JP6477482B2 - Composition, liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a composition used for forming a resin film, a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film. Is.

  A resin film made of an organic material such as a polymer material is widely used as an interlayer insulating film or a protective film in an electronic device because of its ease of formation and insulation performance. Among these, in a liquid crystal display element well known as a display device, a resin film made of an organic material or an inorganic material is used as a liquid crystal alignment film.

  Currently, the composition for forming a resin coating that is industrially used includes a composition containing a polyimide polymer excellent in durability and a polysiloxane polymer obtained by polycondensation of alkoxysilane. It is used.

  In recent years, inorganic resin films formed from a composition containing a polysiloxane polymer have been used for interlayer insulating films, protective films, and liquid crystal alignment films. Among them, in the liquid crystal display element, the purpose is to improve the orientation of the liquid crystal with respect to heat (for example, Patent Document 1), the film hardness of the liquid crystal alignment film is increased, and the printability of the liquid crystal alignment treatment agent is improved. For the purpose of improvement (for example, Patent Document 2), a liquid crystal alignment treatment agent and a liquid crystal alignment film using a polysiloxane polymer have been proposed.

JP 2001-27761 A International Publication No. 2008/044644

  Resin coatings obtained from polysiloxane polymers are widely used for interlayer insulating films and protective films in electronic devices, and liquid crystal alignment films for liquid crystal display elements. For these, it is required to improve the coating properties of the resin coating, the protective film, and the liquid crystal alignment film. That is, the improvement of the coating properties of these films is effective for suppressing defects in electronic devices and liquid crystal display elements that occur due to poor coating properties.

  In recent years, liquid crystal display devices have been widely put into practical use for large-screen liquid crystal televisions and high-definition mobile applications (display portions of digital cameras and mobile phones). Along with this, the size of the substrate used and the unevenness of the step difference in the substrate have become larger than in the past. Even in such a situation, a liquid crystal alignment film is required to be uniformly coated on a large substrate or a step from the viewpoint of improving the display characteristics of the liquid crystal display element and suppressing defects. In particular, the liquid crystal alignment film is required to be coated with a uniform film thickness (also referred to as enhancing the step following property) with respect to the unevenness of the substrate step.

  Since the composition obtained from the polysiloxane polymer and the liquid crystal alignment treatment agent have a low molecular weight of the polysiloxane polymer, the step followability of the resin film and the liquid crystal alignment film (also referred to as a resin film) is reduced. That is, a resin film having a uniform film thickness cannot be obtained with respect to the unevenness of the substrate step. Specifically, the resin film is not coated on the convex portion of the step of the substrate, or the film thickness thereof tends to be thin. Accordingly, the function as an interlayer insulating film and protective film in an electronic device, and further as a liquid crystal alignment film of a liquid crystal display element cannot be expressed, and these defects are likely to occur.

  The liquid crystal alignment film is also used for controlling the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal. In particular, in the VA (Vertical Alignment) mode and the PSA (Polymer Sustained Alignment) mode, the liquid crystal needs to be aligned vertically. Therefore, the liquid crystal alignment film has an ability to align the liquid crystal vertically (vertical alignment and high pretilt). Called corners). Furthermore, the liquid crystal alignment film has become important not only for high vertical alignment but also for its stability. In particular, liquid crystal display elements that use a backlight that generates a large amount of heat and has a large amount of light to obtain high brightness, such as car navigation systems and large televisions, are exposed to high temperatures and light for a long time. There are cases where it is used or left in a dark environment. Under such severe conditions, when the vertical alignment property is deteriorated, problems such as inability to obtain initial display characteristics or occurrence of unevenness in display occur.

  Then, an object of this invention is to provide the composition which has the said characteristic. That is, an object of the present invention is to provide a composition that can suppress the generation of pinholes accompanying repelling when forming a resin film, and further has a high step following property to the unevenness of the step substrate. It is.

  Moreover, in the liquid crystal aligning agent using the composition of the present invention, when a liquid crystal alignment film is formed, generation of pinholes accompanying repelling can be suppressed. It is to provide a liquid crystal alignment treatment agent having high followability. It is another object of the present invention to provide a liquid crystal aligning agent that becomes a liquid crystal alignment film capable of exhibiting a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time.

  In addition, another object is to provide a resin film obtained from the composition, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

  As a result of earnest research, the present inventor has found that a composition containing polysiloxane obtained by polycondensation of a solvent having a specific structure and an alkoxysilane having a specific structure is extremely effective for achieving the above-mentioned object. As a result, the present invention has been completed.

  That is, the present invention has the following gist.

（式中、Ｘ^１およびＸ^２は、それぞれ独立して、炭素数１〜３のアルキル基を示し、Ｘ^３およびＸ^４は、それぞれ独立して、炭素数１〜３のアルキル基を示す）で示される溶媒；ならびに
（Ｂ）成分：下記の式［２ａ］、式［２ｂ］および式［２ｃ］：

｛式中、Ａ^１は、下記の式［２ａ−１］および式［２ａ−２］：

（式中、Ｙ^１は、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^２は、単結合または−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示し、Ｙ^３は、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^４は、ベンゼン環、シクロヘキサン環および複素環から選ばれる少なくとも１種の環状基、またはステロイド骨格を有する炭素数１７〜５１の２価の有機基を示し、前記環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、Ｙ^５は、ベンゼン環、シクロヘキサン環および複素環から選ばれる少なくとも１種の環状基を示し、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、ｎは、０〜４の整数を示し、Ｙ^６は、炭素数１〜２２のアルキル基、炭素数２〜２２のアルケニル基、炭素数１〜２２のフッ素含有アルキル基、炭素数１〜２２のアルコキシル基および炭素数１〜２２のフッ素含有アルコキシル基から選ばれる少なくとも１種を示す）および

（式中、Ｙ^７は、単結合、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^８は、炭素数８〜２２のアルキル基または炭素数６〜１８のフッ素含有アルキル基を示す）で示される構造から選ばれる少なくとも１種の構造を示し、Ａ^２は、それぞれ独立して、水素原子または炭素数１〜５のアルキル基を示し、Ａ^３は、それぞれ独立して、炭素数１〜５のアルキル基を示し、ｍ^１は、１または２の整数を示し、ｎ^１は、０〜２の整数を示し、ｐ^１は、０〜３の整数を示すが、ただし、ｍ^１＋ｎ^１＋ｐ^１は、４の整数を示す｝；

（式中、Ｂ^１は、それぞれ独立して、ビニル基、エポキシ基、アミノ基、メルカプト基、イソシアネート基、メタクリル基、アクリル基、ウレイド基およびシンナモイル基から選ばれる少なくとも１種を有する炭素数２〜１２の有機基を示し、Ｂ^２は、それぞれ独立して、水素原子または炭素数１〜５のアルキル基を示し、Ｂ^３は、それぞれ独立して、炭素数１〜５のアルキル基または炭素数１〜５のアルコキシアルキル基を示し、ｍ^２は、１または２の整数を示し、ｎ^２は、０〜２の整数を示し、ｐ^２は、０〜３の整数を示すが、ただし、ｍ^２＋ｎ^２＋ｐ^２は、４の整数を示す）；および

（式中、Ｄ^１は、それぞれ独立して、水素原子または炭素数１〜５のアルキル基を示し、Ｄ^２は、それぞれ独立して、炭素数１〜５のアルキル基を示し、ｎ^３は、０〜３の整数を示す）
で示されるアルコキシシランから選ばれる少なくとも１種を含むアルコキシシランを重縮合させて得られるポリシロキサン
を含有する組成物。(1) Component (A): Formula [1] below:

(Wherein, X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms, and X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms) And a component (B): the following formula [2a], formula [2b] and formula [2c]:

{In the formula, A ¹ represents the following formula [2a-1] and formula [2a-2]:

Wherein Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON. At least one linking group selected from (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and —OCO—, and Y ² represents a single bond or — (CH ₂ ) _b — (b Is an integer of 1 to 15, and Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO. -And -OCO- represents at least one linking group selected from -OCO-, Y ⁴ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, or a C 17-51 carbon having a steroid skeleton A divalent organic group, wherein any hydrogen atom on the cyclic group has 1 to 3 carbon atoms Alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms may be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms, Y ⁵ is a benzene ring , At least one cyclic group selected from a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a carbon number 1 to 3 fluorine-containing alkyl groups, 1 to 3 carbon-containing fluorine-containing alkoxyl groups or fluorine atoms may be substituted, n represents an integer of 0 to 4 and Y ⁶ represents 1 to 22 carbon atoms. An alkyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 22 carbon atoms. At least one selected) and

Wherein Y ⁷ is a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and -OCO- represents at least one linking group selected from -OCO-, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms). Each of A ² independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A ³ independently represents an alkyl group having 1 to 5 carbon atoms, m ¹ represents an integer of 1 or 2, n ¹ represents an integer of 0 to 2, and p ¹ represents an integer of 0 to 3, provided that m ¹ + n ¹ + p ¹ represents an integer of 4. Show};

(In the formula, each B ¹ independently has 2 carbon atoms having at least one selected from vinyl group, epoxy group, amino group, mercapto group, isocyanate group, methacryl group, acrylic group, ureido group and cinnamoyl group. To 12 organic groups, B ² independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and B ³ independently represents an alkyl group or carbon having 1 to 5 carbon atoms. 1 represents an alkoxyalkyl group of 1 to 5, m ² represents an integer of 1 or 2, n ² represents an integer of 0 to 2, and p ² represents an integer of 0 to 3, provided that m ² + n ² + p ² represents an integer of 4); and

(In the formula, each D ¹ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, each D ² independently represents an alkyl group having 1 to 5 carbon atoms, and n ³ is Represents an integer of 0 to 3)
A composition containing a polysiloxane obtained by polycondensation of an alkoxysilane containing at least one selected from the alkoxysilanes represented by formula (1).

で示される溶媒である、上記（１）に記載の組成物。(2) The solvent of the component (A) is represented by the following formula [1a]:

The composition as described in said (1) which is a solvent shown by these.

(3) The alkoxysilane represented by the formula [2b] of the component (B) is allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris ( 2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate, which is at least one alkoxysilane selected from the above ( The composition according to 1) or (2) above.

(4) The alkoxysilane represented by the formula [2b] of the component (B) is 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane and 2 The composition as described in (1) or (2) above, which is at least one alkoxysilane selected from-(3,4-epoxycyclohexyl) ethyltrimethoxysilane.

(5) The polysiloxane of the component (B) is a polysiloxane obtained by polycondensation of alkoxysilanes represented by the formulas [2a] and [2b], or represented by the formulas [2a] and [2c]. The composition according to any one of (1) to (4) above, which is a polysiloxane containing any one of the polysiloxanes obtained by polycondensation of alkoxysilane.

(6) The above (1) to the above, wherein the polysiloxane of the component (B) is a polysiloxane obtained by polycondensation of alkoxysilanes represented by formula [2a], formula [2b] and formula [2c] The composition according to any one of (5).

(7) In the composition, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1,3-propanediol, 1,3-butanediol, 1 , 4-butanediol, 2,3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, the comprising at least one solvent selected from dipropylene glycol dimethyl ether and furfuryl alcohol (1) to composition according to any one of the above (6).

(8) The composition contains at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and 1,3-dimethyl-imidazolidinone, The composition according to any one of (1) to (7).

(9) In the composition, at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. The composition according to any one of (1) to (8) above, which comprises at least one crosslinkable compound selected from a crosslinkable compound having a polymerizable unsaturated bond and a crosslinkable compound having a polymerizable unsaturated bond.

(10) The composition according to any one of (1) to (9) above, wherein the component (A) is 20 to 80% by mass of the entire solvent contained in the composition.

(11) The composition according to any one of (1) to (10), wherein the component (B) is 0.1% by mass to 30% by mass in the composition.

(12) A resin film obtained from the composition according to any one of (1) to (11) above.

(13) A liquid crystal aligning agent obtained from the composition according to any one of (1) to (11) above.

(14) A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to (13).

(15) A liquid crystal alignment film obtained by an ink jet method using the liquid crystal alignment treatment agent according to (13).

(16) A liquid crystal display device having the liquid crystal alignment film according to (14) or (15).

(17) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (14) or (15), wherein the liquid crystal alignment film is used for a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(18) A liquid crystal display device comprising the liquid crystal alignment film according to (17).

(19) A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (14) or (15), wherein the liquid crystal alignment film is used for a liquid crystal display device produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(20) A liquid crystal display element comprising the liquid crystal alignment film according to (19).

  The composition containing a polysiloxane obtained from a solvent having a specific structure and an alkoxysilane having a specific structure according to the present invention can suppress the generation of pinholes when forming a resin film. It can provide as a composition with high level | step difference followability with respect to an unevenness | corrugation.

  In addition, by using the composition of the present invention as a liquid crystal alignment treatment agent, it is possible to suppress the generation of pinholes, and further to provide a liquid crystal alignment film having a high step following property to the unevenness of the step substrate. Can do. Furthermore, the liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. Therefore, the liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used.

It is a figure showing the level | step difference board | substrate which comprised the resin film obtained by apply | coating the composition of this invention.

As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.
The present invention relates to a composition containing the following components (A) and (B), a liquid crystal alignment treatment agent, a resin film obtained using the composition, and a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent. Furthermore, the present invention relates to a liquid crystal display element having the liquid crystal alignment film.

（式［１］中、Ｘ^１およびＸ^２は、それぞれ独立して、炭素数１〜３のアルキル基を示し、Ｘ^３およびＸ^４は、それぞれ独立して、炭素数１〜３のアルキル基を示す）。Component (A): A solvent represented by the following formula [1] (also referred to as a specific solvent).

(In Formula [1], X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms, and X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms. Showing).

（式［２ａ］中、Ａ^１は、下記の式［２ａ−１］および式［２ａ−２］で示される構造（合わせて特定側鎖構造ともいう）から選ばれる少なくとも１種の構造を示し、Ａ^２は、それぞれ独立して、水素原子または炭素数１〜５のアルキル基を示し、Ａ^３はそれぞれ独立して、炭素数１〜５のアルキル基を示し、ｍ^１は、１または２の整数を示し、ｎ^１は、０〜２の整数を示し、ｐ^１は、０〜３の整数を示す。ただし、ｍ^１＋ｎ^１＋ｐ^１は４の整数を示す）。

（式［２ａ−１］中、Ｙ^１は、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^２は、単結合または−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示し、Ｙ^３は、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^４は、ベンゼン環、シクロヘキサン環および複素環から選ばれる少なくとも１種の環状基、またはステロイド骨格を有する炭素数１７〜５１の２価の有機基を示し、前記環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、Ｙ^５は、ベンゼン環、シクロヘキサン環および複素環から選ばれる少なくとも１種の環状基を示し、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、ｎは０〜４の整数を示し、Ｙ^６は、炭素数１〜２２のアルキル基、炭素数２〜２２のアルケニル基、炭素数１〜２２のフッ素含有アルキル基、炭素数１〜２２のアルコキシル基および炭素数１〜２２のフッ素含有アルコキシル基から選ばれる少なくとも１種を示す）。

（式［２ａ−２］中、Ｙ^７は、単結合、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、Ｙ^８は、炭素数８〜２２のアルキル基または炭素数６〜１８のフッ素含有アルキル基を示す）。

（式［２ｂ］中、Ｂ^１は、それぞれ独立して、ビニル基、エポキシ基、アミノ基、メルカプト基、イソシアネート基、メタクリル基、アクリル基、ウレイド基およびシンナモイル基から選ばれる少なくとも１種を有する炭素数２〜１２の有機基を示し、Ｂ^２は、それぞれ独立して、水素原子または炭素数１〜５のアルキル基を示し、Ｂ^３は、それぞれ独立して、炭素数１〜５のアルキル基または炭素数１〜５のアルコキシアルキル基を示し、ｍ^２は、１または２の整数を示し、ｎ^２は、０〜２の整数を示し、ｐ^２は、０〜３の整数を示す。ただし、ｍ^２＋ｎ^２＋ｐ^２は、４の整数を示す）。

（式［２ｃ］中、Ｄ^１は、それぞれ独立して、水素原子または炭素数１〜５のアルキル基を示し、Ｄ^２はそれぞれ独立して、炭素数１〜５のアルキル基を示し、ｎ^３は、０〜３の整数を示す）。Component (B): polysiloxane obtained by polycondensation of an alkoxysilane containing at least one selected from alkoxysilanes represented by the following formula [2a], formula [2b] and formula [2c] (also referred to as a specific polysiloxane) Say).

(In the formula [2a], A ¹ represents at least one structure selected from the structures represented by the following formulas [2a-1] and [2a-2] (also referred to as specific side chain structures). , A ² each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A ³ independently represents an alkyl group having 1 to 5 carbon atoms, and m ¹ represents 1 or 2 N ¹ represents an integer of 0 to 2, and p ¹ represents an integer of 0 to 3. However, m ¹ + n ¹ + p ¹ represents an integer of 4.

(In Formula [2a-1], Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, — _{NHCO -, - CON (CH 3} ) -, - N (CH 3) CO -, - COO- and -OCO- represents at least one bond group selected from, ^{Y 2} is a single bond or - (CH ₂ ) _b - indicates (b is an integer of 1 to 15), ^{Y 3} represents a single _{bond, - (CH 2) c -} (c is an integer of 1~15), - O -, - CH 2 O -, - COO- and -OCO- represents at least one bond group selected from, Y ⁴ is a carbon having at least one cyclic group, or steroid skeleton, selected from benzene ring, cyclohexane ring and heterocyclic 17 represents a divalent organic group of 17 to 51, and an arbitrary hydrogen atom on the cyclic group is Alkyl group prime 1-3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, may be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms, Y ⁵ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms. May be substituted with an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4, and Y ⁶ represents carbon An alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and a fluorine-containing alkoxy having 1 to 22 carbon atoms At least one selected from the group consisting of

(In formula [2a-2], Y ⁷ represents a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—. , -COO- and -OCO-, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms).

(In Formula [2b], each B ¹ independently has at least one selected from a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acrylic group, a ureido group, and a cinnamoyl group. An organic group having 2 to 12 carbon atoms, B ² independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and B ³ is independently an alkyl having 1 to 5 carbon atoms. A group or an alkoxyalkyl group having 1 to 5 carbon atoms, m ² represents an integer of 1 or 2, n ² represents an integer of 0 to 2, and p ² represents an integer of 0 to 3. ^{However, m 2 + n 2 + p} 2 is an integer of 4).

(In Formula [2c], each D ¹ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, each D ² independently represents an alkyl group having 1 to 5 carbon atoms, and n ³ represents an integer of 0 to 3).

  The specific solvent of the present invention has a higher viscosity as a solvent than alcohol-based or glycol-based solvents usually used for polysiloxane polymers. Therefore, the composition using the specific solvent of the present invention and the liquid crystal aligning agent (also referred to as a coating solution), when coated on the substrate, the coverage with respect to the nucleated foreign matter on the substrate is increased, A resin film and a liquid crystal alignment film that can suppress the generation of pinholes can be obtained. Furthermore, for the reasons described above, the coating solution using the specific solvent of the present invention increases the step following property to the unevenness of the substrate step, and it is also possible to obtain a resin film or a liquid crystal alignment film having a uniform film thickness.

  In addition, the specific solvent of the present invention has a lower surface tension than N-methyl-2-pyrrolidone (also referred to as NMP) or γ-butyrolactone (also referred to as γ-BL), which has a high viscosity as a solvent. Therefore, the coating solution using the specific solvent of the present invention has a high wettability with respect to core-free foreign matters (for example, oily stains) and obtains a resin film and a liquid crystal alignment film that can suppress the occurrence of repellency. be able to.

In addition, the component (B) of the present invention is obtained by polycondensing an alkoxysilane containing at least one selected from the alkoxysilanes represented by the formula [2a], the formula [2b] and the formula [2c]. Siloxane. Above all, the case of a liquid crystal alignment film using a composition of the present invention to a liquid crystal alignment treating agent, alkoxysilane A ¹ in the formula [2a] is a specific side chain structure represented by the formula [2a-1] It is preferable that the polysiloxane is used. This specific side chain structure has a benzene ring, cyclohexyl ring or heterocyclic divalent cyclic group or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton in the side chain portion. These divalent cyclic groups such as a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton exhibit a rigid structure as compared with a long-chain alkyl group of the prior art. . As a result, the stability of the side chain site to heat and ultraviolet light is improved, and a liquid crystal alignment film having a stable pretilt angle against heat and light is obtained.

  From the above points, the composition containing the specific solvent and specific polysiloxane of the present invention is a composition capable of forming a resin film having excellent coating properties.

  In addition, the liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film having excellent coating properties, and further, a liquid crystal that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. It becomes an alignment film. Therefore, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having excellent display characteristics can be obtained.

  Hereinafter, embodiments of the present invention will be described in more detail.

<Specific solvent>
The specific solvent of the present invention is a solvent represented by the following formula [1].

In the formula [1], X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group or an isopropyl group), preferably a methyl group or an ethyl group. And particularly preferably a methyl group.

In the formula [1], X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, or an isopropyl group), preferably a methyl group or an ethyl group. And particularly preferably a methyl group.

Specifically, what is represented by the following formula [1a] is preferable.

  The specific solvent of the present invention is 10 to 90% by mass of the total solvent contained in the composition and the liquid crystal aligning agent in order to enhance the effect of improving the step following property and wettability of the coating solution with respect to the unevenness of the substrate. It is preferable. Especially, 15-80 mass% is preferable. More preferably, it is 20-80 mass%, More preferably, it is 30-70 mass%.

  Of the total solvent in the composition and the liquid crystal alignment treatment agent, the greater the amount of the specific solvent of the present invention, the higher the effect of the present invention, and it is possible to obtain a resin film and a liquid crystal alignment film excellent in coating properties. it can.

<Specific polysiloxane>
The specific polysiloxane which is the component (B) of the present invention is obtained by polycondensing an alkoxysilane containing at least one selected from the alkoxysilanes represented by the following formula [2a], formula [2b] and formula [2c]. The resulting polysiloxane.

The alkoxysilane represented by the formula [A1] of the present invention is an alkoxysilane having a structure represented by the following formula [A1].

In Formula [2a], A ¹ represents at least one specific side chain structure selected from the structures represented by Formula [2a-1] and Formula [2a-2] below.

In formula [2a-1], Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, —NHCO. _{-, - CON (CH 3)} -, - N (CH 3) CO -, - COO- represents at least one linking group selected from and -OCO-. Among these, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or —COO. -Is preferred. More preferred is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

In formula [2a-1], Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.

In formula [2a-1], Y ³ represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO—, and —OCO. -At least 1 type of coupling group chosen from-is shown. Among these, from the viewpoint of ease of synthesis, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, or —COO— is preferable. More preferred is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

In Formula [2a-1], Y ⁴ is at least one divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 carbon atom. -3 alkyl group, C1-C3 alkoxyl group, C1-C3 fluorine-containing alkyl group, C1-C3 fluorine-containing alkoxyl group, or a fluorine atom. Further, Y ⁴ may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms having a steroid skeleton. Among these, from the viewpoint of ease of synthesis, a divalent cyclic group of a benzene ring or a cyclohexane ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton is preferable.

In Formula [2a-1], Y ⁵ represents at least one divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 carbon atom. -3 alkyl group, C1-C3 alkoxyl group, C1-C3 fluorine-containing alkyl group, C1-C3 fluorine-containing alkoxyl group, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.

  In formula [2a-1], n represents an integer of 0 to 4. Especially, 0-3 are preferable from the point of the availability of a raw material and the ease of a synthesis | combination. More preferably, it is 0-2.

In Formula [2a-1], Y ⁶ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and At least 1 type chosen from a C1-C22 fluorine-containing alkoxyl group is shown. Among them, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl having 1 to 10 carbon atoms. Groups are preferred. More preferably, they are a C1-C12 alkyl group, a C2-C12 alkenyl group, or a C1-C12 alkoxyl group. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Preferable combinations of Y ^{1 to} Y ⁶ and n in the formula [2a-1] are listed in Tables 6 to 47 on pages 13 to 34 of International Publication No. 2011/132751 (published 2011.10.27). (2-1) to (2-629) are the same combinations. In each table of International Publication, ^Y 1 to Y ⁶ in the present invention is shown as Y1 to Y6, Y1 to ^Y6, shall read Y 1 to Y ^6. Moreover, in (2-605)-(2-629) published in each table | surface of international publication gazette, the C17-C51 organic group which has a steroid skeleton in this invention has 12-12 carbon atoms which have a steroid skeleton. An organic group having 25 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

In Formula [2a-2], Y ⁷ represents a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, It represents at least one linking group selected from —COO— and —OCO—. Among these, a single bond, —O—, —CH ₂ O—, —CONH—, —CON (CH ₃ ) —, or —COO— is preferable. More preferably, they are a single bond, -O-, -CONH-, or -COO-.

In formula [2a-2], Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Of these, an alkyl group having 8 to 18 carbon atoms is preferable.

  As the specific side chain structure of the present invention, it is preferable to use a structure represented by the formula [2a-1] from the viewpoint that a high and stable liquid crystal vertical alignment can be obtained.

In the formula [2a], A ² each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.

In formula [2a], A ³ each independently represents an alkyl group having 1 to 5 carbon atoms. Especially, the C1-C3 alkyl group is preferable from the reactive point of polycondensation.

In the formula [2a], m ¹ is an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis.

Wherein [2a], ^{n 1} is an integer of 0-2.

Wherein [2a], ^{p 1} is an integer of 0 to 3. Especially, the integer of 1-3 is preferable from the reactive point of polycondensation. More preferably, it is 2 or 3.

In the formula [2a], m ¹ + n ¹ + p ¹ is an integer of 4.

（式［ａ−１］〜式［ａ−４］中、Ｒ^１、Ｒ^３、Ｒ^５およびＲ^７は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−１］〜式［ａ−４］中、Ｒ^２、Ｒ^４、Ｒ^６およびＲ^８は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−１］〜式［ａ−４］中、ｍは、それぞれ独立して、２または３を示し、式［ａ−１］〜式［ａ−４］中、ｎは、それぞれ独立して、０または１を示すが、ただし、ｍ＋ｎは、３である）。

（式［ａ−５］〜式［ａ−８］中、Ｒ^１、Ｒ^３、Ｒ^５およびＲ^７は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−５］〜式［ａ−８］中、Ｒ^２、Ｒ^４、Ｒ^６およびＲ^８は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−５］〜式［ａ−８］中、ｍは、それぞれ独立して、２または３を示し、式［ａ−５］〜式［ａ−８］中、ｎは、それぞれ独立して、０または１を示すが、ただし、ｍ＋ｎは、３である）。

（式［ａ−９］〜式［ａ−１２］中、Ｒ^１、Ｒ^３、Ｒ^５およびＲ^７は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−９］〜式［ａ−１２］中、Ｒ^２、Ｒ^４、Ｒ^６およびＲ^８は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−９］〜式［ａ−１２］中、ｍは、それぞれ独立して、２または３を示し、式［ａ−９］〜式［ａ−１２］中、ｎは、それぞれ独立して、０または１を示すが、ただし、ｍ＋ｎは、３である）。

（式［ａ−１３］〜式［ａ−１６］中、Ｒ^１、Ｒ^３、Ｒ^５およびＲ^７は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−１３］〜式［ａ−１６］中、Ｒ^２、Ｒ^４、Ｒ^６およびＲ^８は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−１３］〜式［ａ−１６］中、ｍは、それぞれ独立して、２または３を示し、式［ａ−１３］〜式［ａ−１６］中、ｎは、それぞれ独立して、０または１を示すが、ただし、ｍ＋ｎは、３である）。

（式［ａ−１７］および式［ａ−１８］中、Ｒ^１およびＲ^３は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−１７］および式［ａ−１８］中、Ｒ^２およびＲ^４は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−１７］および式［ａ−１８］中、ｍは、それぞれ独立して、２または３を示し、式［ａ−１７］および式［ａ−１８］中、ｎは、それぞれ独立して、０または１を示すが、ただし、ｍ＋ｎは、３である）。

（式［ａ−１９］〜式［ａ−２２］中、Ｒ^１、Ｒ^５、Ｒ^９およびＲ^１３は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−１９］〜式［ａ−２２］中、Ｒ^２、Ｒ^６、Ｒ^１０およびＲ^１４は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−１９］〜式［ａ−２２］中、Ｒ^３、Ｒ^７、Ｒ^１１およびＲ^１５は、それぞれ独立して、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−および−ＣＨ_２ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、式［ａ−１９］〜式［ａ−２２］中、Ｒ^４、Ｒ^８、Ｒ^１２およびＲ^１６は、それぞれ独立して、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数１〜１２のフッ素含有アルキル基または炭素数１〜１２のフッ素含有アルコキシ基を示し、式［ａ−１９］〜式［ａ−２２］中、ｍは、それぞれ独立して、２または３を示し、式［ａ−１９］〜式［ａ−２２］中、ｎは、それぞれ独立して、０または１を示すが、ただし、ｍ＋ｎは、３であり、式［ａ−２０］〜式［ａ−２２］中の１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体を示す）。

（式［ａ−２３］および式［ａ−２４］中、Ｒ^１およびＲ^５は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−２３］および式［ａ−２４］中、Ｒ^２およびＲ^６は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−２３］および式［ａ−２４］中、Ｒ^３およびＲ^７は、それぞれ独立して、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−および−ＣＨ_２ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、式［ａ−２３］および式［ａ−２４］中、Ｒ^４およびＲ^８は、それぞれ独立して、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数１〜１２のフッ素含有アルキル基、炭素数１〜１２のフッ素含有アルコキシ基、フッ素基、シアノ基、トリフルオロメチル基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基および水酸基から選ばれる少なくとも１種の有機基を示し、式［ａ−２３］および式［ａ−２４］中、ｍは、それぞれ独立して、２または３を示し、式［ａ−２３］および式［ａ−２４］中、ｎは、それぞれ独立して、０または１を示すが、ただし、ｍ＋ｎは、３である）。

（式［ａ−２５］〜式［ａ−２８］中、Ｒ^１、Ｒ^５、Ｒ^９およびＲ^１３は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−２５］〜式［ａ−２８］中、Ｒ^２、Ｒ^６、Ｒ^１０およびＲ^１４は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−２５］〜式［ａ−２８］中、Ｒ^３、Ｒ^７、Ｒ^１１およびＲ^１５は、それぞれ独立して、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−および−ＣＨ_２ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、式［ａ−２５］〜式［ａ−２８］中、Ｒ^４、Ｒ^８、Ｒ^１２およびＲ^１６は、それぞれ独立して、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数１〜１２のフッ素含有アルキル基または炭素数１〜１２のフッ素含有アルコキシ基を示し、式［ａ−２５］〜式［ａ−２８］中、ｍは、それぞれ独立して、２または３を示し、式［ａ−２５］〜式［ａ−２８］中、ｎは、それぞれ独立して、０または１を示すが、ただし、ｍ＋ｎは、３であり、式［ａ−２６］〜式［ａ−２８］中の１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体を示す）。

（式［ａ−２９］〜式［ａ−３１］中、Ｒ^１、Ｒ^５およびＲ^９は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−２９］〜式［ａ−３１］中、Ｒ^２、Ｒ^６およびＲ^１０は、それぞれ独立して、炭素数１〜３のアルキル基を示し、式［ａ−２９］〜式［ａ−３１］中、Ｒ^３、Ｒ^７およびＲ^１１は、それぞれ独立して、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−および−ＣＨ_２ＯＣＯ−から選ばれる少なくとも１種の結合基を示し、式［ａ−２９］〜式［ａ−３１］中、Ｒ^４、Ｒ^８およびＲ^１２は、それぞれ独立して、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数１〜１２のフッ素含有アルキル基または炭素数１〜１２のフッ素含有アルコキシ基を示し、式［ａ−２９］〜式［ａ−３１］中、ｍは、それぞれ独立して、２または３を示し、式［ａ−２９］〜式［ａ−３１］中、ｎは、それぞれ独立して、０または１を示すが、ただし、ｍ＋ｎは、３であり、式［ａ−２９］〜式［ａ−３１］中の１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体を示す）。

（式［ａ−３２］中、Ｒ^１は、それぞれ炭素数１〜３のアルキル基を示し、Ｒ^２は、それぞれ炭素数１〜３のアルキル基を示し、ｍは、２または３を示し、ｎは、０または１を示すが、ただし、ｍ＋ｎは、３であり、Ｂ^１４は、フッ素原子で置換されていてもよい炭素数３〜２０のアルキル基を示し、Ｂ^１３は、１，４−シクロへキシレン基または１，４−フェニレン基を示し、Ｂ^１２は、酸素原子またはＣＯＯ−＊（但し、「＊」を付した結合手がＢ^３と結合する。）を示し、Ｂ^１１は、酸素原子またはＣＯＯ−＊（但し、「＊」を付した結合手が（ＣＨ_２）ａ^２と結合する。）である。また、ａ^１は、０または１の整数を示し、ａ^２は、２〜１０の整数を示し、ａ^３は、０または１の整数を示す）。Specific examples of the specific alkoxysilane (a) represented by the formula [2a] include alkoxysilanes represented by the following formulas [a-1] to [a-32].

(In the formula [a-1] to the formula [a-4], R ¹ , R ³ , R ⁵ and R ⁷ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-1 ] To [a-4], R ² , R ⁴ , R ⁶ and R ⁸ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-1] to the formula [a- 4], m independently represents 2 or 3, and in formulas [a-1] to [a-4], n independently represents 0 or 1, provided that m + n is 3.)

(In the formulas [a-5] to [a-8], R ¹ , R ³ , R ⁵ and R ⁷ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-5 ] To formula [a-8], R ² , R ⁴ , R ⁶ and R ⁸ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-5] to the formula [a- 8], m independently represents 2 or 3, and in the formulas [a-5] to [a-8], n each independently represents 0 or 1, provided that m + n is 3.)

(In formula [a-9] to formula [a-12], R ¹ , R ³ , R ⁵ and R ⁷ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-9 ] To the formula [a-12], R ² , R ⁴ , R ⁶ and R ⁸ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-9] to the formula [a- 12], m independently represents 2 or 3, and in the formulas [a-9] to [a-12], n independently represents 0 or 1, provided that m + n is 3.)

(In Formula [a-13] to Formula [a-16], R ¹ , R ³ , R ⁵ and R ⁷ each independently represents an alkyl group having 1 to 3 carbon atoms, and Formula [a-13 ] To [a-16], R ² , R ⁴ , R ⁶ and R ⁸ each independently represent an alkyl group having 1 to 3 carbon atoms, and the formula [a-13] to the formula [a- 16], m independently represents 2 or 3, and in the formulas [a-13] to [a-16], n independently represents 0 or 1, provided that m + n is 3.)

(In the formula [a-17] and the formula [a-18], R ¹ and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-17] and the formula [a- 18], R ² and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms, and in formula [a-17] and [a-18], m is each independently 2 or 3, and in the formula [a-17] and [a-18], n independently represents 0 or 1, provided that m + n is 3.

(In formula [a-19] to formula [a-22], R ¹ , R ⁵ , R ⁹ and R ¹³ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-19 ] To [a-22], R ² , R ⁶ , R ¹⁰ and R ¹⁴ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-19] to the formula [a- 22], R ³ , R ⁷ , R ¹¹ and R ¹⁵ are each independently —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, At least one linking group selected from —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, and —CH ₂ OCO—, during ^{[a-22], R 4} , R 8, R 12 and ^{R 16} are each independently alkyl having 1 to 12 carbon atoms A group, an alkoxy group having 1 to 12 carbon atoms, a fluorine-containing alkyl group having 1 to 12 carbon atoms or a fluorine-containing alkoxy group having 1 to 12 carbon atoms, and in formula [a-19] to formula [a-22], m independently represents 2 or 3, and in formulas [a-19] to [a-22], n independently represents 0 or 1, provided that m + n represents 3 And cis-trans isomerism of 1,4-cyclohexylene in the formulas [a-20] to [a-22] represents a trans isomer).

(In the formula [a-23] and the formula [a-24], R ¹ and R ⁵ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-23] and the formula [a- 24], R ² and R ⁶ each independently represent an alkyl group having 1 to 3 carbon atoms. In the formula [a-23] and the formula [a-24], R ³ and R ⁷ are respectively Independently, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O -, - COOCH ₂ - and represents at least one linking group selected from _-CH 2 OCO-, wherein [a-23] and the formula [a-24], ^{R 4} and ^{R 8} are each independently An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a fluorine group having 1 to 12 carbon atoms. At least one organic compound selected from a containing alkyl group, a fluorine-containing alkoxy group having 1 to 12 carbon atoms, a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, and a hydroxyl group In the formula [a-23] and the formula [a-24], m independently represents 2 or 3, and in the formula [a-23] and the formula [a-24], n represents Each independently represents 0 or 1, provided that m + n is 3.

(In formula [a-25] to formula [a-28], R ¹ , R ⁵ , R ⁹ and R ¹³ each independently represent an alkyl group having 1 to 3 carbon atoms, and the formula [a-25 ] To [a-28], R ² , R ⁶ , R ¹⁰ and R ¹⁴ each independently represents an alkyl group having 1 to 3 carbon atoms, and the formula [a-25] to the formula [a- 28], R ³ , R ⁷ , R ¹¹ and R ¹⁵ are each independently —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, 1 represents at least one linking group selected from —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, and —CH ₂ OCO—, represented by the formula [a-25] to the formula during ^{[a-28], R 4} , R 8, R 12 and ^{R 16} are each independently alkyl having 1 to 12 carbon atoms Group, an alkoxy group having 1 to 12 carbon atoms, a fluorine-containing alkyl group having 1 to 12 carbon atoms or a fluorine-containing alkoxy group having 1 to 12 carbon atoms, and in formula [a-25] to formula [a-28], m independently represents 2 or 3, and in the formulas [a-25] to [a-28], n independently represents 0 or 1, provided that m + n represents 3 And the cis-trans isomerism of 1,4-cyclohexylene in the formulas [a-26] to [a-28] represents a trans isomer).

(In Formula [a-29] to Formula [a-31], R ¹ , R ⁵ and R ⁹ each independently represents an alkyl group having 1 to 3 carbon atoms, and Formula [a-29] to Formula [A-29] In [a-31], R ² , R ^6, and R ¹⁰ each independently represent an alkyl group having 1 to 3 carbon atoms, and in Formula [a-29] to Formula [a-31], R ³ , R ⁷ and R ¹¹ are each independently —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, In formula (a-29) to formula [a-31], R ⁴ represents at least one linking group selected from —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, and —CH ₂ OCO—. , R ⁸ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, carbon 1 represents a fluorine-containing alkyl group having 1 to 12 carbon atoms or a fluorine-containing alkoxy group having 1 to 12 carbon atoms, and in formulas [a-29] to [a-31], m independently represents 2 or 3; In the formulas [a-29] to [a-31], n independently represents 0 or 1, provided that m + n is 3, and the formulas [a-29] to [a] The cis-trans isomerism of 1,4-cyclohexylene in a-31] represents the trans isomer).

(In the formula [a-32], R ¹ represents an alkyl group having 1 to 3 carbon atoms, R ² represents an alkyl group having 1 to 3 carbon atoms, m represents 2 or 3, n represents 0 or 1, provided that m + n is 3, B ¹⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and B ¹³ represents 1, 4 -A cyclohexylene group or a 1,4-phenylene group, B ¹² represents an oxygen atom or COO- * (where a bond marked with "*" is bonded to B ³ ), and B ¹¹ represents , An oxygen atom or COO- * (where a bond marked with “*” is bonded to (CH ₂ ) a ² ), and a ¹ represents an integer of 0 or 1, and a ² is represents an integer of 2 to 10, ^{a 3} represents an integer of 0 or 1).

  Further, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, pentyltriethoxysilane, heptadecyltrimethoxysilane , Heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, isooctyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, triethoxy-1H, 1H, 2H, And 2H-tridecafluoro-n-octylsilane.

  The alkoxysilane represented by the formula [2a] of the present invention is soluble in the solvent of the specific polysiloxane of the present invention, the coating property of the composition and the liquid crystal aligning agent, and further the liquid crystal of the liquid crystal alignment film. One type or a mixture of two or more types can be used in accordance with characteristics such as orientation, voltage holding ratio, and accumulated charge.

The alkoxysilane represented by the formula [2b] of the present invention is an alkoxysilane having a structure represented by the following formula [2b].

In the formula [2b], each B ¹ is a carbon having at least one selected from a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acrylic group, a ureido group, and a cinnamoyl group. The organic group of several 2-12 is shown. Among these, a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, or a ureido group is preferable from the viewpoint of availability. More preferably, they are a methacryl group, an acryl group, or a ureido group.

In formula [2b], B ² each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.

In formula [2b], B ³ each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group having 1 to 5 carbon atoms. Especially, the C1-C3 alkyl group is preferable from the reactive point of polycondensation.

In formula [2b], m ² represents an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis.

In the formula [2b], n ² represents an integer of 0 to 2.

Wherein [2b], ^{p 2} is an integer of 0 to 3. Especially, the integer of 1-3 is preferable from the reactive point of polycondensation. More preferably, it is 2 or 3.

In formula [2b], m ² + n ² + p ² represents an integer of 4.

  Specific examples of the alkoxysilane represented by the formula [2b] include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy). Silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltri Methoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4- Poxycyclohexyl) ethyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, 3-mercaptopropyl (dimethoxy) methylsilane, (3-mercapto Propyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) Propyl methacrylate, 3- (triethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 2- (triethoxysilyl) ethyl methacrylate, 2- (trimethoxysilyl) ethyl methacrylate, 2- (triethoxysilyl) Ethyl acrylate, 2- (trimethoxysilyl) ethyl acrylate, (triethoxysilyl) methyl methacrylate, (trimethoxysilyl) methyl methacrylate, (triethoxysilyl) methyl acrylate, (trimethoxysilyl) methyl acrylate, γ-ureidopropyltri Ethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N′-triethoxysilylpropyl Rare, (R) -N-1-phenylethyl-N'-trimethoxysilylpropylurea and the like.

  Among them, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2 -(3,4-Epoxycyclohexyl) ethyltrimethoxysilane is preferred.

  The alkoxysilane represented by the formula [2b] of the present invention is soluble in the solvent of the specific polysiloxane of the present invention, the coating property of the composition and the liquid crystal aligning agent, and further, the liquid crystal of the liquid crystal alignment film. One type or a mixture of two or more types can be used in accordance with characteristics such as orientation, voltage holding ratio, and accumulated charge.

The alkoxysilane represented by the formula [2c] of the present invention is an alkoxysilane having a structure represented by the following formula [2c].

In formula [2c], D ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, respectively, and these may be substituted with a halogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom. Among these, D ¹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In Formula [2c], D ² represents an alkyl group having 1 to 5 carbon atoms. Especially, the C1-C3 alkyl group is preferable from the reactive point of polycondensation.

  In the formula [2c], n represents an integer of 0 to 3.

  Specific examples of the alkoxysilane represented by the formula [2c] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. , Propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dibutoxydimethylsilane, (chloromethyl) triethoxysilane, 3-chloropropyldimethoxymethylsilane 3-chloropropyltriethoxysilane, 2-cyanoethyltriethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane or 3-trimethoxysilane Such as Le propyl chloride.

  Examples of the alkoxysilane in which n is 0 in the formula [2c] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Examples of the alkoxysilane represented by the formula [2c] It is preferable to use alkoxysilane.

  The alkoxysilane represented by the formula [2c] of the present invention is soluble in the solvent of the specific polysiloxane of the present invention, the coating property of the composition and the liquid crystal aligning agent, and further the liquid crystal of the liquid crystal alignment film. One type or a mixture of two or more types can be used in accordance with characteristics such as orientation, voltage holding ratio, and accumulated charge.

  The specific polysiloxane of the present invention is a polysiloxane obtained by polycondensing an alkoxysilane containing at least one selected from the alkoxysilanes represented by the formula [2a], the formula [2b] or the formula [2c]. Polysiloxanes obtained by polycondensation of alkoxysilanes containing a plurality of these alkoxysilanes are preferred. That is, polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by the formulas [2a] and [2b], and two types of alkoxysilanes represented by the formulas [2a] and [2c] Polysiloxane obtained by condensation, polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by the formula [2b] and formula [2c], and the formula [2a], formula [2b] and formula [2] 2c] is a polysiloxane obtained by polycondensation of three types of alkoxysilanes. Among them, polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by formula [2a] and formula [2b], and polycondensation of two types of alkoxysilanes represented by formula [2a] and formula [2c] And polysiloxane obtained by polycondensation of three types of alkoxysilanes represented by formula [2a], formula [2b] and formula [2c] are preferred.

  When the hydrophobicity of the resin film obtained from the composition of the present invention is increased, or when the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is used for a liquid crystal display element that performs display by vertically aligning liquid crystals. Is preferably a polysiloxane using the alkoxysilane of the formula [2a] among the above-mentioned combinations.

  When preparing the specific polysiloxane of the present invention, when a plurality of types of alkoxysilanes are used, the alkoxysilane represented by the formula [2a] is preferably 1 to 40 mol% in all alkoxysilanes, more preferably. Is 1-30 mol%. Moreover, it is preferable that the alkoxysilane shown by Formula [2b] is 1-70 mol% in all the alkoxysilanes, More preferably, it is 1-60 mol%. Furthermore, the alkoxysilane represented by the formula [2c] is preferably 1 to 99 mol%, more preferably 1 to 80 mol% in all alkoxysilanes.

  The method for obtaining the specific polysiloxane used in the present invention is not particularly limited. The specific polysiloxane in the present invention is obtained by polymerizing an alkoxysilane containing any one of the alkoxysilanes represented by the formula [2a], the formula [2b] or the formula [2c] in a solvent, or the formula [2a] It can be obtained by polymerizing a plurality of types of alkoxysilanes from the alkoxysilanes represented by 2a], [2b] and [2c] in a solvent. The specific polysiloxane of the present invention is obtained as a solution obtained by polycondensation of alkoxysilane and uniformly dissolved in a solvent.

  The method for polycondensing the specific polysiloxane of the present invention is not particularly limited. For example, a method in which an alkoxysilane is hydrolyzed and polycondensed in the specific solvent, alcohol solvent or glycol solvent of the present invention can be mentioned. At that time, the hydrolysis / polycondensation reaction may be partially hydrolyzed or completely hydrolyzed. In the case of complete hydrolysis, it is theoretically necessary to add 0.5 times the molar amount of water of all alkoxy groups in the alkoxysilane, but usually an excess amount of water is added more than 0.5 times the molar amount. It is preferable. In order to obtain the specific polysiloxane of the present invention, the amount of water used in the hydrolysis / polycondensation reaction can be appropriately selected according to the purpose, but 0.5% of all alkoxy groups in the alkoxysilane can be selected. It is preferable that it is -2.5 times molar amount.

  For the purpose of promoting hydrolysis and polycondensation reactions, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid or fumaric acid, alkaline substances such as ammonia, methylamine, ethylamine, ethanolamine or triethylamine A compound or a catalyst such as a metal salt such as hydrochloric acid, nitric acid or nitric acid can be used. In addition, the hydrolysis / polycondensation reaction can be promoted by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected according to the purpose. For example, conditions such as heating and stirring at 50 ° C. for 24 hours and then heating and stirring for 1 hour under reflux can be mentioned.

  Furthermore, as another method for polycondensation, a method in which a polycondensation reaction is performed by heating a mixture of an alkoxysilane, a solvent, and oxalic acid. Specifically, in this method, oxalic acid is added in advance to the specific solvent, alcohol solvent or glycol solvent of the present invention to obtain a solution of oxalic acid, and then the alkoxysilane is mixed while the solution is heated. In that case, it is preferable that the quantity of the oxalic acid used for the said reaction shall be 0.2-2.0 mol with respect to 1 mol of all the alkoxy groups in alkoxysilane. This reaction can be carried out at a solution temperature of 50 to 180 ° C., but is preferably carried out under reflux for several tens of minutes to several tens of hours so that the solvent does not evaporate or volatilize.

  In the polycondensation reaction for obtaining the specific polysiloxane of the present invention, when a plurality of alkoxysilanes represented by the formula [2a], the formula [2b] and the formula [2c] are used, a mixture in which a plurality of types of alkoxysilanes are mixed in advance is used. Even if it reacts using, it may react, adding several types of alkoxysilane sequentially.

  The solvent used for the polycondensation reaction of the alkoxysilane is not particularly limited as long as the alkoxysilane can be dissolved, including the specific solvent of the present invention. Moreover, even if it is a solvent in which an alkoxysilane does not melt | dissolve, what is melt | dissolved will be sufficient as long as the polycondensation reaction of alkoxysilane progresses. As a solvent used for the polycondensation reaction, an alcohol is generally generated by a polycondensation reaction of alkoxysilane, and therefore, an alcohol solvent, a glycol solvent, a glycol ether solvent, or a solvent that is compatible with alcohol is used. Specific examples of the solvent used in such a polycondensation reaction include alcohol solvents such as methanol, ethanol, propanol, butanol or diacetone alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1, 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4 -Glucol solvents such as pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol or 1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Lenglycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol ether solvents such as glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether or propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone , N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide or a solvent compatible with alcohol such as m-cresol.

  In the present invention, these solvents used in the polycondensation reaction can be used alone or in combination of two or more.

In the polymerization solution of the specific polysiloxane obtained by the above method, the concentration of silicon atoms contained in all alkoxysilanes charged as a raw material in terms of SiO ₂ (also referred to as SiO ₂ conversion concentration) is 20% by mass or less. preferable. Especially, it is preferable that it is 5-15 mass%. By selecting an arbitrary concentration within this concentration range, the generation of gel in the solution can be suppressed, and a uniform polycondensation solution of specific polysiloxane can be obtained.

  In the present invention, the polycondensation solution of the specific polysiloxane obtained by the above method may be used as it is as the solution of the specific polysiloxane of the component (B) of the present invention, and if necessary, it may be obtained by the above method. The polycondensation solution of the specific polysiloxane may be concentrated, diluted by adding a solvent, or substituted with another solvent to obtain a solution of the specific polysiloxane as the component (B).

  A solvent (also referred to as an addition solvent) used when the above solvent is added for dilution may be a solvent used for the polycondensation reaction or other solvents. The additive solvent is not particularly limited as long as the specific polysiloxane is uniformly dissolved, and one or more kinds can be arbitrarily selected and used. Examples of such an additive solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvent used in the polycondensation reaction.

<Composition / Liquid crystal aligning agent>
The composition of the present invention and a liquid crystal aligning agent using the same are coating solutions for forming a resin film and a liquid crystal alignment film (also collectively referred to as a resin film), and contain a specific solvent and a specific polysiloxane. A coating solution for forming a resin film.

  All the polymer components in the composition and the liquid crystal aligning agent of the present invention may all be the specific polysiloxane of the present invention, or other polymers may be mixed. Examples of other polymers include acrylic polymer, methacrylic polymer, polystyrene, polyamic acid, and polyimide. In that case, content of other polymers other than that is 0.5 mass part-30 mass parts with respect to 100 mass parts of specific polysiloxane of this invention. Especially, 1 mass part-20 mass parts are preferable.

  The solvent in the composition and the liquid crystal aligning agent of the present invention preferably has a solvent content of 70 to 99.9% by mass from the viewpoint of forming a uniform resin film by coating. This content can be appropriately changed depending on the film thickness of the target resin film and the coating method.

  In addition, as the solvent at that time, all may be the specific solvent of the present invention, but any solvent that dissolves the specific polysiloxane of the present invention (also referred to as other solvent) may be used at the same time. . Specific examples of other solvents are shown below, but the invention is not limited to these examples.

  For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl 2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 -Butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, Dioxane, ethylene glycol dimethyl ether, ethylene glycol Recall diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- Heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- ( Methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether Ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monobutyl ether 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether Cetrate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) Ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate Methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropionate Ethyl acetate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate Be mentioned

  Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2 -Pentanone, 1-hexanol, cyclohexanol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl Ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether Ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, or furfuryl alcohol.

  It is preferable that the other solvent of this invention is 10-90 mass% of the whole solvent contained in a composition and a liquid-crystal aligning agent. Especially, 15-80 mass% is preferable. More preferably, it is 20-80 mass%, More preferably, it is 30-70 mass%.

  The other solvent of the present invention can be used alone or in combination of two or more depending on the solubility of the specific polysiloxane of the present invention in the solvent and the applicability of the composition and the liquid crystal alignment treatment agent.

  The composition and the liquid crystal aligning agent of the present invention include at least one substitution selected from a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. It is preferable to introduce a crosslinkable compound having a group or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.

  Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane or 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3 -Epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4A].

  Specific examples include crosslinkable compounds represented by formulas [4a] to [4k] described in paragraphs 58 to 59 of International Publication No. 2011/132751 (published 2011.10.27).

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].

  Specifically, the crosslinkable compounds represented by the formulas [5-1] to [5-42] described in the items 76 to 82 of International Publication No. 2012/014898 (2012.2.2 publication) Can be mentioned.

  Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group or both can be used. The melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

  Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring. Eight-substituted MW-30 (Sanwa Chemical Co., Ltd.) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 and the like Methoxymethylated etoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cyanamide). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.

  Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.

  More specifically, the crosslinkability represented by the formulas [6-1] to [6-48] described in pages 62 to 66 of International Publication No. 2011/132751 (published 2011.10.27). Compounds.

  Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol. Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalic acid neo A crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as pentyl glycol di (meth) acrylate, in addition to 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro It has one polymerizable unsaturated group in the molecule such as 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester, or N-methylol (meth) acrylamide. Examples thereof include a crosslinkable compound.

（式［７Ａ］中、Ｅ^１は、シクロヘキサン環、ビシクロヘキサン環、ベンゼン環、ビフェニル環、ターフェニル環、ナフタレン環、フルオレン環、アントラセン環およびフェナントレン環から選ばれる少なくとも１種を示し、Ｅ^２は、下記の式［７ａ］または式［７ｂ］から選ばれる基を示し、ｎは、１〜４の整数を示す。）

In addition, a compound represented by the following formula [7A] can also be used.

(In the formula [7A], E ¹ represents at least one selected from a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring, and E ² Represents a group selected from the following formula [7a] or [7b], and n represents an integer of 1 to 4.

  The said compound is an example of a crosslinkable compound, It is not limited to these. Moreover, the crosslinkable compound used for the composition of this invention and a liquid-crystal aligning agent may be one type, and may combine two or more types.

  The content of the crosslinkable compound in the composition and the liquid crystal aligning agent of the present invention is preferably 0.1 parts by mass to 150 parts by mass with respect to 100 parts by mass of all the polymer components. Especially, in order for a crosslinking reaction to advance and to express the target effect, 0.1 mass part-100 mass parts are preferable with respect to 100 mass parts of all the polymer components. More preferred is 1 part by mass to 50 parts by mass.

  Unless the effects of the present invention are impaired, the composition and liquid crystal alignment treatment agent of the present invention improve the uniformity of the film thickness and surface smoothness of the resin film when the composition and the liquid crystal alignment treatment agent are applied. Can be used.

  Examples of the compound that improves the film thickness uniformity and surface smoothness of the resin coating include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

  More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) and the like.

  The ratio of these surfactants to be used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.00 parts by mass with respect to 100 parts by mass of all the polymer components contained in the composition and the liquid crystal aligning agent. 01 parts by mass to 1 part by mass.

  Furthermore, in the composition and the liquid crystal alignment treatment agent of the present invention, International Publication No. 2011/132751 (2011.10.27) is disclosed as a compound that promotes charge transfer in the resin film and promotes charge release of the device. The nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed on pages 69 to 73, can also be added. This amine compound may be added directly to the composition and the liquid crystal aligning agent, but it is made into a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with an appropriate solvent. It is preferable to add from the above. The solvent is not particularly limited as long as it is a solvent that dissolves the specific polysiloxane described above.

  In addition to the above-mentioned other solvents, crosslinkable compounds, compounds that improve the film thickness uniformity and surface smoothness, and compounds that promote charge release, the composition and liquid crystal alignment treatment agent of the present invention include As long as the effects of the invention are not impaired, a dielectric material or a conductive material for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the resin coating may be added.

<Resin coating>
The composition of the present invention can be used as a resin film after coating and baking on a substrate. As a substrate used at this time, a plastic substrate such as a glass substrate, a silicon wafer, an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate can be used depending on a target device. Further, the resin coating can be used as it is as a film substrate. The coating method of the composition is not particularly limited, but industrially, there are methods such as a dipping method, a roll coater method, a slit coater method, a spinner method, a spray method, screen printing, offset printing, flexographic printing, or an inkjet method. It is common. You may use these according to the objective.

  After coating the composition on the substrate, it is 30 to 300 ° C., preferably 30 to 250, depending on the solvent used in the composition by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. The solvent can be evaporated at a temperature of 0 ° C. to form a resin film. The thickness of the resin film after baking can be adjusted to 0.01-100 micrometers according to the objective.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment treatment agent using the composition of the present invention can be used as a liquid crystal alignment film by applying alignment treatment by rubbing treatment or light irradiation after coating and baking on a substrate. Further, it can be used as a liquid crystal alignment film for a liquid crystal display element that performs display by vertically aligning liquid crystals without an alignment treatment. The substrate used in this case is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate can also be used. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO (indium tin oxide) electrode or the like for driving a liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.

  The method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.

  After applying the liquid crystal alignment treatment agent on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal alignment treatment agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. Can evaporate the solvent at a temperature of 30 to 250 ° C. to obtain a liquid crystal alignment film. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 150 nm. When the liquid crystal is horizontally aligned or tilted, the fired liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.

  The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the above-mentioned method and then preparing a liquid crystal cell by a known method.

  As a method for manufacturing a liquid crystal cell, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of bonding the substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are dispersed, and the like.

  Furthermore, the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board | substrates provided with the electrode, The polymeric compound superposed | polymerized by at least one of an active energy ray and a heat | fever between a pair of board | substrates. The liquid crystal composition is also preferably used for a liquid crystal display device produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes. Here, ultraviolet rays are suitable as the active energy ray. The ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

  The liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound. The pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. The PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.

  That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above method, a liquid crystal cell is prepared, and a polymerizable compound is applied by at least one of ultraviolet irradiation and heating. Polymerization can control the orientation of liquid crystal molecules.

  To give an example of manufacturing a PSA type liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. Can be mentioned.

  In the liquid crystal, a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, it is preferable that a polymeric compound is 0.01-10 mass parts with respect to 100 mass parts of a liquid-crystal component, More preferably, it is 0.1-5 mass parts. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases and the liquid crystal display element. The seizure characteristics of the steel deteriorate.

  After the liquid crystal cell is produced, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.

  In addition, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of disposing a liquid crystal alignment film containing a group and applying a voltage between the electrodes. Here, ultraviolet rays are suitable as the active energy ray. The ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

  In order to obtain a liquid crystal alignment film containing a polymerizable group that polymerizes from at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, A method using a coalescing component may be mentioned. Since the liquid crystal aligning agent of the present invention contains a specific compound having a double bond site that reacts by irradiation with heat or ultraviolet rays, the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. .

  If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which the substrate is attached and sealed after the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed.

  After the liquid crystal cell is manufactured, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.

  As described above, the liquid crystal aligning agent of the present invention becomes a liquid crystal alignment film having excellent coating properties, and can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. It becomes a liquid crystal alignment film. Therefore, the liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used.

  The present invention will be described in more detail with reference to the following examples, but is not limited thereto.

"Abbreviations used in the synthesis examples, examples and comparative examples of the present invention"
Abbreviations used in the synthesis examples, examples and comparative examples are as follows.

<Monomer for producing the polysiloxane polymer of the present invention>
B1: An alkoxysilane monomer represented by the following formula [B1] (an alkoxysilane monomer represented by the formula [2a] having a specific side chain structure represented by the formula [2a-1] of the present invention)
B2: Octadecyltriethoxysilane (alkoxysilane monomer represented by the formula [2a] having a specific side chain structure represented by the formula [2a-2] of the present invention)
B3: 3-methacryloxypropyltrimethoxysilane (alkoxysilane monomer represented by the formula [2b] of the present invention)
B4: 3-ureidopropyltriethoxysilane (alkoxysilane monomer represented by the formula [2b] of the present invention)
B5: Tetraethoxysilane (alkoxysilane monomer represented by the formula [2c] of the present invention)

<Crosslinkable compound used in the present invention>
K1: Crosslinkable compound represented by the following formula [K1]

<Specific solvent of the present invention>
S1: Solvent represented by the following formula [S1] (solvent represented by the formula [1a] of the present invention)

<Other solvents>
EC: diethylene glycol monoethyl ether BCS: ethylene glycol monobutyl ether PB: propylene glycol monobutyl ether DME: dipropylene glycol dimethyl ether NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone

"Synthesis of the polysiloxane polymer of the present invention"
<Synthesis Example 1>
Prepare a solution of alkoxysilane monomer by mixing EC (29.8 g), B1 (4.10 g) and B5 (39.6 g) in a 200 ml four-neck reaction flask equipped with a thermometer and reflux tube. did. To this solution, a solution prepared by mixing EC (14.9 g), water (10.8 g) and oxalic acid (0.90 g) as a catalyst in advance was added dropwise at 25 ° C. over 30 minutes, and further at room temperature at 25 ° C. For 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 60 minutes, and then allowed to cool to obtain a polysiloxane solution (1) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 2>
Prepare a solution of alkoxysilane monomer by mixing EC (29.7 g), B2 (4.20 g) and B5 (39.6 g) in a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube. did. To this solution, a solution prepared by mixing EC (14.9 g), water (10.8 g) and oxalic acid (0.90 g) as a catalyst in advance was added dropwise at 25 ° C. over 30 minutes, and further at room temperature at 25 ° C. For 30 minutes. Then, after heating using an oil bath and refluxing for 60 minutes, it was allowed to cool to obtain a polysiloxane solution (2) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 3>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, EC (28.2 g), B1 (4.10 g), B3 (14.9 g) and B5 (27.1 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, EC (14.1 g), water (10.8 g) and a solution prepared by mixing oxalic acid (0.90 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 60 minutes, the mixture was allowed to cool to obtain a polysiloxane solution (3) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 4>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, S1 (28.1 g), B2 (4.20 g), B3 (14.9 g) and B5 (27.1 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, a solution prepared by mixing Sakaji (14.1 g), water (10.8 g) and oxalic acid (0.90 g) as a catalyst was added dropwise at 25 ° C. over 30 minutes. The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 60 minutes, it was allowed to cool to obtain a polysiloxane solution (4) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 5>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, EC (27.4 g), B1 (4.10 g), B3 (14.9 g) and B5 (26.3 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, a solution prepared by mixing EC (13.7 g), water (10.8 g) and oxalic acid (0.90 g) as a catalyst in advance at 25 ° C. was added dropwise over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.15 g) with a B4 content of 92 mass% and EC (0.90 g) was added. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (5) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 6>
EC (29.5 g), B3 (14.9 g) and B5 (29.2 g) were mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a solution of alkoxysilane monomer. did. To this solution, EC (14.7 g), water (10.8 g) and a solution prepared by mixing oxalic acid (0.90 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 60 minutes, the mixture was allowed to cool to obtain a polysiloxane solution (6) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 7>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, S1 (30.3 g) and B5 (40.8 g) were mixed to prepare an alkoxysilane monomer solution. To this solution, a solution prepared by mixing S1 (15.2 g), water (10.8 g) and oxalic acid (0.90 g) as a catalyst in advance at 25 ° C. was added dropwise over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.15 g) with a B4 content of 92% by mass and S1 (0.90 g) was added. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (7) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 8>
EC (28.7 g), B3 (14.9 g) and B5 (28.3 g) were mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a solution of alkoxysilane monomer. did. To this solution, EC (14.4 g), water (10.8 g) and a solution prepared by mixing oxalic acid (0.90 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.15 g) with a B4 content of 92 mass% and EC (0.90 g) was added. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (8) having a SiO ₂ equivalent concentration of 12% by mass.

  The polysiloxane (polysiloxane solution) of the present invention is shown in Table 1.

“Production of Composition and Liquid Crystal Alignment Treatment Agent of the Present Invention”
In Examples 1 to 13 and Comparative Examples 1 to 3 described below, production examples of the composition are described. These compositions are also used for evaluation of liquid crystal aligning agents.

  Tables 2 to 4 show the compositions and liquid crystal aligning agents of the present invention.

  “Evaluation of printability of composition and liquid crystal alignment treatment agent (pinhole evaluation)”, “Composition and liquid crystal alignment treatment” using the compositions and liquid crystal alignment treatment agents obtained in Examples and Comparative Examples of the present invention "Evaluation of printability of agent (evaluation of level difference followability)", "Preparation of liquid crystal cell and evaluation of pretilt angle (ordinary cell)", "Evaluation of inkjet coating property of liquid crystal alignment treatment agent", "Preparation of liquid crystal cell and "Evaluation of liquid crystal alignment (PSA cell)" and "Production of liquid crystal cell and evaluation of liquid crystal alignment (SC-PVA cell)" were performed.

"Evaluation of printability of composition and liquid crystal aligning agent (Evaluation of pinhole)"
Using the compositions obtained by the methods of Examples and Comparative Examples of the present invention, pinholes in the resin coating were evaluated. Specifically, these compositions were subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and printed on an unwashed Cr vapor deposition substrate (length 100 mm × width 100 mm, thickness 1.0 mm). A simple printing machine S15 type (made by Nissha Printing Co., Ltd.) was used as the printing machine. The printing area was in the range of 80 × 80 mm with respect to the center of the substrate, the printing pressure was 0.2 mm, the number of discarded substrates was 5, and printing was temporarily performed. The time until drying was 90 seconds, and temporary drying was performed on a hot plate at 70 ° C. for 5 minutes.

  Thereafter, the number of pinholes in the obtained substrate with a resin coating was confirmed. Specifically, the substrate with resin coating was visually observed under a sodium lamp, and the number of pinholes on the resin coating was counted. The smaller the number of pinholes, the fewer the precipitates in the composition, and the better the evaluation.

  Tables 5 to 7 show the number of pinholes obtained in Examples and Comparative Examples.

  In addition, the composition obtained by the Example and comparative example of this invention can be used for a liquid-crystal aligning agent. Therefore, the evaluation of pinholes in the resin film of the compositions obtained in the examples and comparative examples of the present invention was also evaluated as pinholes in the liquid crystal alignment film.

“Evaluation of printability of composition and liquid crystal alignment treatment agent (evaluation of level difference)”
Using the compositions obtained by the methods of Examples and Comparative Examples of the present invention, the printability of the resin coating on the stepped substrate was evaluated. Specifically, these compositions were filtered under pressure with a membrane filter having a pore diameter of 1 μm, and a dot pattern of 100 × 100 μm (a distance between dots of 50 μm, dot thickness within a range of 70 × 70 mm with respect to the center of the substrate). Printing was performed on a glass substrate (length 100 mm × width 100 mm, thickness 0.7 mm) provided with 0.5 μm). A simple printing machine S15 type (made by Nissha Printing Co., Ltd.) was used as the printing machine. The printing area was in the range of 80 × 80 mm with respect to the center of the substrate, the printing pressure was 0.2 mm, the number of discarded substrates was 5, and printing was temporarily performed. The time until drying was 90 seconds, and temporary drying was performed on a hot plate at 70 ° C. for 5 minutes.

  With respect to the obtained resin coating, the followability of the resin coating with respect to the stepped substrate was evaluated. Specifically, the cross section of the obtained resin-coated substrate was observed with a scanning electron microscope (S-4800) (manufactured by Hitachi High-Tech), and the film thickness of the resin film above the dots and the resin film between the dots were observed. This was done by checking the film thickness. More specifically, the film thickness (1) in FIG. 1 (the film thickness of the resin film above the dots, the film thickness at the center of the dots) and the film thickness (2) (the film of the resin film between the dots) The thickness of the central portion between dots was confirmed, and the smaller the difference, the better the followability of the resin film to the stepped substrate.

  Tables 5 to 7 show the film thickness of (1), the film thickness of (2) and the film thickness ratio ((film thickness of (1) / (2)) obtained in Examples and Comparative Examples. Film thickness) × 100).

  In addition, the composition obtained by the Example and comparative example of this invention can be used for a liquid-crystal aligning agent. Therefore, the evaluation of the step followability of the compositions obtained in the examples and comparative examples of the present invention was also evaluated as the step followability of the liquid crystal alignment film.

"Production of liquid crystal cell and evaluation of pretilt angle (normal cell)"
Using the liquid crystal aligning agents obtained by the methods of Examples and Comparative Examples of the present invention, production of liquid crystal cells and evaluation of pretilt angles were performed. Specifically, these liquid crystal alignment treatment agents were pressure filtered through a membrane filter having a pore size of 1 μm and washed with pure water and IPA (isopropyl alcohol) (40 mm long × 30 mm wide, thickness) 0.7 mm) ITO surface is spin-coated, and heated at 80 ° C. for 5 minutes on a hot plate, and then heated at 220 ° C. for 30 minutes in a heat-circulating clean oven for a polyimide liquid crystal alignment film having a thickness of 100 nm. An attached ITO substrate was obtained. The surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.

  Two ITO substrates with the above-mentioned liquid crystal alignment film were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to prepare an empty cell. A nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).

The pretilt angle was evaluated using the obtained liquid crystal cell. The pretilt angle is 95 ° C. after injecting the liquid crystal after 5 minutes isotropic treatment at 95 ° C. (also referred to immediately after the production of the liquid crystal cell), after 5 hours of heat treatment at 120 ° C. (also referred to after storage in the high-temperature bath), and after the injection of the liquid crystal. Then, the liquid crystal cell after the isotropic treatment for 5 minutes was irradiated with ultraviolet rays of 10 J / cm ^{2 in} terms of 365 nm (also referred to as after ultraviolet irradiation).
The pretilt angle was measured at room temperature using PAS-301 (ELSICON). Furthermore, ultraviolet irradiation was performed using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite).

  The evaluation was such that the smaller the change in the pretilt angle after storage in a high-temperature tank or after ultraviolet irradiation with respect to the pretilt angle immediately after production of the liquid crystal cell, the better, that is, the stability of the pretilt angle with respect to heat and ultraviolet rays was higher.

  Tables 8 and 9 show the pretilt angle values obtained in the examples and comparative examples.

"Evaluation of inkjet coating properties of liquid crystal alignment treatment agents"
Liquid crystal aligning agent (4) obtained by the method of Example 4 of the present invention, Liquid crystal aligning agent (7) obtained by the method of Example 7 and Liquid crystal aligning agent obtained by the method of Example 10 Using (10), the inkjet coating property was evaluated. Specifically, these liquid crystal aligning agents are pressure filtered through a membrane filter having a pore size of 1 μm, and washed with pure water and IPA using an HIS-200 (manufactured by Hitachi Plant Technology) as an inkjet coating machine. On the ITO deposited substrate, the coated area is 70 × 70 mm, the nozzle pitch is 0.423 mm, the scan pitch is 0.5 mm, the coating speed is 40 mm / second, the time from coating to temporary drying is 60 seconds, and temporary drying is performed. Application was performed on a hot plate at 70 ° C. for 5 minutes.

  The obtained substrate with a liquid crystal alignment film was visually observed under a sodium lamp and the number of pinholes on the liquid crystal alignment film was counted. The number was 5 or less. Moreover, the liquid crystal aligning film excellent in the coating-film uniformity was obtained in any Example.

  Further, using the obtained substrate with a liquid crystal alignment film, the preparation of the liquid crystal cell and the evaluation of the pretilt angle (normal cell) were performed under the conditions of the above-mentioned “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”. It was.

"Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)"
Using the liquid crystal aligning agent (3) obtained by the method of Example 3 of the present invention and the liquid crystal aligning agent (6) obtained by the method of Example 6, preparation of a liquid crystal cell and evaluation of liquid crystal alignment properties (PSA cell) was performed. Specifically, these liquid crystal aligning agents were pressure filtered through a membrane filter having a pore size of 1 μm, washed with pure water and IPA, and a substrate with ITO electrodes (length: 40 mm × width) of 10 × 10 mm and a pattern spacing of 20 μm. 30 mm, thickness 0.7 mm) and spin coated on the ITO surface of a 10 x 40 mm ITO electrode substrate (length 40 mm x width 30 mm, thickness 0.7 mm) at the center and hot plate at 100 ° C for 5 minutes Then, heat treatment was performed at 230 ° C. for 30 minutes in a heat circulation clean oven to obtain a substrate with a liquid crystal alignment film having a film thickness of 100 nm.

These substrates with a liquid crystal alignment film were combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to produce an empty cell. A nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Ltd.) was added to the empty cell by a reduced pressure injection method, and a polymerizable compound (1) represented by the following formula was added to 100% by mass of the nematic liquid crystal (MLC-6608). Liquid crystal mixed with 0.3% by mass of the polymerizable compound (1) was injected, and the injection port was sealed to obtain a liquid crystal cell.

While applying an AC voltage of 5 V to the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60 mW, the wavelength of 350 nm or less was cut, and ultraviolet irradiation of 20 J / cm ^{2 in} terms of 365 nm was performed, and the alignment direction of the liquid crystal A liquid crystal cell (PSA cell) was controlled. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.

  The response speed of the liquid crystal before and after the ultraviolet irradiation of the liquid crystal cell was measured. As the response speed, T90 → T10 from 90% transmittance to 10% transmittance was measured.

  The PSA cell obtained in any of the examples confirmed that the alignment direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation was higher than that of the liquid crystal cell before ultraviolet irradiation. . Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.

"Production of liquid crystal cell and evaluation of liquid crystal alignment (SC-PVA cell)"
Using the liquid crystal aligning agent (3) obtained by the method of Example 3 of the present invention and the liquid crystal aligning agent (6) obtained by the method of Example 6, preparation of a liquid crystal cell and evaluation of liquid crystal alignment properties (SC-PVA cell) was performed. Specifically, the polymerizable compound (1) shown above is added to these liquid crystal aligning agents in an amount of 2% by mass with respect to 100% by mass of the total polymer components in the liquid crystal aligning agent, and at 25 ° C. for 4 hours. Stir. Thereafter, the obtained liquid crystal aligning agent was pressure filtered through a membrane filter having a pore size of 1 μm, washed with pure water and IPA, and a 10 × 10 mm substrate with an ITO electrode having a pattern spacing of 20 μm (length 40 mm × width 30 mm). , Thickness 0.7mm) and the center of the 10 × 40mm ITO electrode-attached substrate (length 40mm x width 30mm, thickness 0.7mm) is spin-coated on a hot plate at 100 ° C for 5 minutes, The substrate with a liquid crystal alignment film having a film thickness of 100 nm was obtained by heat treatment at 200 ° C. for 30 minutes in a thermal circulation clean oven.

  These substrates with a liquid crystal alignment film were combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to produce an empty cell. A nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.

While applying an AC voltage of 5 V to the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60 mW, the wavelength of 350 nm or less was cut, and ultraviolet irradiation of 20 J / cm ^{2 in} terms of 365 nm was performed, and the alignment direction of the liquid crystal A liquid crystal cell (SC-PVA cell) was controlled. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.

  The response speed of the liquid crystal before and after the ultraviolet irradiation of the liquid crystal cell was measured. As the response speed, T90 → T10 from 90% transmittance to 10% transmittance was measured.

  The SC-PVA cell obtained in any of the examples showed that the response speed of the liquid crystal cell after ultraviolet irradiation was faster than that of the liquid crystal cell before ultraviolet irradiation. confirmed. Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.

<Example 1>
EC (0.90 g), S1 (8.46 g) and BCS (5.64 g) were added to the polysiloxane solution (1) (15.0 g) obtained by the method of Synthesis Example 1, and the mixture was added at 25 ° C. for 3 hours. Stir to obtain composition (1). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (1) was used for evaluation also as a liquid-crystal aligning agent (1).

  Using the obtained composition (1) and liquid crystal aligning agent (1), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of step following ability)" and "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)" were performed.

<Example 2>
EC (0.90 g), S1 (8.46 g) and PB (5.64 g) were added to the polysiloxane solution (2) (15.0 g) obtained by the method of Synthesis Example 2, and the mixture was added at 25 ° C. for 3 hours. The mixture was stirred to obtain a composition (2). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (2) was used for evaluation also as a liquid-crystal aligning agent (2).

  Using the obtained composition (2) and liquid crystal aligning agent (2), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of step following ability)" and "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)" were performed.

<Example 3>
EC (0.93 g), S1 (11.7 g) and PB (2.91 g) were added to the polysiloxane solution (3) (15.5 g) obtained by the method of Synthesis Example 3, and the mixture was added at 25 ° C. for 3 hours. Stir to obtain a composition (3). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (3) was used for evaluation also as a liquid-crystal aligning agent (3).

  Using the obtained composition (3) and liquid crystal aligning agent (3), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of step following ability)", "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" and "Liquid crystal cell Production and Evaluation of Liquid Crystal Orientation (SC-PVA Cell) ”were performed.

<Example 4>
EC (7.74 g), S1 (9.93), PB (3.31 g) and γ-BL (3.31 g) were added to the polysiloxane solution (3) (10.0 g) obtained by the method of Synthesis Example 3. ) And stirred at 25 ° C. for 3 hours to obtain a composition (4). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (4) was used for evaluation as a liquid-crystal aligning agent (4).

  Using the obtained liquid crystal aligning agent (4), “evaluation of inkjet applicability of liquid crystal aligning agent” and “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)” were performed.

<Example 5>
S1 (3.72 g), BCS (8.46 g) and NMP (2.82 g) were added to the polysiloxane solution (4) (15.0 g) obtained by the method of Synthesis Example 4, and 3 hours at 25 ° C. Stir to obtain a composition (5). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (5) was used for evaluation also as a liquid-crystal aligning agent (5).

  Using the obtained composition (5) and liquid crystal aligning agent (5), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of step following ability)" and "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)" were performed.

<Example 6>
S1 (0.93 g), BCS (5.83 g) and PB (8.74 g) were added to the polysiloxane solution (4) (15.5 g) obtained by the method of Synthesis Example 4, and 3 hours at 25 ° C. The mixture was stirred to obtain a composition (6). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (6) was used for evaluation also as a liquid-crystal aligning agent (6).

  Using the obtained composition (6) and liquid crystal aligning agent (6), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of step following ability)", "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" and "Liquid crystal cell Production and Evaluation of Liquid Crystal Orientation (SC-PVA Cell) ”were performed.

<Example 7>
To the polysiloxane solution (4) (11.0 g) obtained by the method of Synthesis Example 4, S1 (8.52 g), PB (10.9 g) and γ-BL (7.28 g) were added, and at 25 ° C. The mixture was stirred for 3 hours to obtain a composition (7). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (7) was used for evaluation as a liquid-crystal aligning agent (7).

  Using the obtained liquid crystal aligning agent (7), “evaluation of ink jet coatability of liquid crystal aligning agent” and “production of liquid crystal cell and evaluation of pretilt angle (normal cell)” were performed.

<Example 8>
EC (0.90 g), S1 (11.3 g) and NEP (2.82 g) were added to the polysiloxane solution (5) (15.0 g) obtained by the method of Synthesis Example 5, and the mixture was added at 25 ° C. for 3 hours. The mixture was stirred to obtain a composition (8). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (8) was used for evaluation also as a liquid-crystal aligning agent (8).

  Using the obtained composition (8) and liquid crystal aligning agent (8), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of step following ability)" and "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)" were performed.

<Example 9>
To the polysiloxane solution (5) (15.0 g) obtained by the method of Synthesis Example 5, K1 (0.09 g), EC (0.90 g), S1 (8.46 g), DME (2.82 g) and γ-BL (2.82 g) was added, and the mixture was stirred at 25 ° C. for 6 hours to obtain a composition (9). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (9) was used for evaluation also as a liquid-crystal aligning agent (9).

  Using the obtained composition (9) and liquid crystal aligning agent (9), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of step following ability)" and "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)" were performed.

<Example 10>
EC (8.52 g), S1 (12.7 g), DME (1.82 g) and γ-BL (3.64 g) were added to the polysiloxane solution (5) (11.0 g) obtained by the method of Synthesis Example 5. And stirred at 25 ° C. for 3 hours to obtain a composition (10). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (10) was used for evaluation as a liquid-crystal aligning agent (10).

  Using the obtained liquid crystal aligning agent (10), “evaluation of ink jet coatability of liquid crystal aligning agent” and “production of liquid crystal cell and evaluation of pretilt angle (normal cell)” were performed.

<Example 11>
EC (0.96 g), S1 (12.0 g) and PB (3.01 g) were added to the polysiloxane solution (6) (16.0 g) obtained by the method of Synthesis Example 6, and the mixture was added at 25 ° C. for 3 hours. The mixture was stirred to obtain a composition (11). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.

  Using the obtained composition (11), “evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)” and “evaluation of printability of composition and liquid crystal aligning agent (step following property) Evaluation).

<Example 12>
S1 (6.98 g), BCS (6.02 g) and PB (3.01 g) were added to the polysiloxane solution (7) (16.0 g) obtained by the method of Synthesis Example 7, and the mixture was added at 25 ° C. for 3 hours. The mixture was stirred to obtain a composition (12). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.

  Using the obtained composition (12), “evaluation of printability of composition and liquid crystal aligning agent (pinhole evaluation)” and “evaluation of printability of composition and liquid crystal aligning agent (step following property) Evaluation).

<Example 13>
EC (0.90 g), S1 (11.3 g), DME (1.41 g) and NEP (1.41 g) were added to the polysiloxane solution (8) (15.0 g) obtained by the method of Synthesis Example 8. In addition, the mixture was stirred at 25 ° C. for 3 hours to obtain a composition (13). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.

  Using the obtained composition (13), “evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)” and “evaluation of printability of composition and liquid crystal aligning agent (step followability) Evaluation).

<Comparative Example 1>
EC (9.98 g) and BCS (6.02 g) were added to the polysiloxane solution (1) (16.0 g) obtained by the method of Synthesis Example 1, and the mixture was stirred at 25 ° C. for 3 hours. ) In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (14) was used for evaluation also as a liquid-crystal aligning agent (14).

  Using the obtained composition (14) and liquid crystal aligning agent (14), "evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)", "composition and liquid crystal aligning agent "Evaluation of printability (evaluation of step following ability)" and "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)" were performed.

<Comparative example 2>
EC (9.98 g) and BCS (6.02 g) were added to the polysiloxane solution (2) (16.0 g) obtained by the method of Synthesis Example 2, and the mixture was stirred at 25 ° C. for 3 hours. ) In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (15) was used for evaluation also as a liquid-crystal aligning agent (15).

  Using the obtained composition (15) and liquid crystal alignment treatment agent (15), "evaluation of printability of composition and liquid crystal alignment treatment agent (evaluation of pinhole)", "composition and liquid crystal alignment treatment agent "Evaluation of printability (evaluation of step following ability)" and "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)" were performed.

<Comparative Example 3>
EC (12.2 g) and PB (2.82 g) were added to the polysiloxane solution (6) (15.0 g) obtained by the method of Synthesis Example 6, and the mixture was stirred at 25 ° C. for 3 hours. ) In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.

  Using the obtained composition (16), “evaluation of printability of composition and liquid crystal aligning agent (pinhole evaluation)” and “evaluation of printability of composition and liquid crystal aligning agent (step following property) Evaluation).

  As can be seen from the above results, the polyimide film obtained from the composition of the example of the present invention has a uniform coating property that does not generate pinholes compared to the polyimide film obtained from the composition of the comparative example. Indicated. Furthermore, it was possible to obtain a resin film having a high step following property with respect to the unevenness of the step substrate.

  Specifically, the composition using the specific solvent which is the component (A) of the present invention and the composition not using it, that is, the comparison between Example 1 and Comparative Example 1, Example 2 and It is a comparison with Comparative Example 2 and a comparison between Example 11 and Comparative Example 3. In these comparative examples, the number of pinholes on the resin film was larger than in the corresponding examples, and the level difference following the unevenness of the level difference substrate was low. Moreover, since the composition of these Examples was used also for evaluation as a liquid-crystal aligning agent, the result of the Example using these compositions was also made into the result of a liquid-crystal aligning agent.

  Furthermore, the liquid crystal aligning agent using the component (A) of the present invention has a pretilt angle after storage in a high-temperature tank and after ultraviolet irradiation with respect to the pretilt angle immediately after production of the liquid crystal cell, as compared with a liquid crystal aligning agent not using the same. The change of became small. That is, the stability of the pretilt angle against high temperatures and ultraviolet rays was high. Specifically, this is a comparison between Example 1 and Comparative Example 1 and a comparison between Example 2 and Comparative Example 2.

  In addition, when the specific side chain structure of the present invention uses the structure represented by the formula [2a-1], changes in the pretilt angle after storage in a high-temperature tank and after ultraviolet irradiation with respect to the pretilt angle immediately after the liquid crystal cell is produced But smaller. Specifically, it is a comparison between Example 1 and Example 2.

  The composition of the present invention can suppress the generation of pinholes when forming a resin film, and further can obtain a resin film having a high level of follow-up to the unevenness of the step substrate.

  In addition, by using the composition of the present invention as a liquid crystal alignment treatment agent, it is possible to suppress the generation of pinholes, and furthermore, it is possible to obtain a liquid crystal alignment film having a high level of follow-up to the unevenness of the step substrate. it can. Furthermore, the liquid crystal aligning agent of the present invention becomes a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time.

  Therefore, the liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used, and is useful for a TN element, STN element, TFT liquid crystal element, and particularly a vertical alignment type liquid crystal display element such as a VA mode, a PSA mode, and an SC-PVA mode.

Claims (16)

Component (A): Formula [1] below:

(Wherein, X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms, and X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms) And the component (B): the following formula [2a], formula [2b] and formula [2c]:

{In the formula, A ¹ represents the following formula [2a-1] and formula [2a-2]:

Wherein Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON. At least one linking group selected from (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and —OCO—, and Y ² represents a single bond or — (CH ₂ ) _b — (b Is an integer of 1 to 15, and Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO. -And -OCO- represents at least one linking group selected from -OCO-, Y ⁴ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, or a C 17-51 carbon having a steroid skeleton A divalent organic group, wherein any hydrogen atom on the cyclic group has 1 to 3 carbon atoms Alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms may be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms, Y ⁵ is a benzene ring , At least one cyclic group selected from a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a carbon number 1 to 3 fluorine-containing alkyl groups, 1 to 3 carbon-containing fluorine-containing alkoxyl groups or fluorine atoms may be substituted, n represents an integer of 0 to 4 and Y ⁶ represents 1 to 22 carbon atoms. An alkyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 22 carbon atoms. At least one selected) and

Wherein Y ⁷ is a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and -OCO- represents at least one linking group selected from -OCO-, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms). Each of A ² independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A ³ independently represents an alkyl group having 1 to 5 carbon atoms, m ¹ represents an integer of 1 or 2, n ¹ represents an integer of 0 to 2, and p ¹ represents an integer of 0 to 3, provided that m ¹ + n ¹ + p ¹ represents an integer of 4. Show } ;

(In the formula, each B ¹ independently has 2 carbon atoms having at least one selected from vinyl group, epoxy group, amino group, mercapto group, isocyanate group, methacryl group, acrylic group, ureido group and cinnamoyl group. To 12 organic groups, B ² independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and B ³ independently represents an alkyl group or carbon having 1 to 5 carbon atoms. 1 to 5 represents an alkoxyalkyl group, m ² represents an integer of 1 or 2, n ² represents an integer of 0 to 2, and p ² represents an integer of 0 to ^3. However, m ² + n ² + p ² represents an integer of 4); and

(In the formula, each D ¹ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, each D ² independently represents an alkyl group having 1 to 5 carbon atoms, and n ³ is Represents an integer of 0 to 3)
A composition containing a polysiloxane obtained by polycondensation of an alkoxysilane containing at least one selected from the alkoxysilanes represented by formula (1). The solvent of the component (A) is represented by the following formula [1a]:

The composition of Claim 1 which is a solvent shown by these.   The alkoxysilane represented by the formula [2b] of the component (B) is allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxy). The at least one alkoxysilane selected from ethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate. Item 3. The composition according to Item 2.   The alkoxysilane represented by the formula [2b] of the component (B) is 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane and 2- (3 The composition according to claim 1, which is at least one alkoxysilane selected from (1,4-epoxycyclohexyl) ethyltrimethoxysilane.   The polysiloxane of the component (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula [2a] and the formula [2b], or an alkoxysilane represented by the formula [2a] and the formula [2c]. The composition according to any one of claims 1 to 4, which is a polysiloxane containing any one of polysiloxanes obtained by polycondensation.   The polysiloxane as the component (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula [2a], the formula [2b] and the formula [2c]. A composition according to claim 1.   In the composition, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1,3-propanediol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol Bruno methyl ether A composition according to any one of claims 1 to 6 which contains at least one solvent selected from dipropylene glycol dimethyl ether and furfuryl alcohol.   The composition contains at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and 1,3-dimethyl-imidazolidinone. The composition according to claim 7.   Crosslinkability having at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group in the composition The composition according to any one of claims 1 to 8, comprising at least one crosslinkable compound selected from a compound and a crosslinkable compound having a polymerizable unsaturated bond.   The composition as described in any one of Claims 1-9 whose said (A) component is 20-80 mass% of the whole solvent contained in a composition.   The composition as described in any one of Claims 1-10 whose said (B) component is 0.1 mass%-30 mass% in a composition.   The resin film obtained from the composition as described in any one of Claims 1-11.   The liquid-crystal aligning agent obtained from the composition as described in any one of Claims 1-11.   The liquid crystal aligning film obtained using the liquid-crystal aligning agent of Claim 13.   The liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent of Claim 13.   The liquid crystal display element which has a liquid crystal aligning film of Claim 14 or Claim 15.

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