KR101740939B1 - Liquid crystal aligning agent for retardation film, liquid crystal alignment film for retardation film, and retardation film and process for production thereof - Google Patents

Abstract

(Summary) An object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film for a phase difference film which can be photo-radiated even by irradiation with a small amount of radiation and which does not require a heating step during irradiation and after irradiation, and a liquid crystal alignment film for this phase difference film And has excellent liquid crystal alignability and thermal stability, and a process for producing the same.
(Solution) The present invention relates to a liquid crystal aligning agent for a retardation film containing a polyorganosiloxane having [A] photo aligning group. The photo-orientable group is preferably a group having a cinnamic acid structure.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment agent for a retardation film, a liquid crystal alignment film for a retardation film, a retardation film, and a method of manufacturing the same. BACKGROUND ART [0002]

The present invention relates to a liquid crystal aligning agent for a retardation film, a liquid crystal alignment film for a retardation film, a retardation film and a manufacturing method thereof.

BACKGROUND ART Liquid crystal displays (LCDs) are widely used in televisions and various monitors. As a display element of an LCD, for example, a super twisted nematic (STN) type, a twisted nematic (TN) type, an inp plane switching (IPS) type, a vertically aligned (VA) type, a polymer sustained alig (See Patent Documents 1 and 2). A variety of optical materials are used for the liquid crystal display element. Among them, the retardation film is intended to solve the coloring of the display, and to solve the viewing angle dependency such as the display color and the contrast ratio change depending on the viewing angle (See Patent Documents 3 and 4).

BACKGROUND ART Conventionally, a retardation film has been produced by using a stretching process of a plastic film, and for a retardation film having more complicated optical characteristics, a polymerizable liquid crystal is cured. In this method, a method of forming a liquid crystal alignment film on the substrate surface is generally used in order to orient the polymerizable liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a rubbing method in which the surface of the organic film formed on the substrate surface is rubbed in one direction with the inclusion of rayon or the like. However, when the rubbing process is performed, dust or static electricity is liable to be generated in the process, so dust may adhere to the surface of the liquid crystal alignment film, resulting in a display failure. Further, in the rubbing treatment, the limitations accompanying the manufacturing process are large, and it is difficult to precisely control the liquid crystal alignment direction in an arbitrary direction.

Thus, as a method different from the rubbing treatment, there is known a photo alignment method in which a liquid crystal aligning ability is imparted by irradiating polarized or unpolarized radiation to a photosensitive thin film such as polyvinyl cinnamate formed on the substrate surface 5-15). According to this photo alignment method, uniform liquid crystal alignment can be realized without generating dust or static electricity. Further, the liquid crystal alignment direction can be controlled in arbitrary direction and with precision compared with the rubbing treatment. Further, by using a photomask or the like in the irradiation of radiation, it is possible to arbitrarily form a plurality of regions having different liquid crystal alignment directions on one substrate. However, in the conventional technique, heating is required at the time of irradiation with radiation, but there is an inconvenience that an enormous integration exposure amount is required (see Patent Document 16).

On the other hand, in recent years, a technology for expressing a 3D image has been developed, and a display in which a 3D image can be viewed even in the home has been spreading. As a display system of a 3D image, for example, Patent Document 17 discloses a polarizing plate for providing a polarizing plate in which an image having a different polarization state from a right eye image and a left eye image is formed and arranged so that only images in respective polarization states can be viewed A method of using glasses is introduced (refer to Patent Document 17). A stereoscopic image obtained by this method has no flicker, and a viewer can observe a stereoscopic image by attaching polarizing glasses which are lightweight and inexpensive.

As a conventional technique for forming an image having a different polarization state from the right eye image and the left eye image, two polarizing projectors are used in the projection display to superimpose the two images on the screen to form a stereoscopic image, ) Display is formed by synthesizing an image of two display devices with a half mirror or a polarizing mirror or arranging polarizing transmittance axes of the polarizing films arranged on the substrate surface differently for each pixel. However, in order to simultaneously illuminate two images having different polarization axes at the same time, two display apparatuses and a projection apparatus are required, which is not suitable for home use. As a conventional technique for forming an image having a different polarization state from a right eye image and a left eye image with one display device, a polarizing layer having a mosaic shape in which polarization axes are orthogonal to each other between adjacent pixels is formed on the front surface of one display device, And the observer can observe the stereoscopic image by attaching the polarizing glasses.

As the polarizing layer, a patterning retardation film patterned on the order of 탆 is required. As a method of producing such a patterning retardation film, for example, Patent Document 18 discloses a method of irradiating polarized light to a photosensitive polymer layer and the like. However, an enormous amount of irradiation is required for polarizing irradiation, and the thermal stability of the photosensitive polymer layer is not sufficiently satisfactory.

In view of such circumstances, there is a demand for development of a liquid crystal aligning agent for a retardation film having high productivity, which is capable of efficiently producing a patterning retardation film excellent in liquid crystal alignability and thermal stability and precisely controlled.

Japanese Laid-Open Patent Publication No. 56-91277 Japanese Unexamined Patent Application Publication No. 1-120528 Japanese Patent Application Laid-Open No. 4-229828 Japanese Patent Application Laid-Open No. 4-258923 Japanese Patent Application Laid-Open No. 6-287453 Japanese Patent Application Laid-Open No. 10-251646 Japanese Laid-Open Patent Publication No. 11-2815 Japanese Patent Application Laid-Open No. 11-152475 Japanese Patent Application Laid-Open No. 2000-144136 Japanese Patent Application Laid-Open No. 2000-319510 Japanese Patent Application Laid-Open No. 2000-281724 Japanese Patent Application Laid-Open No. 9-297313 Japanese Patent Application Laid-Open No. 2003-307736 Japanese Laid-Open Patent Publication No. 2004-163646 Japanese Patent Application Laid-Open No. 2002-250924 Japanese Patent Application Laid-Open No. 10-278123 Japanese Patent No. 3461680 Japanese Patent Application Laid-Open No. 2005-49865

The object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film for a phase difference film which can be photo-radiated even by irradiation with a small amount of radiation and which does not require a heating step during irradiation and after irradiation, And a phase difference film having the liquid crystal alignment film for the phase difference film and excellent in liquid crystal alignability and thermal stability, and a method for producing the same.

According to an aspect of the present invention,

[A] A liquid crystal aligning agent for a retardation film containing a polyorganosiloxane having a photo-aligning group (hereinafter sometimes referred to as "[A] photo-aligned polyorganosiloxane").

Since the liquid crystal aligning agent contains the [A] photo-orientable polyorganosiloxane, the light irradiation amount required for alignment can be reduced by the photo-alignment property with high sensitivity. In addition, since the liquid crystal aligning agent does not require a heating step during and after the irradiation of radiation, the retardation film can be efficiently produced. Further, since the polyorganosiloxane is employed as the main chain, the retardation film formed from the liquid crystal aligning agent has excellent chemical stability and thermal stability.

In the liquid crystal aligning agent, it is preferable that the photo-orientable group is a group having a cinnamic acid structure. By using a group having a cinnamic acid structure having a basic skeleton of cinnamic acid or a derivative thereof as a photo-alignable group, the introduction is facilitated and the retardation film formed with the liquid crystal aligning agent has a higher photo alignment performance.

In the liquid crystal aligning agent, the group having the cinnamic acid structure is at least one selected from the group consisting of a group derived from a compound represented by the following formula (1) and a compound derived from a compound represented by the formula (2) The group derived from the compound represented by the formula (1) and the compound represented by the formula (2) are sometimes referred to as "specific cinnamic acid derivative"):

(In the formula (1), R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group;

A part or all of the hydrogen atoms of the phenylene group, the biphenylene group, the terphenylene group or the cyclohexylene group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a fluorine atom, May be substituted by an anger;

R ² is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, -CH = CH-, -NH-, -COO- or -OCO-;

a is an integer of 0 to 3;

Provided that when a is 2 or more, each of R ¹ and R ² may be the same or different;

R ³ is a fluorine atom or a cyano group;

b is an integer of 0 to 4;

In the formula (2), R ⁴ is a phenylene group or a cyclohexylene group;

A part or all of the hydrogen atoms of the phenylene group or the cyclohexylene group may be substituted with a straight or cyclic alkyl group having 1 to 10 carbon atoms, a straight or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group ;

R ⁵ is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-;

c is an integer of 1 to 3;

Provided that when c is 2 or more, R ⁴ and R ⁵ may be the same or different;

R ⁶ is a fluorine atom or a cyano group;

d is an integer from 0 to 4;

R ⁷ is an oxygen atom, -COO- or -OCO-;

However, the coupling hand denominated * is combined with R ^8, and;

R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group;

R ⁹ is a single bond, -OCO- (CH ₂ ) _f - * or -O (CH ₂ ) _g - *;

However, the combined hand with * attached to the carboxyl group;

f and g are each an integer of 1 to 10;

e is an integer from 0 to 3;

Provided that when e is 2 or more, R ⁷ and R ⁸ may be the same or different).

By using a group derived from the specific cinnamic acid derivative as a group having the above-described cinnamic acid structure, the photo-alignment performance can be further improved.

In the liquid crystal aligning agent of the present invention, the photo-orientable polyorganosiloxane [A] preferably contains at least one member selected from the group consisting of a polyorganosiloxane having an epoxy group, a hydrolyzate thereof and a condensate of the hydrolyzate thereof, 1) and at least one member selected from the group consisting of the compound represented by the formula (2). By using the reactivity between the polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative in the liquid crystal aligning agent, side chain groups derived from a specific cinnamic acid derivative having a photo-alignment property can be easily formed in the polyorganosiloxane as a main chain Can be introduced.

(B) at least one polymer selected from the group consisting of a polyamic acid, a polyimide, an ethylenically unsaturated compound polymer and a polyorganosiloxane having no photo-aligning group (hereinafter referred to as "[B] other polymer (Hereinafter sometimes referred to as " anionic surfactant "). In the case of containing these [B] other polymers, it has become clear that in the liquid crystal alignment film for a retardation film formed from the liquid crystal aligning agent, the polyorganosiloxane is localized near the surface layer thereof. Therefore, even if the content of the polyorganosiloxane in the liquid crystal aligning agent is reduced by increasing the content of the other polymer, the polyorganosiloxane is localized on the surface of the alignment film, so that sufficient liquid crystal alignability can be obtained. Therefore, in the present invention, it is possible to reduce the content of the polyorganosiloxane having a high production cost in the liquid crystal aligning agent, and consequently, the manufacturing cost of the liquid crystal aligning agent can be lowered.

The liquid crystal aligning agent is at least one selected from the group consisting of an acetal ester structure of the [C] carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkyl cycloalkyl alkyl ester structure of a carboxylic acid, and a t- (Hereinafter sometimes referred to as a " compound containing a [C] ester structure ") having two or more species of structures. The liquid crystal aligning agent contains a [C] ester structure-containing compound, whereby an acid is generated in the baking step (post baking) and the crosslinking of the photo-aligned polyorganosiloxane [A] is promoted by the generated acid. As a result, The heat resistance of the retardation film can be improved.

The liquid crystal aligning agent preferably further comprises [D] a solvent represented by the following formula (6) (hereinafter sometimes referred to as "[D] solvent"):

R ^d1 -COO-R ^d2 (6)

(In the formula (6), R ^d1 is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group or a benzyl group;

Provided that the alkyl group may have -O- between the carbon-carbon bonds;

R ^d2 is a monovalent organic group having 1 to 8 carbon atoms).

The adhesion of the liquid crystal aligning agent to the substrate for a retardation film can be improved by containing the [D] solvent having the specific structure having the ester group in the liquid crystal aligning agent.

It is preferable that the liquid crystal aligning agent further contains a solvent having erosion resistance to the substrate for the [E] retardation film (hereinafter sometimes referred to as " [E] solvent "). The liquid crystal aligning agent contains the [E] solvent having erosion resistance to the substrate for the retardation film, so that the adhesion between the liquid crystal aligning agent and the substrate for the retardation film can be further improved.

The liquid crystal aligning agent preferably further contains a compound (hereinafter also referred to as "[F] compound") containing a group having a polymerizable carbon-carbon double bond [F]. By containing the [F] compound, the liquid crystal aligning agent can further improve the adhesion to the substrate for a retardation film or the liquid crystal layer.

The liquid crystal aligning agent can be suitably used for forming a liquid crystal alignment film, in particular, a liquid crystal alignment film used for producing a retardation film by the photo alignment method. The present invention preferably includes a liquid crystal alignment film for a retardation film including two or more regions having different liquid crystal alignment directions, and a retardation film having such a liquid crystal alignment film for a retardation film.

The method for producing a retardation film included in the present invention is a method for producing a retardation film,

(1) a step of coating the liquid crystal aligning agent for the retardation film on a substrate to form a coating film (coating film)

(2) a step of irradiating the coating film with radiation to impart a liquid crystal aligning ability and forming a liquid crystal alignment film for a retardation film,

(3) a step of applying the polymerizable liquid crystal to at least a part of the liquid crystal alignment film for the retardation film, and

(4) a step of curing the coating film coated with the polymerizable liquid crystal.

In the production method of the present invention, light can be radiated even by irradiation with a small amount of radiation, and a heating step during and after irradiation is not necessary. Therefore, the retardation film can be efficiently produced, and the productivity is high, contributing to the reduction of the manufacturing cost.

In addition, the present invention suitably includes a method for producing a retardation film including different retardation regions in 3D image applications and the like. In this manufacturing method,

The step (2)

(2-1) a step of irradiating the coating film with radiation in a first direction to give a liquid crystal alignment capability in the first direction and

(2-2) A step of irradiating a part of the coating film with radiation in a second direction different from the first direction to further give liquid crystal aligning ability in the second direction.

As other production methods,

The step (2)

(2-1 ') a step of irradiating the coated film with radiation in a first direction to give a liquid crystal aligning ability in the first direction and

(2-2 ') a step of irradiating a portion of the coating film not irradiated with at least radiation with a radiation in a second direction different from the first direction to give liquid crystal alignment capability in the second direction.

According to the liquid crystal aligning agent for a retardation film of the present invention, light can be radiated even by irradiation with a small amount of radiation, and a heating step during and after irradiation becomes unnecessary. Therefore, the liquid crystal alignment film and the retardation film for the retardation film using the liquid crystal aligning agent for the retardation film are excellent in liquid crystal alignability and thermal stability. Further, according to the method for producing a retardation film of the present invention, it is possible to easily and reliably produce a retardation film having excellent liquid crystal alignability and thermal stability.

(Mode for carrying out the invention)

≪ Liquid crystal aligning agent for retardation film >

The liquid crystal aligning agent for a retardation film of the present invention contains [A] photo-orientable polyorganosiloxane. By containing the [A] photo-orientable polyorganosiloxane, the light irradiation amount required for orientation can be reduced by the photo-alignment property with high sensitivity. In addition, since the liquid crystal aligning agent does not require a heating step during and after the irradiation of radiation, the retardation film can be efficiently produced. Further, the retardation film obtained from the liquid crystal aligning agent is excellent in liquid crystal alignability and thermal stability. The liquid crystal aligning agent preferably contains a [B] other polymer, a compound having an ester structure, a solvent [D], a solvent [E] and a compound [F] May contain any other optional components. Hereinafter, the [A] photo-aligned polyorganosiloxane, the [B] other polymer, the [C] ester structure-containing compound, the [D] solvent, the [E] solvent, the [F] compound and optional components will be described in detail.

≪ [A] Photoinduced polyorganosiloxane >

The photo-orientable polyorganosiloxane [A] has a photo-orientable group introduced into at least one selected from the group consisting of a polyorganosiloxane as a main chain, a hydrolyzate thereof and a condensate of the hydrolyzate thereof. The photosensitivity improves the sensitivity of the photo alignment, realizes a low light irradiation amount, and is excellent in the liquid crystal alignability of the retardation film. Further, since the polyorganosiloxane is employed as the main chain, the retardation film formed from the liquid crystal aligning agent has excellent chemical stability and thermal stability.

As the photo-aligning group, groups derived from various compounds exhibiting photo-alignment properties can be adopted. For example, azobenzene-containing groups containing azobenzene or derivatives thereof as a basic skeleton, Shinnam acid Containing group as a basic skeleton, a chalcone-containing group containing a chalcone-containing group as a basic skeleton, a benzophenone-containing group containing a benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group having a coumarin or a derivative thereof as a basic skeleton, Or a polyimide-containing structure containing a derivative thereof as a basic skeleton. Among these photo-aligned groups, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton is preferable in view of high alignment ability and ease of introduction.

The structure of a group having a cinnamic acid structure is not particularly limited as long as it contains cinnamic acid or a derivative thereof as a basic skeleton, but a group derived from the above specific cinnamic acid derivative is preferable. Also, R ¹ is a phenylene group, a biphenylene group, a terphenylene group, or a cyclohexylene group. A part or all of the hydrogen atoms of the phenylene group, the biphenylene group, the terphenylene group or the cyclohexylene group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a fluorine atom, It may be substituted by an anger. R ² is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, -CH = CH-, -NH-, -COO- or -OCO-. a is an integer of 0 to 3; Provided that when a is 2 or more, each of R ¹ and R ² may be the same or different. R ³ is a fluorine atom or a cyano group. b is an integer of 0 to 4;

Examples of the compound represented by the formula (1) include compounds represented by the following formulas.

Of these, R ¹ is preferably a phenylene group which is substituted by a non-substituted group, or a phenylene group which is substituted by a fluorine atom or an alkyl group of 1 to 3 carbon atoms. R ² is preferably a single bond, an oxygen atom or -CH ₂ ═CH ₂ -. b is preferably 0 to 1. When a is 1 to 3, it is particularly preferable that b is 0.

In the above formula (2), R ⁴ is a phenylene group or a cyclohexylene group. Part or all of the hydrogen atoms of the phenylene group or the cyclohexylene group may be substituted with a straight or cyclic alkyl group having 1 to 10 carbon atoms, a straight or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group . R ⁵ is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-. and c is an integer of 1 to 3. Provided that when c is 2 or more, R ⁴ and R ⁵ may be the same or different. R ⁶ is a fluorine atom or a cyano group. and d is an integer of 0 to 4. R ⁷ is an oxygen atom, -COO- or -OCO- *. However, the combined hand denominated * combines with R ^8. R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group. R ⁹ is a single bond, -OCO- (CH ₂ ) _f - * or -O (CH ₂ ) _g - *. However, the combined hands with * are combined with the carboxyl groups. f and g are each an integer of 1 to 10; and e is an integer of 0 to 3. Provided that when e is 2 or more, R ⁷ and R ⁸ may be the same or different.

Examples of the compound represented by the formula (2) include compounds represented by the following formulas (2-1) to (2-2):

(Wherein Q is a straight or cyclic alkyl group of 1 to 10 carbon atoms, a straight or cyclic alkoxy group of 1 to 10 carbon atoms, a fluorine atom or a cyano group;

f is the same as equation (2)).

The synthesis procedure of the specific cinnamic acid derivative is not particularly limited and can be carried out by combining conventionally known methods. (I) a method in which a compound having a benzene ring skeleton substituted with a halogen atom is reacted with acrylic acid in the presence of a transition metal catalyst to obtain a specific cinnamic acid derivative under basic conditions, (ii) a method in which basic conditions , A method of reacting a compound having a benzene ring in which a hydrogen atom of a benzene ring is substituted with a halogen atom and a compound having a benzene ring skeleton substituted with a halogen atom in the presence of a transition metal catalyst to obtain a specific cinnamic acid derivative.

As the portion derived from at least one kind selected from the group consisting of the polyorganosiloxane, the hydrolyzate thereof and the hydrolyzate thereof, contained as the main chain in the photo-orientable polyorganosiloxane [A], the photo- Is not particularly limited as long as it has a moiety derived from a structure capable of introducing a group. The photo-orientable polyorganosiloxane [A] is derived from at least one member selected from the group consisting of a polyorganosiloxane, a hydrolyzate thereof, and a condensate of the hydrolyzate thereof, and a component derived from the photo- .

Examples of the structure capable of introducing the photo-orientable group include a hydroxyl group, an epoxy group, an amino group, a carboxyl group, a mercapto group, an ester group, and an amide group. Of these, an epoxy group is preferable in view of ease of introduction and preparation.

The photo-orientable polyorganosiloxane [A] is at least one selected from the group consisting of a polyorganosiloxane having an epoxy group, a hydrolyzate thereof and a condensate of the hydrolyzate thereof (hereinafter referred to as " polyorganosiloxane having an epoxy group " , And a compound represented by the above formula (1) and / or (2). In the liquid crystal aligning agent, a group derived from a specific cinnamic acid derivative having photo-alignment properties is easily introduced into the polyorganosiloxane as a main chain by utilizing the reactivity between a polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative can do.

The polyorganosiloxane having an epoxy group is not particularly limited as long as an epoxy group is introduced into the polyorganosiloxane as a side chain. The polyorganosiloxane having an epoxy group is preferably at least one selected from the group consisting of a polyorganosiloxane having a structural unit represented by the following formula (3), a hydrolyzate thereof and a condensate of the hydrolyzate thereof:

(In the formula (3), X ¹ is a monovalent organic group having an epoxy group;

Y ¹ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

The hydrolysis-condensation product of the polyorganosiloxane having the structural unit represented by the above formula (3) is not only the hydrolysis-condensation product of the polyorganosiloxanes but also the hydrolysis-condensation product of the structural unit represented by the formula (3) And a hydrolytic condensate in the case where the polyorganosiloxane obtained by branching or crosslinking of the main chain in the process of producing the polyorganosiloxane by condensation has a structural unit represented by the formula (3) .

X ¹ in the formula (3) is not particularly limited as long as it is a monovalent organic group having an epoxy group, and examples thereof include a glycidyl group, a glycidyloxy group and a group containing an epoxycyclohexyl group . As X ¹ , it is preferable to be represented by the following formula (X ¹ -1) or (X ¹ -2):

(In the formula (X ¹ -1), A is an oxygen atom or a single bond;

h is an integer from 1 to 3;

i is an integer from 0 to 6;

Provided that when i is 0, A is a single bond;

In the formula (X ¹ -2), j is an integer of 1 to 6;

In the formulas (X ¹ -1) and (X ¹ -2), * indicates that each is a bonding hand).

Among the epoxy groups represented by the above formula (X ¹ -1) or (X ¹ -2), groups represented by the following formula (X ¹ -1-1) or (X ¹ -2-1) are preferable:

(In the formula (X ¹ -1-1) or the formula (X ¹ -2-1), * indicates a bonding hand).

In Y ¹ in the formula (3)

Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, ethoxy group and the like;

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-hexadecyl group, Practical group, n-eicosyl group, etc .;

As the aryl group having 6 to 20 carbon atoms, for example, a phenyl group and the like can be given.

The weight average molecular weight (Mw) of the polyorganosiloxane having an epoxy group in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 500 to 100,000, more preferably 1,000 to 10,000, and particularly preferably 1,000 to 5,000 desirable.

In the present specification, Mw is a polystyrene conversion value measured by GPC under the following specifications.

Column: TSKgelGRCXLII, manufactured by Toso K.K.

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 6.8 MPa

The polyorganosiloxane having such an epoxy group is preferably obtained by hydrolyzing a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and other silane compounds, preferably in the presence of an appropriate organic solvent, water and a catalyst, Can be synthesized by decomposition and condensation.

Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra- -Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri- , Fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec -Methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltri- Tri-sec-butoxy silane, 2- (trifluoromethyl) ethyl trichlorosilane, 2- (Trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyl tri-n-butoxysilane, 2- (trifluoromethyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- N-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro- (Perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri- Octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- (Perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (Perfluoro-n-octyl) ethyl tri-n-octyl) ethyl tri-i-propoxysilane, 2- (perfluoro- Tri-sec-butoxysilane, hydroxymethyl trichlorosilane, hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propyl (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri- (Meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltriethoxysilane, Mercaptopropyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, N-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxy Silane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyl Triethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri- butoxysilane, methyldi-n-butoxysilane, methyldi-n-butoxysilane, methyldi-n-butoxysilane, methyldimethoxysilane, methyldiethoxysilane, butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyldimethoxy silane, dimethyl diethoxy silane, dimethyl di- (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, methyl (methyl) (Perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro- (Methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (Perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (Methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) diethoxysilane, (methyl) (Methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (3-mercaptopropyl) (Vinyl) di (vinyl) di (meth) acrylate, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, , Divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxy Silane, diphenyl diethoxy silane, diphenyl di-n-propoxy silane, diphenyl di-i-propoxy silane, diphenyl di- n-butoxysilane, diphenyl di-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, Propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (meth) (Methoxy) (methyl) diphenylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, And a silane compound having one silicon atom.

As a product name, for example,

KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X- X-22-170B, X-22-170D, X-22-170DX, X-22-176B, X-22-170B, X- 22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X- X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, KR-212, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, K56002, KF6003, KR- KR5230, KR5235, KR9218, KR9706 (all, Shin-Etsu Chemical Co., Ltd.);

Glass resin (manufactured by Showa Denko K.K.);

SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray, Dow Corning);

FZ3711 and FZ3722 (manufactured by Nippon Unicar Co., Ltd.);

DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, Chisso Corporation);

Methyl silicate MS51, methyl silicate MS56 (all available from Mitsubishi Chemical Corporation);

Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, Kolkot K.K.);

GR100, GR650, GR908, and GR950 (all trade names, manufactured by Showa Denko K.K.).

Among these silane compounds, from the viewpoints of orientation and chemical stability of the obtained liquid crystal alignment film, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane (Meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane is preferable .

The polyorganosiloxane having an epoxy group to be used in the present invention is preferably a polyorganosiloxane having an epoxy group and an epoxy group in order to suppress unintended side reactions caused by excessive introduction of an epoxy group while introducing a side chain having a photo- The equivalent is preferably 100 g / mol to 10,000 g / mol, more preferably 150 g / mol to 1,000 g / mol. Therefore, in the synthesis of the polyorganosiloxane having an epoxy group, it is preferable to prepare the epoxyalkylene compound having an epoxy equivalent of the obtained polyorganosiloxane in the above range so that the ratio of the silane compound having an epoxy group to the other silane compound is obtained.

Specifically, such another silane compound is preferably used in an amount of 0% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total amount of the polyorganosiloxane having an epoxy group and the other silane compound .

Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane having an epoxy group include a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, and an alcohol compound.

Examples of the hydrocarbon compound include toluene, xylene, and the like;

Examples of the ketone compound include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone;

Examples of the ester compound include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like;

Examples of the ether compound include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;

Examples of the alcohol compound include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Of these, water-insoluble ones are preferable. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be used is preferably 10 parts by mass to 10,000 parts by mass, more preferably 50 parts by mass to 1,000 parts by mass, per 100 parts by mass of the total silane compound. The amount of water to be used in the production of the polyorganosiloxane having an epoxy group is preferably 0.5 to 1 mol, more preferably 1 to 30 mol, per mol of the total silane compound.

As the catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound and the like can be used.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene;

And quaternary organic ammonium salts such as tetramethylammonium hydroxide. In view of the fact that the reaction proceeds mildly among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine;

And a quaternary organic ammonium salt such as tetramethylammonium hydroxide.

As the catalyst for producing the polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, a desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing a side reaction such as ring-opening of an epoxy group and the like, desirable. The organic semiconductor alignment composition of the present invention containing the reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a specific cinnamic acid derivative has excellent storage stability Therefore, it is appropriate.

The reason for this is as follows. As indicated in "Chemical Reviews", vol. 95, p1409 (1995), when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis and condensation reaction, Or a basket structure is formed, and a polyorganosiloxane having a small content of silanol groups is obtained. In the case where the condensation reaction between the silanol groups is suppressed because the content of the silanol groups is small and the composition for orienting the organic semiconductor of the present invention contains the other polymer described later, the condensation reaction between the silanol group and the other polymer It is deduced that the result is excellent in storage stability.

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used differs depending on the kind of the organic base, reaction conditions such as temperature, and the like, and can be appropriately set. The specific amount of the organic base to be used is, for example, preferably 0.01 to 3 moles per mole, more preferably 0.05 to 1 mole per mole of the total silane compound.

The hydrolysis or hydrolytic condensation reaction in the production of a polyorganosiloxane having an epoxy group can be carried out by dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, For example, by heating with an oil bath or the like.

In the hydrolysis / condensation reaction, the heating temperature of the oil bath is preferably 130 ° C or lower, more preferably 40 ° C to 100 ° C, preferably 0.5 hours to 12 hours, more preferably 1 hour to 8 hours It is preferable to heat it. During the heating, the mixed solution may be stirred or refluxed.

After completion of the reaction, it is preferable to wash the organic solvent layer obtained by fractionation from the reaction solution with water. In this cleaning, it is preferable to wash with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 mass% or the like in that the cleaning operation becomes easy. The washing is carried out until the water layer after washing becomes neutral. Thereafter, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain the intended epoxy group To obtain a polyorganosiloxane.

In the present invention, a commercially available polyorganosiloxane having an epoxy group may be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21 and EMS-32 (manufactured by Chisso Corporation).

The photo-orientable polyorganosiloxane compound [A] may be a part derived from a hydrolyzate generated by hydrolysis of the polyorganosiloxane itself having an epoxy group, or a part derived from a hydrolyzed and condensed polyorganosiloxane having an epoxy group, And may contain a part derived from water. These hydrolysates and hydrolyzed condensates, which are the constituent materials of the above-mentioned parts, can also be prepared in the same manner as the hydrolysis or condensation conditions of the polyorganosiloxane having an epoxy group.

≪ Synthesis of photo-oriented polyorganosiloxane [A]

The photo-aligned polyorganosiloxane [A] used in the present invention can be synthesized, for example, by reacting a polyorganosiloxane having an epoxy group with a specific cinnamic acid derivative, preferably in the presence of a catalyst.

The amount of the specific cinnamic acid derivative to be used here is preferably 0.001 mol to 10 mol, more preferably 0.01 mol to 5 mol, and particularly preferably 0.05 mol to 2 mol, based on 1 mol of the epoxy group of the polyorganosiloxane.

As the catalyst, known compounds can be used as so-called curing accelerators for promoting the reaction between an organic base or an epoxy compound and an acid anhydride. Examples of the organic base include the same ones as described above.

As the curing accelerator, for example,

Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine and triethanolamine;

2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) 1- (2-cyanoethyl) -2-n-octylimidazole, 1- (2-cyanoethyl) 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- (2-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate (2- cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- (2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s - triazine, 2 , Isocyanuric acid adduct of 4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl- An isocyanuric acid adduct of phenylimidazole and an isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine Imidazole compounds;

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenphosphate;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphor N-butylphosphonium tetraborate, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium tetraphenylborate, tetra-n-butylphosphonium tetraphenylborate, Quaternary phosphonium salts such as tetra-n-butylphosphonium tetrafluoroborate and tetra-n-butylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and its organic acid salts;

Organometallic compounds such as zinc octylate, tin octylate and aluminum acetyl acetone complex;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride;

Boron compounds such as boron trichloride and triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

A high melting point dispersed latent curing accelerator such as an amine addition type accelerator such as dicyandiamide or an adduct of an amine with an epoxy resin;

A microcapsulated latent curing accelerator in which the surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;

Amine salt type latent curing accelerator;

And latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

Among these catalysts, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride are preferable.

The amount of the catalyst to be used is preferably 100 parts by mass or less, more preferably 0.01 parts by mass to 100 parts by mass, and particularly preferably 0.1 parts by mass to 20 parts by mass, based on 100 parts by mass of the polyorganosiloxane having an epoxy group.

The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The reaction time is preferably 0.1 hour to 50 hours, more preferably 0.5 hours to 20 hours.

[A] Photoadjacent polyorganosiloxane can be synthesized in the presence of an organic solvent if necessary. Examples of such an organic solvent include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, and an alcohol compound. Of these, ether compounds, ester compounds, and ketone compounds are preferable from the viewpoints of solubility of raw materials and products, and easiness of product purification. The solvent preferably has a solid content concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) of preferably 0.1% by mass or more and 70% by mass or less, more preferably 5% As shown in FIG.

The Mw of the photo-aligned polyorganosiloxane [A] thus obtained is not particularly limited, but is preferably 1,000 to 20,000, more preferably 3,000 to 15,000. By setting the molecular weight within such a range, good alignment and stability of the liquid crystal alignment film can be secured.

The photo-orientable polyorganosiloxane [A] introduces a structure derived from a specific cinnamic acid derivative by ring-opening addition of a carboxyl group of a specific cinnamic acid derivative to an epoxy in a polyorganosiloxane having an epoxy group. This production method is extremely convenient in that it is simple, and further, the introduction rate of a structure derived from a specific cinnamic acid derivative can be increased.

In the present invention, a part of the specific cinnamic acid derivative may be substituted by a compound represented by the following formula (4) within the range not to impair the effect of the present invention. In this case, the synthesis of the photo-orientable polyorganosiloxane compound [A] is carried out by reacting a mixture of a polyorganosiloxane having an epoxy group with a specific cinnamic acid derivative and a compound represented by the following formula (4).

The R ¹⁰ in the formula (4) is preferably an alkyl group or alkoxy group having 8 to 20 carbon atoms, or a fluoroalkyl group or fluoroalkoxy group having 4 to 21 carbon atoms. R ¹¹ is preferably a single bond, a 1,4-cyclohexylene group or a 1,4-phenylene group. R ¹² is preferably a carboxyl group.

Examples of the compound represented by the formula (4) include compounds represented by the following formulas (4-1) to (4-3).

The compound represented by the formula (4) can contribute to the improvement of the stability of the liquid crystal aligning agent by inactivating the active site of the photo-orientable polyorganosiloxane [A]. In the present invention, when the compound represented by the formula (4) is used together with the specific cinnamic acid derivative, the total use ratio of the specific cinnamic acid derivative and the compound represented by the formula (4) Is preferably from 0.001 mol to 1.5 mol, more preferably from 0.01 mol to 1 mol, and particularly preferably from 0.05 mol to 0.9 mol, per mol of the epoxy group. In this case, the amount of the compound represented by the formula (4) is preferably 50% by mole or less, more preferably 25% by mole or less, based on the total amount of the compound with the specific cinnamic acid derivative. When the ratio of the compound represented by the formula (4) is more than 50 mol%, there is a possibility that the orientation property in the liquid crystal alignment film is lowered.

<[B] Other polymers>

The liquid crystal aligning agent may contain [B] other polymer as a suitable component. Examples of the [B] other polymer include at least one selected from the group consisting of a polyamic acid, a polyimide, an ethylenically unsaturated compound polymer, and a polyorganosiloxane having no photo-aligning group. In the case of containing such [B] other polymer, it has become clear that in the liquid crystal alignment film for a retardation film formed from the liquid crystal aligning agent, the polyorganosiloxane is localized near the surface layer thereof. Therefore, even if the content of the polyorganosiloxane in the liquid crystal aligning agent is reduced by increasing the content of the other polymer, the polyorganosiloxane is localized on the surface of the alignment film, so that sufficient liquid crystal alignability can be obtained. Therefore, in the present invention, it is possible to reduce the content of the polyorganosiloxane having a high production cost in the liquid crystal aligning agent, and consequently, the manufacturing cost of the liquid crystal aligning agent can be lowered.

[Polyamic acid]

The polyamic acid is obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound.

Examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic acid dianhydride. These tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

Examples of the aliphatic tetracarboxylic acid dianhydride include butane tetracarboxylic dianhydride.

Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3,3,0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane -3,5,8,10-tetraone, and the like.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride and the like, and tetracarboxylic dianhydrides described in JP-A-2010-97188.

Among these tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic dianhydrides are preferable, and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferable. Especially preferred is 2,3,5-tricarboxycyclopentylacetic acid dianhydride.

The amount of 2,3,5-tricarboxycyclopentylacetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride is preferably 10 mol% or more based on the total tetracarboxylic dianhydride, More preferably 20 mol% or more, and it is particularly preferable that it is composed of only 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride.

Examples of the diamine compound include an aliphatic diamine, an alicyclic diamine, a diaminoorganosiloxane, and an aromatic diamine. These diamine compounds may be used alone or in combination of two or more.

Examples of the aliphatic diamine include, for example, meta-xylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and the like.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) cyclohexane.

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, as well as the diamines described in JP-A-2010-97188.

Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9- 4,4'- (m-tert-butylphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 - diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl- , 6-diaminocarbazole, N- (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis (4-aminophenyl) -Bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy- , 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecanoxy- Diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy- Diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid Cholestanol, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3 , 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyl) Oxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 4-heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) 4-aminobenzylamine, and 3-aminobenzylamine represented by the following formula (A-1): embedded image wherein R 1, R 2, R 3, R 4, 1): &lt; EMI ID =

(Wherein (A-1) of, X ^I is an alkyl group having a carbon number of 1~3, * -O-, * -COO- or * -OCO- gt;

However, the bonding hands attached with * are bonded to the diaminophenyl group;

r is 0 or 1;

s is an integer from 0 to 2;

and t is an integer of 1 to 20).

The ratio of the tetracarboxylic acid dianhydride and the diamine compound to be used in the synthesis reaction of the polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid dianhydride with respect to 1 equivalent of the amino group contained in the diamine compound, More preferably 0.3 equivalents to 1.2 equivalents.

The synthesis reaction is preferably carried out in an organic solvent. The reaction temperature is preferably -20 占 폚 to 150 占 폚, more preferably 0 占 폚 to 100 占 폚. The reaction time is preferably 0.5 hours to 24 hours, more preferably 2 hours to 12 hours.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. Examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, , Aprotic polar solvents such as N, N-dimethylimidazolidinone, dimethylsulfoxide,? -Butyrolactone, tetramethylurea and hexamethylphosphoric triamide;

phenol-based solvents such as m-cresol, xylenol, phenol, and halogenated phenol.

The amount (a) of the organic solvent to be used is preferably from 0.1% by mass to 50% by mass, more preferably from 5% by mass to 5% by mass, based on the sum (a + b) of the total amount (b) of the tetracarboxylic acid dianhydride and the diamine compound and the amount And more preferably from 30% by mass to 30% by mass.

The polyamic acid solution obtained after the reaction may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent. After the isolated polyamic acid is purified, It may be provided in the preparation of the article. Examples of the method of isolating the polyamic acid include a method of pouring the reaction solution into a large amount of a poor solvent to dry the precipitate obtained under reduced pressure, and a method of distilling off the reaction solution under reduced pressure using a diverter. Examples of the method for purifying polyamic acid include a method in which the isolated polyamic acid is dissolved again in an organic solvent and then precipitated with a poor solvent, and a method in which a step of distilling off an organic solvent or the like under reduced pressure is carried out once or plural times have.

[Polyimide]

The polyimide can be produced by dehydrating and cyclizing the arid acid structure of the polyamic acid to imidize it. The polyimide may be a completely imide cargo which is dehydrated and closed by all of the arboric acid structure possessed by the polyamic acid which is a precursor thereof and may be a partially imidated cargo which is dehydrated and closed only in a part of the arboric acid structure, .

The polyimide may be synthesized by, for example, (i) a method of heating a polyamic acid (hereinafter sometimes referred to as "method (i)"), (ii) dissolving a polyamic acid in an organic solvent, And a method of adding a dehydrating agent and a dehydrating ring-closure catalyst, and heating them if necessary (hereinafter sometimes referred to as &quot; method (ii) &quot;).

The reaction temperature in the method (i) is preferably 50 ° C to 200 ° C, more preferably 60 ° C to 170 ° C. If the reaction temperature is less than 50 캜, the dehydration ring-closure reaction does not sufficiently proceed, and if the reaction temperature exceeds 200 캜, the molecular weight of the obtained polyimide may be lowered. The reaction time is preferably 0.5 hours to 48 hours, more preferably 2 hours to 20 hours.

The polyimide obtained in the method (i) may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, after the polyimide is isolated, the polyimide may be supplied to the preparation of the liquid crystal aligning agent, And may be provided in the preparation of the liquid crystal aligning agent after purification.

Examples of the dehydrating agent in the method (ii) include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride.

The amount of the dehydrating agent to be used is appropriately selected according to the desired imidization rate, but it is preferably 0.01 to 20 moles per mole of the acid structure of the polyamic acid.

Examples of the dehydration ring closure catalyst in the method (ii) include pyridine, collidine, lutidine, triethylamine, and the like.

The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent contained. The imidization rate can be increased as the content of the dehydrating agent and the dehydration ring-closing catalyst is larger.

Examples of the organic solvent used in the method (ii) include the same organic solvents as those exemplified for the synthesis of polyamic acid.

The reaction temperature in the method (ii) is preferably 0 ° C to 180 ° C, more preferably 10 ° C to 150 ° C. The reaction time is preferably 0.5 hours to 20 hours, more preferably 1 hour to 8 hours. By setting the reaction conditions in the above range, the dehydration ring-closure reaction proceeds sufficiently, and the molecular weight of the obtained polyimide can be made appropriate.

In the method (ii), a reaction solution containing polyimide is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided to the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated, Or may be provided in the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. As a method for removing the dehydrating agent and the dehydration cyclization catalyst from the reaction solution, for example, a method of solvent substitution and the like can be given. Examples of the polyimide isolation and purification methods include the same methods as those exemplified as the polyamic acid isolation and purification methods.

[Ethylenically unsaturated compound polymer]

[B] The ethylenically unsaturated compound polymer as the other polymer is obtained by polymerizing a known ethylenically unsaturated compound by a known method. For example, the following aspects can be cited. [B] The ethylenically unsaturated compound polymer as the other polymer may be used in combination of two or more kinds of polymers.

[B] The ethylenically unsaturated compound polymer as the other polymer is, for example,

(a) an epoxy group-containing ethylenically unsaturated compound (hereinafter sometimes referred to as "(a) unsaturated compound"),

(b) an ethylenically unsaturated compound containing a carboxyl group or a hydroxyl group (hereinafter sometimes referred to as "(b) unsaturated compound") and

(c) a polymerizable unsaturated compound other than (a) an unsaturated compound and (b) an unsaturated compound (hereinafter sometimes referred to as "(c) unsaturated compound"

(Hereinafter may be referred to as &quot; (A) copolymer &quot;) of at least two kinds of unsaturated compounds selected from the group consisting of Here, the epoxy group includes an oxiranyl group and an oxetanyl group. Further, as the ethylenically unsaturated compound polymer as the [B] other polymer, two or more kinds of the respective unsaturated compounds may be used in combination.

As the unsaturated compound (a), for example,

(Hereinafter may be referred to as "(a-1) unsaturated compound") containing an oxiranyl group as an epoxy group, glycidyl (meth) acrylate, glycidyl Glycidyl, glycidyl? -N-butyl acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxybutyl? -Ethyl acrylate, 6,7-epoxyheptyl (meth) 6,7-epoxyheptyl acrylate and the like;

3 - ((meth) acryloyloxymethyl) oxetane, 3 - ((meth) acryloyloxymethyl) oxetane as an unsaturated compound containing an oxetanyl group as an epoxy group (Meth) acryloyloxymethyl) -3-ethyloxetane, 3 - ((meth) acryloyloxymethyl) -2-methyloxetane, 3- (Meth) acryloyloxymethyl) -2-phenyloxetane, 3 - ((meth) acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (Meth) acryloyloxymethyl) -2,2-difluorooxetane, 3 - ((meth) acryloyloxymethyl) -2,2,4- (Meth) acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, 3 - ((meth) acryloyloxyethyl) oxetane, 3- ((Meth) acryloyloxyethyl) -2-trifluoromethyloxane, 3-ethyl- (Meth) acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro (meth) acryloyloxyethyl) -2-pentafluoroethyloxetane, 3 - 3 - ((meth) acryloyloxyethyl) oxetane, 3 - ((meth) acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- Oxyethyl) -2,2,4,4-tetrafluorooxetane and the like.

As the unsaturated compound (b), for example,

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid,? - ethyl acrylic acid,? - n-propyl acrylic acid,? - n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

Unsaturated polycarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride and cis-1,2,3,4-tetrahydrophthalic anhydride;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (Meth) acrylate having a hydroxyl group such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2- ) Acryloyl acid esters and the like.

As the unsaturated compound (c), for example,

(Meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec- Butyl (meth) acrylate and t-butyl (meth) acrylate;

(Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan- .1.0 ^2,6] decan-8-one referred to as "de-cycloalkyl fentanyl" a), (meth) acrylate, 2-di-bicyclo fentanyl oxyethyl (meth) acrylate, isobutyl beam (meth) acrylic acid alicyclic ester such as carbonyl Ryu;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and tolyl (meth) acrylate;

(Meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate and phenylethyl (meth) acrylate;

Heterocyclic esters such as tetrahydrofurfuryl (meth) acrylate, and tetrahydropyranyl (meth) acrylate;

Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Unsaturated dicarbonylimide derivatives such as N-succinimidyl-3-maleimidopropionate and N- (9-acridyl) maleimide;

(Meth) acrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide;

Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide and N- (meth) acryloylmorpholine;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, o-methylstyrene and p-methoxystyrene;

Indene derivatives such as indene and 1-methylindene;

Vinylidene chloride, vinylidene chloride, and vinyl acetate, in addition to conjugated diene compounds such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

In the copolymer (A), the content of the structural unit derived from the unsaturated compound (a) is preferably from 10% by mass to 100% by mass, more preferably from 20% by mass to 100% by mass, , And still more preferably from 30 mass% to 80 mass%. The content of the structural unit derived from the unsaturated compound (a-1) is preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 60% by mass relative to the total structural units. The content of the structural unit derived from the (a-2) unsaturated compound is preferably 5% by mass to 40% by mass, and more preferably 10% by mass to 30% by mass, based on the total structural units. The content of the structural unit derived from the unsaturated compound (a-2) relative to the total structural units derived from the unsaturated compound (a) is preferably 0% by mass to 80% by mass, more preferably 10% , And still more preferably from 20 mass% to 60 mass%.

In the copolymer (A), the content of the structural unit derived from the unsaturated compound (b) is preferably 0% by mass to 40% by mass, more preferably 5% by mass to 40% by mass, , And more preferably 10% by mass to 30% by mass.

In the copolymer (A), the content of the structural unit derived from the unsaturated compound (c) is preferably 0% by mass to 80% by mass, more preferably 0% by mass to 70% by mass, , And more preferably from 20% by mass to 60% by mass.

The (A) copolymer can be synthesized by radical polymerization, for example, in the presence of an appropriate organic solvent and polymerization initiator, with each unsaturated compound. Examples of the organic solvent include the same organic solvents as those exemplified for the synthesis of polyamic acid.

As the polymerization initiator, for example,

(2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethyl Azo compounds such as valeronitrile);

Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane;

Hydrogen peroxide;

And a redox-type initiator comprising these peroxides and a reducing agent. These polymerization initiators may be used alone or in combination of two or more.

[Polyorganosiloxane having no photo-alignment group]

The liquid crystal aligning agent may further contain, in addition to the [A] photo-orientable polyorganosiloxane, a polyorganosiloxane having no photo-orienting group as the [B] other polymer. As the polyorganosiloxane having no photo-aligning group, at least one member selected from the group consisting of a polyorganosiloxane having a structural unit represented by the following formula (5), a hydrolyzate thereof and a condensate of the hydrolyzate thereof is preferable. In addition, when the liquid crystal aligning agent contains a polyorganosiloxane having no photo-aligning group, most of the polyorganosiloxane having no photo-aligning group is present independently of the photo-aligned polyorganosiloxane [A] And a part thereof may exist as a condensate with the [A] photo-orientable polyorganosiloxane.

In the formula (5), X ² is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Y ² is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, A nonadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group and the like can be given.

Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and isobutoxy group.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.

The polyorganosiloxane having no photo-aligning group is preferably a polyorganosiloxane having at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter sometimes referred to as &quot; raw silane compound & Can be synthesized by hydrolysis or hydrolysis / condensation in an appropriate organic solvent in the presence of water and a catalyst.

As the raw material silane compound, for example,

Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetrachlorosilane and the like;

Butoxysilane, methyltri-sec-butoxysilane, methyltri-sec-butoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri- propyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopropoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri- butoxy silane, ethyl tri-sec-butoxysilane, ethyl tri-tert-butoxysilane, ethyl trichlorosilane, phenyl trimethoxysilane, phenyl triethoxysilane, phenyl trichlorosilane and the like;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane and the like;

Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and the like.

Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane or trimethylethoxysilane is preferred.

Examples of the organic solvent that can optionally be used in the synthesis of the polyorganosiloxane having no photo-aligning group include an alcohol compound, a ketone compound, an amide compound, an ester compound or other aprotic compound. These may be used alone or in combination of two or more.

The amount of water used when synthesizing the polyorganosiloxane having no photo-aligning group is preferably from 0.01 to 100 moles, more preferably from 0.1 to 30 moles, per mole of the total of the alkoxy group and the halogen atom in the raw material silane compound And particularly preferably 1 mol to 1.5 mol.

Examples of the catalyst that can be used for synthesizing the polyorganosiloxane having no photo-aligning group include a metal chelate compound, an organic acid, an inorganic acid, an organic base, an alkali metal compound, an alkaline earth metal compound, ammonia and the like. These may be used alone or in combination of two or more.

The amount of the catalyst to be used is preferably 0.001 part by mass to 10 parts by mass, more preferably 0.001 part by mass to 1 part by mass, per 100 parts by mass of the raw material silane compound.

The water to be added when synthesizing the polyorganosiloxane having no photo-aligning group can be added intermittently or continuously in a silane compound as a raw material or in a solution in which a silane compound is dissolved in an organic solvent. The catalyst may be added in advance in the silane compound as a raw material or in a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.

The reaction temperature in the synthesis of the polyorganosiloxane having no photo-aligning group is preferably 0 deg. C to 100 deg. C, more preferably 15 deg. C to 80 deg. The reaction time is preferably 0.5 hours to 24 hours, more preferably 1 hour to 8 hours.

When the liquid crystal aligning agent contains the [B] other polymer, the content of the [B] other polymer differs depending on the kind of the [B] other polymer. When the amount of the liquid crystal aligning agent is in the range of 100 parts by mass per 100 parts by mass of the [A] photoadhering polyorganosiloxane To 10,000 parts by mass or less.

&Lt; Compound containing ester structure [C]

The liquid crystal aligning agent contains a [C] ester structure-containing compound, whereby a liquid crystal alignment film for a retardation film having excellent heat resistance and the like can be formed.

The [C] ester structure-containing compound is selected from the group consisting of an acetal ester structure of a carbonic acid, a ketal ester structure of a carbonic acid, a 1-alkylcycloalkyl ester structure of a carbonic acid, and a t-butyl ester structure of a carbonic acid in a molecule Or a compound having at least two structures of at least one kind. The [C] ester structure-containing compound may be a compound having two or more structures of the same kind among these structures, or a compound having two or more structures of different types of these structures. Examples of the group containing an acetal ester structure of the above carbonic acid include groups represented by the following formulas (C-1) and (C-2):

(In the formula (C-1), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an aliphatic group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms ;

In the formula (C-2), n1 is an integer of 2 to 10).

In R ¹³ in the formula (C-1), the alkyl group having 1 to 20 carbon atoms is preferably a methyl group, the cycloaliphatic group having 3 to 10 carbon atoms is preferably a cyclohexyl group, and the aryl group having 6 to 10 carbon atoms A phenyl group is preferable, and as the aralkyl group having 7 to 10 carbon atoms, a benzyl group is preferable. The alkyl group having 1 to 20 carbon atoms as R ¹⁴ is preferably an alkyl group having 1 to 6 carbon atoms, the alicyclic group having 3 to 10 carbon atoms is preferably an alicyclic group having 6 to 10 carbon atoms, and the aryl group having 6 to 10 carbon atoms is preferably a phenyl group And the aralkyl group having 7 to 10 carbon atoms is preferably a benzyl group or a 2-phenylethyl group. As n1 in the formula (C-2), 3 or 4 is preferable.

Examples of the group represented by the formula (C-1) include 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, Butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 1-t-butoxyethoxycarbonyl group, 1-t-butoxyethoxycarbonyl group, 1- (Cyclohexyl) methoxycarbonyl group, a (cyclohexyl) (methoxycarbonyl) methoxycarbonyl group, a (cyclohexyl) methoxycarbonyl group, a cyclohexyloxycarbonyl group, (Phenyl) (methoxycarbonyl) methoxycarbonyl, (phenyl) (cyclohexyloxy) methoxycarbonyl, (phenyl) methoxycarbonyl, (Benzyl) (methoxycarbonyl) methoxycarbonyl, (benzyl) (methoxycarbonyl) methoxycarbonyl, (phenyl) (benzyloxy) methoxycarbonyl, (Phenoxy) methoxycarbonyl group, (Benzyl) (benzyloxy) methoxycarbonyl group and the like.

Examples of the group represented by the formula (C-2) include a 2-tetrahydrofuranyloxycarbonyl group and a 2-tetrahydropyranyloxycarbonyl group.

Of these, preferred are a 1-ethoxyethoxycarbonyl group, a 1-n-propoxyethoxycarbonyl group, a 1-cyclohexyloxyethoxycarbonyl group, a 2-tetrahydrofuranyloxycarbonyl group, a 2-tetrahydropyranyloxy Carbonyl groups are preferred.

Examples of the group containing the ketal ester structure of the carbonic acid include groups represented by the following formulas (C-3) to (C-5):

(In the formula (C-3), R ¹⁵ is an alkyl group having 1 to 12 carbon atoms;

R ¹⁶ and R ¹⁷ each independently represent an alkyl group having 1 to 12 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms;

In the formula (C-4), R ¹⁸ is an alkyl group having 1 to 12 carbon atoms;

n2 is an integer from 2 to 8;

In the formula (C-5), R ¹⁹ is an alkyl group having 1 to 12 carbon atoms;

and n3 is an integer of 2 to 8).

As the alkyl group having 1 to 12 carbon atoms for R ¹⁵ in the formula (C-3), a methyl group is preferable, and the alkyl group having 1 to 12 carbon atoms for R ¹⁶ is preferably a methyl group and the alicyclic group having 3 to 20 carbon atoms The cyclohexyl group is preferable, and the aryl group having 6 to 20 carbon atoms is preferably a phenyl group, and the aralkyl group having 7 to 20 carbon atoms is preferably a benzyl group. The alkyl group having 1 to 12 carbon atoms for R &lt; ¹⁷ &gt; is preferably an alkyl group having 1 to 6 carbon atoms. The alicyclic group having 3 to 20 carbon atoms is preferably an alicyclic group having 6 to 10 carbon atoms. As the aryl group having 6 to 20 carbon atoms, a phenyl group is preferable. As the aralkyl group having 7 to 20 carbon atoms, a benzyl group or a 2-phenylethyl group is preferable. The alkyl group having 1 to 12 carbon atoms represented by R ^{18 in} the formula (C-4) is preferably a methyl group. As n2, 3 or 4 is preferable. The alkyl group having 1 to 12 carbon atoms represented by R &lt; ¹⁹ &gt; in the formula (C-5) is preferably a methyl group. As n3, 3 or 4 is preferable.

Examples of the group represented by the above formula (C-3) include 1-methyl-1-methoxyethoxycarbonyl group, 1-methyl- butoxyethoxycarbonyl group, 1-methyl-1-i-butoxyethoxycarbonyl group, 1-methyl-1-sec-butoxyethoxycarbonyl group, Methyl-1-cyclohexyloxyethoxycarbonyl group, 1-methyl-1-nonyloxyethoxycarbonyl group, 1-methyl-1-phenoxyethoxycarbonyl group, 1-methyl- 1-cyclohexyloxyethoxycarbonyl group, 1-cyclohexyl-1-cyclohexyloxyethoxycarbonyl group, 1-cyclohexyl-1-cyclohexyloxyethoxycarbonyl group, , 1-cyclohexyl-1-phenoxyethoxycarbonyl, 1-phenyl-1-methoxyethoxycarbonyl, 1-phenyl-1-ethoxyethoxycarbonyl, 1-phenyl- 1-phenyl-1-benzyloxyethoxycarbonyl group, 1-benzyl-1-methoxyethoxycarbonyl group, 1-benzyl-1- 1-benzyl-1-phenoxyethoxycarbonyl group, 1-benzyl-1-benzyloxyethoxycarbonyl group, and the like.

Examples of the group represented by the above formula (C-4) include a 2- (2-methyltetrahydrofuranyl) oxycarbonyl group and a 2- (2-methyltetrahydropyranyl) oxycarbonyl group.

Examples of the group represented by the formula (C-5) include a 1-methoxycyclopentyloxycarbonyl group, a 1-methoxycyclohexyloxycarbonyl group and the like.

Of these, 1-methyl-1-methoxyethoxycarbonyl group and 1-methyl-1-cyclohexyloxyethoxycarbonyl group are preferable.

Examples of the group containing the 1-alkyl cycloalkyl ester structure of the above carboxylic acid include groups represented by the following formula (C-6):

(In the formula (C-6), R ²⁰ is an alkyl group having 1 to 12 carbon atoms;

and n4 is an integer of 1 to 8).

The alkyl group having 1 to 12 carbon atoms represented by R ²⁰ in the formula (C-6) is preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the group represented by the above formula (C-6) include 1-methylcyclopropoxycarbonyl group, 1-methylcyclobutoxycarbonyl group, 1-methylcyclopentoxycarbonyl group, 1-methylcyclohexyloxycarbonyl group Ethylcyclohexyloxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1- Propylcyclohexyloxycarbonyl group, 1- (iso) butylcyclobutoxycarbonyl group, 1- (iso) butylcarbonyloxy group, Butyl cyclohexyloxycarbonyl group, 1- (iso) butylcyclohexyloxycarbonyl group, 1- (iso) pentylcycloheptyloxycarbonyl group, 1- Oxycarbonyl group, 1- (iso) pentylcyclooctyloxycarbonyl group (Iso) hexylcyclohexyloxycarbonyl group, a 1- (iso) hexylcyclohexyloxycarbonyl group, a 1- (benzyloxycyclohexyloxycarbonyl) group, 1- (iso) hexylcyclohexyloxycarbonyl group, 1- (iso) hexylcyclodecyloxycarbonyl group, 1- (iso) octylcyclopropoxycarbonyl group, 1- (Iso) octylcyclohexyloxycarbonyl group, 1- (iso) octylcyclohexyloxycarbonyl group, 1- (iso) octylcyclohexyloxycarbonyl group, 1- ) Octyl cyclodecyloxycarbonyl group, and the like.

The group containing the t-butyl ester structure of the carbonic acid is a t-butoxycarbonyl group.

As the [C] ester structure-containing compound in the present invention, a compound represented by the following formula (C) is preferable:

T _n R (C)

(In the formula (C), T is a group represented by any one of the above-mentioned formulas (C-1) to (C-6) or a t-butoxycarbonyl group, n is 2 and R is a single bond, An integer of 2 to 10, and R is an n-valent group obtained by removing hydrogen from a heterocyclic compound having 3 to 10 carbon atoms or an n-valent hydrocarbon group having 1 to 18 carbon atoms).

n is preferably 2 or 3.

Examples of R in the formula (C) include a single bond, an alkanediyl group having 1 to 12 carbon atoms, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4- , A 6-naphthalenyl group, a 5-sodium sulfo-1,3-phenylene group, and a 5-tetrabutylphosphonium sulfo-1,3-phenylene group.

When n is 3, examples of R include a group represented by the following formula, benzene-1,3,5-triyl group, and the like.

The alkanediyl group is preferably a straight-chain group.

The [C] ester-containing compound represented by the above formula (C) can be synthesized by a method of organic chemistry or a method of combining organic chemistry properly.

For example (excluding the case of single, R ¹³ is a phenyl group), a T in the formula (C) compounds represented by the above equation due to (C-1) is preferably a compound in the presence of an acid catalyst R- (COOH) _n (wherein R and n each have the same meaning as in the above formula (C)) and a compound R ¹⁴ -O-CH = R ^{13 'in which} R ¹⁴ is the same as in formula (C-1) Wherein R ^{13 '} is a group obtained by removing a hydrogen atom from the 1-position carbon atom of R ¹³ in the formula (C-1)).

The compound in which T in the formula (C) is a group represented by the formula (C-2) is preferably a compound R- (COOH) _{n in which} R and n are as defined in the above formula C)) and a compound represented by the formula:

(Wherein n1 is as defined in the above formula (C-2)).

The content of the [C] ester structure-containing compound in the liquid crystal aligning agent is not particularly limited as long as it is determined in consideration of the required heat resistance and the like, and the content of the ester structure [C] relative to 100 parts by mass of the [A] photoadhering polyorganosiloxane More preferably from 1 part by mass to 20 parts by mass, and particularly preferably from 2 parts by mass to 10 parts by mass.

<[D] Solvent>

The liquid crystal aligning agent may contain a [D] solvent as a suitable component. [D] The solvent is represented by the above formula (6). By containing the liquid crystal aligning agent and the [D] solvent, adhesion between the liquid crystal aligning agent and the substrate for a retardation film can be improved.

In the formula (6), R ^d1 is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group or a benzyl group. However, the alkyl group may have -O- between carbon-carbon bonds. R ^d2 is a monovalent organic group having 1 to 8 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^d1 include a methyl group, an ethyl group, a propyl group, and a butyl group. Of these, a methyl group, an ethyl group and a propyl group are preferable, and a methyl group is more preferable.

Examples of the cycloalkyl group having 3 to 6 carbon atoms represented by R ^d1 include a cyclopropyl group and a cyclobutyl group.

Examples of the monovalent organic group having 1 to 8 carbon atoms represented by R ^d2 include linear or branched alkyl groups having 1 to 8 carbon atoms and the like. And the like.

Examples of the solvent [D] include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, dibutyl acetate, isobutyl acetate, amyl acetate, amyl acetate, isoamyl acetate, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propyleneglycol monomethyl ether acetate, methyl amyl acetate, methyl propionate, ethyl propionate, propyl propyl ester, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, cellosolve acetate, propyleneglycol monoethyl ether acetate, Ethylhexyl acetate, benzyl acetate, methyl carbitol acetate, carbitol acetate, methyl carbitol acetate, methyl carbitol acetate, butyl cellosolve acetate, phenyl acetate, acetic acid 2-ethylhexyl acetate, , Propyleneglycol monomethyl ether acetate, butyl butyrate, isoamyl butyrate, methyl benzoate, ethyl benzoate, benzyl benzoate, benzoyl benzoate, benzoic acid benzoate, , Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, ethyl-3-ethoxypropionate and butyl cellosolve acetate.

Among them, as the [D] solvent, a solvent having a boiling point of 150 캜 or lower is preferable from the viewpoint that a solvent capable of volatilizing at a low temperature is preferable when the liquid crystal alignment film is formed from the liquid crystal aligning agent. Examples of such solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, dibutyl acetate, isobutyl acetate, amyl acetate, amyl acetate, isoamyl acetate, methyl cellosolve acetate, propylene glycol monomethyl Ether acetate, methyl amyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, methyl butyrate and ethyl butyrate.

The [D] solvent is preferably a solvent which does not affect the substrate for the retardation film to which the liquid crystal aligning agent is applied, such as deformation and dissolution. For example, when a triacetylcellulose (TAC) film is used as the substrate for the retardation film, an acetic acid ester-based solvent and a propionic acid ester-based solvent are more preferable, and an acetic acid ester-based solvent is more preferable. Among them, propyl acetate, isopropyl acetate, butyl acetate, dibutyl acetate and isobutyl acetate are particularly preferable.

When the liquid crystal aligning agent contains the [D] solvent, the content ratio of the [D] solvent is preferably 50 parts by weight or more, and more preferably 75 parts by weight or more, based on the total solvent. Further, two or more kinds of [D] solvents may be mixed and used.

<[E] Solvent>

The liquid crystal aligning agent may contain a [E] solvent as a suitable component. The [E] solvent is an organic solvent having erosion resistance to a substrate for a retardation film. By containing the liquid crystal aligning agent [E] solvent, adhesion between the liquid crystal aligning agent and the substrate for a retardation film can be further improved.

Examples of the substrate for the retardation film include glass substrates such as float glass and soda glass, glass substrates such as triacetylcellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyamide, polyimide, And transparent substrates including plastic substrates such as acrylate, polycarbonate and the like. Of these, a transparent substrate containing a plastic substrate is preferable, and TAC is more preferable among them.

Herein, the organic solvent having an erosion property to the substrate for a retardation film refers to an organic solvent having a property of deforming and / or dissolving a part or the whole of the substrate when the substrate is coated on the retardation film substrate.

Examples of such an [E] solvent include methyl ethyl ketone (MEK), acetone, cyclohexanone, cyclopentanone, methyl acetate, ethyl acetate, ethyl lactate, methyl-3- Ethoxypropionate and the like. Of these, MEK and ethyl acetate are preferable from the viewpoint of improving the adhesion.

When the liquid crystal aligning agent contains the [E] solvent, the content of the [E] solvent is preferably 0.5 to 50 parts by mass, particularly preferably 2 to 30 parts by mass, per 100 parts by mass of the total solvent. The [E] solvent may be used by mixing two or more kinds thereof.

The liquid crystal aligning agent may contain the [E] solvent alone as a solvent, or may be used in combination with other solvents. From the viewpoint of improving the adhesion, it is preferable to use in combination with the [D] solvent. When the [D] solvent and the [E] solvent are used together, the amount of the [E] solvent is preferably 0.5 part by mass or more and less than 50 parts by mass, more preferably 1 part by mass or less and less than 40 parts by mass More preferably 2 parts by mass or more and less than 30 parts by mass. Further, with respect to a solvent that simultaneously satisfies the requirements of the [D] solvent and the [E] solvent, the same effects as those in the case of the above combination can be expected even if they are used alone.

Examples of the liquid crystal aligning agent when the TAC film is used as the substrate to which the liquid crystal aligning agent is applied include, for example, [D] propyl acetate as a solvent, isopropyl acetate, n-butyl acetate, sec- -Butyl or isobutyl acetate and [E] MEK or ethyl acetate as a solvent.

&Lt; [F] Compound &gt;

The liquid crystal aligning agent may contain a [F] compound containing a group having a polymerizable carbon-carbon double bond as a suitable component. By containing the [F] compound, the liquid crystal aligning agent can further improve the adhesion to the substrate for a retardation film or the liquid crystal layer.

Here, the group having a polymerizable carbon-carbon double bond is a group in which the carbon atom forming the double bond is capable of generating a new carbon-carbon bond by addition polymerization. Examples of the group having a polymerizable carbon-carbon double bond include a vinyl group, an allyl group, a styryl group, an acryloyl group, a methacryloyl group, an acrylamide group, a crotonoyl group, an isocrotonoyl group, Diary, and the like.

Examples of the [F] compound include monomer compounds such as (meth) acrylate monomers and polymers such as acrylic and siloxane polymers having a (meth) acryloyl group. Of these, acrylic type and siloxane type polymers having a (meth) acryloyl group and the like are preferable, and acrylic type and siloxane type polymers having a (meth) acryloyl group are more preferable, and a (meth) acryloyl group is preferable And the like are more preferable.

The content of the [F] compound in the liquid crystal aligning agent is preferably 0.1 part by mass to 30 parts by mass of the [F] compound per 100 parts by mass of the total of the [A] photoadhering polyorganosiloxane and the [B] More preferably 0.5 parts by mass to 20 parts by mass, and particularly preferably 1 part by mass to 10 parts by mass.

&Lt; Other optional components &gt;

The liquid crystal aligning agent may contain, in addition to the above radiation sensitive polymer, a compound having a curing agent, a curing catalyst, a curing accelerator, and at least one epoxy group in a molecule (hereinafter referred to as an "epoxy compound" (Hereinafter sometimes referred to as "other solvent") other than the functional silane compound, the surfactant, the photosensitizer, the [D] solvent and the [E] solvent . Hereinafter, these other optional components will be described in detail.

[Curing agent, curing catalyst and curing accelerator]

The curing agent and the curing catalyst may be contained in the liquid crystal aligning agent for the purpose of strengthening the crosslinking reaction of the [A] photo-orientable polyorganosiloxane. The curing accelerator may be contained in the liquid crystal aligning agent for the purpose of accelerating the curing reaction which the curing agent is responsible for.

As the curing agent, a curing agent generally used for curing a curable composition containing an epoxy group or a compound having an epoxy group can be used. For example, a curing agent such as a polyvalent amine, a polyvalent carboxylic acid anhydride, .

Examples of the polyvalent carboxylic acid anhydride include anhydrides of cyclohexanetricarboxylic acid and other polyvalent carboxylic acid anhydrides. Examples of the cyclohexanetricarboxylic anhydride include cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid -2,3-anhydride, and the like.

Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadonic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, Aldrich reaction product of an alicyclic compound having a conjugated double bond such as? -Terpinene, alo cymene and the like and maleic anhydride, and a reaction product of And the like.

(In the formula (7), p is an integer of 1 to 20).

The use ratio of the curing agent is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the [A] photoadhering polyorganosiloxane. When the liquid crystal aligning agent contains a curing catalyst, the content of the liquid crystal aligning agent is preferably 100 parts by mass or less based on 100 parts by mass of the total of 100 parts by mass of the [A] photo-orientable polyorganosiloxane and the optional [B] More preferably 50 parts by mass or less.

Examples of the curing catalyst include a diazonium salt, an iodonium salt, a sulfonium salt, an aluminum alcoholate, and an aluminum chelate. Examples of commercially available products include AMERICURE (BF ₄ ) (diazonium salt of ACC), ULTRASET (BF ₄ , PF ₆ ) (diazonium salt of Asahi Denka Kogyo KK), UVE series (iodonium salt of GE), Photoinitiator 2074 _{C 6 F 6) 4 B)} ( Long, Franc's iodo salts), CYRACURE UVI-6974, CYRACURE UVI-6990 ( or more, UCC's sulfonium salt), UVI-508, UVI- 509 ( above, GE's sulfonium salt ), OPTOMER SP-150, OPTOMER SP-170 (a sulfonium salt of Asahi Denka Kogyo K.K.), Sanade SI-60L, Sanade SI-80L, Sanade SI-100L, Sanade SI-110L IRUGACURE 261 (a metallocene compound of Ciba-Geigy Corp.), and aluminum chelate A (W) (Kawaken Fine Chemicals Co., Ltd.). These curing catalysts may be used singly or as a mixture of two or more kinds.

The use ratio of the curing catalyst is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the [A] photoadhering polyorganosiloxane. When the liquid crystal aligning agent contains a curing catalyst, the content thereof is preferably 30 parts by mass or less based on 100 parts by mass of the total of 100 parts by mass of the [A] photo-orientable polyorganosiloxane and optionally the [B] And more preferably 20 parts by mass or less.

Of these curing catalysts, a sulfonium salt and an aluminum chelate are preferable, and among the sulfonium salts, a compound including antimony hexafluoride, hexafluorophosphate and the like is more preferable as the anion species. Examples of the sulfonium salts include hexafluoroantimonium salts of methylphenyldimethylsulfonium, hexafluoroantimonium salts of ethylphenyldimethylsulfonium, hexafluorophosphate salts of methylphenyldimethylsulfonium, and the like. These sulfonium salts may be used singly or as a mixture of two or more kinds. UVI-6992, UVI-6974 (above, U.S.A.), and the like are commercially available as commercially available products of these sulphonamides, such as SANEID SI-60L, SANEID SI-80L, SANEID SI-100L (available from SANSHIN KAGAKU KOGYO Co., Ltd.), ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-170, ADEKA OPTON CP-66, ADEKA OPTON CP-77 (available from Asahi Denka Kogyo K.K.), IRGACURE 261 Chiba Kogyo K.K.) and the like.

As the curing accelerator, for example, an imidazole compound;

A quaternary compound;

Quaternary amine compounds;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 or an organic acid salt thereof;

Organometallic compounds such as zinc octylate, tin octylate, and aluminum acetyl acetone complex;

Boron compounds such as boron trifluoride, triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

Amine-type accelerators such as dicyandiamide, adducts of amines and epoxy resins, and the like;

A microcapsulated latent curing accelerator in which a surface of a quaternary phosphonium salt or the like is coated with a polymer;

Amine salt type latent curing accelerator;

High-temperature dissociation type thermal cationic polymerization latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

The use ratio of the curing accelerator is preferably 20 parts by mass or less based on 100 parts by mass of the [A] photo-orientable polyorganosiloxane. When the liquid crystal aligning agent contains a curing accelerator, the content thereof is preferably 30 parts by mass or less based on 100 parts by mass of the total of 100 parts by mass of the [A] photo-orientable polyorganosiloxane and optionally the [B] desirable.

[Epoxy Compound]

The epoxy compound may be contained in the liquid crystal aligning agent for the purpose of further improving the adhesiveness of the formed liquid crystal alignment film to the substrate surface.

As the epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl 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-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidylbenzylamine, N, Aminomethylcyclohexane, and the like.

The content of the epoxy compound is preferably 40 parts by mass or less, more preferably 0.1 parts by mass to 30 parts by mass relative to 100 parts by mass of the total amount of the [A] photo-orientable polyorganosiloxane and the optional polymer [B] desirable. When the liquid crystal aligning agent contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of efficiently causing a crosslinking reaction.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the adhesion of the liquid crystal alignment film to be formed on the substrate surface.

Examples of the functional silane compound include 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-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silane triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (Oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetracarboxylic acid dianhydride and amino group And a reaction product of a tetracarboxylic acid dianhydride and an amino group-containing silane compound described in JP-A-63-291922, and the like.

The content of the functional silane compound is preferably 50 parts by mass or less, more preferably 20 parts by mass or less based on 100 parts by mass in total of the [A] photo-orientable polyorganosiloxane and the optional polymer [B] desirable.

[Surfactants]

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants.

The ratio of the surfactant to be used is preferably 10 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the liquid crystal aligning agent.

[Photosensitizer]

Art photosensitizers which can be contained in the liquid crystal aligning agent, a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (where, R is a hydrogen atom or an alkyl group having a carbon number of 1~6), -CH = CH ₂ and SO ₂ Cl, and a compound having a photosensitizing structure. By reacting a mixture of the polyorganosiloxane having an epoxy group with a specific cinnamic acid derivative and a photosensitizer, the [A] photo-orientable polyorganosiloxane contained in the liquid crystal aligning agent is preferably a photosensitive polyorganosiloxane derived from a specific cinnamic acid derivative Structure (Shin-Nam-san structure) and photosensitization structure derived from photosensitizer. This madness-sensitive structure is excited by irradiation of light, and has a function of imparting this excitation energy to a nearby photosensitive structure in the polymer. This excitation state may be singlet state or triplet state, but it is preferably triplet in consideration of long lifetime and efficient energy transfer. The light absorbed by the photosensitive structure is preferably an ultraviolet ray or a visible ray having a wavelength in the range of 150 nm to 600 nm. Light having a wavelength shorter than the above lower limit can not be handled as a normal optical system and thus can not be suitably used for the photo alignment method. On the other hand, light having a longer wavelength than the upper limit has a small energy, and it is difficult to cause the excited state of the photosensitive structure.

Examples of such a sensitizing structure include an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, a fluorene structure, a naphthalene structure, an anthracene structure, These may be used singly or in combination of two or more kinds. Each of these sensitizing structures may be substituted with one to four hydrogen atoms from an acetophenone, benzophenone, anthraquinone, biphenyl, carbazole, nitrobenzene or dinitrobenzene, naphthalene, fluorene, anthracene, And the like. Each of the acetophenone structure, carbazole structure and indole structure is preferably a structure composed of groups obtained by removing 1 to 4 hydrogen atoms contained in the benzene ring of acetophenone, carbazole or indole. Among these photosensitivity structures, at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure and a naphthalene structure is preferable, and an acetophenone structure, A phenol structure and a nitroaryl structure are particularly preferable.

The photosensitizer is preferably a compound having a carboxyl group and a photosensitizing structure, and more preferred examples thereof include compounds represented by the following formulas (H-1) to (H-10)

(Wherein q is an integer of 1 to 6).

The photo-orientable polyorganosiloxane compound to be used in the present invention is preferably a photo-orientable polyorganosiloxane compound in addition to the above-mentioned polyorganosiloxane having a epoxy group and a specific cinnamic acid derivative in combination with a photosensitizer, preferably in an organic solvent Or the like.

In this case, the amount of the specific cinnamic acid derivative to be used is preferably 0.001 mol to 10 mol, more preferably 0.01 mol to 5 mol, and particularly preferably 0.05 mol to 2 mol, relative to 1 mol of the silicon atom of the polyorganosiloxane having an epoxy group Do. The amount of the photosensitizer to be used is preferably 0.0001 mol to 0.5 mol, more preferably 0.0005 mol to 0.2 mol, and particularly preferably 0.001 mol to 0.1 mol, per 1 mol of the silicon atom of the polyorganosiloxane having an epoxy group.

[Other solvents]

The liquid crystal aligning agent may contain, in addition to the [D] solvent and the [E] solvent, other solvents. As other solvent, it is preferable to dissolve the [A] photo-orientable polyorganosiloxane and optionally other components to be used, and not react with them. The organic solvent that can be preferably used for the liquid crystal aligning agent varies depending on the kind of the other polymer optionally contained.

Preferred organic solvents in the case where the liquid crystal aligning agent contains [A] photo-orientable polyorganosiloxane and [B] other polymer include, in addition to the organic solvents exemplified for the synthesis of polyamic acid, ethylene glycol Monobutyl ether (EGMB), and diethylene glycol methyl ethyl ether (DEGME). Of these, NMP, EGMB and DEGME are preferred. These organic solvents may be used alone or in combination of two or more.

&Lt; Preparation of liquid crystal aligning agent for retardation film &

As described above, the liquid crystal aligning agent for a retardation film of the present invention contains a [A] photo-orientable polyorganosiloxane as an essential component and, if necessary, a suitable component and other optional components, Is dissolved in [D] solvent and / or [E] solvent, which is a compatible component, as a composition in a solution state. As the solvent used in the preparation of the liquid crystal aligning agent, other solvents as described above may be suitably used.

The solvent used for preparing the liquid crystal aligning agent is such that the components contained in the liquid crystal aligning agent are not precipitated at the following preferable solid concentration and the surface tension of the liquid crystal aligning agent is in the range of 25 mN / m to 40 mN / m .

The solid concentration of the liquid crystal aligning agent of the present invention, i.e., the ratio of the total mass of the liquid crystal aligning agent other than the solvent in the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., % To 10% by mass. When the solid concentration is less than 1% by mass, the film thickness of the liquid crystal alignment film formed with the liquid crystal aligning agent becomes too small to obtain a good liquid crystal alignment film. On the other hand, if the solid concentration exceeds 10% by mass, the film thickness of the coating film becomes excessive, and a good liquid crystal alignment film may not be obtained. In addition, the viscosity of the liquid crystal aligning agent may increase and coating properties may be insufficient. The preferable range of the solid content concentration differs depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the solid content concentration is preferably 1.5% by mass to 4.5% by mass. In the case of the printing method, it is preferable that the solid concentration is set in the range of 3% by mass to 9% by mass, and the solution viscosity is accordingly set in the range of 12 mPa · s to 50 mPa · s. In the case of the ink-jet method, it is preferable that the solid concentration is in the range of 1% by mass to 5% by mass, and the solution viscosity is accordingly in the range of 3 mPa · s to 15 mPa · s.

The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 0 deg. C to 200 deg. C, more preferably 0 deg. C to 40 deg.

<Liquid crystal alignment film for retardation film and method of forming the same>

The liquid crystal aligning agent can be suitably used for forming a liquid crystal alignment film, in particular, a liquid crystal alignment film used for producing a retardation film by the photo alignment method.

As a method of forming a liquid crystal alignment film for a retardation film, for example, there can be mentioned a method of forming a coating film of a liquid crystal alignment film on a substrate and then giving the liquid crystal aligning ability to the coating film by a photo alignment method.

The liquid crystal alignment film for a retardation film using the liquid crystal aligning agent can be produced, for example, by the following method. The liquid crystal aligning agent is applied to a substrate by a suitable coating method such as a roll coater method, a spinner method, a printing method, or an ink jet method. Next, the applied surface is pre-heated (pre-baked), and then post baked to form a coated film. The prebaking condition is, for example, 0.1 to 5 minutes at 40 to 120 캜. The post-baking conditions are preferably 100 占 폚 to 300 占 폚, more preferably 110 占 폚 to 250 占 폚, and preferably 1 to 200 minutes, more preferably 5 to 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 mu m to 1 mu m, more preferably 0.005 mu m to 0.5 mu m.

Examples of the substrate include glass substrates such as float glass and soda glass, glass substrates such as triacetylcellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyamide, polyimide, polymethyl methacrylate, And a transparent substrate containing a plastic substrate such as polycarbonate. In particular, TAC is generally used as a protective layer of a polarizing film which has an important function in an LCD. In most cases, the retardation film is used in combination with a polarizing film. It is necessary that the retardation film is precisely controlled to be bonded at an angle capable of exhibiting a desired optical characteristic with respect to the polarization axis of the polarizing film. Therefore, if a liquid crystal alignment film capable of aligning the liquid crystal in an arbitrary direction on the TAC film by the photo alignment method is formed and a retardation film formed by coating and curing the polymerizable liquid crystal so as to exhibit desired optical characteristics can be produced, It is possible to omit the step of bonding the conventional polarizing film and the retardation film, thereby contributing to the improvement of productivity. In addition, it contributes to the miniaturization and lightening of LCD materials, and can be applied to flexible displays and the like. However, the TAC film is characterized in that the content (usable) solvent is inferior, and the solvent that can be used for forming the alignment film is limited, and a solvent having high solubility such as NMP can not be used. In addition, the TAC film has a low heat resistance and is characterized in that it can not be processed at a high temperature for forming an alignment film.

The liquid crystal aligning agent can be used as a liquid crystal alignment layer, for example, on an LCD component member called a color filter, on an optical film including a polarizing plate and a retardation film, and through a radiation irradiation process to be described later. Further, the liquid crystal aligning agent may be applied repeatedly on the retardation film produced using the liquid crystal aligning agent, and the liquid crystal aligning agent may be used as a liquid crystal alignment film through the same process.

When applying the liquid crystal aligning agent, a functional silane compound, titanate, or the like may be previously coated on the substrate in order to further improve the adhesion between the substrate and the coating film.

Subsequently, the coating film is irradiated with linearly polarized light, partially polarized radiation, or non-polarized radiation, thereby imparting liquid crystal aligning ability. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferable. When the radiation to be used is linearly polarized light or partially polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, in an oblique direction to give a pre-tilt angle, or in combination. In the case of irradiating non-polarized radiation, the irradiation direction needs to be inclined. In the present specification, the term "pretilt angle" refers to the angle of the slope of the liquid crystal molecules from the direction parallel to the substrate surface.

Examples of the light source to be used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser mercury-xenon lamp (Hg-Xe lamp). The ultraviolet ray of the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with a filter, a diffraction grating, or the like.

The irradiation dose of the radiation is preferably 1 J / m 2 or more and less than 10,000 J / m 2, more preferably 10 J / m 2 to 3,000 J / m 2. When a liquid crystal aligning ability is imparted to a coating film formed by a conventionally known liquid crystal aligning agent by a photo alignment method, a radiation dose of 10,000 J / m 2 or more is required. When the liquid crystal aligning agent is used, A good liquid crystal aligning ability can be imparted even if the irradiation dose is 3,000 J / m 2 or less and 1,000 J / m 2 or less, which contributes to reduction of manufacturing cost of the liquid crystal display element.

&Lt; Phase difference film and manufacturing method thereof &gt;

In the present invention, a retardation film having a liquid crystal alignment film for a retardation film is also suitably included. The retardation film formed using the liquid crystal aligning agent can be produced, for example, as follows. The method for forming a retardation film, which is included in the present invention,

(1) a step of applying the liquid crystal aligning agent for the retardation film on a substrate to form a coating film,

(2) a step of irradiating the coating film with radiation to impart a liquid crystal aligning ability and forming a liquid crystal alignment film for a retardation film,

(3) a step of applying the polymerizable liquid crystal to at least a part of the liquid crystal alignment film for the retardation film, and

(4) a step of curing the coating film coated with the polymerizable liquid crystal.

In steps (1) and (2), a liquid crystal alignment film for a retardation film is formed on a substrate in the same manner as the above-described liquid crystal alignment film formation method for a retardation film. In the step (3), the polymerizable liquid crystal is applied to at least a part of the formed liquid crystal alignment film for a retardation film. Examples of the method of applying the polymerizable liquid crystal include a suitable coating method such as a roll coater method, a spinner method, a printing method, and an ink jet method. Subsequently, in the step (4), the solvent contained in the polymerizable liquid crystal is dried by heating and / or non-deflected irradiation with radiation or the like to cure the polymerizable liquid crystal. The polymerization may be carried out under air or in an atmosphere of an inert gas such as nitrogen. Suitable conditions may be selected depending on the polymerizable group of the polymerizable liquid crystal to be used and the initiator. The film thus obtained can immobilize the polymerizable liquid crystal in an intended orientation state and can be used as a retardation film.

The polymerizable liquid crystal is not particularly limited as long as it is a compound that can be polymerized by heating or irradiation with radiation. For example, a nematic liquid crystal compound described in &quot; UV curable liquid crystal and its application &quot; (Liquid Crystal 3, No. 1, 1999, pages 34 to 42) . And may contain a known photopolymerization initiator or a thermal polymerization initiator. These polymerizable liquid crystal compounds and mixtures thereof can be used by dissolving them in a suitable solvent. Further, by adding a chiral agent or the like, it is possible to use a liquid crystal in which the twisted nematic alignment is twisted in a direction perpendicular to the substrate, a cholesteric liquid crystal, or a discotic liquid crystal.

The film thickness of the polymerizable liquid crystal is selected so that the desired optical characteristics can be obtained. For example, in the case of producing a 1/2 wave plate in a visible light having a wavelength of 540 nm, the film thickness at which the retardation of the formed retardation film becomes 240 nm to 300 nm is selected, and for example, 1/4 If the wavelength plate is used, the film thickness at which the phase difference becomes 120 nm to 150 nm is selected. The film thickness at which the aimed retardation is obtained differs depending on the optical characteristics of the polymerizable liquid crystal used. For example, when a polymerizable liquid crystal (RMS03-013C) manufactured by Merck is used, the film thickness for producing a 1/4 wavelength plate is selected in the range of 0.6 탆 to 1.5 탆.

As the temperature for heating the polymerizable liquid crystal, a temperature at which good orientation can be obtained is selected. For example, when the polymerizable liquid crystal, RMS03-013C manufactured by Merck, is used, it is selected in the range of 40 占 폚 to 80 占 폚.

Examples of the radiation when irradiating with radiation include ultraviolet rays of non-deflection. The irradiation dose of the radiation is preferably from 1,000 J / m 2 to 100,000 J / m 2, more preferably from 10,000 J / m 2 to 50,000 J / m 2.

&Lt; Process for producing a retardation film including two or more regions having different liquid crystal alignment directions &gt;

Also, the present invention suitably includes a method for producing a retardation film including two or more regions having different liquid crystal alignment directions for 3D image use or the like. A retardation film having regions having different liquid crystal alignment directions for 3D image use formed using the liquid crystal aligning agent can be produced, for example, as follows. The method for producing the retardation film includes:

The step (2)

(2-1) a step of irradiating the coating film with radiation in a first direction to give a liquid crystal alignment capability in the first direction and

(2-2) A step of irradiating a part of the coating film with radiation in a second direction different from the first direction to further give liquid crystal aligning ability in the second direction.

As other production methods,

The step (2)

(2-1 ') a step of irradiating the coated film with radiation in a first direction to give a liquid crystal aligning ability in the first direction and

(2-2 ') a step of irradiating a portion of the coating film not irradiated with at least radiation with a radiation in a second direction different from the first direction to give liquid crystal alignment capability in the second direction.

Here, the &quot; direction &quot; means the incidence direction or polarization direction of radiation. In the second direction in the steps (2-2) and (2-2 '), in the step (2-1) or (2-1'), the first direction in which the liquid crystal aligning ability is imparted by irradiation with radiation But the direction of the rotated polarization direction is preferably 70 ° to 110 °, more preferably 85 ° to 95 °, and most preferably 90 °. As means for irradiating in different directions, a method of irradiating the radiation through a mask can be mentioned. It is preferable that the mask is patterned in a monolayer shape so that the transmissive portion and the shielding portion alternately lie.

(Example)

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. The required amounts of the starting compounds and polymers used in the following examples were ensured by repeating the synthesis of the starting compounds and the polymers in the synthetic scale shown in the following Synthesis Examples as necessary.

&Lt; Synthesis of polyorganosiloxane having epoxy group &gt;

[Synthesis Example 1]

100 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube And the mixture was mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out, washed with a 0.2 mass% aqueous ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a viscous polyorganosiloxane having an epoxy group Viscous) transparent liquid.

The polyorganosiloxane having the epoxy group was subjected to ¹ H-NMR analysis. As a result, a peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm at the theoretical intensity, and no side reaction of the epoxy group occurred during the reaction The tone was confirmed. The polyorganosiloxane having an epoxy group thus obtained had an Mw of 2,200 and an epoxy equivalent of 186 g / mol.

&Lt; Synthesis of specific cinnamic acid derivatives &gt;

All synthesis reactions of specific cinnamic acid derivatives were carried out in an inert atmosphere.

[Synthesis Example 2]

In a 500 mL three-necked flask equipped with a cooling tube, 20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine and 135 mL of dimethylacetamide were mixed. Next, 7 g of acrylic acid as a syringe was added to the mixed solution and stirred. This mixed solution was further heated and stirred at 120 DEG C for 3 hours. After completion of the reaction was confirmed by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. The precipitate was separated by filtration, and the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution to recover the precipitate. These precipitates were recrystallized from a 1: 1 (by mass) solution of ethyl acetate and hexane to obtain 8.4 g of a compound represented by the following formula (K-1) (specific cinnamic acid derivative (K-1)).

[Synthesis Example 3]

In a 300-mL three-necked flask equipped with a condenser tube, 6.5 g of 4-fluorophenylboronic acid, 10 g of 4-bromominic acid, 2.7 g of tetrakistriphenylphosphine palladium, 4 g of sodium carbonate, 80 mL of tetrahydrofuran, Water) were mixed. Subsequently, the reaction solution was heated and stirred at 80 DEG C for 8 hours, and the completion of the reaction was confirmed by TLC. The reaction solution was cooled to room temperature, poured into 200 mL of 1N-hydrochloric acid aqueous solution, and the precipitated solid was filtered off. The resulting solid was dissolved in ethyl acetate, and the solution was washed with 100 mL of 1 N aqueous hydrochloric acid solution, 100 mL of pure water and 100 mL of saturated brine in that order. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained solid was vacuum-dried to obtain 9 g of a compound (specific cinnamic acid derivative (K-2)) represented by the following formula (K-2).

[Synthesis Example 4]

In a 200 ml three-necked flask equipped with a cooling tube, 3.6 g of 4-fluorostyrene, 6 g of 4-bromominic acid, 0.059 g of palladium acetate, 0.32 g of tris (2-tolyl) phosphine, 11 g of triethylamine, Amide were mixed. This solution was heated and stirred at 120 DEG C for 3 hours, and after completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The precipitate was separated by filtration, and the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution to recover the precipitate. These precipitates were recrystallized from ethyl acetate to obtain 4.1 g of a compound represented by the following formula (K-3) (specific cinnamic acid derivative (K-3)).

[Synthesis Example 5]

In a 200 ml three-necked flask equipped with a condenser tube, 9.5 g of 4-vinylbiphenyl, 10 g of 4-bromominic acid, 0.099 g of palladium acetate, 0.54 g of tris (2-tolyl) phosphine, 18 g of triethylamine, Were mixed. This solution was heated and stirred at 120 DEG C for 3 hours, and after completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The precipitate was separated by filtration, and the filtrate was poured into 500 mL of a 1N hydrochloric acid aqueous solution to recover the precipitate. These precipitates were recrystallized from a 1: 1 (by mass) solution of dimethylacetamide and ethanol to obtain 11 g of a compound represented by the following formula (K-4) (specific cinnamic acid derivative (K-4)).

&Lt; Synthesis of photo-oriented polyorganosiloxane [A]

[Synthesis Example 6]

9.3 g of the polyorganosiloxane having the epoxy group obtained in Synthesis Example 1, 26 g of methyl isobutyl ketone, 3 g of the specific cinnamic acid derivative (K-1) obtained in Synthesis Example 2 and 3 g of the quaternary amine salt Ltd., UCAT 18X) were placed, and the mixture was stirred at 80 占 폚 for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. This solution was washed three times with water, and then the solvent was distilled off to obtain [A] optically orientable polyorganosiloxane (S- 1) as a white powder. [A] The weight average molecular weight Mw of the photo-orientable polyorganosiloxane (S-1) was 3,500.

[Synthesis Example 7]

7.0 g of white powder of photo-orientable polyorganosiloxane (S-2) of [A] was obtained in the same manner as in Synthesis Example 6 except that 3 g of the specific cinnamic acid derivative (K-2) obtained in Synthesis Example 3 was used . [A] The weight average molecular weight Mw of the photo-orientable polyorganosiloxane (S-2) was 4,900.

[Synthesis Example 8]

10 g of white powder of photo-orientable polyorganosiloxane (S-3) of [A] was obtained in the same manner as in Synthesis Example 6 except that 4 g of the specific cinnamic acid derivative (K-3) obtained in Synthesis Example 4 was used. [A] The photo-orientable polyorganosiloxane (S-3) had a weight average molecular weight Mw of 5,000.

[Synthesis Example 9]

10 g of a white powder of a photo-orientable polyorganosiloxane (S-4) of [A] was obtained in the same manner as in Synthesis Example 6, except that 4.1 g of the specific cinnamic acid derivative (K-4) . [A] The weight average molecular weight Mw of the photo-orientable polyorganosiloxane (S-4) was 4,200.

<Synthesis of [B] other polymer>

[Synthesis Example 10]

19.61 g (0.1 mole) of cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mole) of 4,4'-diamino-2,2'-dimethylbiphenyl were dissolved in 367.6 g of NMP and reacted at room temperature for 6 hours . The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 35 g of polyamic acid (PA-1).

[Synthesis Example 11]

22.4 g (0.1 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g (0.1 mole) of cyclohexane bis (methylamine) were dissolved in 329.3 g of NMP and reacted at 60 ° C for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 占 폚 for 15 hours to obtain 32 g of polyamic acid (PA-2).

[Synthesis Example 12]

17.5 g of (PA-2) obtained in Synthesis Example 11, 232.5 g of NMP, 3.8 g of pyridine and 4.9 g of acetic anhydride were added, and imidization was carried out at 120 DEG C for 4 hours. Subsequently, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to obtain 15 g of polyimide (PI-1).

[Synthesis Example 13]

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether (DEGME) were prepared. Subsequently, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of styrene, 30 parts by mass of methacrylic acid and 20 parts by mass of cyclohexylmaleimide were purged with nitrogen, and stirring was started slowly. The solution temperature was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (MA-1) of poly (meth) acrylate. The solid concentration of the obtained polymer solution was 33.1 mass%. The number average molecular weight of the obtained polymer was 7,000.

<Synthesis of ester structure-containing compound>

According to the following reaction formula, an ester structure-containing compound (C-1-1) was synthesized.

[Synthesis Example 14]

21 g of trimethic acid, 60 g of n-butyl vinyl ether and 0.09 g of phosphoric acid were placed in a 500 mL three-necked flask equipped with a reflux condenser, a thermometer and a nitrogen inlet tube, and the reaction was carried out at 50 DEG C for 30 hours with stirring. After completion of the reaction, 500 mL of hexane was added to the reaction mixture, and the resulting organic layer was washed twice with 1 M aqueous sodium hydroxide solution and three times with water. Thereafter, the solvent was distilled off from the organic layer to obtain 50 g of the ester structure-containing compound (C-1-1) as a colorless transparent liquid.

&Lt; Preparation of liquid crystal aligning agent for retardation film &

[Example 1]

[B] An amount corresponding to 1,000 parts by mass of the polyamic acid (PA-1) contained in the solution containing the polyamic acid (PA-1) obtained in Synthesis Example 10 as the other polymer was taken 100 parts by mass of the [A] photo-orientable polyorganosiloxane (S-1) obtained in Example 6 was further added and NMP and ethylene glycol monobutyl ether (EGMB) were further mixed to prepare a solution having a solvent composition of NMP: EGMB = 50: 50 Mass ratio), and a solid content concentration of 4.0 mass%. This solution was filtered with a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent (A-1) for a retardation film.

[Examples 2 to 6]

A photo-orientable polyorganosiloxane of the kind and amount shown in Table 1, a [B] other polymer, a compound containing an ester structure and a solvent were added in the same manner as in Example 1, (A-2) to (A-6) (solids concentration of 4.0 mass%, respectively) were prepared.

[Example 7]

(B) A solution containing a copolymer (MA-1) of the poly (meth) acrylate obtained in Synthesis Example 13 as the other polymer was converted into a copolymer (MA-1) of the poly (meth) 100 parts by mass of the [A] photo-orientable polyorganosiloxane (S-2) obtained in Synthesis Example 7 was further added thereto, and a sulfonium salt (acid aide SI-60L 50 parts by mass of butyl acetate and diethylene glycol methyl ethyl ether (DEGME) were mixed to obtain a copolymer having a solvent composition of butyl acetate: DEGME = 90: 10 (mass ratio), a solid content of 4.0 Mass% solution. This solution was filtered with a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent (A-7) for a retardation film.

[Examples 8 to 10]

(A) photo-orientable polyorganosiloxane of the kind and amount shown in the following Table 1 and a solvent were added, and then aluminum tris (acetylacetonate) (aluminum chelate A (W), manufactured by Kawaken Fine Chemical Co., (A-8) to (A-10) (each having a solid concentration of 4.0% by mass) for retardation films were prepared in the same manner as in Example 7 except that 50 parts by mass of the liquid crystal aligning agent

[Example 11]

, 50 parts by mass of silsesquioxane (ACSQ; AC-SQ TA-100, manufactured by Toagosei Co., Ltd.) having an acryloyl group as the [F] compound, 1,000 parts by mass of the [A] photo-orientable polyorganosiloxane (S- 50 parts by mass of a sulfonium salt (San-eide Kagaku Kogyo Co., Ltd., San-eide SI-60L) was further added as a curing catalyst, and EGMB and DEGME were mixed as a solvent. The solvent composition was EGMB: DEGME = 90: , And a solid content concentration of 4.0 mass%. This solution was filtered with a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent (A-11) for a retardation film.

[Referential Example 1]

13.1 g of poly (2-hydroxyethyl methacrylate) was dissolved in 50 mL of NMP by heating, cooled to room temperature, and then 10 mL of pyridine was added. 17.0 g of cinnamoyl chloride was added and stirred for 8 hours. The reaction mixture was diluted with NMP and then added to methanol. The precipitate was sufficiently washed with water and dried to obtain 25 g of a polymer. NMP and ethylene glycol monobutyl ether were added to obtain a solution having a solvent composition of NMP: EGMB = 50: 50 (mass ratio) and a solid content concentration of 4.0 mass%. This solution was filtered with a filter having a pore size of 1 탆 to prepare a composition (CA-1).

[Reference Example 2]

1.00 g of 4- (2-methacryloyloxyethoxy) azobenzene, 0.01 g of 2,2'-azobis (isobutyronitrile) and 2.00 g of dried benzene were degassed by degassing in an ampoule, (Sealed tube), which was poured into methanol to obtain a precipitate of a polymer compound. After filtration, the precipitate was again dissolved in benzene, re-precipitated with methanol and filtered, and then dried twice. NMP and EGMB were added thereto to prepare a solution having a solvent composition of NMP: EGMB = 50: 50 (mass ratio) and a solid content concentration of 4.0 mass%. This solution was filtered with a filter having a pore size of 1 탆 to prepare a composition (CA-2).

&Lt; Production of liquid crystal alignment film for retardation film &gt;

[Example 12]

A liquid crystal aligning agent (A-1) for a retardation film prepared in Example 1 was coated on one surface of a transparent glass substrate using a spinner and pre-baked on a hot plate at 80 DEG C for 1 minute, Post baking was performed in an oven at 200 DEG C for 1 hour to form a coating film having a thickness of 0.1 mu m. Subsequently, a polarizing ultraviolet ray (300 J / m 2) including a bright line of 313 nm was vertically irradiated from the substrate normal to the surface of the coating film using an Hg-Xe lamp and a Glan-Taylor prism to prepare a liquid crystal alignment film for a retardation film.

[Examples 13 to 22, Reference Examples 3 to 5]

A liquid crystal alignment film for a retardation film was produced in the same manner as in Example 12 except that the ultraviolet ray having a predetermined dose was used by using the liquid crystal aligning agent for a retardation film shown in Table 2.

[Evaluation of coating property on TAC film and liquid crystal alignment property]

(Si-adi SI-60L) as a curing catalyst was added to the liquid crystal aligning agent for a retardation film of the above-mentioned (A-2), and the catalyst concentration was 5 mass% . (A-3) was prepared by the same operation except that aluminum tris (acetylacetonate) (Kaken Fine Chemical Co., aluminum chelate A (W)) was used as a curing catalyst. In addition, (A-7) to (A-11) were prepared by the same operation except that a sulfonium salt (Sansei Kagakukyo Kagaku Co., Ltd., San Aid SI-60L) was used as a curing catalyst. A liquid crystal aligning agent for a retardation film was coated on one surface of a TAC film using a spinner and prebaked on a hot plate at 80 DEG C for 1 minute and then heated in an oven where the inside of the tube was replaced with nitrogen at 120 DEG C for 10 minutes, Baked to form a coating film having a thickness of 0.1 mu m. At that time, when the TAC film showed no dissolution, the TAC application property was good. For the good TAC coating property, polarizing ultraviolet rays of 300 J / m &lt; 2 &gt; including a bright line of 313 nm were vertically irradiated onto the surface of this coating film from the normal to the substrate using a Hg-Xe lamp and a Glan- A liquid crystal alignment film was formed, and the liquid crystal alignment property and the adhesion property, which will be described later, were evaluated. The results are shown in Table 1.

[Evaluation of adhesion]

The liquid crystal alignment film for a retardation film formed on the TAC film was cut with a cutter knife at intervals of 1 mm using a constant interval spacer having a guide to form a grid pattern of 10 x 10. Subsequently, a cellophane tape was placed on the grid pattern and tightly adhered, and then the cellophane tape was peeled off. The cut portion of the coated film after peeling off the cellophane tape was observed. (A), 10% or more when the number of lattice peels in which peeling occurs at a point intersecting or intersecting the coating line is less than 10% with respect to the total number of grid patterns, (&Quot; B &quot;) in the case of less than 40% and less than 40%, and a poor adhesion (&quot; C &quot;

&Lt; Production of retardation film &gt;

[Examples 23 to 33, Comparative Examples 1 to 3]

The polymerizable liquid crystal (Merck, RMS03-013C) was filtered with a filter having a pore size of 0.2 탆 on the surface of the liquid crystal alignment film for a retardation film prepared in Examples 12 to 22 and Reference Examples 3 to 5 using a spinner After baking for 1 minute on a hot plate at 60 DEG C, 30,000 J / m &lt; 2 &gt; of ultraviolet ray of unpolarized light including a bright line of 365 nm was irradiated onto the polymerizable liquid crystal coating surface using an Hg-Xe lamp to prepare a retardation film , And the following evaluation was made. The results are shown in Table 3.

[Evaluation of liquid crystal alignment property]

For the retardation films prepared in Examples 23 to 33 and Comparative Examples 1 to 3, the presence or absence of an abnormal domain was observed by a polarizing microscope, and a case where abnormal domains were not observed was referred to as liquid crystal alignment property "A" The observed state was evaluated as the liquid crystal alignment property &quot; B &quot;.

[Evaluation of thermal stability]

A retardation film was produced in the same manner as above except that the liquid crystal alignment film for a retardation film was formed under the irradiation condition that the liquid crystal alignment property was "A", and the film was heated at 150 ° C. for 1 hour before the application of the polymerizable liquid crystal, Quot; A &quot; when the abnormal domain was not observed and the thermal stability &quot; B &quot; when the abnormal domain was observed.

As is clear from the results in Table 3, the amount of light irradiation necessary for photo alignment in the production of the liquid crystal alignment film for a phase difference film using the liquid crystal aligning agent is extremely low, and the phase difference film comprising the liquid crystal alignment film for the phase retardation film has excellent Liquid crystal alignability, heat resistance, and adhesiveness to a substrate.

&Lt; Production of a retardation film including regions having different liquid crystal alignment directions &gt;

[Example 34]

A liquid crystal alignment film for a phase difference film was formed on a substrate in the same manner as in Example 12, and then, through a mask patterned in a monolayer form so that the transmissive portion and the light shield portion were alternately arranged in the polarization direction rotated by 90 ° from the first polarized ultraviolet ray, The polarized ultraviolet ray (300J / m &lt; 2 &gt; of polarized ultraviolet ray including a 313 nm bright line obtained by using Hg-Xe lamp and Glan-Taylor prism) was irradiated. Next, a polymerizable liquid crystal (Merck, RMS03-013C) was filtered with a filter having a pore size of 0.2 mu m on the surface on which the liquid crystal alignment film for a retardation film was formed, and then applied using a spinner. After baking, 30,000 J / m 2 of unpolarized ultraviolet ray including a bright line of 365 nm was irradiated onto the polymerizable liquid crystal coating surface using a Hg-Xe lamp to prepare a retardation film including regions having different liquid crystal alignment directions.

[Example 35]

After applying a liquid crystal aligning agent for a retardation film on a substrate in the same manner as in Example 12, half of the substrate was shaded, and a first polarized ultraviolet ray (313 nm) obtained by using an Hg-Xe lamp and a Glan- And a polarized ultraviolet ray 300 J / m 2 containing a bright line). Next, the first exposed portion is exposed in the polarization direction rotated by 90 DEG from the first polarized ultraviolet ray so that the unexposed portion is irradiated with the polarized ultraviolet light, and the second polarized ultraviolet ray irradiation (Hg-Xe lamp and And a polarized ultraviolet ray (300 J / m 2) containing a bright line of 313 nm was irradiated using a Glan-Taylor prism. Next, a polymerizable liquid crystal (Merck, RMS03-013C) was filtered with a filter having a pore size of 0.2 mu m on the surface on which the liquid crystal alignment film for a retardation film was formed, and then applied using a spinner. After baking, 30,000 J / m 2 of unpolarized ultraviolet ray including a bright line of 365 nm was irradiated onto the polymerizable liquid crystal coating surface using a Hg-Xe lamp to prepare a retardation film including regions having different liquid crystal alignment directions.

[Evaluation of phase difference film including regions in which liquid crystal alignment directions are different]

The retardation film obtained in Example 34 was placed between polarizing plates arranged under Cross-Nicol conditions and observed with the use of the transmitted light from the opposite direction to the observation side. The polarizing film was arranged so as to be parallel or perpendicular to the polarization direction of the irradiated polarized ultraviolet light In all cases, the entire surface was dark regardless of the patterning. On the other hand, when the retardation film was rotated by 45 DEG in its plane, the retardation film showed a birefringence due to the brightening of the entire surface regardless of the patterning.

The retardation film obtained in Example 35 was observed in the same manner as described above. When the polarizing film was arranged so as to be parallel or perpendicular to the polarization direction of the irradiated polarized ultraviolet ray, the entire surface was dark regardless of the polarized direction of the irradiated polarized ultraviolet ray. On the other hand, when the retardation film was rotated by 45 degrees in its plane, the retardation film showed the entire surface to be bright regardless of the polarization direction of the irradiated polarized ultraviolet ray and had birefringence.

Further, the retardation film produced by the same operation as in Example 23 was used, and a retardation film containing a region in which the polarizing direction of the irradiated polarized ultraviolet ray and the two liquid crystal alignment directions obtained in Examples 34 and 35 were different It was confirmed that the polarized light of the irradiated polarized ultraviolet ray was arranged so as to be parallel or at right angles and observed under the crossed Nicol condition, the brightened pattern and the darkened pattern existed in an outer shape delimited by a clear edge.

According to the present invention, there is provided a liquid crystal aligning agent capable of forming a liquid crystal alignment film for a phase difference film which can be light-radiated by irradiation with a small amount of radiation and which does not require a heating step during irradiation and after irradiation, and a liquid crystal alignment film for the phase difference film, , A retardation film excellent in thermal stability and adhesion to a substrate, and a method for producing the same.

Claims (15)

[A] a polyorganosiloxane having a photo-orientable group, and
[B] Ethylenically unsaturated compound polymer
&Lt; / RTI &gt;
(B) an ethylenically unsaturated compound containing a carboxyl group or a hydroxyl group; (c) an unsaturated compound (a) and (b) an unsaturated compound (b) A copolymer of at least two kinds of unsaturated compounds selected from the group consisting of other polymerizable unsaturated compounds
Wherein the liquid crystal aligning agent is a liquid crystal aligning agent for a retardation film. The method according to claim 1,
Wherein the photo-orientable group is a group having a cinnamic acid structure. 3. The method of claim 2,
A liquid crystal aligning agent for a retardation film wherein the group having a cinnamic acid structure is at least one selected from the group consisting of a group derived from a compound represented by the following formula (1) and a compound derived from a compound represented by the formula (2)

(In the formula (1), R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group;
A part or all of the hydrogen atoms of the phenylene group, the biphenylene group, the terphenylene group or the cyclohexylene group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a fluorine atom, May be substituted by an anger;
R ² is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, -CH = CH-, -NH-, -COO- or -OCO-;
a is an integer of 0 to 3;
Provided that when a is 2 or more, each of R ¹ and R ² may be the same or different;
R ³ is a fluorine atom or a cyano group;
b is an integer of 0 to 4;
In the formula (2), R ⁴ is a phenylene group or a cyclohexylene group;
A part or all of the hydrogen atoms of the phenylene group or the cyclohexylene group may be substituted with a straight or cyclic alkyl group having 1 to 10 carbon atoms, a straight or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group ;
R ⁵ is a single bond, an alkanediyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-;
c is an integer of 1 to 3;
Provided that when c is 2 or more, R ⁴ and R ⁵ may be the same or different;
R ⁶ is a fluorine atom or a cyano group;
d is an integer from 0 to 4;
R ⁷ is an oxygen atom, -COO- or -OCO-;
However, the combined hand denominated * combined with R ^8, and;
R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group;
R ⁹ is a single bond, -OCO- (CH ₂ ) _f - * or -O (CH ₂ ) _g - *;
However, the combined hand with * attached to the carboxyl group;
f and g are each an integer of 1 to 10;
e is an integer from 0 to 3;
Provided that when e is 2 or more, R ⁷ and R ⁸ may be the same or different). The method of claim 3,
[A] The polyorganosiloxane having a photo-
At least one member selected from the group consisting of a polyorganosiloxane having an epoxy group, a hydrolyzate thereof and a condensate of the hydrolyzate thereof,
Is a reaction product of at least one compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2). 5. The method according to any one of claims 1 to 4,
[B '] A liquid crystal aligning agent for a retardation film further containing at least one polymer selected from the group consisting of polyamic acid, polyimide and polyorganosiloxane having no photo-aligning group. 5. The method according to any one of claims 1 to 4,
[C] at least one structure selected from the group consisting of an acetal ester structure of a carbonic acid, a ketal ester structure of a carbonic acid, a 1-alkyl cycloalkyl ester structure of a carbonic acid and a t-butyl ester structure of a carbonic acid, Or more of a compound having at least two or more amino groups in the molecule. 5. The method according to any one of claims 1 to 4,
[D] a liquid crystal aligning agent for a retardation film further containing a solvent represented by the following formula (6)
R ^d1 -COO-R ^d2 (6)
(In the formula (6), R ^d1 is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group or a benzyl group;
Provided that the alkyl group may have -O- between the carbon-carbon bonds;
R ^d2 is a monovalent organic group having 1 to 8 carbon atoms). 5. The method according to any one of claims 1 to 4,
[E] A liquid crystal aligning agent for a retardation film further containing a solvent having erosion resistance to a substrate for a retardation film. 5. The method according to any one of claims 1 to 4,
[F] A liquid crystal aligning agent for a retardation film further containing a compound containing a group having a polymerizable carbon-carbon double bond. A liquid crystal alignment film for a retardation film formed by the liquid crystal aligning agent for a retardation film according to any one of claims 1 to 4. 11. The method of claim 10,
A liquid crystal alignment layer for a phase difference film comprising two or more regions having different liquid crystal alignment directions. A retardation film comprising the liquid crystal alignment film for a retardation film according to claim 10. (1) a step of applying a liquid crystal aligning agent for a retardation film according to any one of claims 1 to 4 on a substrate to form a coating film (coating film)
(2) a step of irradiating the coating film with radiation to impart a liquid crystal aligning ability and forming a liquid crystal alignment film for a retardation film,
(3) a step of applying the polymerizable liquid crystal to at least a part of the liquid crystal alignment film for the retardation film, and
(4) A process for producing a retardation film having a step of curing a coating film coated with a polymerizable liquid crystal. 14. The method of claim 13,
The step (2)
(2-1) a step of irradiating the coating film with radiation in a first direction to give a liquid crystal alignment capability in the first direction and
(2-2) A process for producing a retardation film, which comprises irradiating a part of a coating film with radiation in a second direction different from the first direction, thereby further imparting a liquid crystal aligning ability in the second direction. 14. The method of claim 13,
The step (2)
(2-1 ') a step of irradiating the coated film with radiation in a first direction to give a liquid crystal aligning ability in the first direction and
(2-2 ') a step of irradiating at least a part of the coating film not irradiated with radiation with a radiation in a second direction different from the first direction to give a liquid crystal aligning ability in the second direction Way.