JP6319295B2 - 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 obtained from the composition, a liquid crystal alignment film, and a liquid crystal display element.

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.
As a composition for forming a resin film currently used industrially, a composition containing a polysiloxane polymer obtained by polycondensation of a polyimide polymer having excellent durability and an alkoxysilane is available. 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 liquid crystal display elements, to improve the orientation of the liquid crystal against heat (Patent Document 1, etc.), to increase the film hardness of the liquid crystal alignment film, and to improve the print applicability of the liquid crystal alignment treatment agent. For the purpose, a liquid crystal alignment treatment agent and a liquid crystal alignment film using a polysiloxane polymer have been proposed (Patent Document 2 and the like).
Furthermore, in order to improve the reliability associated with the long-term driving of the liquid crystal display element, a liquid crystal alignment treatment agent and a liquid crystal alignment film containing a polysiloxane polymer and a polyimide polymer (polyimide precursor or polyimide) have been proposed. (Patent Document 3 etc.).

Japanese Patent No. 4243651 International Publication WO2008 / 044644 Japanese Unexamined Patent Publication No. 2010-097007

Resin coatings obtained from polysiloxane polymers are widely used for interlayer insulating films and protective films in electronic devices, as well as liquid crystal alignment films for liquid crystal display elements. And it is calculated | required with respect to these to improve the coating property of a resin film, a protective film, and a liquid crystal aligning 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 or liquid crystal aligning agent obtained from the polysiloxane polymer has a low molecular weight of the polysiloxane polymer, the step following property of the resin film or the liquid crystal alignment film becomes low. That is, it is impossible to obtain a resin film or a liquid crystal alignment film having a uniform film thickness with respect to the unevenness of the substrate step. In particular, the resin film or the liquid crystal alignment film is not coated on the convex part of the step of the substrate, or the film thickness thereof tends to be thin. Accordingly, the function as an interlayer insulating film or 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.
In addition, if a liquid crystal alignment treatment agent containing a polysiloxane polymer and a polyimide polymer is used in order to improve the level difference in the liquid crystal alignment film, the compatibility between the polysiloxane polymer and the polyimide polymer is poor. Become. That is, the compatibility between the polyimide polymer having a high hydrophobicity and the polysiloxane polymer having a high polarity is deteriorated, and precipitation of these polymers occurs while the liquid crystal aligning agent is stored. When coating is applied to the substrate, problems such as the occurrence of pinholes due to repellence occur on the liquid crystal alignment film. Therefore, in the liquid crystal aligning agent containing a polysiloxane polymer and a polyimide polymer, the storage stability is low, and alignment defects associated with pinholes easily occur on the liquid crystal alignment film. In addition, the storage stability of the liquid crystal alignment treatment agent and pinholes on the liquid crystal alignment film are also problematic in the composition and the resin coating obtained therefrom.

Then, an object of this invention is to provide the composition which has the said characteristic.
That is, the present invention is a composition containing a cellulosic polymer and a polysiloxane polymer, and is excellent in storage stability without causing precipitation of the polymer during storage of the composition. Another object of the present invention is to provide a composition suitable for the preparation of a liquid crystal aligning agent, which can suppress the generation of pinholes accompanying repelling and has high step followability with respect to the unevenness of the step substrate.
Moreover, an object of this invention is to provide the liquid crystal display element provided with the liquid crystal aligning film corresponding to the above-mentioned request | requirement.

As a result of intensive studies, the present inventors have found that a composition containing a polysiloxane obtained by polycondensing a cellulose polymer having a specific structure and an alkoxysilane having a specific structure is effective in achieving the above object. As a result, the present invention has been completed.
That is, the present invention has the following gist.

（Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６は、それぞれ独立して、下記の式［１ａ］〜式［１ｍ］から選ばれる構造の基を示す。ｎは１００〜１００００００の整数を示す。）(1) A composition comprising the following component (A) and component (B):
(A) Component: A polymer having a structure represented by the following formula [1].

(X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group having a structure selected from the following formulas [1a] to [1m]. N is 100 to 1000000. Indicates an integer.)

（Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１、Ｘ^１２、Ｘ^１３及びＸ^１４は、それぞれ独立して、ベンゼン環、メチル基、エチル基、ｎ−プロピル基、イソプロピル基又はブチル基を示す。ｎは０〜３の整数を示す。ｍは０〜３の整数を示す。）

(X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a benzene ring, methyl group, ethyl group, n-propyl group, isopropyl group or butyl group. N represents an integer of 0 to 3. m represents an integer of 0 to 3.)

（Ａ^１は、下記の式［２］で示される構造、炭素数６〜１８のアルキル基、又はベンゼン環、シクロヘキサン環又は複素環を有する炭素数６〜２４の有機基を示す。Ａ^２は水素原子又は炭素数１〜５のアルキル基を示す。Ａ^３は炭素数１〜５のアルキル基を示す。ｍは１又は２の整数、ｎは０〜２の整数、ｐは０〜３の整数を示す。ただし、ｍ＋ｎ＋ｐは４である。）Component (B): a polysiloxane obtained by polycondensing an alkoxysilane containing at least one selected from the group consisting of alkoxysilanes represented by the following formulas [A1], [A2] and [A3].

(A ¹ represents a structure represented by the following formula [2], an alkyl group having 6 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms having a benzene ring, a cyclohexane ring or a heterocyclic ring. A ² represents A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A ³ represents an alkyl group having 1 to 5 carbon atoms, m is an integer of 1 or 2, n is an integer of 0 to 2, and p is 0 to 3. Represents an integer, where m + n + p is 4.)

（Ｂ^１はビニル基、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、ウレイド基又はシンナモイル基を有する炭素数２〜１２の有機基を示す。Ｂ^２は水素原子又は炭素数１〜５のアルキル基を示す。Ｂ^３は、炭素数１〜５のアルキル基を示す。ｍは１又は２の整数、ｎは０〜２の整数、ｐは０〜３の整数を示す。ただし、ｍ＋ｎ＋ｐは４である。）

(B ¹ is a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, methacryl group, acryl group, .B ² showing an organic group having 2 to 12 carbon atoms having a ureido group or a cinnamoyl group is a hydrogen atom or a C Represents an alkyl group having 1 to 5. B ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3. (However, m + n + p is 4.)

（Ｄ^１は水素原子又は炭素数１〜５のアルキル基を示す。Ｄ^２は炭素数１〜５のアルキル基を示す。ｎは０〜３の整数を示す。）

^{(D 1} is .D ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is an integer of .n 0-3 represents an alkyl group having 1 to 5 carbon atoms.)

（Ｙ^１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を示す。Ｙ^２は単結合又は−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示す。Ｙ^３は単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を示す。Ｙ^４はベンゼン環、シクロヘキサン環及び複素環から選ばれる２価の環状基、又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は、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又はフッ素原子で置換されていてもよい。Ｙ^５はベンゼン環、シクロヘキサン環及び複素環から選ばれる２価の環状基を示し、これらの環状基上の任意の水素原子は、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又はフッ素原子で置換されていてもよい。ｎは０〜４の整数を示す。Ｙ^６は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基を示す。）

(Y ¹ represents a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—, where Y ² represents a single bond. A bond or — (CH ₂ ) _b — (b is an integer of 1 to 15) Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O —, —CH ₂ O—, —COO— or —OCO—, wherein Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or 2 having 17 to 51 carbon atoms having a steroid skeleton. An arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or 1 carbon atom. optionally substituted with to 3 fluorine-containing alkoxyl group or a fluorine atom .Y ⁵ is a benzene ring, shea A divalent cyclic group selected from a rhohexane ring and a heterocyclic ring is shown, 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 1 to 1 carbon atoms. 3 may be substituted with a fluorine-containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4. Y ⁶ is an alkyl group having 1 to 18 carbon atoms, A C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group is shown.)

  (2) The alkoxysilane represented by the formula [A2] is allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy). The composition according to (1) above, which is at least one selected from the group consisting of silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, and 3- (trimethoxysilyl) propyl methacrylate. object.

  (3) The alkoxysilane represented by the formula [A2] is selected from the group consisting of 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane and 2- (3,4 -The composition as described in said (1) which is at least 1 sort (s) chosen from the group which consists of -epoxy cyclohexyl) ethyl trimethoxysilane.

(4) The proportion of the alkoxysilane represented by the formula [A1], the formula [A2] and the formula [A3] in the component (B) is 1 to 40 mol% and 1 to 70 mol, respectively, in all alkoxysilanes. %, The composition in any one of said (1)-(3) which is 1-99 mol%.
(5) Any of the above (1) to (4), wherein the ratio of the component (A) to the component (B) is such that the component (B) is 1 and the component (A) is 0.1 to 9 in terms of mass ratio. A composition according to claim 1.
(6) The composition according to any one of (1) to (5), further containing 50 to 99.9% by mass of a solvent.

(7) A resin film obtained from the composition according to any one of (1) to (6) above.
(8) A liquid crystal aligning agent comprising the composition according to any one of (1) to (6) above.
(9) A liquid crystal alignment film obtained using the liquid crystal aligning agent according to (8).
(10) A liquid crystal alignment film formed by an ink jet method using the liquid crystal alignment treatment agent according to (8).
(11) A liquid crystal display device having the liquid crystal alignment film according to (9) or (10).

(12) 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 (9) or (10), which is used in a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.
(13) A liquid crystal display device having the liquid crystal alignment film according to (12).

(14) 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 (9) or (10), which is used for a liquid crystal display device produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.
(15) A liquid crystal display device having the liquid crystal alignment film according to (14).

The composition of the present invention is excellent in storage stability, such as no precipitation of a polymer during storage of the composition, and can suppress the occurrence of pinholes when forming a resin film. High level of flatness following unevenness.
In addition, the liquid crystal aligning agent using the composition of the present invention has excellent storage stability, such as no precipitation of a polymer during storage of the liquid crystal aligning agent, and generation of pinholes when forming a liquid crystal alignment film. Furthermore, the step following property is high with respect to the unevenness of the step substrate. As a result, the liquid crystal display element having the obtained liquid crystal alignment film has no defects due to poor alignment of liquid crystals and has high reliability.

It is the schematic of the level | step difference board | substrate which has the resin film of this invention. In FIG. 1, (a) means a dot, (b) means a resin film (liquid crystal alignment film), and (c) means a glass substrate. In addition, the film thickness of (1) in FIG. 1 is the film thickness of the resin film above the dots and means the film thickness of the central part of the dots, and the film thickness of (2) is the film of the resin film between the dots. Thickness means the film thickness at the center between dots. The smaller the difference between the film thickness of (1) and the film thickness of (2), the better the followability of the resin film to the stepped substrate.

  The present invention is selected from the group consisting of component (A) which is a cellulose polymer having the structure of the following formula [1], and alkoxysilanes represented by the following formulas [A1], [A2] and [A3]. It is a composition containing (B) component obtained by polycondensing the alkoxysilane containing at least 1 sort (s).

（Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６は、それぞれ独立に、下記の式［１ａ］〜［１ｍ］から選ばれる構造の基を示し、ｎは１００〜１００００００の整数を示す。）Component (A): a polymer having a structure represented by the following formula [1] (also referred to as a specific cellulose polymer).

(X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group having a structure selected from the following formulas [1a] to [1m], and n is an integer of 100 to 1000000. Is shown.)

（Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１、Ｘ^１２、Ｘ^１３及びＸ^１４は、それぞれ独立に、ベンゼン環、メチル基、エチル基、ｎ−プロピル基、イソプロピル基又はブチル基を示す。ｎは０〜３の整数を示す。ｍは０〜３の整数を示す。）

(X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a benzene ring, methyl group, ethyl group, n-propyl group, isopropyl group or butyl group. N represents an integer of 0 to 3. m represents an integer of 0 to 3.)

（Ａ^１は下記の式［２］で示される構造、炭素数６〜１８のアルキル基、又はベンゼン環、シクロヘキサン環又は複素環を有する炭素数６〜２４の有機基を示す。Ａ^２は水素原子又は炭素数１〜５のアルキル基を示す。Ａ^３は炭素数１〜５のアルキル基を示す。ｍは１又は２の整数、ｎは０〜２の整数、ｐは０〜３の整数。ただし、ｍ＋ｎ＋ｐは４である。）Component (B): polysiloxane obtained by polycondensation of alkoxysilane containing at least one selected from the group consisting of alkoxysilanes represented by the following formula [A1], formula [A2] and formula [A3] (specific Also called polysiloxane).

(A ¹ represents a structure represented by the following formula [2], an alkyl group having 6 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms having a benzene ring, a cyclohexane ring or a heterocyclic ring. A ² represents hydrogen. An atom or an alkyl group having 1 to 5 carbon atoms, A ³ represents an alkyl group having 1 to 5 carbon atoms, m is an integer of 1 or 2, n is an integer of 0 to 2, and p is an integer of 0 to 3. (However, m + n + p is 4.)

（Ｙ^１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を示す。Ｙ^２は単結合又は−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示す。Ｙ^３は単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を示す。Ｙ^４はベンゼン環、シクロヘキサン環及び複素環から選ばれる２価の環状基、又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は、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又はフッ素原子で置換されていてもよい。Ｙ^５はベンゼン環、シクロヘキサン環及び複素環から選ばれる２価の環状基を示し、これらの環状基上の任意の水素原子は、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又はフッ素原子で置換されていてもよい。ｎは０〜４の整数を示す。Ｙ^６は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基を示す。）

(Y ¹ represents a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—, where Y ² represents a single bond. A bond or — (CH ₂ ) _b — (b is an integer of 1 to 15) Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O —, —CH ₂ O—, —COO— or —OCO—, wherein Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or 2 having 17 to 51 carbon atoms having a steroid skeleton. An arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or 1 carbon atom. optionally substituted with to 3 fluorine-containing alkoxyl group or a fluorine atom .Y ⁵ is a benzene ring, shea A divalent cyclic group selected from a rhohexane ring and a heterocyclic ring is shown, 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 1 to 1 carbon atoms. 3 may be substituted with a fluorine-containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4. Y ⁶ is an alkyl group having 1 to 18 carbon atoms, A C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group is shown.)

（Ｂ^１はビニル基、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、ウレイド基又はシンナモイル基を有する炭素数２〜１２の有機基を示す。Ｂ^２は水素原子又は炭素数１〜５のアルキル基を示す。Ｂ^３は炭素数１〜５のアルキル基を示す。ｍは１又は２の整数、ｎは０〜２の整数、ｐは０〜３の整数。ただし、ｍ＋ｎ＋ｐは４である。）

(B ¹ is a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, methacryl group, acryl group, .B ² showing an organic group having 2 to 12 carbon atoms having a ureido group or a cinnamoyl group is a hydrogen atom or a C Represents an alkyl group having 1 to 5. B ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3. However, m + n + p is 4.)

（Ｄ^１は水素原子又は炭素数１〜５のアルキル基を示す。Ｄ^２は炭素数１〜５のアルキル基を示す。ｎは０〜３の整数を示す。）

^{(D 1} is .D ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is an integer of .n 0-3 represents an alkyl group having 1 to 5 carbon atoms.)

The specific cellulose polymer of the present invention has high compatibility with the specific polysiloxane polymer. Therefore, the composition containing these and the liquid crystal aligning agent using the composition (also referred to as the liquid crystal aligning agent of the present invention) are excellent in storage stability without precipitation of the polymer during storage. It becomes a composition or a liquid crystal aligning agent.
Moreover, since the compatibility of the specific cellulose polymer and the specific polysiloxane polymer is high, the resin film or the liquid crystal alignment formed when the composition and the liquid crystal alignment treatment agent using the composition are applied to the substrate. Generation of pinholes on the film can be suppressed.

Since the composition of the present invention and the liquid crystal alignment treatment agent contain a specific cellulose polymer, the resin film or liquid crystal alignment film formed therefrom has a high step following property, that is, with respect to the unevenness of the substrate step. A resin film or a liquid crystal alignment film having a uniform film thickness can be obtained.
Furthermore, since the composition of this invention contains the specific polysiloxane excellent in light resistance and heat resistance with the specific cellulose polymer, stability of the resin film with respect to light and heat becomes high.
In addition, the specific cellulose polymer has many OH groups (hydroxyl groups) and COOH groups (carboxylic acid groups), and can trap ionic impurities such as metals and low molecular weight organic compounds. . Therefore, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in voltage holding ratio even when irradiated with light in a state where an insulating film made of an organic member is present under the liquid crystal alignment film.

That is, the composition of the present invention is excellent in storage stability, such as no precipitation of a polymer during storage, and can suppress the occurrence of pinholes when forming a resin film. High step following property to unevenness.
In addition, the liquid crystal alignment treatment agent of the present invention also has excellent storage stability, such as no polymer precipitation during storage of the liquid crystal alignment treatment agent, and suppresses the generation of pinholes when forming a liquid crystal alignment film. Furthermore, the step following property is high with respect to the unevenness of the step substrate.
Hereinafter, each component contained in the composition of the present invention will be described.

式[１]中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６は、それぞれ独立して、下記の式［１ａ］〜［１ｍ］から選ばれる構造の基を示す。<Specific cellulose polymer>
The specific cellulose polymer as the component (A) is a polymer having a structure represented by the following formula [1].

In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group having a structure selected from the following formulas [1a] to [1m].

In the formulas [1c] to [1m], X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are respectively a benzene ring, a methyl group, an ethyl group, and an n-propyl group. Represents an isopropyl group or a butyl group.
In the formula [1h], n represents an integer of 0 to 3. Among these, an integer of 0 or 1 is preferable.
In formula [1i], m represents an integer of 0 to 3. Among these, an integer of 0 or 1 is preferable.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group having a structure selected from the formulas [1a] to [1m]. There may be two or more types. In particular, it is preferable to use two or more types of groups from the viewpoint of the solubility of a specific cellulose polymer in a solvent and the coating properties of a composition or a liquid crystal alignment treatment agent. More preferably, a group having a structure of the formula [1a] and a group having a structure selected from the formulas [1b] to [1k] are used. Furthermore, it is preferable to use a group having the structure of the formula [1a] and a group having the structure of the formula [1c], the formula [1d], the formula [1e], the formula [1h], or the formula [1i].
In formula [1], n shows the integer of 100-1 million. Especially, the point of the handleability at the time of adjusting the solubility to the solvent of a specific cellulose polymer and a composition or a liquid-crystal aligning agent is preferable. More preferably, it is 100-100000.

Specific examples of the specific cellulose polymer of the present invention include the following, but are not limited to these examples.
For example, cellulose, methylcellulose, ethylcellulose, propylcellulose, butylcellulose, methylethylcellulose, acetylcellulose, cellulose propionate, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose Phthalate, methylaminocellulose, ethylaminocellulose, propylaminocellulose, benzylcellulose, tribenzoylcellulose, cellulose acetate butyrate, cellulose acetate propionate, carboxymethylcellulose, carboxymethylethylcellulose or carboxymethyl Hydroxyethyl cellulose, and the like. Among them, methylcellulose, ethylcellulose, propylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate, benzylcellulose, cellulose acetate propionate, carboxymethylethylcellulose or carboxy Methyl hydroxyethyl cellulose is preferred. More preferred are methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate or carboxymethylethylcellulose. Particularly preferred are methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose or hydroxypropylmethylcellulose phthalate.

These specific cellulose derivatives are generally available. Moreover, there is no restriction | limiting in particular in the method of introduce | transducing group of the structure shown by Formula [1b]-[1m], The existing method can be used.
For example, when introducing a group having the structure of formula [1b], there is a method of reacting cellulose and benzyl chloride in the presence of an alkali. When introducing a group having the structure of formula [1c], cellulose and X ^{7 are used.} There is a method of reacting a halogen compound having the structure of groups in the presence of an alkali, to introduce a group of the structure of formula [1d] is an alkali and an acid chloride compound having a group of the structure of cellulose and X ⁸ Examples thereof include a method of reacting in the presence and a method of reacting cellulose and acetic anhydride.

In addition, when a group having the structure of the formula [1e] is introduced, there is a method in which cellulose and a halogen compound having a group having a structure of X ⁹ -OH are reacted in the presence of an alkali. In the case of introducing, a method of reacting cellulose and a halogen compound having a group having a structure of X ¹⁰ —COOH in the presence of an alkali can be mentioned. Further, when a group having the structure of the formula [1g] is introduced, there is a method in which cellulose and a halogen compound having a group of the structure of X ¹¹ -NH ₂ are reacted in the presence of an alkali. how the case to be introduced, there is a method of reacting a cellulose with phthalic acid, when introducing the structure of formula [1i] can be reacted in the presence of alkali and a halogen compound having a cellulose and X ¹² and phthalic acid skeleton In the case of introducing the structure of the formula [1k], there can be mentioned a method of reacting cellulose and maleic anhydride.

  These specific cellulose-based polymers represented by the formula [1] are soluble in the solvent of the specific cellulose-based polymer of the present invention, the coating properties of the composition and the liquid crystal alignment treatment agent, and further, the liquid crystal alignment film. In this case, one type or a mixture of two or more types can be used according to the characteristics such as the orientation of the liquid crystal, the voltage holding ratio, and the accumulated charge.

<Specific polysiloxane>
The specific polysiloxane which is the component (B) of the present invention includes an alkoxysilane containing at least one selected from the group consisting of alkoxysilanes represented by the following formula [A1], formula [A2] and formula [A3]. It is a polysiloxane obtained by condensation.

式［Ａ１］中、Ａ^１は下記の式［２］で示される構造の何れか、炭素数６〜１８のアルキル基、又はベンゼン環、シクロヘキサン環若しくは複素環を有する炭素数６〜２４の有機基を示す。なかでも、下記の式［２］で示される構造の何れか、又は炭素数６〜１８のアルキル基が好ましい。The alkoxysilane represented by the formula [A1] of the present invention is an alkoxysilane having the following structure.

Wherein [A1], A ¹ is any of structures represented by the following formula [2], the alkyl group having 6 to 18 carbon atoms, or a benzene ring, the organic having 6 to 24 carbon atoms having a cyclohexane ring or heterocyclic ring Indicates a group. Among these, any of the structures represented by the following formula [2] or an alkyl group having 6 to 18 carbon atoms is preferable.

式［２］中、Ｙ^１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を示す。なかでも、原料の入手性や合成の容易さの点から、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−が好ましい。より好ましいのは、単結合、−（ＣＨ_２）_ａ−（ａは１〜１０の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−である。

In Formula [2], Y ¹ represents a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —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—.

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.
Y ³ represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. 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—.

Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom in these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxyl having 1 to 3 carbon atoms. 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. Furthermore, Y ⁴ may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms and having a steroid skeleton. Among these, from the viewpoint of ease of synthesis, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable.

Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxyl having 1 to 3 carbon atoms. 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. Of these, a benzene ring or a cyclohexane ring is preferable.
n shows the integer of 0-4. 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.

Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl 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.

As a preferable combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2], pages 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.27) The same combinations as (2-1) to (2-629) listed in Tables 6 to 47 are mentioned. Incidentally, Y1 to Y6 in the tables of WO, respectively, should be read as ^Y 1 to Y ⁶ of the present invention. In addition, the organic group having 12 to 25 carbon atoms having a steroid skeleton in (2-605) to (2-629) listed in each table of the International Publication has a carbon number of 17 to 17 having a steroid skeleton of the present invention. It shall be read as 51 organic groups.

In formula [A1], A ² is 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.
A ³ is an alkyl group having 1 to 5 carbon atoms. Especially, the C1-C3 alkyl group is preferable from the reactive point of polycondensation.
m is an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis.
n is an integer of 0-2. p is an integer of 0-3. Especially, the integer of 1-3 is preferable from the reactive point of polycondensation. More preferably, it is 2 or 3.
m + n + p is 4.

  Specific examples of the alkoxysilane represented by the formula [A1] include octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxy. Silane, pentyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane Silane, pentafluorophenylpropyltrimethoxysilane, m-styrylethyltrimethoxysilane, p-styrylethyltrimethoxysilane, 1-na Triethoxysilane, 1-naphthyl trimethoxysilane, triethoxy-1H, IH, 2H, 2H-tridecafluoro -n- octyl silane, dimethoxy diphenyl silane, dimethoxy methyl phenyl silane, such as triethoxy phenyl silane.

Furthermore, the alkoxysilane shown by following formula [A1-1]-[A1-32] can be mentioned.

（Ｒ^１は炭素数１〜３のアルキル基を示す。Ｒ^２は炭素数１〜３のアルキル基を示す。ｍは２又は３を示し、ｎは０又は１を示す。）

(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, and n represents 0 or 1)

（Ｒ^１は炭素数１〜３のアルキル基を示す。Ｒ^２は炭素数１〜３のアルキル基を示す。ｍは２又は３を示し、ｎは０又は１を示す。
Ｒ^３は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−又は−ＣＨ_２ＯＣＯ−を示す。
Ｒ^４は炭素数１〜１２のアルキル基、アルコキシ基フッ素含有アルキル基又はフッ素含有アルコキシ基を示す。）

(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, and n represents 0 or 1.
R ³ represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O—. , -COOCH ₂ - or an _-CH 2 OCO-.
R ⁴ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group. )

（Ｒ^１は炭素数１〜３のアルキル基を示す。Ｒ^２は炭素数１〜３のアルキル基を示す。ｍは２又は３を示し、ｎは０又は１を示す。
Ｒ^３は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−又は−ＣＨ_２ＯＣＯ−を示す。
Ｒ^４は炭素数１〜１２のアルキル基、アルコキシ基フッ素含有アルキル基、はフッ素含有アルコキシ基、フッ素基、シアノ基、トリフルオロメタン基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基又は水酸基を示す。）

(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, and n represents 0 or 1.
R ³ represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O—. , -COOCH ₂ - or an _-CH 2 OCO-.
R ⁴ is an alkyl group having 1 to 12 carbon atoms, alkoxy group, fluorine-containing alkyl group, fluorine-containing alkoxy group, fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or A hydroxyl group is shown. )

（Ｒ^１は炭素数１〜３のアルキル基を示す。Ｒ^２は炭素数１〜３のアルキル基を示す。ｍは２又は３を示し、ｎは０又は１を示す。
Ｒ^３は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−又は−ＣＨ_２ＯＣＯ−を示す。
Ｒ^４は炭素数１〜１２のアルキル基、アルコキシ基フッ素含有アルキル基又はフッ素含有アルコキシ基を示す。）

(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, and n represents 0 or 1.
R ³ represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O—. , -COOCH ₂ - or an _-CH 2 OCO-.
R ⁴ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group. )

（Ｒ^１は炭素数１〜３のアルキル基を示す。Ｒ^２は炭素数１〜３のアルキル基を示す。ｍは２又は３を示し、ｎは０又は１を示す。
Ｂ^４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^３は１，４−シクロへキシレン基又は１，４−フェニレン基を示す。Ｂ^２は酸素原子又は−ＣＯＯ−＊（但し、「＊」を付した結合手がＢ^３と結合する。）を示し、Ｂ^１は酸素原子又は−ＣＯＯ−＊（但し、「＊」を付した結合手が（ＣＨ_２）ａ^２）と結合する。）を示す。また、ａ^１は０又は１の整数を示し、ａ^２は２〜１０の整数を示し、ａ^３は０又は１の整数を示す。）

(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, and n represents 0 or 1.
B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group. B ² represents an oxygen atom or —COO— * (where a bond with “*” is bonded to B ³ ), and B ¹ represents an oxygen atom or —COO— * (where “*” is attached). The resulting bond is bonded to (CH ₂ ) a ² ). ). Further, ^{a 1} represents an integer of 0 or 1, ^{a 2} represents an integer of 2 to 10, ^{a 3} represents an integer of 0 or 1. )

  The alkoxysilane represented by the above formula [A1] is the solubility of the specific polysiloxane of the present invention in the solvent, the coating property of the composition and the liquid crystal alignment treatment agent, and the alignment of the liquid crystal when the liquid crystal alignment film is formed. Depending on the characteristics such as property, voltage holding ratio, accumulated charge, etc., one kind or a mixture of two or more kinds can be used.

式［Ａ２］中、Ｂ^１はビニル基、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、ウレイド基又はシンナモイル基を有する炭素数２〜１２の有機基であるなかでも、入手の容易さの点から、ビニル基、エポキシ基、アミノ基、メタクリル基、アクリル基又はウレイド基が好ましい。より好ましくは、メタクリル基、アクリル基又はウレイド基である。The alkoxysilane represented by the formula [A2] of the present invention is an alkoxysilane having the following structure.

Wherein [A2], B ¹ is a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacrylic group, among which an acrylic group, an organic group having 2 to 12 carbon atoms having a ureido group or a cinnamoyl group, From the viewpoint of easy availability, a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group or a ureido group is preferred. More preferably, they are a methacryl group, an acryl group, or a ureido group.

In formula [A2], B ² is 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. B ³ is an alkyl group having 1 to 5 carbon atoms. Especially, the C1-C3 alkyl group is preferable from the reactive point of polycondensation. m is an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis. n is an integer of 0-2. p is an integer of 0-3. Especially, the integer of 1-3 is preferable from the reactive point of polycondensation. More preferably, it is 2 or 3. m + n + p is 4.

  Specific examples of the alkoxysilane represented by the formula [A2] 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, 3- (triethoxysilyl) ethyl methacrylate, 3- (trimethoxysilyl) ethyl methacrylate, 3- (triethoxysilyl) Ethyl acrylate, 3- (trimethoxysilyl) ethyl acrylate, 3- (triethoxysilyl) methyl methacrylate, 3- (trimethoxysilyl) methyl methacrylate, 3- (triethoxysilyl) methyl acrylate, 3- (trimethoxysilyl) Methyl acrylate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N′-triet Sisilylpropylurea, (R) -N-1-phenylethyl-N′-trimethoxysilylpropylurea, bis [3- (trimethoxysilyl) propyl] urea, bis [3- (tripropoxysilyl) propyl] urea 1- [3- (trimethoxysilyl) propyl] urea 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 above formula [A2] is the solubility of the specific polysiloxane of the present invention in the solvent, the applicability of the composition and the liquid crystal alignment treatment agent, and the alignment of the liquid crystal when the liquid crystal alignment film is formed. Depending on the characteristics such as property, voltage holding ratio, accumulated charge, etc., one kind or a mixture of two or more kinds can be used.

式［Ａ３］中、Ｄ^１は水素原子又は炭素数１〜５のアルキル基である。これらは、ハロゲン原子、窒素原子、酸素原子、硫黄原子等で置換されていても良い。Ｄ^１としては、水素原子又は炭素数１〜３のアルキル基が好ましい。
Ｄ^２は炭素数１〜５のアルキル基である。なかでも、重縮合の反応性の点から、炭素数１〜３のアルキル基が好ましい。ｎは０〜３の整数である。The alkoxysilane represented by the formula [A3] of the present invention is an alkoxysilane having the following structure.

In formula [A3], D ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. These may be substituted with a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom or the like. D ¹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
D ² is an alkyl group having 1 to 5 carbon atoms. Especially, the C1-C3 alkyl group is preferable from the reactive point of polycondensation. n is an integer of 0-3.

Specific examples of the alkoxysilane represented by the formula [A3] 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, hexyltrimethoxysilane Emissions, such as 3-trimethoxysilylpropyl chloride.
In the formula [A3], examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and these alkoxysilanes are preferably used.

  The alkoxysilane represented by the above formula [A3] is the solubility of the specific polysiloxane of the present invention in the solvent, the coating property of the composition and the liquid crystal aligning agent, and the alignment of the liquid crystal when the liquid crystal alignment film is formed. Depending on the characteristics such as property, voltage holding ratio, accumulated charge, etc., one kind or a mixture of two or more kinds can be used.

The specific polysiloxane of the present invention is a polysiloxane obtained by polycondensing an alkoxysilane containing at least one selected from the group consisting of alkoxysilanes represented by the formula [A1], formula [A2] and formula [A3]. However, 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 [A1] and [A2], and two types of alkoxysilanes represented by the formulas [A1] and [A3] Polysiloxane obtained by condensation, polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by the formula [A2] and formula [A3], and the formula [A1], formula [A2] and formula [ A polysiloxane obtained by polycondensation of three types of alkoxysilanes represented by A3] is preferred.
In particular, when the hydrophobicity of the resin film obtained from the composition of the present invention is increased, or 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 aligning liquid crystals vertically. In this case, it is preferable to use a polysiloxane obtained by using the alkoxysilane of the formula [A1] among the above-mentioned combinations.

  When preparing the specific polysiloxane, when using a plurality of types of alkoxysilane, the alkoxysilane represented by the formula [A1] is preferably 1 to 40 mol% in all alkoxysilanes, more preferably, 1 to 30 mol%. Moreover, it is preferable that the alkoxysilane shown by Formula [A2] is 1-70 mol% in all the alkoxysilanes, More preferably, it is 1-60 mol%. Furthermore, the alkoxysilane represented by the formula [A3] is preferably 1 to 99 mol%, more preferably 1 to 80 mol% in all alkoxysilanes.

  The method for obtaining the specific polysiloxane is not particularly limited. The specific polysiloxane in the present invention is obtained by polymerizing an alkoxysilane containing at least one selected from the group consisting of alkoxysilanes represented by the formula [A1], formula [A2] and formula [A3] 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 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.
The amount of water used in the hydrolysis / polycondensation reaction for obtaining the specific polysiloxane can be appropriately selected according to the purpose, but is 0.5 to 3.0 times that of all alkoxy groups in the alkoxysilane. Molar amount is preferable, and 0.5 to 2.5 times molar amount is more preferable.

  Also, for the purpose of promoting hydrolysis and polycondensation reaction, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; alkaline such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine Compounds; metal salts such as hydrochloric acid and nitric acid; and the like can be used as catalysts. Furthermore, 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, another method for polycondensation includes a method in which a polycondensation reaction is carried out by heating a mixture of an alkoxysilane, an organic solvent and oxalic acid. Specifically, in this method, oxalic acid is added to the specific solvent or alcohol solvent of the present invention to prepare a oxalic acid solution, and then the alkoxysilane is mixed while the solution is heated. In that case, 0.2-2.5 mol is preferable with respect to 1 mol of all the alkoxy groups in alkoxysilane, and, as for the quantity of the oxalic acid used for the said reaction, 0.5-2.0 mol is more preferable. 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, when a plurality of alkoxysilanes represented by the formulas [A1], [A2] and [A3] are used, a mixture in which a plurality of alkoxysilanes are mixed in advance is used. Even if it reacts, you may react, adding several types of alkoxysilane sequentially.
The solvent used for the polycondensation reaction of alkoxysilane is not particularly limited as long as it can dissolve alkoxysilane. 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 an alkoxysilane progresses.

As the solvent used in the polycondensation reaction, alcohol is generally generated by the polycondensation reaction of alkoxysilane, and therefore, an alcohol solvent, a glycol solvent, a glycol ether solvent, or an organic 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, 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 -Glycol solvents such as pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Cole 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 Glycol ether solvents such as monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, Examples thereof include organic solvents having good compatibility with alcohols such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, and 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 30% by mass or less. preferable. Especially, 5-20 mass% is preferable and 5-15 mass% is more preferable. 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, or if necessary, obtained by the above method. The obtained 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 of component (B).

As a solvent (also referred to as an additive solvent) used for dilution by adding a solvent, a solvent used for a polycondensation reaction or other solvents may be used. 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 solvents used in the polycondensation reaction.
In the present invention, the specific polysiloxane of the component (B) is obtained by subjecting the alcohol generated in the polycondensation reaction when the specific polysiloxane is obtained to normal pressure or reduced pressure before mixing the specific cellulose polymer of the component (A). It is preferable to distill off.

<Composition / Liquid crystal aligning agent>
The composition or liquid crystal alignment treatment agent of the present invention is a coating solution for forming a resin film or a liquid crystal alignment film (also collectively referred to as a resin film) and contains a specific cellulose polymer, a specific polysiloxane, and a solvent. It is a coating solution for forming a coating film.
The ratio of the specific cellulose polymer and the specific polysiloxane in the composition of the present invention or the liquid crystal aligning agent is 1 (mass ratio) when the specific polysiloxane is 1, and the ratio of the specific cellulose polymer is 0.01 to 99. Preferable is 0.1-9, and particularly preferable is 0.1-3.

All the polymer components in the composition or liquid crystal liquid crystal alignment treatment agent of the present invention may be all of the specific cellulose polymer and specific polysiloxane of the present invention, and other polymers are mixed. It may be.
Content of the polymer component in the composition or liquid crystal aligning agent of this invention is 0.1-50 mass%, Preferably it is 1-40 mass%, More preferably, it is 1-35 mass%.
At that time, the content of the other polymer is 0.5 to 15% by mass, preferably 0.5% when all the polymer components are 100% by mass. -10 mass%.
Other polymers include polymers other than cellulosic polymers and polysiloxanes, specifically, polyamic acid, polyimide, polyamide, polyester, acrylic polymer, methacrylic polymer, polyhydroxystyrene, novolac resin, and the like. Can be mentioned.

The content of the solvent in the composition or the liquid crystal aligning agent of the present invention can be appropriately selected from the viewpoint of obtaining the coating method of the composition or the liquid crystal aligning agent and the target film thickness. Especially, it is preferable that content of the solvent in a composition or a liquid-crystal aligning agent is 50-99.9 mass% from a viewpoint that a uniform resin film or liquid crystal aligning film is formed by application | coating. Especially, 60-99 mass% is preferable, Most preferably, it is 65-99 mass%. Moreover, when producing a film using the composition of this invention, it is necessary to make low content of the solvent in a composition. It is preferable that content of the solvent in the composition in that case is 40-95 mass%.
As the solvent used in the composition or the liquid crystal aligning agent of the present invention, the polycondensation solution of the specific polysiloxane may be used as it is, or a new solvent may be added to the polycondensation solution of the specific polysiloxane. The polycondensation solution of the characteristic polysiloxane may be replaced with a new solvent.

The new solvent used at that time is not particularly limited as long as it is an organic solvent capable of dissolving the specific cellulose polymer and the specific polysiloxane. Although the specific example is given to the following, it 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 isopropyl 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 acetate , 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 lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, Methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, lactate ethyl ester, lactate n-propyl ester, lactate n- Examples include butyl ester and isoamyl lactate.

（式［Ｓ１］中、Ｘ^１は炭素数１〜３のアルキル基を示す。式［Ｓ２］中、Ｘ^２は炭素数１〜３のアルキル基を示す。）Furthermore, the solvent shown by following formula [S1] and formula [S2] is also mentioned.

(In formula [S1], X ¹ represents an alkyl group having 1 to 3 carbon atoms. In formula [S2], X ² represents an alkyl group having 1 to 3 carbon atoms.)

  Among them, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 2-methyl-1-butanol, 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 methyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol isobutyl ether Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, furfuryl alcohol.

  Particularly preferably, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1,3-propanediol, 1,3-butanediol, 1,4-butane Diol, 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 Methyl ether, dipropylene glycol dimethyl ether furfuryl alcohol.

Depending on the solubility of the specific cellulose polymer and the specific polysiloxane, the coating properties of the resin film or the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, and the properties of the surface smoothness are 1 One kind or a mixture of two or more kinds can be used.
As long as the effects of the present invention are not impaired, the composition or the liquid crystal aligning agent of the present invention includes a 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 also possible to introduce compounds having at least one substituent selected from the group (also collectively referred to as crosslinkable compounds). In that case, it is necessary to have two or more of these substituents 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, Liglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane, 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.

具体的には、国際公開公報ＷＯ２０１１／１３２７５１（２０１１．１０．２７公開）の５８頁〜５９頁に掲載される式［４ａ］〜［４ｋ］で示される架橋性化合物が挙げられる。The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

Specific examples include crosslinkable compounds represented by formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).

具体的には、国際公開公報ＷＯ２０１２／０１４８９８（２０１２．２．２公開）の７６頁〜８２頁に掲載される式［５−１］〜［５−４２］で示される架橋性化合物が挙げられる。The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

Specific examples include crosslinkable compounds represented by formulas [5-1] to [5-42] published on pages 76 to 82 of International Publication No. WO2012 / 014898 (2012.2.2 publication). .

  Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include amino resins having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde. Examples thereof include resins, succinylamide-formaldehyde resins, and ethylene urea-formaldehyde resins. Specifically, a melamine derivative in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both, a benzoguanamine derivative, glycoluril, or the like 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.

As an example of such a melamine derivative or a benzoguanamine derivative, MX-750 in which an average of 3.7 methoxymethyl groups is substituted per one triazine ring in a commercially available product, and an average of 5. methoxymethyl groups per one triazine ring. 8-substituted MW-30 (Sanwa Chemical Co., Ltd.), 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, and 254, butoxymethylated melamine such as Cymel 506 and 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 and the like Methoxymethylated ethoxy Mitylated 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, methoxymethylolated glycoluril such as Powderlink 1174, and the like.

Examples of crosslinkable compounds such as benzene having a hydroxyl group or an alkoxyl group and phenolic compounds include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1 , 4-bis (sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.
More specifically, the crosslinkable compounds represented by the formulas [6-1] to [6-48] described on pages 62 to 66 of International Publication No. WO2011 / 132751 (published 2011.10.27) Can be mentioned.

  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 and glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meta ) 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, diglycidyl phthalate di (meth) acrylate, neopentyl glycol dihydroxypivalate ( Crosslinkable compounds having two polymerizable unsaturated groups in the molecule such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropylene (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl ( Examples thereof include crosslinkable compounds having one polymerizable unsaturated group in the molecule, such as (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester and N-methylol (meth) acrylamide. .

（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、アントラセン環及びフェナントレン環からなる群から選ばれる基を示す。Ｅ_２は下記の式［７ａ］及び式［７ｂ］から選ばれる基を示し、ｎは１〜４の整数を示す。）

上記した化合物は架橋性化合物の一例であり、これらに限定されるものではない。また、本発明の組成物又は液晶配向処理剤に用いる架橋性化合物は、１種類であってもよく、２種類以上組み合わせてもよい。Furthermore, a compound represented by the following formula [7] can also be used as a crosslinkable compound.

(E ₁ represents a group selected from the group consisting of cyclohexane ring, bicyclohexane ring, benzene ring, biphenyl ring, terphenyl ring, naphthalene ring, fluorene ring, anthracene ring and phenanthrene ring. E ₂ represents the following formula [7a And a group selected from formula [7b], n represents an integer of 1 to 4.

The above-mentioned compound is an example of a crosslinkable compound, and is not limited to these. Moreover, the crosslinkable compound used for the composition or liquid crystal aligning agent of the present invention may be one kind or a combination of two or more kinds.

  Content of the crosslinkable compound in the composition or liquid crystal aligning agent of this invention is 0.1-150 mass parts with respect to 100 mass parts of all the polymer components in a composition or liquid crystal aligning agent. It is preferable. In order for the crosslinking reaction to proceed and to achieve the desired effect, 0.1 to 100 parts by mass is more preferable, and 1 to 50 parts by mass is most preferable with respect to 100 parts by mass of all polymer components.

  In the composition or liquid crystal aligning agent of the present invention, as a compound that promotes charge transfer in a resin film or liquid crystal alignment film, pages 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.27). It is preferable to add a nitrogen-containing heterocyclic amine compound represented by the formulas [M1] to [M156]. This amine compound may be added directly to the composition or the liquid crystal aligning agent, but diluted with a suitable solvent to make a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. It is preferable to add from the above. The solvent to be used is not particularly limited as long as it is a solvent that dissolves the specific cellulose polymer and the specific polysiloxane.

In the composition or liquid crystal alignment treatment agent of the present invention, unless the effect is impaired, the uniformity of the film thickness of the resin film or liquid crystal alignment film when the composition or the liquid crystal alignment treatment agent using the composition is applied, and the surface A compound that improves smoothness can be used. Furthermore, a compound that improves the adhesion between the resin coating or the liquid crystal alignment film and the substrate can also be used.
Examples of the compound that improves the film thickness uniformity and surface smoothness of the resin coating or the liquid crystal alignment film 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) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components in the composition or the liquid crystal aligning agent. Part.

Specific examples of the compound that improves the adhesion between the resin film or the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds described below.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like.

When using the compound which adhere | attaches these substrates, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of all the polymer components in a composition or a liquid-crystal aligning agent, More preferably, 1 ˜20 parts by mass. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the storage stability of the composition or the liquid crystal aligning agent may be deteriorated.
In the composition or the liquid crystal alignment treatment agent of the present invention, in addition to the compounds other than the above, the electrical characteristics such as the dielectric constant and conductivity of the vertical liquid crystal alignment film are changed as long as the effects of the present invention are not impaired. A target dielectric material or conductive material 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 in this case, a glass substrate, a silicon wafer, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like 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, 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, and an inkjet method are common Is. Any of these methods may be used depending on the purpose.
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 simplification of the process, it is preferable to use a substrate on which an ITO electrode 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 aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet method are common. 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 aligning agent on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning 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 100 nm. When the liquid crystal is horizontally aligned or tilted, the fired liquid crystal alignment film is treated by rubbing, irradiation with polarized ultraviolet rays, or the like.

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 alignment treatment agent of the present invention by the method described above, 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. Examples of the method include sealing the substrate by injecting liquid crystal under reduced pressure, and dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and then sealing the substrate by bonding the substrate.

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 preferably used also for a liquid crystal display element produced through a step of polymerizing a polymerizable compound by applying at least one of 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 such as 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, The pretilt of liquid crystal molecules is controlled by the polymer produced by irradiation with ultraviolet rays. Since the orientation 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, a liquid crystal cell is prepared after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and a polymerizable compound is obtained by at least one of ultraviolet irradiation and heating. It is possible to control the orientation of the liquid crystal molecules by polymerizing.
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, the liquid crystal is injected under reduced pressure, and 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. It is done.

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 alignment of the liquid crystal cannot be controlled. 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.

Furthermore, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates. The liquid crystal display element manufactured through the process of arrange | positioning the liquid crystal aligning film containing this, and applying a voltage between electrodes is used preferably.
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 is polymerized by 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 this invention contains the specific compound with the double bond site | part which reacts by irradiation of a heat | fever or an ultraviolet-ray, it can control the orientation of a liquid crystal molecule by at least one of an ultraviolet irradiation and a 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 bonded and the liquid crystal is injected under reduced pressure and sealed, and a method in which the substrate is bonded 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.
The liquid crystal display element produced using the liquid crystal aligning agent of this invention becomes the thing excellent in reliability, and can be utilized suitably for a large-screen, high-definition liquid crystal television.

The present invention will be described in more detail with reference to the following examples, but should not be construed as being limited thereto.
[Abbreviations of compounds used in Synthesis Examples, Examples and Comparative Examples]
<Specific Cellulose Polymer as Component (A)>
CE-1: Hydroxyethyl cellulose (manufactured by WAKO)
CE-2: Hydroxypropyl methylcellulose phthalate (manufactured by ACROS)
CE-3: Hydroxypropyl methylcellulose acetate succinate (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Monomer for Producing Specific Polysiloxane as Component (B)>
B1: Alkoxysilane monomer represented by the following formula [B1] (alkoxysilane monomer represented by the formula [A1])
B2: Octadecyltriethoxysilane (alkoxysilane monomer represented by the formula [A1])
B3: 3-Methacryloxypropyltrimethoxysilane (alkoxysilane monomer represented by the formula [A2])
B4: 3-ureidopropyltriethoxysilane (alkoxysilane monomer represented by the formula [A2])
B5: Tetraethoxysilane (alkoxysilane monomer represented by the formula [A3])

＜溶媒＞
ＥＣ：ジエチレングリコールモノエチルエーテル
ＢＣＳ：エチレングリコールモノブチルエーテル
ＰＢ：プロピレングリコールモノブチルエーテル
ＮＭＰ：Ｎ−メチル−２−ピロリドン<Monomer for producing polyimide polymer>
C1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride C2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride C3: p-phenylenediamine C4 : 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

<Solvent>
EC: diethylene glycol monoethyl ether BCS: ethylene glycol monobutyl ether PB: propylene glycol monobutyl ether NMP: N-methyl-2-pyrrolidone

[Method for measuring molecular weight of polyimide polymer]
The molecular weight of the polyimide precursor and polyimide is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (Showa Denko) and columns (KD-803, KD-805) (Shodex). It measured as follows.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, 10 ml / L of tetrahydrofuran (THF))
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

[Measurement method of imidization rate]
20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

[Synthesis of specific polysiloxane]
<Synthesis Example 1>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, EC (31.6 g) and B5 (41.7 g) were mixed to prepare a solution of alkoxysilane monomer. To this solution, a solution in which EC (15.8 g), water (10.8 g) and oxalic acid (0.20 g) as a catalyst were mixed in advance was added dropwise at 25 ° C. over 30 minutes. 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>
EC (28.3 g), B3 (7.45 g) and B5 (32.5 g) were mixed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube to prepare a solution of alkoxysilane monomer. did. To this solution, EC (12.6 g), water (10.8 g) and a solution prepared by mixing oxalic acid (0.70 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes, Furthermore, it stirred at 25 degreeC for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 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 (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 (28.3 g), B1 (4.10 g), B3 (7.45 g) and B5 (32.5 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, EC (14.2 g), water (10.8 g) and a solution prepared by mixing oxalic acid (0.70 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes, Furthermore, it stirred at 25 degreeC for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 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 (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, EC (28.3 g), B2 (4.10 g), B3 (7.45 g) and B5 (32.5 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, EC (14.2 g), water (10.8 g) and a solution prepared by mixing oxalic acid (0.70 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes, Furthermore, it stirred at 25 degreeC for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 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 (4) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 5>
Prepare a solution of alkoxysilane monomer by mixing EC (29.2 g), B1 (4.10 g) and B5 (38.8 g) in a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube. did. To this solution, EC (14.6 g), water (10.8 g) and a solution prepared by mixing oxalic acid (0.50 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes, Furthermore, it stirred at 25 degreeC for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 g) containing 92% by mass of B4 and EC (0.90 g) was added. It was. 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.
Table 1 shows the alkoxysilane monomers used in Synthesis Examples 1 to 5 and the amounts used.

[Synthesis of polyimide polymer]
<Synthesis Example 6>
C2 (4.06 g, 16.2 mmol) and C3 (3.49 g, 32.4 mmol) were mixed in NMP (21.3 g), reacted at 50 ° C. for 2 hours, and then C1 (3.12 g, 15 0.9 mmol) and NMP (10.7 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 25 mass%. The number average molecular weight of this polyamic acid was 25,900, and the weight average molecular weight was 76,400.

<Synthesis Example 7>
C2 (3.83 g, 15.3 mmol), C3 (1.65 g, 15.3 mmol) and C4 (6.04 g, 15.3 mmol) were mixed in NMP (28.9 g) and reacted at 50 ° C. for 2 hours. After that, C1 (2.94 g, 15.0 mmol) and NMP (14.5 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25 mass%. . The number average molecular weight of this polyamic acid was 19,300, and the weight average molecular weight was 68,200.

<Synthesis Example 8>
After adding NMP to the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 7 and diluting to 6% by mass, acetic anhydride (3.90 g) and pyridine (2.40 g) were used as imidization catalysts. In addition, the mixture was reacted at 70 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 61%, the number average molecular weight was 21,200, and the weight average molecular weight was 59,500.

[Production of composition and liquid crystal aligning agent]
In Examples 1-14 and Comparative Examples 1-4, the manufacture example of a composition is described. These compositions are also used for evaluating liquid crystal alignment treatment agents.
A composition and a liquid-crystal aligning agent are shown to Tables 2-4.
Using compositions obtained in Examples and Comparative Examples (may be used for liquid crystal alignment treatment agents), [Storage stability test of composition or liquid crystal alignment treatment agent], [Composition or liquid crystal alignment on stepped substrate Evaluation of printability of treatment agent], [Evaluation of inkjet coating property of liquid crystal alignment treatment agent], [Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)], [Preparation of liquid crystal cell and evaluation of liquid crystal alignment] (PSA cell)] and [Evaluation of voltage holding ratio in insulating film coated substrate]. The conditions in the above test and evaluation are as follows.

[Storage stability test of composition or liquid crystal aligning agent]
Using the compositions obtained in Examples and Comparative Examples, storage stability tests of these compositions were performed. Specifically, these compositions were pressure filtered through a membrane filter having a pore size of 1 μm and stored at −15 ° C. for 72 hours. Thereafter, the occurrence of turbidity and precipitates in the composition was confirmed by visual observation.
In Tables 5-7, the result of the storage stability test of the composition (liquid crystal aligning agent containing) obtained by the Example and the comparative example is shown. In addition, in the table | surface, what was turbidity and a precipitate was not seen, but what was a uniform solution was set to (circle), and what showed turbidity and a precipitate was set to x.

Moreover, the ITO surface of the glass substrate with an ITO electrode (length 40mm x width 30mm, thickness 0.7mm) which washed the composition stored at -15 degreeC for 72 hours with pure water and IPA (isopropyl alcohol). And an ITO substrate with a resin coating was produced by heat treatment at 100 ° C. for 5 minutes on a hot plate. Then, the pinhole of the obtained board | substrate with a resin film was evaluated. 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.
In Tables 5-7, the evaluation result of the number of the pinholes on the resin film formed from the composition (liquid crystal aligning agent containing) obtained by the Example and the comparative example is shown.
In addition, the composition obtained by the Example and the comparative example can be used for a liquid-crystal aligning agent. Therefore, the result of the storage stability test of the compositions obtained in Examples and Comparative Examples can be the result of the storage stability test as a liquid crystal alignment treatment agent.

[Evaluation of printability of composition or liquid crystal alignment treatment agent (evaluation of followability of resin film or liquid crystal alignment film on stepped substrate)]
Using the compositions (including the liquid crystal alignment treatment agent) obtained in the examples and comparative examples, the printability for the stepped substrate was evaluated. Specifically, these compositions were subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm. Thereafter, using the filtered composition, a glass substrate with a dot pattern of 100 × 100 μm (a distance between dots of 50 μm and a dot thickness of 0.5 μm) in a range of 70 × 70 mm with respect to the center of the substrate ( Printing was performed on 100 mm long × 100 mm wide and 0.7 mm thick. 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 substrate with a resin film is 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 This was done by confirming and comparing 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.

In Tables 5-7, as evaluation of the printability of the compositions (including liquid crystal alignment treatment agents) obtained in Examples and Comparative Examples, the film thickness of (1), the film thickness and film of (2) in FIG. The results of the thickness ratio (((1) film thickness / (2) film thickness) × 100) are collectively shown.
In addition, the composition obtained by the Example and the comparative example can be used for a liquid-crystal aligning agent. Therefore, the result of the followability of the resin film with respect to the stepped substrate of the composition obtained in Examples and Comparative Examples can be the result of the followability of the resin film with respect to the stepped substrate of the liquid crystal aligning agent.

[Evaluation of inkjet coating properties of liquid crystal aligning agent]
The liquid crystal aligning agent (3) obtained in Example 6 and the liquid crystal aligning agent (9) obtained in Example 12 were pressure filtered through a membrane filter having a pore diameter of 1 μm to evaluate ink jet coatability. It was. Specifically, using an HIS-200 (manufactured by Hitachi Plant Technology Co., Ltd.), an inkjet coater is coated on an ITO (indium tin oxide) vapor-deposited substrate washed with pure water and IPA (isopropyl alcohol). Area 70 × 70 mm, nozzle pitch 0.423 mm, scan pitch 0.5 mm, coating speed 40 mm / second, time from coating to temporary drying 60 seconds, temporary drying 5 at 70 ° C. on a hot plate Application was performed under the condition of 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 3 or less. Moreover, the liquid crystal aligning film excellent in the coating-film uniformity was obtained in any Example.

[Preparation of liquid crystal cell and evaluation of liquid crystal orientation (normal cell)]
The liquid crystal aligning agent obtained in Examples and Comparative Examples was pressure filtered through a membrane filter having a pore size of 1 μm, and the liquid crystal aligning agent stored for 72 hours at −15 ° C. was used to produce a liquid crystal cell (usually Cell). Specifically, these liquid crystal alignment treatment agents are spin-coated on an ITO surface of a 30 × 40 mm ITO electrode substrate (40 mm long × 30 mm wide, 0.7 mm thick) cleaned with pure water and IPA, and hot An ITO substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm was obtained by heat treatment on a plate at 100 ° C. for 5 minutes and further in a heat-circulating clean oven at 200 ° C. for 30 minutes.

Two obtained ITO substrates with a liquid crystal alignment film were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface inside, and a sealant (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed. Next, after bonding the other substrate and the liquid crystal alignment film face each other, the sealing agent is cured by heat treatment at 120 ° C. for 90 minutes in a heat-circulating clean oven to produce an empty cell. did. 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 liquid crystal alignment was evaluated using the obtained liquid crystal cell. The liquid crystal alignment was confirmed by observing the liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to check for the presence of alignment defects. Specifically, those in which no alignment defect was observed were considered to be excellent in this evaluation (shown as “good” in Tables 8 and 9).
Tables 8 and 9 show the results of the liquid crystal alignment properties of the liquid crystal cells formed using the liquid crystal alignment treatment agents obtained in the examples and comparative examples.

[Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)]
The liquid crystal aligning agent (1) obtained in Example 4, the liquid crystal aligning agent (4) obtained in Example 7 and the liquid crystal aligning agent (8) obtained in Example 11 were used as a membrane having a pore diameter of 1 μm. Using a solution filtered under pressure with a filter and stored at −15 ° C. for 48 hours, production of a liquid crystal cell and evaluation of liquid crystal alignment (PSA cell) were performed.
These liquid crystal alignment treatment agents were washed with pure water and IPA, and a 10 × 10 mm substrate with an ITO electrode having a pattern interval of 20 μm in the center (vertical 40 mm × width 30 mm, thickness 0.7 mm) and a center of 10 × 40 mm Spin coated on ITO surface of substrate with ITO electrode (length 40mm x width 30mm, thickness 0.7mm), heated on hot plate at 100 ° C for 5 minutes, and further heated at 200 ° C for 30 minutes in thermal circulation clean oven It processed and obtained the polyimide coating film with a film thickness of 100 nm.

得られた液晶セルに、交流５Ｖの電圧を印加しながら、照度６０ｍＷのメタルハライドランプを用いて、３５０ｎｍ以下の波長をカットし、３６５ｎｍ換算で２０Ｊ／ｃｍ^２の紫外線照射を行い、液晶の配向方向が制御された液晶セル（ＰＳＡセル）を得た。液晶セルに紫外線を照射している際の照射装置内の温度は、５０℃であった。This substrate with a liquid crystal alignment film was combined with the liquid crystal alignment film surface inside, with a 6 μm spacer in between, 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). A liquid crystal cell was obtained by injecting 0.3% by mass of a liquid crystal mixed with the mixture and sealing the inlet.

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.
In the PSA cell obtained in the example, the response speed of the liquid crystal cell after the ultraviolet irradiation was higher than that of the liquid crystal cell before the ultraviolet irradiation, so that it was confirmed that the alignment direction of the liquid crystal was controlled. 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.

[Evaluation of voltage holding ratio on insulating film coated substrate]
(Preparation of composition for insulating film)
In a 100 ml eggplant type flask, a propylene glycol monomethyl ether acetate solution of acrylic resin ((meth) acrylic acid / hydroxyethyl (meth) acrylate / methyl (meth) acrylate = 9 / 25.5 / 65.5 (molar ratio)), Solid content concentration: 22.0 wt%, weight average molecular weight 6000 (polystyrene conversion) (7.07 g), propylene glycol monomethyl ether acetate (25.1 g), KAYARDADDHA-40H (manufactured by Nippon Kayaku Co., Ltd.) (3.30 g) ), I-369 (manufactured by Ciba Specialty Chemicals) (0.30 g), ITX (manufactured by First Chemical Corporation), and MegaFac R-30 (0.015 g) were added and stirred at 25 ° C. for 3 hours. An insulating film composition was obtained. No insoluble matter was found in the composition for insulating film, and a uniform solution was obtained.

(Preparation of insulating film coated substrate)
The insulating film composition obtained above was filtered using a 0.2 μm filter. Thereafter, the filtered composition was washed with pure water and IPA at the center and a 10 × 10 mm ITO electrode substrate with a pattern spacing of 20 μm (length 40 mm × width 30 mm, thickness 0.7 mm) and the center 10 ×. The ITO surface of a 40 mm ITO electrode-attached substrate (40 mm long × 30 mm wide, 0.7 mm thick) was spin-coated, and heat-treated at 110 ° C. for 5 minutes on a hot plate. This coating film was irradiated with ultraviolet rays having an irradiation amount of 365 m of 500 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) (manufactured by Canon Inc.), and subjected to heat treatment at 120 ° C. for 1 minute on a hot plate. did. Thereafter, a heat treatment was further performed on a hot plate at 200 ° C. for 60 minutes to obtain a substrate coated with an insulating film having a thickness of 1.12 μm.

(Production of liquid crystal cell)
The liquid crystal aligning agents obtained in Examples and Comparative Examples were pressure filtered through a membrane filter having a pore diameter of 1 μm to produce a liquid crystal cell. These liquid crystal alignment treatment agents are spin-coated on the insulating film-coated surface of the insulating film-coated substrate obtained above, and heated on a hot plate at 100 ° C. for 5 minutes and further in a heat circulating clean oven for 30 minutes at 200 ° C. The ITO substrate with a polyimide liquid crystal aligning film with a film thickness of 100 nm was obtained by processing.
Two obtained ITO substrates with a liquid crystal alignment film were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface inside, and a sealant (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed. Next, after bonding the other substrate and the liquid crystal alignment film face each other, the sealing agent was cured by heat treatment at 120 ° C. for 90 minutes in a heat-circulating clean oven to produce an empty cell. . Liquid crystal was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.

(Evaluation of voltage holding ratio)
A voltage of 1 V was applied to the liquid crystal cell obtained above at a temperature of 70 ° C. for 60 μs, and the voltage after 16.67 ms and 50 ms was measured. Calculated). The measurement was performed using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ± 1 V, Pulse Width: 60 μs, Frame Period: 16.67 ms and 50 ms.
The liquid crystal cell for which the measurement of the voltage holding ratio was completed was irradiated with ultraviolet rays of 10 J / cm ^{2 in} terms of 365 nm, and then VHR was measured under the same conditions. In addition, ultraviolet irradiation was performed using the desktop type UV curing device (HCT3B28HEX-1) (manufactured by Senlite Corporation (SEN LIGHT CORPORATION)).
Tables 8 and 9 show the results of the evaluation of the voltage holding ratio of the insulating film-coated substrates produced using the liquid crystal aligning agents obtained in the examples and comparative examples.

Below, the preparation method of the composition (it may be used for a liquid-crystal aligning agent) in Examples 1-14 and Comparative Examples 1-4 is described.
Tables 2 to 4 collectively show the specific cellulose-based polymer, specific polysiloxane, solvent, and solid content concentration (%) in the composition used in each example and comparative example.
In addition, evaluation of the obtained composition (including liquid crystal alignment treatment agent) is [storage stability test of composition or liquid crystal alignment treatment agent], [evaluation of printability of composition or liquid crystal alignment treatment agent on a stepped substrate] , [Evaluation of ink-jet coating properties of liquid crystal alignment treatment agent], [Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)], [Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)] and [Insulation] Evaluation of voltage holding ratio on film coated substrate] and the like were performed.
The result of the said evaluation of the composition (The liquid crystal aligning agent containing) obtained in Examples 1-14 and Comparative Examples 1-4 is put together in Tables 5-9, and is shown.

<Example 1>
CE-2 (0.72 g) was mixed in EC (9.00 g) and BCS (10.5 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (1) (6.00 g) obtained by the synthesis method of Synthesis Example 1 was added, and the mixture was stirred at 25 ° C. for 2 hours to obtain a 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.

<Example 2>
CE-1 (0.15 g) was mixed in EC (2.20 g) and BCS (13.6 g) and stirred at 40 ° C. for 6 hours. Then, the polysiloxane solution (2) (11.3 g) obtained by the synthesis method of Synthesis Example 2 was added and stirred at 25 ° C. for 2 hours 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.

<Example 3>
CE-2 (0.95 g) was mixed in EC (12.5 g) and BCS (10.1 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (2) (5.28 g) obtained by the synthesis method of Synthesis Example 2 was added, and the mixture was stirred at 25 ° C. for 2 hours 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.

<Example 4>
CE-2 (0.65 g) was mixed in EC (11.9 g) and BCS (8.90 g) and stirred at 40 ° C. for 6 hours. Then, the polysiloxane solution (3) (8.13 g) obtained by the synthesis method of Synthesis Example 3 was added and stirred at 25 ° C. for 2 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 also as a liquid-crystal aligning agent (1).

<Example 5>
CE-3 (0.50 g) was mixed in EC (1.90 g) and PB (12.1 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (3) (8.13 g) obtained by the synthesis method of Synthesis Example 3 was added and stirred at 25 ° C. for 2 hours 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 (2).

<Example 6>
CE-2 (0.50 g) was mixed in EC (12.0 g) and PB (22.9 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (3) (6.25 g) obtained by the synthesis method of Synthesis Example 3 was added, and the mixture was stirred at 25 ° C. for 2 hours 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 (3).

<Example 7>
CE-2 (0.80 g) was mixed in EC (7.10 g) and BCS (14.5 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (3) (6.67 g) obtained by the synthesis method of Synthesis Example 3 was added, and the mixture was stirred at 25 ° C. for 2 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 also as a liquid-crystal aligning agent (4).

<Example 8>
CE-2 (0.30 g) was mixed in EC (0.60 g) and PB (16.4 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (4) (10.0 g) obtained by the synthesis method of Synthesis Example 4 was added, and the mixture was stirred at 25 ° C. for 2 hours 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 (5).

<Example 9>
CE-2 (0.65 g) was mixed in EC (9.00 g) and BCS (11.8 g) and stirred at 40 ° C. for 6 hours. Then, the polysiloxane solution (4) (8.13 g) obtained by the synthesis method of Synthesis Example 4 was added and stirred at 25 ° C. for 2 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 (6).

<Example 10>
CE-1 (0.15 g) was mixed in EC (7.70 g) and BCS (8.20 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (4) (11.3 g) obtained by the synthesis method of Synthesis Example 4 was added and stirred at 25 ° C. for 2 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 also as a liquid-crystal aligning agent (7).

<Example 11>
CE-2 (0.50 g) was mixed in EC (9.50 g) and PB (10.6 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (5) (9.72 g) obtained by the synthesis method of Synthesis Example 5 was added, and the mixture was stirred at 25 ° C. for 2 hours 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. In addition, this composition (11) was used for evaluation also as a liquid-crystal aligning agent (8).

<Example 12>
CE-2 (0.45 g) was mixed in EC (23.3 g) and PB (17.5 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (5) (8.75 g) obtained by the synthesis method of Synthesis Example 5 was added, and the mixture was stirred at 25 ° C. for 2 hours 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. In addition, this composition (12) was used for evaluation also as a liquid-crystal aligning agent (9).

<Example 13>
CE-3 (0.40 g) was mixed in EC (8.50 g) and BCS (10.2 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (5) (10.0 g) obtained by the synthesis method of Synthesis Example 5 was added and stirred at 25 ° C. for 2 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. In addition, this composition (13) was used for evaluation also as a liquid-crystal aligning agent (10).

<Example 14>
CE-3 (0.75 g) was mixed in EC (8.00 g) and PB (12.3 g) and stirred at 40 ° C. for 6 hours. Thereafter, the polysiloxane solution (5) (6.25 g) obtained by the synthesis method of Synthesis Example 5 was added and stirred at 25 ° C. for 2 hours to obtain a composition (14). 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 (11).

<Comparative Example 1>
NMP (10.0 g) and BCS (8.90 g) were added to the polyamic acid solution (1) (2.60 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 6, and the mixture was heated to 25 ° C. And stirred for 2 hours. Thereafter, the polysiloxane solution (3) (8.13 g) obtained by the synthesis method of Synthesis Example 3 was added, but a precipitate was generated immediately after that. And it stirred at 25 degreeC for 2 hours, and obtained the composition (15). However, precipitates were observed in this composition. In addition, this composition (15) was used for evaluation also as a liquid-crystal aligning agent (12).

<Comparative example 2>
NMP (10.0 g) and BCS (8.90 g) were added to the polyamic acid solution (2) (2.60 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 7, and the mixture was heated to 25 ° C. And stirred for 2 hours. Thereafter, the polysiloxane solution (3) (8.13 g) obtained by the synthesis method of Synthesis Example 3 was added, but a precipitate was generated immediately after that. And it stirred at 25 degreeC for 2 hours, and obtained the composition (16). However, precipitates were observed in this composition. In addition, this composition (16) was used for evaluation also as a liquid-crystal aligning agent (13).

<Comparative Example 3>
The polyimide powder (3) (0.45 g) obtained by the synthesis method of Synthesis Example 8 was mixed in EC (8.20 g) and BCS (6.10 g) and stirred at 70 ° C. for 15 hours. However, the polyimide powder (3) did not dissolve.
Therefore, polyimide powder (3) (0.45 g) was mixed in NMP (8.20 g) and BCS (6.10 g) and stirred at 70 ° C. for 8 hours. Thereafter, the polysiloxane solution (3) (5.63 g) obtained by the synthesis method of Synthesis Example 3 was added, and a precipitate was generated immediately after that. Then, the mixture was stirred at 25 ° C. for 2 hours to obtain a composition (17). However, precipitates were observed in this composition. In addition, this composition (17) was used for evaluation also as a liquid-crystal aligning agent (14).

<Comparative Example 4>
EC (6.60 g) and BCS (8.20 g) were added to the polysiloxane solution (3) (12.5 g) obtained by the synthesis method of Synthesis Example 3, and the mixture was stirred at 25 ° C. for 4 hours. 18) was obtained. 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 (18) was used for evaluation also as a liquid-crystal aligning agent (15).

＊２：組成物（液晶配向処理剤）中の重合体の占める割合を示す。

* 2: Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).

＊３：組成物（液晶配向処理剤）中の重合体の占める割合を示す。

* 3: Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).

＊４：組成物（液晶配向処理剤）中の重合体の占める割合を示す。

* 4: Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).

＊５：ピンホールによる配向欠陥が１０個以上観察された。

* 5: Ten or more alignment defects due to pinholes were observed.

As can be seen from the above results, the compositions of the examples are superior in storage stability without the precipitation of the polymer during storage of the compositions, compared to the comparative examples, and pinholes when forming the resin film. Occurrence could be suppressed. 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, a composition (Example 4) using the specific polysiloxane as the component (B) and the specific cellulose polymer as the component (A) of the present invention, the specific polysiloxane having the same structure as this, and It is a comparison with the composition (Example 4 and Comparative Example 1, 2 or 3) using polymers other than a specific cellulose polymer. In particular, in Comparative Examples 1 to 3, a polyimide polymer was used as the polymer, and when a specific polysiloxane was mixed with the polyimide polymer, a precipitate was generated, and the storage stability of the composition was also deteriorated. . Moreover, when the liquid crystal cell was produced using the liquid-crystal aligning agent obtained from the composition of these comparative examples, many alignment defects accompanying a pinhole were seen.

Furthermore, a composition using the specific polysiloxane as the component (B) of the present invention and the specific cellulose polymer as the component (A) of the present invention (Example 4), and a composition using only the specific polysiloxane In comparison with (Comparative Example 4), the composition of Comparative Example 4 is excellent in storage stability of the composition and can suppress the occurrence of pinholes when forming a resin film, but the unevenness of the stepped substrate The level-step following ability with respect to became low.
The compositions of these examples were also used for evaluation as liquid crystal aligning agents, but the evaluation results when using the compositions of these examples can be the results as liquid crystal aligning agents. is there.

  Further, in the evaluation of the voltage holding ratio in the insulating film coated substrate, the liquid crystal alignment treatment agent obtained from the composition of the present invention is more liquid crystal alignment film than the liquid crystal alignment treatment agent obtained from the composition of the comparative example. Even when the light was irradiated with an insulating film made of an organic material underneath, an excellent voltage holding ratio was obtained. Specifically, the composition (Example 4) using the specific polysiloxane as the component (B) and the specific cellulose polymer as the component (A) of the present invention, the specific polysiloxane and the specific cellulose having the same structure Comparison with a composition (Comparative Example 1, 2 or 3) using a polymer other than a polymer, and further, a specific polysiloxane which is the component (B) of the present invention and a specific cellulose which is the component (A) It is a comparison with the composition (Example 4) using a polymer, and the composition (Comparative Example 4) using only specific polysiloxane of the same structure.

The composition of the present invention is excellent in storage stability, suppresses the occurrence of pinholes when forming a resin film, and has a high level of follow-up to the unevenness of the stepped substrate.
Furthermore, the liquid crystal aligning agent using the composition of the present invention is suitable for forming a liquid crystal alignment film having excellent voltage holding ratio, and the liquid crystal display device having the liquid crystal alignment film has excellent reliability, It can be suitably used for large-screen, high-definition liquid crystal televisions and the like, and is useful for TN elements, STN elements, TFT liquid crystal elements, particularly vertical alignment type liquid crystal display elements.
In addition, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is useful for manufacturing a PSA type vertical alignment type liquid crystal cell that needs to be irradiated with ultraviolet rays when manufacturing a liquid crystal display element.

  It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2013-055095 filed on March 18, 2013 is cited here as the disclosure of the specification of the present invention. Incorporated.

Claims (12)

A composition comprising the following component (A) and component (B):
Component (A): at least one cellulosic polymer selected from the group consisting of hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose phthalate and hydroxypropylmethylcellulose acetate .
Component (B): alkoxy containing at least one selected from the group consisting of alkoxysilanes represented by the following formula [A1] , alkoxysilanes represented by the following [A2] , and alkoxysilanes represented by the following formula [A3] Polysiloxane obtained by polycondensation of silane.
An alkoxysilane represented by the following formula [A1]:

(A ¹ represents a structure represented by the following formula [2], an alkyl group having 6 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms having a benzene ring, a cyclohexane ring or a heterocyclic ring. A ² represents hydrogen. An atom or an alkyl group having 1 to 5 carbon atoms, A ³ represents an alkyl group having 1 to 5 carbon atoms, m is an integer of 1 or 2, n is an integer of 0 to 2, and p is an integer of 0 to 3. Where m + n + p is 4.)

(Y ¹ represents a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—, where Y ² represents a single bond. A bond or — (CH ₂ ) _b — (b is an integer of 1 to 15) Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O —, —CH ₂ O—, —COO— or —OCO—, wherein Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or 2 having 17 to 51 carbon atoms having a steroid skeleton. An arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or 1 carbon atom. optionally substituted with to 3 fluorine-containing alkoxyl group or a fluorine atom .Y ⁵ is a benzene ring, shea A divalent cyclic group selected from a rhohexane ring and a heterocyclic ring is shown, 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 1 to 1 carbon atoms. 3 may be substituted with a fluorine-containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4. Y ⁶ is an alkyl group having 1 to 18 carbon atoms, A C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group is shown.)
-Alkoxysilane of the following [A2]:
3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, or 3- (trimethoxysilyl) propyl methacrylate
-Alkoxysilane represented by the following [A3]:

^{(D 1} is .D ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is an integer of .n 0-3 represents an alkyl group having 1 to 5 carbon atoms.)
Show. ) The proportion of the alkoxysilane represented by the formula [A1], the formula [A2] and the formula [A3] in the component (B) is 1 to 40 mol%, 1 to 70 mol%, 1 The composition according to claim 1 , which is -99 mol%. The composition according to claim 1 or 2 , wherein the ratio of the component (A) to the component (B) is such that the component (B) is 1 and the component (A) is 0.1 to 9 in mass ratio. Furthermore, a composition according to any one of claims 1 to 3 containing a solvent 50 to 99.9 wt%. The resin film obtained from the composition as described in any one of Claims 1-4 . The liquid-crystal aligning agent which uses the composition as described in any one of Claims 1-4 . The liquid crystal aligning film obtained using the liquid-crystal aligning agent of Claim 6 . The liquid crystal display element which has a liquid crystal aligning film of Claim 7 . A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the electrodes The liquid crystal aligning film of Claim 7 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage in between.   The liquid crystal display element which has a liquid crystal aligning film of Claim 9. A liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates; The liquid crystal aligning film of Claim 7 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric group, applying a voltage in between. The liquid crystal display element which has a liquid crystal aligning film of Claim 11 .

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