) (hereinafter, a polyorganosiloxane having a mercapto group or an amino group ( S4)), and (Micha) addition of (meth) acrylic acid compound (1-4B),
Etc. can be manufactured. Hereinafter, in the case of manufacturing by the method (1), the case of manufacturing by the method (2) will be described sequentially.

{When manufacturing by the method of (1) above}
-Polyorganosiloxane (S3) having a (meth) acryl group The polyorganosiloxane (S3) having a (meth) acryl group used in the method (1) is preferably a silane compound having a (meth) acryl group ( sa) or a mixture of a silane compound (sa) having a (meth) acryl group and another silane compound, preferably in the presence of a suitable organic solvent, water and catalyst, or hydrolysis or hydrolysis / condensation. Can be synthesized.

（式中、Ｒ^３は、炭素数１〜６のアルカンジイル基であり、Ｒ^４は、水素原子又は炭素数１〜３のアルカンジイル基である。「＊」は、珪素原子との結合手であることを示す。） As the silane compound (sa) having the (meth) acryl group, for example, those having a group represented by the following formula (sa-1) as a monovalent group bonded to a silicon atom are preferable.

(In the formula, R ³ is an alkanediyl group having 1 to 6 carbon atoms, and R ⁴ is a hydrogen atom or an alkanediyl group having 1 to 3 carbon atoms. “*” Is a bond with a silicon atom. (Indicates that

  Examples of the silane compound (sa) having such a (meth) acrylic group include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and 3-methacrylic acid. Examples include roxypropyltriethoxysilane. In addition, as a silane compound (sa) which has a (meth) acryl group, you may use individually by 1 type and may be used in combination of 2 or more type.

  Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, Trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, Fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, Rutriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) ) Ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (tri Fluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltri Methoxy Lan, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2 -(Perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluorosilane Fluoro-n-octyl) ethyltri-i-propoxysilane, 2- (Perful Oro-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane,

Hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec- Butoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyl Trimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysila Allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec -Butoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxy Silane,

(Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i -Propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (Methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercapto Propyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di-n -Butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl ) (Vinyl) di-n-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, Divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n- Lopoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxy Silane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane , (Ethoxy) (methyl) diphenylsilane,

3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane Silane compounds having one silicon atom such as 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane Besides,

Product names such as KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X -21-5848, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22 -176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672 , X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-10 3, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, manufactured by Shin-Etsu Chemical Co., Ltd.);
Glass resin (manufactured by Showa Denko KK); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray Dow Corning); FZ3711, FZ3722 (The above is made by Nippon Unicar Co., Ltd.);
DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (manufactured by Chisso Corporation);
Methyl silicate MS51, Methyl silicate MS56 (above, manufactured by Mitsubishi Chemical Corporation);
Examples thereof include partial condensates such as ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.); GR100, GR650, GR908, GR950 (manufactured by Showa Denko Co., Ltd.).

  Among these, as other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3 -Glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenol Le trimethoxysilane, phenyl triethoxysilane, one or more selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane are preferred.

  The use ratio of the silane compound (sa) having a (meth) acryl group is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 40 mol% or more with respect to other silane compounds.

Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane (S3) having a (meth) acryl group include hydrocarbons, ketones, esters, ethers, alcohols, and the like.
Of these, examples of the hydrocarbon include toluene and xylene;
Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone;
Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate;
Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;
Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl. Examples include ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like. Of these, it is preferable to use a water-insoluble organic solvent. In addition, these organic solvents can be used individually or in mixture of 2 or more types.

The amount of the organic solvent used when synthesizing the polyorganosiloxane (S3) having a (meth) acryl group is preferably 10 to 10,000 parts by weight, more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the total silane compound. 1,000 parts by weight.
The amount of water used in producing the polyorganosiloxane (S3) having a (meth) acryl group is preferably 0.5 to 100 times mol, more preferably 1 to 30 times the total silane compound used. Is a mole.

Examples of the catalyst that can be used when synthesizing the polyorganosiloxane (S3) having a (meth) acryl group include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, and the like.
Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, and various Lewis acids.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
Examples thereof include quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide preferable.

Among these, an alkali metal compound or an organic base is preferable as the catalyst. In this case, the storage stability of the liquid crystal aligning agent containing the said specific group containing polyorganosiloxane (S1) obtained by reaction with the polyorganosiloxane (S3) which has a (meth) acryl group, and carboxylic acid compound (1-4A). Can be very excellent. The reason for this is that, as pointed out in Non-Patent Document 1 (Chemical Reviews, Vol. 95, p1409 (1995)), when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis and condensation reaction, a random structure, It is presumed that a ladder structure or a cage structure is formed and a polyorganosiloxane having a low silanol group content is obtained. When the content ratio of the silanol group is small, the condensation reaction between the silanol groups is suppressed, and when the liquid crystal aligning agent of the present invention contains the other polymer described later, the silanol group and the other polymer Since the condensation reaction is suppressed, it is assumed that the storage stability is excellent.
As the catalyst, an organic base is particularly preferable. The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate. For example, the amount is preferably 0.01 to 3 moles relative to the total silane compound, More preferably, it is 0.05-1 times mole.

The hydrolysis or hydrolysis / condensation reaction in producing the polyorganosiloxane (S3) having a (meth) acrylic group is carried out with a silane compound (sa) having a (meth) acrylic group and, if necessary, another silane compound. Is preferably dissolved in an organic solvent, and this solution is mixed with an organic base and water and heated by, for example, an oil bath.
During the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux.
After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by weight is preferable because the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the solvent is removed to achieve the target. A polyorganosiloxane having a (meth) acryl group can be obtained.
In the present invention, commercially available polyorganosiloxane (S3) having a (meth) acryl group may be used. As such a commercial item, AC-SQ, MAC-SQ (above, Toagosei Co., Ltd. product) etc. can be mentioned, for example.

The polyorganosiloxane (S3) having a (meth) acryl group used for synthesizing the specific group-containing polyorganosiloxane (S1) has a polystyrene equivalent weight average molecular weight of 500 measured by gel permeation chromatography (GPC). It is preferable that it is -100,000, It is more preferable that it is 1,000-10,000, Furthermore, it is preferable that it is 1,000-5,000.
In synthesizing the specific group-containing polyorganosiloxane (S1), the polyorganosiloxane (S3) having a (meth) acryl group can be used singly or in combination of two or more.

（式中、Ｒ^５は、炭素数１〜６のアルカンジイル基であり、Ｚ^２は、硫黄原子又は−ＮＲ^２−（但し、Ｒ^２は、水素原子又は炭素数１〜６のアルキル基である。）である。） Carboxylic acid compound (1-4A) The carboxylic acid compound (1-4A) used in the above method (3) is a mercapto group or -NHR ² (where R ² is a hydrogen atom or a carbon number of 1 to 6). A carboxylic acid derivative having an alkyl group.). Examples of such a carboxylic acid compound (1-4A) include, as a mercapto group-containing compound, thioglycolic acid, mercaptopropionic acid, mercaptobutanoic acid, 4-mercaptobenzoic acid, N-acetylcysteine, etc .; Examples of the compound include amino acid derivatives such as glycine and alanine, 4-aminobenzoic acid, sarcosine, and the like. Among these, the carboxylic acid compound (1-4A) is preferably represented by the following formula (1-4A-1).

(In the formula, R ⁵ is an alkanediyl group having 1 to 6 carbon atoms, Z ² is a sulfur atom or —NR ² — (where R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Yes.)

  As the carboxylic acid compound (1-4A), those having a mercapto group are preferable, and thioglycolic acid or mercaptopropionic acid is particularly preferable.

（式中、ａ及びｅは、それぞれ独立に４〜２０の整数であり、ｂ、ｃ及びｄは、それぞれ独立に２〜１０の整数である。） The specific group-containing polyorganosiloxane (S1) of the present invention may have a group (liquid crystal alignment group) for imparting liquid crystal alignment. In order to introduce the liquid crystal alignment group into the specific group-containing polyorganosiloxane (S1), for example, a compound (alignment group-containing compound) for imparting liquid crystal alignment to the polyorganosiloxane (S3) having a (meth) acryl group. (7)) can be reacted.
Examples of such an orientation group-containing compound (7) include the following formulas (7A-1) to (7A-6) and formulas (7B-1) to (7B-3). Among these, the compounds represented by the following formula (7A-1), formula (7A-3), or formula (7A-6) are preferable, and those having a of 7 to 17 are particularly preferable.

(In the formula, a and e are each independently an integer of 4 to 20, and b, c and d are each independently an integer of 2 to 10).

-Reaction of polyorganosiloxane (S3) having (meth) acrylic group and carboxylic acid compound (1-4A) of polyorganosiloxane (S3) having (meth) acrylic group and carboxylic acid compound (1-4A) The reaction can be carried out according to the known Michael addition reaction, preferably in the presence of a suitable catalyst depending on the type of the carboxylic acid compound (1-4A) used.

  In the above addition reaction, the proportion of the carboxylic acid compound (1-4A) used is appropriately determined depending on the desired content of the specific group in the polyorganosiloxane (S3) having a (meth) acryl group and the reactivity of the addition reaction. Is preferably 0.01 to 2.0 mol with respect to 1 mol of the (meth) acryl group of the polyorganosiloxane (S3) having a (meth) acryl group, for example, More preferably, it is 0.1-1.0 mol, More preferably, it is 0.2-0.5 mol. Moreover, with respect to 100 mol% of silicon atoms of the polyorganosiloxane (S3) having a (meth) acryl group, it is preferably 5 to 100 mol%, more preferably 20 to 90 mol%, still more preferably. Is 40 to 85 mol%.

  The use ratio of the alignment group-containing compound (7) should be appropriately set according to the content ratio of the desired liquid crystal alignment group and the reactivity of the addition reaction in the polyorganosiloxane (S3) having a (meth) acryl group. However, for example, it is preferably 1.0 mol or less, more preferably 0.5 mol or less with respect to 1 mol of the (meth) acryl group of the polyorganosiloxane (S3) having a (meth) acryl group. Yes, more preferably 0.2 mol or less. Moreover, with respect to 100 mol% of silicon atoms which the polyorganosiloxane (S3) having a (meth) acryl group has, it is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, still more preferably. Is 10-30 mol%.

The above addition reaction can be performed in the presence of an organic solvent, if necessary. Examples of such organic solvents include hydrocarbon compounds, ether compounds, ester compounds, amide compounds, nitrile compounds, and dimethyl sulfoxide. Of these, ether compounds, ester compounds, nitrile compounds, and dimethyl sulfoxide are preferable from the viewpoint of solubility of raw materials and products. More preferred are acetonitrile and dimethyl sulfoxide.
The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 5 to 100% by weight.
In the above addition reaction, a catalyst can be added as necessary. Examples of such catalysts include tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, potassium carbonate, sodium hydroxide, water An alkali metal compound such as potassium oxide can be used. The usage ratio of the catalyst is preferably 0.001 to 1.5 mol, and more preferably 0.1 to 1.1 mol, with respect to 1 mol of the carboxylic acid compound (1-4A).
The reaction temperature is preferably 0 to 200 ° C, more preferably 10 to 100 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 10 hours.

（式（Ｓ１―４ａ）中、Ｒ^３及びＲ^５は、炭素数１〜６のアルカンジイル基であり、Ｒ^４は、水素原子又は炭素数１〜３のアルカンジイル基である。Ｚ^２は、硫黄原子又は−ＮＲ^２−（但し、Ｒ^２は、水素原子又は炭素数１〜６のアルキル基である。）である。「＊」は、珪素原子との結合手であることを示す。） By reacting the silane compound (s1) having the (meth) acrylic group and the carboxylic acid compound (1-4A), the specific group-containing polyorganosiloxane in the present invention is represented by the above formula (S1-4). A compound having a structure can be obtained. The specific group-containing polyorganosiloxane (S1) obtained by the method (1) was synthesized using a compound in which a monovalent group represented by the formula (sa-1) was bonded to a silicon atom. A compound obtained by reacting a polyorganosiloxane with a compound represented by the above formula (1-4A-1), that is, a polyorganosiloxane having a structure represented by the following formula (S1-4a). It is preferable.

(In the formula (S1-4a), ^{R 3} and ^{R 5} are alkanediyl group having 1 to 6 carbon atoms, ^{R 4} is, .Z ² is a hydrogen atom or an alkanediyl group having 1 to 3 carbon atoms , A sulfur atom, or —NR ² — (wherein R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) “*” indicates a bond with a silicon atom. )

{When manufacturing by the method of (2) above}
-About polyorganosiloxane (S4) having a mercapto group or amino group The polyorganosiloxane (S4) having a mercapto group or amino group used in the method (2) is preferably a silane compound having a mercapto group or amino group (S4). sb), or a mixture of a silane compound (sb) having a mercapto group or amino group and another silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst, or hydrolysis or hydrolysis / condensation Can be synthesized.

（式中、Ｒ^３は、炭素数１〜６のアルカンジイル基であり、Ｚ^２は、硫黄原子又は−ＮＲ^２−（但し、Ｒ^２は、水素原子又は炭素数１〜６のアルキル基である。）である。「＊」は、珪素原子との結合手を示す。） Examples of the silane compound (sb) having a mercapto group or amino group include those in which a monovalent group represented by the following formula (sb-1) is bonded to a silicon atom.

(In the formula, R ³ is an alkanediyl group having 1 to 6 carbon atoms, Z ² is a sulfur atom or —NR ² — (wherein R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). ("*" Indicates a bond with a silicon atom.)

  As such a silane compound (sb) having a mercapto group or amino group, those having a mercapto group are preferable, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxy. Silane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyldimethylethoxysilane, 1-mercaptomethyltrimethoxysilane, 1-mercaptomethyltriethoxysilane, 1-mercaptomethylmethyldimethoxysilane 1-mercaptomethylmethyldiethoxysilane, 1-mercaptomethyldimethylmethoxysilane, 1-mercaptomethyldimethylethoxysilane, 2-mercaptoethylto Silane, 2-mercaptoethyl triethoxysilane, 2-mercaptoethyl methyl dimethoxy silane, 2-mercaptoethyl methyl diethoxy silane, 2-mercaptoethyl dimethyl methoxy silane, 2-mercaptoethyl dimethyl silane is more preferred. In addition, as a silane compound (sb) which has a mercapto group or an amino group, you may use individually by 1 type and may be used in combination of 2 or more type.

  As said other silane compound which can be used in combination with the silane compound (sb) which has a mercapto group or an amino group, others which can be used in combination with the silane compound (sa) which has the said (meth) acryl group, for example The same thing as the silane compound can be mentioned. At this time, the use ratio of the silane compound (sb) having a mercapto group or amino group is preferably 20 mol% or more, more preferably 50 mol% or more, and still more preferably 80 mol% or more with respect to the other silane compound.

As an organic solvent that can be used for synthesizing a polyorganosiloxane having a mercapto group or an amino group (S4), a catalyst and conditions for the synthesis, the polyorganosiloxane having a (meth) acryl group (S3) The explanation can be applied.
In addition, in this invention, you may use what is marketed as polyorganosiloxane (S4) which has a mercapto group or an amino group. Examples of such commercially available products include Composelan HBSQ105-7 (manufactured by Arakawa Chemical Co., Ltd.).

As the polyorganosiloxane (S4) having a mercapto group or amino group used to synthesize the specific group-containing polyorganosiloxane (S1), the polystyrene-reduced weight average molecular weight measured by gel permeation chromatography (GPC) is: It is preferably 500 to 100,000, more preferably 1,000 to 10,000, and still more preferably 1,000 to 5,000.
In synthesizing the specific group-containing polyorganosiloxane (S1), the polyorganosiloxane (S4) having a mercapto group or an amino group can be used alone or in combination of two or more.

（式中、Ｒ^７は、水素原子又は炭素数１〜３のアルキル基である。） -About (meth) acrylic acid compound (1-4B) As (meth) acrylic acid compound (1-4B) used by the method of said (2), following formula (1-) like acrylic acid, methacrylic acid, etc., for example. The compound represented by 4B-1) is preferred.

(In the formula, R ⁷ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

  The reaction between the polyorganosiloxane (S4) having a mercapto group or amino group and the (meth) acrylic acid compound (1-4B) is preferably carried out in the presence of a suitable catalyst according to the known Michael addition reaction. it can. For the addition reaction, the description of the Michael addition method in the method (1) can be applied.

The specific group-containing polyorganosiloxane (S1) synthesized by the method (2) may have a liquid crystal alignment group. In order to introduce a liquid crystal alignment group into the specific group-containing polyorganosiloxane (S1), for example, the polyorganosiloxane (S4) having a mercapto group or an amino group is reacted with the alignment group-containing compound (8). be able to.
Examples of such an orientation group-containing compound (8) include acrylate esters having a long-chain alkyl group such as octyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate; Examples thereof include acrylic acid esters having a steroid skeleton represented by the following formulas (8-1) to (8-4). As the compound (8), only one kind may be used alone, or two or more kinds may be mixed and used.

（式（Ｓ１―４ｂ）中、Ｒ^３は、炭素数１〜６のアルカンジイル基であり、Ｒ^７は、炭素数２〜６のアルカンジイル基である。Ｚ^２は、硫黄原子又は−ＮＲ^２−（但し、Ｒ^２は、水素原子又は炭素数１〜６のアルキル基である。）である。「＊」は、珪素原子との結合手であることを示す。） By reacting the polyorganosiloxane (S4) having the mercapto group or amino group with the (meth) acrylic acid compound (1-4B), the above-mentioned formula (S1- A compound having the structure represented by 4) can be obtained. The specific group-containing polyorganosiloxane (S1) obtained by the method (2) was synthesized using a compound in which a monovalent group represented by the formula (sb-1) was bonded to a silicon atom. A compound obtained by reacting a polyorganosiloxane with a compound represented by the above formula (1-4B-1), that is, a polyorganosiloxane having a structure represented by the following formula (S1-4b). It is preferable.

(In the formula (S1-4b), R ³ is an alkanediyl group having 1 to 6 carbon atoms, and R ⁷ is an alkanediyl group having 2 to 6 carbon atoms. Z ² is a sulfur atom or —NR ^2- (wherein R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). “*” Indicates a bond with a silicon atom.)

（式（Ｓ１−１ａ）〜式（Ｓ１−３ａ）中、Ｒ^６は、単結合又は炭素数１〜６のアルカンジイル基である。Ｒ^８は、炭素数１〜３のアルカンジイル基であり、Ｒ^９は、単結合又は炭素数１〜６のアルカンジイル基であり、Ｙは、単結合又は酸素原子である。但し、Ｒ^９が単結合の場合、Ｙは単結合である。「＊」は、珪素原子との結合手であることを示す。） [When having a structure represented by formulas (S1-1) to (S1-3)]
On the other hand, when the specific group-containing polyorganosiloxane (S1) has a structure represented by any of the above (S1-1) to formula (S1-3), the specific group is present in the side chain of the polyorganosiloxane skeleton. Are specifically represented by the following formulas (S1-1a) to (S1-3a) as the structures represented by the above (S1-1) to formula (S1-3). Is preferred.

(In Formula (S1-1a) to Formula (S1-3a), R ⁶ is a single bond or an alkanediyl group having 1 to 6 carbon atoms. R ⁸ is an alkanediyl group having 1 to 3 carbon atoms. , R ⁹ is a single bond or an alkanediyl group having 1 to 6 carbon atoms, and Y is a single bond or an oxygen atom, provided that when R ⁹ is a single bond, Y is a single bond. "Indicates a bond with a silicon atom.)

In the above formula (S1-1a) and formula (S1-3a), the alkanediyl group having 1 to ⁶ carbon atoms in R ⁶ may be linear or branched. It includes the groups exemplified in the description of the above Z ^1. Preferably it is C1-C3.
In the above formula (S1-2a), when Y is a single bond, the alkanediyl group constituted by R ⁸ and R ⁹ preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.

In order to obtain a polyorganosiloxane having a structure represented by any of the above (S1-1) to formula (S1-3), for example,
(3) Hydrolysis of a silane compound (sc) having an epoxy group or a mixture of a silane compound (sc) having an epoxy group and another silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst Or a method of hydrolysis / condensation,
(4) A silane compound (sd) having an acid anhydride group or a mixture of a silane compound (sd) having an acid anhydride group and another silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst In the method of hydrolysis or hydrolysis / condensation,
Etc.

Examples of the silane compound (sc) having an epoxy group include epoxypropyltrimethoxysilane, epoxypropyltriethoxysilane, epoxypropylmethyldimethoxysilane, epoxypropylmethyldiethoxysilane, epoxypropyldimethylmethoxysilane, and epoxypropyldimethylethoxy. Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxy Silane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3- It can be exemplified Rishi Giro propyl dimethyl ethoxy silane. These can be used alone or in combination of two or more.
Examples of the silane compound (sd) having an acid anhydride group include 3- (trimethoxysilyl) propyl succinic anhydride.

Examples of the other silane compound that can be used in combination with the silane compound (sc) having an epoxy group include other silane compounds that can be used in combination with the silane compound (sa) having the (meth) acryl group. Among them, there can be mentioned silane compounds other than the compound (sc) and the compound (sd).
At this time, the use ratio of the silane compound (sc) having an epoxy group is preferably 1 mol% or more, more preferably 5 to 80 mol%, and further preferably 15 to 60 mol% with respect to all silane compounds used for the synthesis of the polyorganosiloxane. preferable.

As said organic solvent, the thing similar to the organic solvent illustrated by description of the polyorganosiloxane (S3) which has the said (meth) acryl group can be used, for example.
Examples of the catalyst include acid catalysts such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, and various Lewis acids.
The ratio of the catalyst used is, for example, preferably 0.01 to 3 moles, more preferably 0.05 to 1 moles, based on all silane compounds.
The hydrolysis or hydrolysis / condensation reaction in producing the specific group-containing polyorganosiloxane (S1) by the above methods (3) and (4) is, for example, an epoxy group-containing silane compound (sc) or acid anhydride. The silane compound (sd) having a group and, if necessary, another silane compound are dissolved in an organic solvent, mixed with water and a catalyst, and heated by, for example, an oil bath.
During the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux.

The blending amount of the specific group-containing polyorganosiloxane (S1) in the liquid crystal aligning agent of the present invention is preferably 10% by weight or more, more preferably 30% by weight or more based on the total amount of polyorganosiloxane contained in the liquid crystal aligning agent. Preferably, 50% by weight or more is more preferable. By setting it as the said range, the peelability with respect to the board | substrate of the formed coating film can be made more favorable.
In addition, the said specific group containing polyorganosiloxane (S1) may be contained individually by 1 type or 2 or more types in the liquid crystal aligning agent.

<Other polyorganosiloxane (S2)>
The liquid crystal aligning agent of the present invention is a polyorganosiloxane having an epoxy group (hereinafter referred to as an epoxy group-containing polyorgano) as the other polyorganosiloxane (S2) from the viewpoint of improving the liquid crystal alignment property and electrical characteristics in the liquid crystal alignment film. It further preferably contains siloxane (referred to as S2a).

<Epoxy group-containing polyorganosiloxane (S2a)>

（式（Ｘ２−１）中、Ａは、単結合又は酸素原子であり、ｈは、１〜３の整数であり、ｉは、０〜６の整数である。但し、ｉが０の場合、Ａは単結合である。式（Ｘ２−２）中、ｊは、１〜６の整数である。「＊」は珪素原子との結合手であることを示す。） The epoxy group-containing polyorganosiloxane (S2a) is not particularly limited as long as it contains an epoxy group in the side chain of the polyorganosiloxane skeleton, but the following formula (X2-1) or formula (X2- Those having a group represented by 2) are preferred. The group represented by the above formula (X2-1) or formula (X2-2) is particularly 3-epoxypropyl group, 3-glycidyloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl. Groups are preferred.

(In formula (X2-1), A is a single bond or an oxygen atom, h is an integer of 1 to 3, and i is an integer of 0 to 6. However, when i is 0, (A is a single bond. In formula (X2-2), j is an integer of 1 to 6. “*” represents a bond to a silicon atom.)

  The epoxy group-containing polyorganosiloxane (S2a) preferably has a polystyrene-equivalent weight average molecular weight of 500 to 100,000 as measured by gel permeation chromatography (GPC), and preferably 1,000 to 10,000. Is more preferable, and it is more preferable that it is 1,000-5,000.

<Method for producing epoxy group-containing polyorganosiloxane (S2a)>
The epoxy group-containing polyorganosiloxane (S2a) is, for example, an epoxy group-containing silane compound (se) or a mixture of an epoxy group-containing silane compound (se) and another silane compound, preferably an appropriate organic solvent, water. And can be synthesized by hydrolysis or hydrolysis / condensation in the presence of a catalyst.

  Examples of the silane compound (se) having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyl. Methyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples thereof include ethyltriethoxysilane. These can be used alone or in combination of two or more.

Examples of the other silane compound that can be used in combination with the silane compound (se) having an epoxy group include other silane compounds that can be used in combination with the silane compound (sa) having the (meth) acryl group. In addition to the silane compounds other than the compound (se),
3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propoxysilane, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltri Chlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane , - mercaptopropyltrimethoxysilane -sec- butoxysilane, mercaptomethyl trimethoxysilane, mercaptomethyl triethoxysilane,
Etc.

  Among these, as other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltri Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercapto One or more selected from the group consisting of methyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane are preferred.

The epoxy group-containing polyorganosiloxane (S2a) preferably has an epoxy equivalent of 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol. Therefore, in synthesizing the polyorganosiloxane (S2a) having an epoxy group, the proportion of the epoxy group-containing silane compound (se) and the other silane compound is used, and the epoxy equivalent of the obtained polyorganosiloxane is within the above range. It is preferable to adjust and set so that.
Specifically, the silane compound (se) having an epoxy group is preferably 1 mol% or more, preferably 5 to 80 mol% based on the total amount of the silane compound used in the synthesis of the epoxy group-containing polyorganosiloxane (S2a). Is more preferable, and 15-60 mol% is still more preferable.
The epoxy equivalent can be measured according to the “hydrochloric acid-methyl ethyl ketone method” of JIS C2105.

  As an organic solvent that can be used in the production of the polyorganosiloxane having an epoxy group (S2a), a catalyst, and conditions for synthesis, the description of the polyorganosiloxane having a (meth) acrylic group (S3) is given. Can be applied.

  The polyorganosiloxane (S2a) having an epoxy group may be used for the preparation of a liquid crystal aligning agent as it is, but in some of the epoxy groups of the polyorganosiloxane (S2a) having the epoxy group, liquid crystal It is preferable that a group (liquid crystal alignment group) for imparting orientation is ring-opened. According to such a method utilizing the ring-opening addition of an epoxy group, it is possible to simply introduce a liquid crystal alignment group into the polyorganosiloxane skeleton, and to increase the introduction rate of the liquid crystal alignment group. This is very suitable in terms of points.

  In order to introduce a liquid crystal alignment group into the polyorganosiloxane (S2a) having an epoxy group, for example, a polyorganosiloxane (S2a) having an epoxy group and a monovalent carboxylic acid (5), preferably a catalyst and an organic solvent are used. It can carry out by making it react in presence of.

（式中、ｆ、ｇ、ｈ、ｊ、ｋ及びｍは、それぞれ独立に３〜１２の整数である。） Examples of the monovalent carboxylic acid (5) include long-chain alkyl carboxylic acids such as dodecanoic acid, tetradecanoic acid, hexadecanoic acid, stearic acid, and eicosanoic acid; and the following formulas (5-1) to (5-7) The monocarboxylic acid represented by these can be mentioned. In addition, monovalent carboxylic acid (5) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

(In the formula, f, g, h, j, k and m are each independently an integer of 3 to 12.)

  In the reaction of the polyorganosiloxane having an epoxy group (S2a) with the monovalent carboxylic acid (5), other than the monovalent carboxylic acid (5) for introducing a liquid crystal alignment group as the carboxylic acid. These carboxylic acids may be mixed and used. In this case, the use ratio of the other carboxylic acid is preferably 50 mol% or less based on the total amount of the monovalent carboxylic acid (5) and the other carboxylic acid.

  Use of carboxylic acid in reaction of polyorganosiloxane (S2a) having an epoxy group and carboxylic acid (monovalent carboxylic acid (5) or a mixture of monovalent carboxylic acid (5) and other carboxylic acid) The ratio is preferably 1 mol% or more, more preferably 1 to 50 mol%, still more preferably 5 to 40 with respect to 100 mol% of silicon atoms contained in the polyorganosiloxane (S2a) having an epoxy group. It is mol%, Especially preferably, it is 10-30 mol%.

  As a catalyst that can be used in the reaction of the polyorganosiloxane (S2a) having an epoxy group and the monovalent carboxylic acid (5), for example, an organic base or a so-called catalyst that promotes a reaction between an epoxy compound and an acid anhydride. Known compounds can be used as the curing accelerator.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
A quaternary organic amine such as tetramethylammonium hydroxide can be used. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide preferable.
Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine;

2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- ( 2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s -Triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Ethyl-s-triazine, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2,4-diamino-6- 2'methylimidazolyl- - (1 ')] such as imidazole compounds of isocyanuric acid adduct of ethyl -s- triazine;

Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;
Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, Tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate Such as over preparative quaternary phosphonium salts;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;
Boron compounds such as boron trifluoride and triphenyl borate;
Metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as amine addition accelerators such as dicyandiamide and adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator in which the surface of a curing accelerator such as the imidazole compound, organophosphorus compound or quaternary phosphonium salt is coated with a polymer;
An amine salt type latent curing accelerator;
Examples include latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride are preferred.
These catalysts are preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane (S2a) having an epoxy group. Used at a rate of

Examples of the organic solvent that can be used in the reaction of the polyorganosiloxane having an epoxy group (S2a) and the monovalent carboxylic acid (5) include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, Examples include alcohol compounds. Of these, ether compounds, ester compounds, and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of the products, and specific examples of particularly preferred solvents include 2-butanone, 2-hexanone, Examples thereof include methyl isobutyl ketone and butyl acetate.
The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, and more preferably 5%. It is the ratio which becomes -50weight%.
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

  In addition, the liquid crystal aligning agent of this invention may contain polyorganosiloxane other than specific group containing polyorganosiloxane (S1) and epoxy group containing polyorganosiloxane (S2a) as said other polyorganosiloxane (S2). Good. In this case, the polyorganosiloxane may be included together with the epoxy group-containing polyorganosiloxane (S2a) or may not include the epoxy group-containing polyorganosiloxane (S2a). Examples of such a polyorganosiloxane include a polyorganosiloxane having a liquid crystal alignment group but not having an epoxy group.

<Preparation of liquid crystal aligning agent>
As described above, the liquid crystal aligning agent of the present invention contains a specific group-containing polyorganosiloxane (S1), and preferably further contains an epoxy group-containing polyorganosiloxane (S2a). Further, in addition to the above components, other components may be contained as necessary, but are preferably prepared as a solution composition in which each component is dissolved in an organic solvent.

Examples of the organic solvent that can be used to prepare the liquid crystal aligning agent of the present invention include a specific group-containing polyorganosiloxane (S1), an epoxy group-containing polyorganosiloxane (S2a), and other components optionally used. Those that dissolve and do not react with these are preferred.
Examples of such an organic solvent include 1-ethoxy-2-propanol, 2-methyl-2,4-pentanediol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol phenyl ether. , Propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (Butyl cellosolve), ethylene glycol monoamylate , Ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, N-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-acetate -Hexyl, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate and the like.
Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, N-methyl-2-pyrrolidone, Aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, ethylene glycol, 2-methyl-2,4-pentane Examples include diol, propylene glycol phenyl ether, and ethylene glycol monobutyl ether.

The preferable solvent used for preparation of the liquid crystal aligning agent of this invention can be used in combination of 1 type, or 2 or more types of the above-mentioned organic solvent according to the presence or absence of another polymer, and its kind. Moreover, as said organic solvent, in the following preferable solid content density | concentration, each component contained in a liquid crystal aligning agent does not precipitate, but the surface tension of a liquid crystal aligning agent becomes the range of 25-40 mN / m suitably. used.
The solid content concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, Preferably it is the range of 1-10 weight%. The liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal aligning film. When the solid content concentration is less than 1% by weight, the film thickness of this coating film becomes too small. In some cases, it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal aligning agent increases, resulting in insufficient coating characteristics. There is a case. The particularly preferable range of the solid content concentration varies depending on the method employed when applying the liquid crystal aligning agent to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by weight is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 0 ° C. to 200 ° C., more preferably 10 ° C. to 60 ° C.

<< Liquid crystal alignment film and liquid crystal display element >>
The liquid crystal alignment film of the present invention is formed using the liquid crystal alignment agent. Moreover, the liquid crystal display element of this invention comprises the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention as mentioned above. Such a liquid crystal display element includes, for example, a process of forming a coating film by applying the liquid crystal aligning agent of the present invention on the conductive film of a pair of substrates having a conductive film, and a pair of the coating film formed thereon. Forming a liquid crystal cell having a configuration in which the coating film of the substrate is disposed so as to face each other with the liquid crystal layer interposed therebetween.

Specifically, the liquid crystal aligning agent of this invention is first apply | coated on a board | substrate, Then, a coating film is formed on a board | substrate by heating an application surface. At this time, as a pair of two substrates provided with a patterned transparent conductive film, the liquid crystal aligning agent of the present invention, preferably a roll coater method, a spinner method, a printing method, is formed on each transparent conductive film forming surface. Each is applied by an ink jet method. Then, the coated surface is preheated (prebaked) and then baked (postbaked) to form a coating film. The pre-bake conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-bake conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
Examples of the substrate include glass such as float glass and soda glass; and a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and alicyclic polyolefin.

As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. To obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when forming a transparent conductive film, etc. be able to. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface of the substrate surface on which the coating film is to be formed, for example, a functional silane compound, You may give the pretreatment which apply | coats a titanium compound etc. previously.

  The coating film thus formed may be used as it is for the production of the liquid crystal cell in the next step, or may be rubbed as necessary prior to the production of the liquid crystal cell. The rubbing treatment can be performed by rubbing the coating film surface in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton. At this time, after a resist film is formed on a part of the liquid crystal alignment film surface, a rubbing process is performed in a direction different from the previous rubbing process, and then the resist film is removed. You may make it have orientation ability. In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element.

Next, a pair of substrates on which the liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the pair of substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.
The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.
In any case, it is desirable to remove the flow alignment at the time of injection by heating the liquid crystal cell to a temperature at which the liquid crystal used has an isotropic phase and then slowly cooling it to room temperature.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.
As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. When manufacturing a liquid crystal display element having a TN liquid crystal cell or an STN liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy (positive liquid crystal) is preferable. For example, biphenyl liquid crystal, phenyl cyclohexane liquid crystal , Ester liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, and cubane liquid crystals. For example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names C-15 and CB-15 (manufactured by Merck); A ferroelectric liquid crystal such as p-amino-2-methylbutyl cinnamate may be further added and used.
On the other hand, in the case of a vertical alignment type liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy (negative type liquid crystal) is preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal Liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, or the like is used.
For a PSA mode liquid crystal display element, a liquid crystal and a photopolymerizable compound are disposed between two substrates. A conventionally well-known thing can be used as the said photopolymerizable compound.

For the liquid crystal cell prepared as described above, at least one of the liquid crystal alignment films is obtained by performing a step of irradiating radiation with a voltage applied between the conductive films of the pair of substrates (radiation irradiation step). It is also possible to perform a process of changing the pretilt angle of the part area. The liquid crystal alignment film of the present invention is excellent in resistance to radiation such as ultraviolet rays, and has a radiation irradiation amount (for example, 100,000 J / m ² or more) such as irradiation in the process of manufacturing a PSA mode liquid crystal display element. It also shows excellent resistance. Therefore, when the liquid crystal aligning agent of the present invention is used, a liquid crystal display element having good electrical characteristics such as voltage holding ratio and responsiveness to a voltage change and liquid crystal aligning property can be obtained by the manufacturing method including the radiation irradiation process as described above. Can be obtained.

As the radiation used for the radiation irradiation treatment, linearly polarized light, partially polarized radiation, or unpolarized radiation can be used. For example, ultraviolet rays or visible rays including light having a wavelength of 150 to 800 nm are used. However, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination thereof. May be. When irradiating non-polarized radiation, the direction of irradiation is performed from an oblique direction.
As a light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter or a diffraction grating.
The irradiation dose of radiation, preferably less than 1 J / ^{m 2} or more 1,000,000J / ^{m 2,} more preferably from 1,000~100,000J / ^{m 2.}
The applied voltage can be, for example, 5 to 50 V direct current or alternating current.
As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of can be mentioned.

The liquid crystal display element of the present invention is preferably a vertical alignment type liquid crystal display element.
Thus, the manufactured liquid crystal display element of this invention has favorable peelability of the coating film (liquid crystal aligning film) formed on the board | substrate. In addition, the liquid crystal display element has excellent radiation resistance and, for example, in a PSA mode or a photo-alignment method, the liquid crystal display element is in a mode including a step of irradiating a coating film formed on a substrate with radiation. Even if it is adopted, it is excellent in electrical characteristics and pre-tilt angle stability over time.

  The liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, It can be used for display devices such as various monitors and liquid crystal televisions.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In the following examples, the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
The following synthesis examples were repeated at the following synthesis scale as necessary to secure the necessary amount of product to be used in the following synthesis examples and examples.

<Synthesis of specific group-containing polyorganosiloxane (S1)>
(Synthesis Example S-1-1)
In a 200 mL three-necked flask equipped with a thermometer, 33.0 g of AC-SQ TA100 (hydrolysis condensate of 3-acryloxypropyltrimethoxysilane, manufactured by Toagosei Co., Ltd.), 9.2 g of thioglycolic acid (AC- SQ TA100 equivalent to 50 mol% of silicon atoms), 42.3 g of acetonitrile, and 20.2 g of triethylamine were charged and reacted at 50 ° C. for 1 hour. After completion of the reaction, polysiloxane (S-1-1) was obtained by distilling off acetonitrile and triethylamine under reduced pressure. The weight average molecular weight was 3,200.

(Synthesis Example S-1-2 to Synthesis Example S-1-6)
Polyorganosiloxanes (S-1-2) to (S-1-6) were prepared in the same manner as in Synthesis Example S-1-1 except that the types and amounts of the compounds used were as shown in Table 1 below. Was synthesized.

  In Table 1, the compounding amount [mol%] of the carboxylic acid compound and the orientation group-containing compound indicates a value relative to 100 mol% of silicon atoms contained in the used polyorganosiloxane. “MAC-SQ” indicates a hydrolysis condensate of 3-methacryloxypropyltrimethoxysilane (manufactured by Toagosei Co., Ltd.).

(Synthesis Example S-1-7)
In a 200 mL three-necked flask equipped with a thermometer, 8.3 g of AC-SQ TA100, 2.7 g of thioglycolic acid (corresponding to 50 mol% of silicon atoms in AC-SQ TA100), and the above formula (7A-6) 4.1 g (corresponding to 20 mol% of the silicon atom of AC-SQ TA100), 15.0 g of dimethyl sulfoxide, and 7.1 g of triethylamine were charged and reacted at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was reprecipitated with 100 mL of methanol, and the precipitate was collected and dried to obtain polysiloxane (S-1-7). The weight average molecular weight was 6,900.

(Synthesis Example S-1-8)
Into a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 62.64 g of butyl cellosolve, 19.14 g of tetraethoxysilane, 5.41 g of 3-epoxypropyltrimethoxysilane, and 1.79 g of methyltrimethoxysilane. The mixture was stirred and stirred to prepare a mixed solution of alkoxysilane monomers. Subsequently, after heating this solution to 60 degreeC, the oxalic acid solution which mixed 10.94 g of water and the oxalic acid 0.087g as a catalyst was dripped here. After completion of dropping, the solution was heated at a solution temperature of 90 ° C. for 3 hours and then cooled to room temperature to obtain a solution having polyorganosiloxane (S-1-8). The weight average molecular weight Mw of the contained polyorganosiloxane (S-1-8) was 11,000.

(Synthesis Example S-1-9)
A polyorganosiloxane (S-1-9) was synthesized in the same manner as in Synthesis Example S-1-8 except that the types and amounts of the compounds used were as shown in Table 2 below.

In Table 2, the compounding amount [mol%] of the silane compound indicates a value with respect to 100 mol% of the total amount of the silane compound used. The abbreviations of the silane compounds are as follows.
TEOS: Tetraethoxysilane METMS: Methyltrimethoxysilane EPTS: 3-Epoxypropyltrimethoxysilane ECETS: 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane TMSPA: 3- (Trimethoxysilyl) propyl succinic anhydride

(Synthesis Example S-1-10)
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 66.17 g of butyl cellosolve, 16.68 g of tetraethoxysilane, 6.00 g of 3- (trimethoxysilyl) propyl succinic anhydride, methyltrimethoxy Silane 1.56 g was added and stirred to prepare a mixed solution of alkoxysilane monomers. Subsequently, after heating this solution to 60 degreeC, the oxalic acid solution which mixed 9.53g of water and 0.08g of oxalic acid as a catalyst here was dripped here. After completion of dropping, the solution was heated at a solution temperature of 90 ° C. for 3 hours and then cooled to room temperature to obtain a solution having polyorganosiloxane (S-1-10). The weight average molecular weight Mw of the polyorganosiloxane (S-1-10) contained was 10,000.

<Synthesis of Epoxy Group-Containing Polyorganosiloxane (S2a)>
(Synthesis Example E-1)
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 458.7 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 162.8 3-methacryloxypropyltrimethoxysilane, methyl 3108 g of isobutyl ketone and 62.2 g of triethylamine were charged and mixed at room temperature. Next, 621.5 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure, whereby polyorganosiloxane EPS-1 Was obtained as a viscous transparent liquid.
The weight average molecular weight Mw of this polyorganosiloxane EPS-1 was 2,900.

(Synthesis Example E-2 to Synthesis Example E-4)
Polyorganosiloxane EPS-2 to EPS-4 were synthesized by the same method as in Synthesis Example E-1, except that the type and amount of the silane compound used were as shown in Table 3 below.

In Table 3, the compounding amount [mol%] of the silane compound indicates a value relative to 100 mol% of the total amount of the silane compound used. The abbreviations of the silane compounds are as follows.
ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane MTMS: 3-methacryloxypropyltrimethoxysilane ATMS: 3-acryloxypropyltrimethoxysilane

(Synthesis Example S-2-1)
In a 200 mL three-necked flask, 10.0 g of polyorganosiloxane EPS-1 synthesized in Synthesis Example E-1 above, 30.28 g of methyl isobutyl ketone, 3.52 g of OCTBA (based on the silicon atoms of polyorganosiloxane EPS-1) 0.10 g of UCAT 18X (trade name, manufactured by San Apro Co., Ltd., an epoxy compound curing accelerator) was charged and reacted at 90 ° C. with stirring for 72 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. A solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was distilled off to remove polyorganosiloxane (S- The white powder of 2-1) 8.2g was obtained. The weight average molecular weight of the polyorganosiloxane (S-2-1) was 4,500.

(Synthesis Example S-2-2 to Synthesis Example S-2-8)
Polyorganosiloxanes (S-2-2) to (S-2-8) were prepared in the same manner as in Synthesis Example S-2-1 except that the types and amounts of the compounds used were as shown in Table 4 below. Was synthesized.

In Table 4, the compounding amount [mol%] of the carboxylic acid indicates a value relative to 100 mol% of silicon atoms contained in the polyorganosiloxane. Moreover, the abbreviation of carboxylic acid shows the following compounds, respectively.

(Synthesis Example S-2-9)
In a 200 mL three-necked flask, 10.0 g of polyorganosiloxane EPS-1 synthesized in Synthesis Example E-1 above, 30.28 g of methyl isobutyl ketone, 5.50 g of HCSA (based on the silicon atoms of polyorganosiloxane EPS-1) (Corresponding to 20 mol%) and 0.10 g of tetrabutylammonium bromide were charged, and the reaction was carried out at 90 ° C. with stirring for 36 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. A solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and the solvent was distilled off to remove polyorganosiloxane (S- 10.1 g of white powder 2-9) was obtained. The weight average molecular weight of the polyorganosiloxane (S-2-9) was 5,200.

(Synthesis Example S-2-10-Synthesis Example S-2-12)
Polyorganosiloxanes (S-2-10) to (S-2-12) were prepared in the same manner as in Synthesis Example S-2-9 except that the types and amounts of the compounds used were as shown in Table 4 above. Was synthesized.

<Preparation of liquid crystal aligning agent>
Example 1
The polyorganosiloxane (S-1-5) obtained in Synthesis Example S-1-5 was dissolved by adding N-methyl-2-pyrrolidone and butyl cellosolve, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = The solution was 50:50 (mass ratio) and the solid concentration was 4.0% by mass. A liquid crystal aligning agent was prepared by filtering this solution through a filter having a pore size of 0.2 μm.
(Examples 2-27 and Comparative Example 1)
A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the type and amount of polyorganosiloxane used were as shown in Table 5 below. In Table 5 below, the blending amount (parts by weight) of the polyorganosiloxane indicates a ratio with respect to 100 parts by weight of the total amount of the polyorganosiloxane used.

<Manufacture and evaluation of liquid crystal display elements>
Using the liquid crystal aligning agent prepared as described above, a total of six liquid crystal display elements were manufactured and evaluated by changing the transparent electrode pattern (two types) and the ultraviolet irradiation amount (three levels) as follows.

[Manufacture of liquid crystal display element having transparent electrode without pattern]
About each of the liquid crystal aligning agent prepared above, it apply | coated on the transparent electrode surface of the glass substrate which has a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printer (made by Nissha Printing Co., Ltd.), and 80 degreeC After removing the solvent by heating (pre-baking) for 1 minute on a hot plate, it was heated (post-baking) for 10 minutes on a hot plate at 150 ° C. to form a coating film having an average film thickness of 600 mm.
The coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.

Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of substrates having the liquid crystal alignment film, the liquid crystal alignment film surfaces are overlapped and pressure bonded. The adhesive was cured. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal inlet, and then the liquid crystal inlet is sealed with an acrylic photo-curing adhesive to produce a liquid crystal display element. did.
The above operation was repeated to produce three liquid crystal display elements having a transparent electrode without pattern. One of them was used for the evaluation of the pretilt angle described later. The remaining two liquid crystal display elements were each subjected to evaluation of the pretilt angle and voltage holding ratio after being irradiated with light in a state where a voltage was applied between the conductive films by the following method.

For two of the liquid crystal display elements obtained above, an alternating current of 10 Hz is applied between the electrodes, and the liquid crystal is driven, using an ultraviolet gland irradiation apparatus using a metal halide lamp as the light source. , it was irradiated with ultraviolet rays at dose of 10,000 J / ^{m 2} or 100,000J / ^{m 2.} In addition, this irradiation amount is the value measured using the light meter measured on the basis of wavelength 365nm.

[Evaluation of orientation]
About the liquid crystal display element manufactured above, the presence or absence of light leakage and alignment disorder in the state of no voltage application was visually observed under backlight irradiation. In the evaluation, the case where there was no light leakage / alignment disorder was determined as “good”, and the case where there was light leakage / alignment disorder was determined as “bad”. The results are shown in Table 6 below.

[Evaluation of pretilt angle]
Regarding each of the liquid crystal cells produced as described above, Non-Patent Document 1 (T. J. Scheffer et. Al., J. Appl. Phys. Vo. 48, p. 1783 (1977)) and Non-Patent Document 2 (F. In accordance with the method described in Nakano et.al., JPN.J.Appl.Phys.vo.19, p.2013 (1980)), the substrate surface of the liquid crystal molecule is obtained by a crystal rotation method using He-Ne laser light. The tilt angle from was measured and the measured value was defined as the pretilt angle.
Shows the liquid crystal display device of not irradiated with light, the measured results of a pretilt angle of the liquid crystal display element and a liquid crystal display device of the dose 100,000J / ^{m 2} of dose 10,000 J / ^{m 2} in Table 6 below.

[Evaluation of peelability of liquid crystal alignment film]
On the transparent conductive film made of ITO provided on one surface of a glass substrate having a thickness of 1 mm, the liquid crystal aligning agent prepared above is applied by a spinner, and prebaked on a hot plate at 100 ° C. for 90 seconds. A coating film of about 0.08 μm was formed. This operation was repeated to prepare two substrates with a coating film. Next, the two obtained substrates were stored in a dark room at 25 ° C. under a nitrogen atmosphere. After 12 hours and 72 hours from the start of storage, each was taken out from the dark room and immersed in a beaker containing TS-204 (liquid crystal alignment film remover) manufactured by Sanyo Chemical Industries, Ltd. heated to 40 ° C. for 2 minutes. After 2 minutes, the substrate was taken out of the beaker and washed several times with ultrapure water, and then water droplets on the surface were removed by air blow, the substrate was observed, and whether a coating film remained was observed with an optical microscope. Remove from the dark room after 72 hours, “++” if the film is not peeled after NMP soaking and has good releasability. The substrate taken out from the dark room after 72 hours could not be removed, but removed from the dark room after 12 hours. The substrates that were peelable were evaluated as “+” and those that could not be peeled were evaluated as “−”. The evaluation results are shown in Table 6 below.

[Evaluation of voltage holding ratio]
About a 10,000 J / m ² liquid crystal display element manufactured as described above, a voltage of 5 V was applied at 23 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and 167 milliseconds after the application release. The voltage holding ratio was measured. As a measuring device, VHR-1 manufactured by Toyo Corporation was used. The measurement results of the voltage holding ratio are shown in Table 6 below.

[Production of Liquid Crystal Cell Having Patterned Transparent Electrode (1)]
The liquid crystal aligning agent prepared above is patterned into a slit shape as shown in FIG. 1, and a liquid crystal aligning film printing machine is provided on each electrode surface of glass substrates A and B each having ITO electrodes partitioned into a plurality of regions. (Prepared by Nissha Printing Co., Ltd.), heated for 1 minute on a hot plate at 80 ° C. (pre-baked) to remove the solvent, and then heated for 10 minutes on a hot plate at 150 ° C. (post-baked) Thus, a coating film having an average film thickness of 600 mm was formed. The coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.
Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of substrates having the liquid crystal alignment film, the liquid crystal alignment film surfaces are overlapped and pressure-bonded so as to face each other. The adhesive was cured. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal inlet, and then the liquid crystal inlet is sealed with an acrylic photo-curing adhesive to produce a liquid crystal display element. did.

The above operation was repeated to produce three liquid crystal display elements having patterned transparent electrodes. One of them was used for evaluation of response speed as described later. For the remaining two liquid crystal display elements, 10,000 J / m ² or 100,000 J with a voltage applied between the conductive films in the same manner as in the production of the liquid crystal cell having the transparent electrode without pattern. After the light irradiation at an irradiation amount of / m ² , the response speed was evaluated.
The electrode pattern used here is the same type as the electrode pattern in the PSA mode.

[Evaluation of response speed]
For each of the liquid crystal display devices manufactured above, first, the luminance of light transmitted through the liquid crystal display device by irradiating a visible light lamp without applying a voltage was measured with a photomultimeter, and this value was measured with a relative transmittance of 0%. It was. Next, the transmittance when AC 60 V was applied between the electrodes of the liquid crystal display element for 5 seconds was measured in the same manner as described above, and this value was defined as a relative transmittance of 100%.
At this time, when 60 V AC was applied to each liquid crystal display element, the time until the relative transmittance shifted from 10% to 90% was measured, and this time was defined as the response speed and evaluated.
Shows the liquid crystal display device of not irradiated with light, each of the response speed of the liquid crystal display element and a liquid crystal display device of the dose 100,000J / ^{m 2} of dose 10,000 J / ^{m 2} in Table 7 below.

[Production of Liquid Crystal Cell Having Patterned Transparent Electrode (2)]
A liquid crystal cell having the patterned transparent electrode except that glass substrates A and B each having an ITO electrode patterned in a fishbone shape as shown in FIG. in the same manner as in the preparation (1), a liquid crystal display device of not irradiated with light to produce a liquid crystal display device of the dose liquid crystal display device of 10,000 J / ^{m 2} and dose 100,000J / ^{m 2,} and each of the above The response speed was similarly evaluated. The evaluation results are shown in Table 7 below.

[Production of Liquid Crystal Cell Having Patterned Transparent Electrode (3)]
Manufacture of a liquid crystal cell having the patterned transparent electrode, except that the liquid crystal aligning agent of Example 26 prepared above was used and a photopolymerizable compound was added to the injected nematic liquid crystal (MLC-6608, manufactured by Merck). (1) and in the same manner, the liquid crystal display device of not irradiated with light, a liquid crystal display element of the liquid crystal display device of the dose 10,000 J / ^{m 2} and dose 100,000J / ^{m 2} was produced, respectively in the same manner as described above The response speed was evaluated. The evaluation results are shown in Table 7 below. In addition, as a photopolymerizable compound, the well-known thing normally used for the liquid crystal display element of a PSA system was used.

  As shown in Table 6, the coating film formed using the liquid crystal aligning agents of Examples 1 to 26 has a peelability to the substrate as compared with Comparative Example 1 that does not include the specific group-containing polyorganosiloxane (S1). Both were good. Especially, Examples 1-24 were especially favorable in the peelability with respect to a board | substrate. Moreover, as shown in Table 6 and Table 7, the liquid crystal display element manufactured using the liquid crystal aligning agent of Examples 1-26 has liquid crystal orientation, a voltage holding ratio, the responsiveness to a voltage change, the tolerance with respect to an ultraviolet-ray, etc. Various characteristics required for practical use were also good.

  DESCRIPTION OF SYMBOLS 1 ... ITO electrode, 2 ... Slit part, 3 ... Light shielding film.

Claims (9)

A specific group-containing polyorganosiloxane (S1) having a carboxyl group;
Carboxyl group, hydroxyalkyl group, -NHR ¹ (wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and other poly having no specific group selected from the group consisting of mercapto groups. An organosiloxane (S2);
Only including,
Wherein Other polyorganosiloxane (S2), a liquid crystal aligning agent characterized by containing Mukoto an epoxy group-containing polyorganosiloxane (S2a). The liquid crystal aligning agent according to claim 1 , wherein the epoxy group-containing polyorganosiloxane (S2a) has a group represented by the following formula (X2-1) or formula (X2-2).

(In formula (X2-1), A is a single bond or an oxygen atom, h is an integer of 1 to 3, and i is an integer of 0 to 6. However, when i is 0, (A is a single bond. In formula (X2-2), j is an integer of 1 to 6. “*” represents a bond to a silicon atom.) The liquid crystal aligning agent according to claim 1 or 2, wherein the specific group-containing polyorganosiloxane (S1) has a structure represented by the following formula (S1-4).

(In Formula (S1-4), Z ¹ represents a single bond, an alkanediyl group having 1 to 6 carbon atoms, or —O—, —S—, —COO—, —OCO— or —NR ² — (wherein R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) A divalent organic group having 1 to 20 carbon atoms including at least one selected from the group consisting of “*” is a silicon atom. Indicates that this is a bond with The particular group-containing polyorganosiloxane (S1) is a structure represented by the formula (S1-4), according to claim 3 having the structure represented by the following formula (S1-4a) or formula (S1-4b) Liquid crystal aligning agent as described in.

(In Formula (S1-4a) and Formula (S1-4b), R ³ and R ⁵ are each independently an alkanediyl group having 1 to 6 carbon atoms, and R ⁴ is a hydrogen atom or 1 to 3 carbon atoms. R ⁷ is an alkanediyl group having 2 to 6 carbon atoms, Z ² is a sulfur atom or —NR ² — (wherein R ² is a hydrogen atom or having 1 to 6 carbon atoms. (It is an alkyl group.) “*” Indicates a bond with a silicon atom.) A specific group-containing polyorganosiloxane (S1) having a carboxyl group;
Carboxyl group, hydroxyalkyl group, -NHR ¹ (wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and other poly having no specific group selected from the group consisting of mercapto groups. An organosiloxane (S2);
Only including,
The specific group-containing polyorganosiloxane (S1) has a structure represented by the following formula (S1-4a) or formula (S1-4b) .

(In Formula (S1-4a) and Formula (S1-4b), R ³ and R ⁵ are each independently an alkanediyl group having 1 to 6 carbon atoms, and R ⁴ is a hydrogen atom or 1 to 3 carbon atoms. R ⁷ is an alkanediyl group having 2 to 6 carbon atoms, Z ² is a sulfur atom or —NR ² — ( wherein R ² is a hydrogen atom or having 1 to 6 carbon atoms. (It is an alkyl group.) “*” Indicates a bond with a silicon atom.) The said specific group containing polyorganosiloxane (S1) contains 7 * 10 < ^-6 > ^-4 * 10 < ^-4 > [mol / g] of carboxyl groups per solid content weight of this specific group containing polyorganosiloxane. The liquid crystal aligning agent as described in any one of 5 . The liquid crystal aligning film formed with the liquid crystal aligning agent as described in any one of Claims 1 thru | or 6 . A liquid crystal display device comprising the liquid crystal alignment film according to claim 7 . A coating film is formed by applying the liquid crystal aligning agent according to any one of claims 1 to 6 on each of the conductive films of a pair of substrates having a conductive film,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to the liquid crystal layer,
A method for manufacturing a liquid crystal display element, comprising a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between conductive films of the pair of substrates.

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