KR20120120007A - Liquid crystal aligning agent for phase difference film, liquid crystal alignment film for phase difference film, the phase difference film and its manufacturing method - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent for retardation film is provided to be optically arranged by irradiation with a small amount of radiation, and to form a liquid crystalline alignment film not requiring a heating process during or after irradiation. CONSTITUTION: A liquid crystal alignment agent for retardation film contains cellulose comprising a group containing cinnamic acid, and is formed by a liquid crystalline alignment film for the retardation film. A manufacturing method of the retardation film comprises: a step of forming a coating the liquid crystalline alignment agent for the retardation film on the substrate; a step of forming liquid crystalline alignment film for retardation film through irradiation on the coating with radiation; a step of forming a polymerizable liquid crystal layer by coating at least a part of the liquid crystal film for the retardation film with polymerizable liquid crystal.

Description

Liquid crystal aligning agent for retardation film, liquid crystal aligning film for retardation film, retardation film, and its manufacturing method {LIQUID CRYSTAL ALIGNING AGENT FOR PHASE DIFFERENCE FILM

This invention relates to the liquid crystal aligning agent for retardation films, the liquid crystal aligning film for retardation films, a retardation film, and its manufacturing method.

Liquid crystal displays (LCDs) are widely used in televisions and various monitors. As the display elements of the LCD, for example, STN (Super Twisted Nematic) type, TN (Twisted Nematic) type, IPS (In Plane Switching) type, VA (Vertically Aligned) type, PSA (Polymer sustained alignment) type, etc. are known. (See Japanese Laid-Open Patent Publication No. 56-91277 and Japanese Laid-Open Patent Publication No. Hei 1-20528). Various optical materials are used for this liquid crystal display element, and especially the retardation film is used for the purpose of eliminating the coloring of a display, and the purpose of eliminating the viewing angle dependency which a display color and contrast ratio change with viewing angle (Japan) See Japanese Patent Laid-Open No. 4-229828 and Japanese Patent Laid-Open No. 4-258923).

Conventionally, retardation film is generally manufactured using extending | stretching of a plastic film, and when it has a more complicated optical characteristic, it is hardening and manufacturing a polymeric liquid crystal. In this method, in order to orient polymerizable liquid crystal molecules in a predetermined direction with respect to the substrate surface, it is common to form a liquid crystal alignment film on the substrate surface. The said liquid crystal aligning film is formed by the photo-alignment method which irradiates polarized light or non-polarization radiation to photosensitive thin films, such as polyvinyl cinnamate, for example. (JP-A-6-287453, JP-A-10) -251646, Japanese Patent Laid-Open No. 11-2815, Japanese Patent Laid-Open No. 11-152475, Japanese Patent Laid-Open No. 2000-144136, Japanese Patent Laid-Open No. 2000-319510, Japanese Patent Laid-Open No. 2000-281724 , Japanese Patent Application Laid-Open No. 9-297313, Japanese Patent Application Laid-Open No. 2003-307736, Japanese Patent Application Laid-Open No. 2004-163646, Japanese Patent Application Laid-Open No. 2002-250924). According to this photo-alignment method, uniform liquid crystal orientation can be realized, and a plurality of regions different in liquid crystal alignment direction can be arbitrarily formed on one substrate by using a photomask or the like at the time of radiation irradiation. However, in the prior art, there is a problem in that heating is required at the time of irradiation, and a large accumulated exposure amount is required (see Japanese Patent Laid-Open No. 10-278123).

On the other hand, in recent years, the technology of expressing a 3D video is prevalent, and displays capable of viewing 3D video in the home are becoming popular. As a display method of a 3D image, for example, Japanese Patent No. 3461680 forms an image having a different polarization state from a right eye image and a left eye image, and views only an image of each polarization state. The method using the polarizing glasses which can be introduced is introduced. The stereoscopic image obtained in this manner is free of flicker, and the observer can observe the stereoscopic image by attaching lightweight and inexpensive polarizing glasses.

As a conventional technique of forming images having different polarization states in the right eye image and the left eye image, in projection display, two images are superimposed on the screen using two polarization projectors to form a stereoscopic image, and in the direct view display, It forms by synthesizing the image of a large display apparatus with a half mirror or a polarizing mirror, or arrange | positioning the polarization transmission axis of the polarizing film arrange | positioned on a board | substrate differently for every pixel. However, in order to always illuminate two images with different polarization axes at the same time, two display devices and a projection device are required, which is not suitable for home use. As a conventional technique of forming images having different polarization states in a right eye image and a left eye image with one display device, a mosaic-shaped polarization layer orthogonal to each other between pixels adjacent to each other with a polarization axis is provided in front of one display device. It is known that a method in which an observer can observe a three-dimensional image by attaching polarized glasses in close contact therewith is known.

As such a polarizing layer, the retardation film patterned by the micrometer order is required. As a manufacturing method of such a retardation film, for example, Unexamined-Japanese-Patent No. 2005-49865 has disclosed the method etc. which irradiate polarization to the photosensitive polymer layer. However, there are problems such as a need for a large amount of integrated irradiation for polarized light irradiation and an insufficient thermal stability of the photosensitive polymer layer.

In view of such a situation, the development of a liquid crystal aligning agent for a retardation film excellent in liquid crystal alignment property, capable of photoalignment by a small amount of radiation, unnecessary heating step during and after irradiation, and also excellent thermal stability It is requested.

Japanese Laid-Open Patent Publication No. 56-91277 Japanese Patent Application Laid-Open No. Hei1-120528 Japanese Patent Application Laid-Open No. 4-229828 Japanese Patent Application Laid-Open No. 4-258923 Japanese Patent Laid-Open No. 6-287453 Japanese Patent Application Laid-Open No. 10-251646 Japanese Patent Application Laid-Open No. 11-2815 Japanese Patent Application Laid-Open No. 11-152475 Japanese Laid-Open Patent Publication No. 2000-144136 Japanese Laid-Open Patent Publication No. 2000-319510 Japanese Patent Laid-Open No. 2000-281724 Japanese Patent Laid-Open No. 9-297313 Japanese Patent Application Laid-Open No. 2003-307736 Japanese Laid-Open Patent Publication No. 2004-163646 Japanese Laid-Open Patent Publication No. 2002-250924 Japanese Patent Application Laid-Open No. 10-278123 Japanese Patent No. 3541680 Japanese Laid-Open Patent Publication 2005-49865

This invention is made | formed based on the above circumstances, The objective is that liquid crystal orientation is excellent, it is possible to photo-align even by a small amount of radiation irradiation, and the heating process during and after irradiation is unnecessary, and also thermal stability It is providing the liquid crystal aligning agent which can form the excellent liquid crystal aligning film for retardation films. Moreover, the retardation film provided with this liquid crystal aligning film for retardation films, and excellent in liquid crystal orientation and heat stability, and its manufacturing method are provided.

The invention made to solve the above problems,

(A) It is a liquid crystal aligning agent for retardation films containing cellulose containing group which has cinnamic-acid structure.

Since the said liquid crystal aligning agent for retardation films contains the cellulose (henceforth also called "[A] cellulose") containing group which has a [A] cinnamic acid structure, it has a highly sensitive photo-alignment property and the amount of light irradiation required for orientation Can be reduced. Moreover, since the group which has the said cinnamic acid structure uses cinnamic acid or its derivative (s) as a basic skeleton, introduction into a cellulose is easy. Moreover, since the heating process during radiation irradiation and after irradiation is unnecessary, the said liquid crystal aligning agent for retardation films can manufacture retardation film efficiently. Moreover, since cellulose is employ | adopted as a principal chain, the retardation film formed from the said liquid crystal aligning agent for retardation films has the outstanding thermal stability.

[A] It is preferable that cellulose is represented by following formula (1).

(In formula (1), R <^1> -R <^6> is respectively independently a hydrogen atom or a monovalent organic group, and at least 1 is a group which has a cinnamic acid structure; X is an oxygen atom or a sulfur atom; m is an integer of 10-10,000.

When the (A) cellulose is the said specific structure which has a cinnamic acid structure, the said liquid crystal aligning agent for retardation films has high sensitivity photo-alignment property, and can further reduce the amount of light irradiation required for orientation.

[A] It is preferable that cellulose is represented by following formula (1-1).

(In formula (1-1), R <^1> -R <^6> , X and m are synonymous with said Formula (1).).

The said liquid crystal aligning agent for retardation films can improve optical orientation by [A] cellulose having the said specific three-dimensional structure.

The said liquid crystal aligning agent for retardation films has at least 1 sort (s) of compounds chosen from the group which the group which has the said cinnamic acid structure consists of a compound represented by following formula (2), and a compound represented by following formula (3) (hereinafter, "specifically Cinnamic acid derivatives may be referred to as &quot;

(In formula (2), R <^7> is a phenylene group, a biphenylene group, a terphenylene group, or a cyclohexylene group; a part of hydrogen atoms of this phenylene group, biphenylene group, terphenylene group, or cyclohexylene group, or All may be substituted by a C1-C10 alkyl group, a C1-C10 alkoxy group which may have a fluorine atom, a fluorine atom, or a cyano group; R <^8> is a single bond and a C1-C3 alkanediyl group , An oxygen atom, a sulfur atom, -CH = CH-, -NH-, -COO- or -OCO-; a is an integer of 0 to 3, provided that a is a plurality of R ⁷ and R ⁸ may be the same or different, respectively; R ⁹ is a fluorine atom or a cyano group; b is an integer of 0 to 4; provided that when b is 2 or more, a plurality of R ⁹ may be the same or different; ;

In formula (3), R <^10> is a phenylene group or a cyclohexylene group; Some or all of the hydrogen atoms of this phenylene group or cyclohexylene group may be substituted with a C1-C10 linear or cyclic alkyl group, a C1-C10 chain or cyclic alkoxy group, a fluorine atom, or a cyano group. ; R ¹¹ 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, a plurality of R ¹⁰ And R ¹¹ may be the same or different, respectively; R ¹² is a fluorine atom or a cyano group; d is an integer of 0-4; However, when d is two or more, some R <^12> may be same or different; R ¹³ is an oxygen atom, -COO- or -OCO-; R ¹⁴ is an aromatic group, alicyclic group, heterocyclic group or condensed cyclic group; R ¹⁵ is a single bond, -OCO- (CH ₂ ) _f- * or -O (CH ₂ ) _g- *; With the proviso that * is a site that binds to the carboxyl group; f and g are each an integer of 1-10; e is an integer of 0 to 3; However, when e is two or more, some R <^13> and R <^14> may be same or different, respectively).

By using the group derived from said specific cinnamic acid derivative as a group which has the said cinnamic acid structure, the photo-alignment performance of the said liquid crystal aligning agent for retardation films improves further.

In said Formula (1), it is preferable that at least 1 of R <^1> -R <^6> is group represented by following formula (5).

(In Formula (5), R <^19> is a hydrogen atom or a methyl group; h is an integer of 1-10; However, when h is two or more, some R <^19> may be same or different; R <^20> , A single bond or a (h + 1) valent hydrocarbon group having 1 to 20 carbon atoms; R ²¹ is a single bond, -COO- or -OCO-; i is an integer of 0 to 10; j is 0 or 1 R ²² is a methylene group, a C 2-10 alkylene group, a phenylene group, or a cyclohexylene group; k is 0 or 1).

In the liquid crystal aligning film for retardation films formed from the said liquid crystal aligning agent for retardation films, adhesiveness to a board | substrate can be improved because [A] cellulose has an acryl group of the said specific structure.

The liquid crystal aligning agent for retardation film further contains polymers other than [B] [A] cellulose (hereinafter also referred to as "[B] polymer"), and said [B] polymer is represented by said Formula (5). It is preferable to include a group. The liquid crystal aligning film for retardation films formed from the said liquid crystal aligning agent for retardation films can improve adhesiveness to a board | substrate by containing the [B] polymer containing the acryl group of the said specific structure further.

The said liquid crystal aligning agent for retardation films can be used suitably in order to form the liquid crystal aligning film, especially the liquid crystal aligning film used for retardation film manufacture by the photo-alignment method. Moreover, the phase difference film provided with the liquid crystal aligning film for retardation films containing two or more types of regions from which a liquid crystal aligning direction differs, and the liquid crystal aligning film for such retardation films is also suitably included in this invention.

The manufacturing method of the retardation film contained in this invention,

(1) Process of forming a coating film on the board | substrate by application | coating of the said liquid crystal aligning agent for retardation films,

(2) Process of forming liquid crystal aligning film for retardation films by irradiation of radiation to the said coating film,

(3) Process of forming polymeric liquid crystal layer by application | coating of polymeric liquid crystal to at least one part of said liquid crystal aligning film for retardation films

Respectively.

In the production method of the present invention, photo-alignment is possible even by a small amount of radiation, and a heating step during and after irradiation is unnecessary. Therefore, retardation film can be manufactured efficiently, it is high in productivity, and it helps for reduction of manufacturing cost.

Moreover, the manufacturing method of the retardation film containing the area | region of a different phase difference in 3D image use etc. is also contained suitably in this invention. This manufacturing method,

The step (2),

(2-1) Process of providing the liquid-crystal orientation ability of a 1st direction by irradiation of the radiation of the 1st direction to the said coating film, and

(2-2) Process of providing the liquid crystal aligning ability of a 2nd direction further by irradiation of the radiation of a 2nd direction different from a 1st direction to a part of said coating film

Respectively.

In addition, as another manufacturing method,

The step (2),

(2-1 ') Process of providing the liquid-crystal orientation ability of a 1st direction by irradiation of the radiation of a 1st direction to the said coating film, and

(2-2 ') Process of providing the liquid-crystal orientation ability of a 2nd direction by irradiation of the radiation of the 2nd direction different from a 1st direction to the part to which the radiation of the said coating film was not irradiated

Respectively.

Since the liquid crystal aligning agent, liquid crystal aligning film, and retardation film for retardation films of this invention can be photo-aligned by a small amount of radiation irradiation as above-mentioned, and the heating process during and after irradiation is unnecessary, 3D is spreading these days. It is suitably used as a polarizing layer for an image.

(Mode for carrying out the invention)

<Liquid crystal aligning agent for retardation film>

The liquid crystal aligning agent for retardation films of this invention contains [A] cellulose. Since cellulose (A) contains the group which has a cinnamic acid structure, the said liquid crystal aligning agent for retardation films can reduce the amount of light irradiation required for orientation by the highly sensitive photo-alignment property. Moreover, the said liquid crystal aligning agent for retardation films can manufacture retardation film efficiently, since the heating process during irradiation and after irradiation is unnecessary. Moreover, the retardation film obtained from the said liquid crystal aligning agent for retardation films is excellent in liquid crystal orientation and thermal stability.

The said liquid crystal aligning agent for retardation films can further contain polymers other than [B] [A] cellulose, unless the effect of this invention is impaired. [C] at least one structure selected from the group consisting of acetal ester structures of carboxylic acids, ketal ester structures of carboxylic acids, 1-alkylcycloalkyl ester structures of carboxylic acids, and t-butyl ester structures of carboxylic acids It may contain a compound having two or more (hereinafter also referred to as "[C] ester structure containing compound") and other optional components. Hereinafter, [A] cellulose, a [B] polymer, a [C] ester structure containing compound, and other arbitrary components are explained in full detail.

<[A] cellulose>

[A] Cellulose contains a group having a photo-alignment cinnamic acid structure, preferably represented by the formula (1), and more preferably represented by the formula (1-1).

In said formula (1) and (1-1), R <^1> -R <^6> is a hydrogen atom or a monovalent organic group each independently, and at least 1 is group which has a cinnamic acid structure. X is an oxygen atom or a sulfur atom. m is an integer of 10-10,000.

About said monovalent organic group, it divides into "group which has a cinnamic acid structure" and "group which does not have a cinnamic acid structure", and demonstrates below.

[Group having Cinnamic acid structure]

At least one of said R <^1> -R <^6> is a group which has a cinnamic acid structure, As a group which has the cinnamic acid structure, if it contains cinnamic acid or its derivative (s) as a basic skeleton, it will not specifically limit, Said Formula (2 It is preferable that it is group derived from at least 1 sort (s) of compound chosen from the group which consists of a compound represented by the compound represented by Formula (3), and the compound represented by said Formula (3).

In said formula (2), R <^7> is a phenylene group, a biphenylene group, a terphenylene group, or a cyclohexylene group. Some or all of the hydrogen atoms of this phenylene group, biphenylene group, terphenylene group or cyclohexylene group may have a C1-C10 alkyl group and a fluorine atom, a C1-C10 alkoxy group, a fluorine atom, or a cyanide It may be substituted with an anhydrous group. R <^8> is a single bond, a C1-C3 alkylene group, an oxygen atom, a sulfur atom, -CH = CH-, -NH-, -COO-, or -OCO-. a is an integer of 0-3. However, when a is two or more, some R <^7> and R <^8> may be same or different, respectively. R ⁹ is a fluorine atom or a cyano group. b is an integer of 0-4. However, when b is two or more, some R <^9> may be same or different.

As a C1-C10 alkyl group which one part or all hydrogen atoms of the phenylene group, biphenylene group, terphenylene group, or cyclohexylene group represented by said R <^7> may substitute, For example, a methyl group, an ethyl group, a propyl group, Hexyl group etc. are mentioned.

Some or all of the hydrogen atoms of the phenylene group, biphenylene group, terphenylene group or cyclohexylene group represented by said R <^7> may be substituted. As a C1-C10 alkoxy group which may have a fluorine atom, a methoxy group, an ethoxy group, butoxy group, hexyloxy group, the group by which one part or all of the hydrogen atoms which these groups have substituted, etc. are mentioned, for example. Can be.

As a C1-C3 alkanediyl group represented by said R <^8> , a methylene group, an ethanediyl group, and a propanediyl group are mentioned.

As a compound represented by said formula (2), the compound etc. which are represented by a following formula are mentioned, for example.

Among these, a compound in which R ⁷ in Formula (2) is a phenylene group or a phenylene group substituted with a fluorine atom, R ⁸ is a single bond, an oxygen atom, or a compound in which -CH ₂ = CH _2- , b is 0? Compounds of 1 are preferred. Specifically, the compound represented by said formula (2-9), (2-13), (2-14), and (2-17) is preferable.

In said formula (3), R <^10> is a phenylene group or a cyclohexylene group. Some or all of the hydrogen atoms of this phenylene group or cyclohexylene group may be substituted with a C1-C10 linear or cyclic alkyl group, a C1-C10 linear or cyclic alkoxy group, a fluorine atom, or a cyano group. . R ¹¹ is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, or -NH-. c is an integer of 1-3. However, when c is two or more, some R <^10> and R <^11> may be same or different, respectively. R ¹² is a fluorine atom or a cyano group. d is an integer of 0-4. However, when d is two or more, some R <^12> may be same or different. R ¹³ is an oxygen atom, -COO-, or -OCO-. R <^14> is an aromatic group, alicyclic group, heterocyclic group, or condensed cyclic group. R ¹⁵ is a single _{bond, -OCO- (CH 2) f -} * or -O (CH _{2) g} - is a *. However, * is a site | part which couple | bonds with a carboxyl group. f and g are integers of 1-10, respectively. e is an integer of 0-3. However, when e is two or more, some R <^13> and R <^14> may be same or different, respectively.

As a C1-C10 linear or cyclic alkyl group which one part or all of the hydrogen atoms of the phenylene group or cyclohexylene group represented by said R <^10> may substitute, For example, a methyl group, an ethyl group, a propyl group, a butyl group, Cyclopropyl group, cyclobutyl group, etc. are mentioned.

As said C1-C10 linear or cyclic alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group, cyclobutoxy group, cyclohexyloxy group, etc. are mentioned.

As a C1-C3 alkylene group represented by said R <^11> , a methylene group, an ethylene group, etc. are mentioned, for example.

As a compound represented by said Formula (3), the compound etc. which are represented by following formula (3-1), (3-2) are mentioned, for example.

In said formula, Q is a C1-C10 linear or cyclic alkyl group, a C1-C10 linear or cyclic alkoxy group, a fluorine atom, or a cyano group. f is synonymous with Formula (3).

The synthesis | combining method of the said specific cinnamic acid derivative is not specifically limited, It can carry out combining a conventionally well-known method. As a typical synthesis procedure, for example, (i) a method of obtaining a specific cinnamic acid derivative by reacting a compound having a benzene ring skeleton substituted with a halogen atom under basic conditions in the presence of a transition metal catalyst, and (ii) basic conditions There may be mentioned a method of reacting a cinnamic acid 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 form a specific cinnamic acid derivative.

[Group does not have Sinnamsan structure]

As a monovalent organic group which does not have the cinnamic acid structure represented by said R <^1> -R <^6> , a C1-C10 linear hydrocarbon group, a C3-C10 alicyclic hydrocarbon group, a C6-C15 aromatic hydrocarbon group, these groups, And groups formed by combining at least one group selected from the group consisting of -CO-, -COO-, -OCO- and -O-.

As said C1-C10 linear hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a vinyl group, a propenyl group, butenyl group, butadienyl group, pentenyl group, pentadienyl group, Hexenyl group, hexadienyl group, etc. are mentioned.

As said C3-C10 alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a dicyclohexyl group, a tricyclodecyl group, etc. are mentioned, for example.

As said C6-C15 aromatic hydrocarbon group, a phenyl group, a naphthalenyl group, etc. are mentioned, for example.

As monovalent organic group which does not have the cinnamic acid structure represented by said R <^1> -R <^6> , group derived from the compound represented by following formula (4) or group represented by said formula (5) is preferable, and the liquid crystal aligning film for said phase difference films The group represented by said Formula (5) is more preferable from a viewpoint which can improve the adhesiveness of the. Hereinafter, group derived from the compound represented by said Formula (4), and group represented by Formula (5) are explained in full detail.

(Group derived from the compound represented by the following formula (4))

In said formula (4), R <^16> is a C1-C20 alkyl group or an alkoxy group, or a C1-C20 fluoroalkyl group or a fluoroalkoxy group. R <^17> is a single bond, a C1-C20 alkylene group or a cycloalkylene group, or a C6-C20 allylene group. R ¹⁸ is a monovalent organic group.

As said R <^16> , a C8-20 alkyl group and an alkoxy group, and a C4-20 fluoroalkyl group and a fluoroalkoxy group are preferable. As R <^17> , a single bond, a 1, 4- cyclohexylene group, and a 1, 4- phenylene group are preferable. As R ¹⁸ , a carboxyl group and a halogenated carbonyl group are preferable.

As a compound represented by said Formula (4), the compound represented, for example by following formula (4-1)-(4-3) is mentioned as a preferable compound.

As a compound represented by said Formula (4), from the viewpoint of the efficiency of introduction of the said group at the time of the synthesis | combination of [A] cellulose, the carboxylic acid represented by said Formula (4-1)-(4-3), for example. Halides can also be mentioned as preferred compounds.

(Group represented by the formula (5))

In said formula (5), R <^19> is a hydrogen atom or a methyl group. h is an integer of 1-10. However, when h is two or more, some R <^19> may be same or different. R ²⁰ is a single bond or a (h + 1) valent hydrocarbon group having 1 to 20 carbon atoms. i is an integer of 0-10. R ²¹ is -COO- or -OCO-. j is 0 or 1; R <^22> is a methylene group, a C2-C10 alkylene group, a phenylene group, or a cyclohexylene group. k is 0 or 1;

As a (h + 1) valence C1-C20 hydrocarbon group represented by said R <^20> , a (h + 1) valence linear or branched aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc. are mentioned, for example.

As a C2-C10 alkylene group represented by said R <^22> , an ethanediyl group, a propanediyl group, butanediyl group, a pentanediyl group, a hexanediyl group, etc. are mentioned, for example. In addition, the phenylene group and the cyclohexylene group represented by R ²² are each preferably a 1,2-phenylene group and a 1,2-cyclohexylene group.

As a compound which gives the group represented by said formula (5), acrylic acid, methacrylic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 4- (2-methyl- acryloyloxy), for example. Benzoic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid And phthalic acid monohydroxyethyl acrylate, the compounds represented by the following formulas (5-1) and (5-2), and halides of these compounds. When introducing the group represented by the formula (5) into the [A] cellulose, the halide is preferably used from the viewpoint of improving the introduction efficiency of the group.

As a commercial item of the compound which gives the group represented by said Formula (5), For example, acrylic acid, methacrylic acid (above, Tokyo Kaseko Corp. make), light ester HO-MS, light ester HO-HH, copper HOA -MPL, copper HOA-MS, copper HOA-HH (above, Kyoesha Chemical Co., Ltd. make), Aronix (ARONIX) M-5400 (made by Toagose KK), etc. are mentioned.

As [A] cellulose represented by said Formula (1) and (1-1), from a viewpoint of the liquid-crystal orientation of the said liquid crystal aligning agent for retardation films, 2 or more of said R <^1> -R <^6> represents the said cinnamic acid structure. It is preferable that it is a group which has, 3 or more are more preferable, 4 or more are more preferable, and it is especially preferable that all are groups which have the said cinnamic acid structure. Moreover, it is preferable that any of said R <^1> -R <^6> is group represented by said Formula (5) from a viewpoint of adhesiveness to the board | substrate etc. of the liquid crystal aligning film formed from the said liquid crystal aligning agent for retardation films, and two or more are It is more preferable that it is group represented by said formula (5). The said liquid crystal aligning agent for retardation films adjusts the number of groups which have cinnamic acid structure in [A] cellulose, and the number of groups represented by said formula (5) suitably according to the property of the board | substrate to be used, etc., The balance of orientation and adhesiveness can be improved.

As [A] cellulose represented by said Formula (1), the high molecular compound represented by following formula (1-1)-(1-10) is mentioned, for example.

<The synthesis method of [A] cellulose>

[A] The cellulose can be obtained by, for example, reacting hydroxyethylated cellulose having various substitution ratios with the cinnamic acid derivative and / or other compounds, and can be synthesized according to the following reaction formula and the like. In addition, the following reaction formula has shown the synthesis | combining method of [A] cellulose which is group which all of R <^1> -R <^6> has cinnamic acid structure.

In said formula, m is synonymous with said formula (1). R 'is group which has the cinnamic-acid structure represented by a following formula.

In said formula, R <^7> -R <^9> , a and b are synonymous with said Formula (2).

As represented by said Formula (I), the cinnamic acid derivative and thionyl chloride are mixed, and the acid chloride of a cinnamic acid derivative is synthesize | combined. Next, as shown in said Formula (II), HE-cellulose cinnamate as [A] cellulose is made by making hydroxyethyl (HE) -cellulose and the acid chloride of cinnamic acid derivative react in inert solvents, such as nitrobenzene and chloroform. Can be obtained. The mixture after the reaction is diluted with methanol and filtered. It vacuum-dried after that and grind | pulverizing by a vibration mill can obtain HE-cellulose cinnamate used for adjustment of the liquid crystal aligning agent for retardation films.

As the usage-amount of a specific cinnamic acid derivative here, 0.001 mol-10 mol are preferable with respect to 1 mol of hydroxyl groups which celluloses, such as HE-cellulose, have more preferable 0.01 mol-5 mol, and 0.05 mol-2 mol are especially preferable.

As reaction temperature, 0 degreeC-200 degreeC is preferable, and 50 degreeC-150 degreeC is more preferable. As reaction time, 0.1 hour-50 hours are preferable, and 0.5 hour-20 hours are more preferable.

[A] The cellulose can introduce a structure derived from the specific cinnamic acid derivative by binding of an acid chloride or the like of the specific cinnamic acid derivative to the hydroxyl group portion of the HE-cellulose as described above. This manufacturing method is simple and is a very suitable method in that the introduction ratio of the structure derived from the specific cinnamic acid derivative can be increased.

In the present invention, a part of the specific cinnamic acid derivative may be substituted with a compound represented by the above formula (4), a compound giving a group represented by the above formula (5), or the like within a range that does not impair the effects of the present invention. . In this case, the synthesis | combination of [A] cellulose is performed by making a mixture of a cellulose, a specific cinnamic acid derivative, the compound represented by said formula (4), the compound which gives the group represented by said formula (5), etc. react.

The compound represented by said formula (4) deactivates the active site | part of [A] cellulose, and can contribute to the stability improvement of the said liquid crystal aligning agent for retardation films. Moreover, adhesiveness to the board | substrate etc. of the liquid crystal aligning film formed of the said liquid crystal aligning agent for retardation films can be improved when [A] cellulose contains group represented by said formula (5). In the present invention, when using the compound represented by the formula (4) and / or the compound giving the group represented by the formula (5) together with the specific cinnamic acid derivative, the specific cinnamic acid derivative, represented by the formula (4) As a use ratio of the sum total of a compound and the compound which gives the group represented by said Formula (5), 0.001 mol-1.5 mol are preferable with respect to 1 mol of hydroxyl groups which a cellulose has, 0.01 mol-1 mol are more preferable, 0.05 mol-0.9 mol are More preferred. In this case, as a usage-amount of the compound represented by said Formula (4) and the compound which gives the group represented by said Formula (5), 50 mol% or less is preferable with respect to the sum total with a specific cinnamic acid derivative, and 25 mol% or less is more preferable. desirable. When the use ratio of the compound represented by said formula (4) and the compound which gives the group represented by said formula (5) exceeds 50 mol%, there exists a possibility that the problem of the orientation in a liquid crystal aligning film may fall.

<[B] polymer>

The liquid crystal aligning agent for retardation films can contain a [B] polymer. Examples of the polymer (B) include at least one member selected from the group consisting of polyamic acid, polyimide, ethylenically unsaturated compound polymer, and cellulose not containing a group having cinnamic acid structure. When the liquid crystal aligning agent for retardation films contains these [B] polymers, in the liquid crystal aligning film for retardation films formed from the liquid crystal aligning agent for retardation films, it is clear that cellulose is unevenly distributed in the vicinity of the surface layer. For this reason, even if it reduces content of the cellulose in the said liquid crystal aligning agent for retardation films by increasing content of a [B] polymer, since cellulose is unevenly distributed on the surface of an oriented film, sufficient liquid-crystal orientation can be obtained. Therefore, in this invention, it becomes possible to reduce content in the said liquid crystal aligning agent for retardation films of the cellulose containing group which has the expensive cinnamic acid structure, and, as a result, reduces the manufacturing cost of the said liquid crystal aligning agent for retardation films. can do.

The polymer (B) is preferably a polymer containing a group represented by the formula (5). The liquid crystal aligning film formed from the liquid crystal aligning agent for retardation films can improve adhesiveness to a board | substrate etc. by the said liquid crystal aligning agent for retardation films containing the polymer containing the said specific group. As the polymer [B], any of polyamic acid, polyimide, ethylenically unsaturated compound polymer, and cellulose which does not contain a group having a cinnamic acid structure may include the specific group described above, but includes a group having a cinnamic acid structure. It is more preferable that cellulose which does not contain contains the said specific group.

[Polyamic acid]

Polyamic acid can be obtained by making tetracarboxylic dianhydride and a diamine compound react.

As tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types.

As aliphatic tetracarboxylic dianhydride, butane tetracarboxylic dianhydride etc. are mentioned, for example.

Examples of the alicyclic tetracarboxylic dianhydride include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 1,3,3a, 4 , 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3 Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro- 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid 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-tetraon etc. are mentioned.

As aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride etc. are mentioned, for example, The tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 is mentioned, for example.

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

As the usage-amount of 2,3,5- tricarboxy cyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 10 mol% or more is preferable with respect to the total tetracarboxylic dianhydride, 20 mol% or more is more preferable, It is further more preferable to consist only of 2,3,5- tricarboxy cyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane tetracarboxylic dianhydride.

As a diamine compound, aliphatic diamine, alicyclic diamine, diamino organosiloxane, aromatic diamine, etc. are mentioned, for example. These diamine compounds can be used individually or in combination of 2 or more types.

As aliphatic diamine, metaxylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc. are mentioned, for example.

As alicyclic diamine, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc. are mentioned, for example.

As diamino organosiloxane, 1, 3-bis (3-aminopropyl)-tetramethyl disiloxane, etc. are mentioned, for example, Diamine of Unexamined-Japanese-Patent No. 2010-97188 is mentioned. .

As aromatic diamine, p-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl sulfide, 1, 5- diamino naphthalene, 2,2'-, for example. Dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-dia Minodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-amino Phenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m -Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3, 4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl- 3,6-diaminocarbazole, N- Nyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4 -Bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2 , 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecaneoxy-2,5 -Diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5- Diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid Cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethyl Benzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((amino Phenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl ) Methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine and the following formula (A- The diamine compound etc. which are represented by 1) are mentioned.

In said formula (A-1), X <^I> is a C1-C3 alkyl group, * -O-, * -COO-, or * -OCO-. However, * is a site | part which couple | bonds with a diaminophenyl group. r is 0 or 1; s is an integer of 0-2. t is an integer of 1-20.

As an use ratio of the tetracarboxylic dianhydride and a diamine compound provided for the synthesis reaction of a polyamic acid, 0.2 equivalent-2 equivalent of the acid anhydride group of tetracarboxylic dianhydride is preferable with respect to 1 equivalent of the amino group contained in a diamine compound, 0.3 equivalent-1.2 equivalent are more preferable.

It is preferable to perform a synthesis reaction in an organic solvent. As reaction temperature, -20 degreeC-150 degreeC is preferable, and 0 degreeC-100 degreeC is more preferable. As reaction time, 0.5 hour-24 hours are preferable, and 2 hours-12 hours are more preferable.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. For example, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, N, N-dimethylform Aprotic polar solvents such as amide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea and hexamethylphosphortriamide; Phenol solvents, such as m-cresol, a xylenol, a phenol, and a halogenated phenol, are mentioned.

As the usage-amount (a) of an organic solvent, 0.1 mass%-50 mass% are preferable with respect to the total amount (b) of the total amount (b) of tetracarboxylic dianhydride and a diamine compound, and the usage-amount (a) of an organic solvent, 5 Mass%-30 mass% are more preferable.

The polyamic acid solution obtained after reaction may be provided as it is to the preparation of the liquid crystal aligning agent for retardation films as it is, may be provided to preparation of the liquid crystal aligning agent for retardation films after isolating the polyamic acid contained in reaction solution, and is isolated After refine | purifying a polyamic acid, you may provide for preparation of the said liquid crystal aligning agent for retardation films. As a method for isolating polyamic acid, for example, a method of pouring the reaction solution into a large amount of poor solvents and drying the precipitate obtained under reduced pressure, a method of distilling the reaction solution under reduced pressure with an evaporator, and the like can be given. As a purification method of a polyamic acid, the method of dissolving isolated polyamic acid again in an organic solvent, precipitating with a poor solvent, the method of carrying out the process of distilling a vacuum solvent and the like off under reduced pressure in an evaporator once or several times is mentioned. have.

[Polyimide]

Polyimide can be manufactured by dehydrating and ring-closing the acid-acid structure which the said polyamic acid has, and imidizing it. The polyimide may be a complete imide that dehydrates and cyclizes all of the dark acid structures possessed by the polyamic acid as a precursor thereof. The polyimide may be partially dehydrated and cyclically dehydrated, and a partial imide compound in which the dark acid structure and the imide ring structure coexist. It may be.

As a method for synthesizing the polyimide, for example, (i) a method of heating the polyamic acid (hereinafter may be referred to as "method (i)") and (ii) the polyamic acid is dissolved in an organic solvent, and this solution The method by the dehydration ring closure reaction of polyamic acid, such as the method of adding a dehydrating agent and a dehydration ring closure catalyst, and heating as needed (henceforth a "method (ii)") is mentioned.

As reaction temperature in a method (i), 50 degreeC-200 degreeC is preferable, and 60 degreeC-170 degreeC is more preferable. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance and when the reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide obtained may fall. As reaction time, 0.5 hour-48 hours are preferable, and 2 hours-20 hours are more preferable.

The polyimide obtained in the method (i) may be provided as it is to the preparation of the liquid crystal aligning agent for retardation film as it is, and after isolation of the polyimide, may be provided to the preparation of the liquid crystal aligning agent for retardation film or isolated polyimide After refine | purifying or after refine | purifying the polyimide obtained, you may provide for preparation of the said liquid crystal aligning agent for retardation films.

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

As a usage-amount of a dehydrating agent, although it selects suitably according to a desired imidation ratio, 0.01 mol-20 mol are preferable with respect to 1 mol of dark acid structures of polyamic acid.

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

As a usage-amount of a dehydration ring-closure catalyst, 0.01 mol-10 mol are preferable with respect to 1 mol of dehydrating agents that contain. The imidation ratio can be made higher as the content of the dehydrating agent and the dehydrating ring closure catalyst increases.

As an organic solvent used for method (ii), the organic solvent similar to the organic solvent illustrated as what is used for synthesis | combination of polyamic acid, etc. are mentioned, for example.

As reaction temperature in a method (ii), 0 degreeC-180 degreeC is preferable, and 10 degreeC-150 degreeC is more preferable. As reaction time, 0.5 hour-20 hours are preferable, and 1 hour-8 hours are more preferable. By making reaction conditions into the said range, dehydration ring-closure reaction fully advances and the molecular weight of the polyimide obtained can be made into the appropriate thing.

In the method (ii), the reaction solution containing a polyimide can be obtained. This reaction solution may be provided as it is to the preparation of the liquid crystal aligning agent for retardation film, may be provided to the preparation of the liquid crystal aligning agent for retardation film after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution, and after isolate | separating polyimide You may provide for preparation of the said liquid crystal aligning agent for retardation films, or after refine | purifying an isolated polyimide, you may provide for preparation of the liquid crystal aligning agent for retardation films. As a method of removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, the method of solvent substitution etc. are mentioned, for example. As an isolation method and a purification method of a polyimide, the method similar to what was illustrated as an isolation method and a purification method of polyamic acid, etc. are mentioned, for example.

[Ethylenically unsaturated compound polymer]

Ethylenic unsaturated compound as polymer [B] A polymer can be obtained by superposing | polymerizing a well-known ethylenically unsaturated compound by a well-known method. For example, (a) an epoxy group containing ethylenically unsaturated compound (henceforth a "(a) unsaturated compound" may be called), and (b1) ethylenically unsaturated carbonic acid and / or polymerizable unsaturated polyhydric anhydride (henceforth) And "(b1) unsaturated compound" may be referred to as a polymerizable unsaturated compound (hereinafter, may be referred to as "(b2) unsaturated compound") other than (a) unsaturated compound and (b1) unsaturated compound. It can obtain by superposing | polymerizing a copolymer (henceforth a "(B1) copolymer").

As the (a) unsaturated compound, for example, glycidyl (meth) acrylate, glycidyl (alpha) -ethyl acrylate, glycidyl (alpha) -n-propyl acrylate, glycidyl (alpha)-butyl acrylate, (meth) 3, 4- epoxy butyl acrylate, 3, 4- epoxy butyl (alpha)-ethyl acrylate, 6, 7- epoxy heptyl (meth) acrylic acid, 6, 7- epoxy heptyl (alpha)-ethyl acrylate.

As the (b1) unsaturated compound, for example,

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

Unsaturated polyhydric carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride, and the like.

As the (b2) unsaturated compound, for example,

(Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-methacrylate (meth) acrylate (Meth) acrylic-acid alkylesters, such as butyl and t-butyl (meth) acrylate;

(Meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (hereinafter tricyclo [5.2 .1.0 ^2,6 ] Decan-8-yl (meth) acrylic acid alicyclic ester, such as "dicyclopentanyl"), 2-dicyclopentanyloxyethyl (meth) acrylate, and isoboronyl (meth) acrylate Ryu;

(Meth) acrylic-acid aryl esters, such as (meth) acrylic-acid phenyl and (meth) acrylic-acid benzyl;

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

N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Unsaturated dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridyl) maleimide;

Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

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

Aromatic vinyl compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene;

Indene derivatives such as indene and 1-methylindene;

Vinyl chloride, vinylidene chloride, vinyl acetate, etc. are mentioned besides conjugated diene type compounds, such as 1, 3- butadiene, isoprene, and 2, 3- dimethyl- 1, 3- butadiene.

In the copolymer (B1), the content of the structural unit derived from the (a) unsaturated compound is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass relative to the total structural units. As a total content rate of the structural unit derived from (b1) an unsaturated compound, 5 mass%-40 mass% are preferable with respect to all the structural units, 10 mass%-30 mass% are more preferable, (b2) unsaturated compound As content rate of the structural unit derived from 10 mass%-70 mass% are preferable with respect to all the structural units, and 20 mass%-50 mass% are more preferable.

The copolymer (B1) can synthesize each unsaturated compound in the presence of a suitable solvent and a polymerization initiator, for example, by radical polymerization. Examples of the organic solvent include the same organic solvents as those exemplified for the synthesis of polyamic acid.

As a polymerization initiator, for example,

2,2'-azobisisobutyronitrile, 2,2'-azobis- (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 peroxide pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane;

Hydrogen peroxide;

Redox type initiator etc. which consist of these peroxides and a reducing agent are mentioned. These polymerization initiators can be used individually or in mixture of 2 or more types.

[Cellulose not containing groups having cinnamic acid structure]

As a cellulose which does not contain the group which has a cinnamic acid structure, For example, HE-cellulose used as a material of the synthesis | combination of [A] cellulose, group derived from the compound represented by said formula (4), and / or said formula (5) Cellulose, such as cellulose containing the group represented by), is mentioned. Among these, the cellulose containing group represented by said formula (5) is preferable, The liquid crystal aligning film formed from the said liquid crystal aligning agent for retardation films by using this [B] polymer in combination with [A] cellulose is used as a board | substrate etc. Adhesion can be improved. In addition, when the said liquid crystal aligning agent for retardation films contains the cellulose which does not contain the group which has a cinnamic acid structure, most of the cellulose which does not contain the group which has a cinnamic acid structure exist if it exists independently from [A] cellulose, Some may exist as a condensate with [A] cellulose. In addition, each description in description of [A] cellulose is applicable about group derived from the compound represented by said Formula (4), and group represented by said Formula (5).

When the liquid crystal aligning agent for retardation films contains a [B] polymer, as a content rate of the [B] polymer, although it changes with kinds of [B] polymer, it is 10,000 mass parts or less with respect to 100 mass parts of [A] celluloses. Is preferred.

<[C] ester structure containing compound>

The said liquid crystal aligning agent for retardation films can contain a [C] ester structure containing compound. When the liquid crystal aligning agent for retardation films contains a [C] ester structure containing compound, the liquid crystal aligning film for retardation films excellent in heat resistance etc. can be formed.

[C] The ester structure-containing compound is selected from the group consisting of acetal ester structures of carboxylic acids, ketal ester structures of carboxylic acids, 1-alkylcycloalkyl ester structures of carboxylic acids, and t-butyl ester structures of carboxylic acids in a molecule. It is a compound which has 2 or more types of at least 1 type. The ester structure-containing compound (C) may be a compound having two or more of the same kind of structures, or a compound having two or more of different kinds of structures in these structures. As group containing the acetal ester structure of the said carboxylic acid, group represented by a following formula (C-1) and a formula (C-2), etc. are mentioned, for example.

In said Formula (C-1), R <^23> and R <^24> is respectively independently a C1-C20 alkyl group, a C3-C10 alicyclic group, a C6-C10 aryl group, or a C7-C10 aralkyl group All. In said formula (C-2), n1 is an integer of 2-10.

In said formula (C-1), a methyl group is preferable as a C1-C20 alkyl group represented by R <^23> , a cyclohexyl group is preferable as a C3-C10 alicyclic group, and a phenyl group is a C6-C10 aryl group Preferably, a benzyl group is preferable as an aralkyl group having 7 to 10 carbon atoms. As a C1-C20 alkyl group represented by R <^24> , a C1-C6 alkyl group is preferable, As a C3-C10 alicyclic group, a C6-C10 alicyclic group is preferable, As a C6-C10 aryl group, A phenyl group is mentioned. Preferably, a benzyl group or 2-phenylethyl group is preferable as a C7-10 aralkyl group. As n1 in 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, and 1-n-part. Methoxyethoxycarbonyl group, 1-i-butoxyethoxycarbonyl group, 1-sec-butoxyethoxycarbonyl group, 1-t-butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 1 -Norbornyloxyethoxycarbonyl group, 1-phenoxyethoxycarbonyl group, (cyclohexyl) (methoxy) methoxycarbonyl group, (cyclohexyl) (cyclohexyloxy) methoxycarbonyl group, (cyclohexyl) (Phenoxy) methoxycarbonyl group, (cyclohexyl) (benzyloxy) methoxycarbonyl group, (phenyl) (methoxy) methoxycarbonyl group, (phenyl) (cyclohexyloxy) methoxycarbonyl group, (phenyl ) (Phenoxy) methoxycarbonyl group, (phenyl) (benzyloxy) methoxycarbonyl group, (benzyl) (methoxy) methoxycarbonyl group, (benzyl) (cyclohexyloxy) methoxycarbonyl group, (benzyl (Phenoxy) methoxycarbonyl group, (Benzyl) (benzyloxy) methoxycarbonyl group, etc. are mentioned.

As group represented by said formula (C-2), 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, etc. are mentioned, for example.

Among them, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxy Carbonyl groups are preferred.

As group containing the ketal ester structure of the said carboxylic acid, group represented by following formula (C-3) (C-5)-etc. are mentioned, for example.

In said formula (C-3), R <^25> is a C1-C12 alkyl group. R ²⁶ and R ²⁷ are each independently 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 said formula (C-4), R <^28> is a C1-C12 alkyl group. n2 is an integer of 2-8. In said formula (C-5), R <^29> is a C1-C12 alkyl group. n3 is an integer of 2-8.

The formula (C-3) a methyl group is preferable as the C 1? Alkyl group of 12 of R ²⁵ in a methyl group is preferable as the alkyl group having 1? 12 in R ^26, and, as alicyclic group having a carbon number of 3? 20 A cyclohexyl group is preferable, A phenyl group is preferable as a C6-C20 aryl group, A benzyl group is preferable as a C7-20 aralkyl group. As a C1-C12 alkyl group in R <^27> , a C1-C6 alkyl group is preferable, As a C3-C20 alicyclic group, a C6-C10 alicyclic group is preferable, As a C6-C20 aryl group, It is a phenyl group Is preferable, and as a C7-20 aralkyl group, a benzyl group or 2-phenylethyl group is preferable. As a C1-C12 alkyl group of R <^28> in Formula (C-4), a methyl group is preferable. As n2, 3 or 4 is preferable. As a C1-C12 alkyl group of R <^29> in Formula (C-5), a methyl group is preferable. As n3, 3 or 4 is preferable.

As group represented by said formula (C-3), it is a 1-methyl-1- methoxyethoxycarbonyl group, the 1-methyl-1-n-propoxy ethoxycarbonyl group, 1-methyl-1-, for example. n-butoxyethoxycarbonyl group, 1-methyl-1-i-butoxyethoxycarbonyl group, 1-methyl-1-sec-butoxyethoxycarbonyl group, 1-methyl-1-t-butoxye Oxycarbonyl group, 1-methyl-1-cyclohexyloxyethoxycarbonyl group, 1-methyl-1-norbornyloxyethoxycarbonyl group, 1-methyl-1-phenoxyethoxycarbonyl group, 1-methyl-1 -Benzyloxyethoxycarbonyl group, 1-methyl-1-phenethyloxyethoxycarbonyl group, 1-cyclohexyl-1-methoxyethoxycarbonyl group, 1-cyclohexyl-1-cyclohexyloxyethoxycarbonyl group , 1-cyclohexyl-1-phenoxyethoxycarbonyl group, 1-phenyl-1-methoxyethoxycarbonyl group, 1-phenyl-1-ethoxyethoxycarbonyl group, 1-phenyl-1-phenoxy Oxycarbonyl group, 1-phenyl-1-benzyloxyethoxycarbonyl group, 1-benzyl-1-methoxyethoxycarbonyl group, 1-benzyl-1-between A clohexyloxy ethoxy carbonyl group, the 1-benzyl-1- phenoxy ethoxy carbonyl group, the 1-benzyl-1- benzyloxy ethoxy carbonyl group, etc. are mentioned.

As group represented by said Formula (C-4), 2- (2-methyltetrahydrofuranyl) oxycarbonyl group, 2- (2-methyltetrahydropyranyl) oxycarbonyl group, etc. are mentioned, for example. .

As group represented by said formula (C-5), a 1-methoxycyclopentyloxycarbonyl group, a 1-methoxycyclohexyloxycarbonyl group, etc. are mentioned, for example.

Among them, 1-methyl-1-methoxyethoxycarbonyl group and 1-methyl-1-cyclohexyloxyethoxycarbonyl group are preferable.

As group containing the 1-alkylcycloalkylester structure of the said carboxylic acid, group represented by a following formula (C-6) is mentioned, for example.

In said formula (C-6), R <^30> is a C1-C12 alkyl group. n4 is an integer of 1-8.

As a C1-C12 alkyl group of R <^30> in said Formula (C-6), a C1-C10 alkyl group is preferable.

As group represented by said Formula (C-6), for example, 1-methylcyclopropoxycarbonyl group, 1-methylcyclobutoxycarbonyl group, 1-methylcyclopentoxycarbonyl group, 1-methylcyclohexyloxycarbonyl group , 1-methylcyclodecyloxycarbonyl group, 1-ethylcyclobutoxycarbonyl group, 1-ethylcyclopentoxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1-ethylcyclodecyloxycarbonyl group, 1- (iso ) Propylcyclopropoxycarbonyl group, 1- (iso) propylcyclobutoxycarbonyl group, 1- (iso) propylcyclodecyloxycarbonyl group, 1- (iso) butylcyclobutoxycarbonyl group, 1- (iso) butyl Cyclopentoxycarbonyl group, 1- (iso) butylcyclohexyloxycarbonyl group, 1- (iso) butylcycloheptyloxycarbonyl group, 1- (iso) butylcyclodecyloxycarbonyl group, 1- (iso) pentylcycloheptyl Oxycarbonyl group, 1- (iso) pentylcyclooctyloxycarbonyl Group, 1- (iso) hexylcyclopropoxycarbonyl group, 1- (iso) hexylcyclobutoxycarbonyl group, 1- (iso) hexylcyclopentoxycarbonyl group, 1- (iso) hexylcyclohexyloxycarbonyl group, 1- (iso) hexylcyclononyloxycarbonyl group, 1- (iso) hexylcyclodecyloxycarbonyl group, 1- (iso) octylcyclopropoxycarbonyl group, 1- (iso) octylcyclobutoxycarbonyl group, 1- (Iso) octylcyclopentoxycarbonyl group, 1- (iso) octylcyclohexyloxycarbonyl group, 1- (iso) octylcycloheptyloxycarbonyl group, 1- (iso) octylcyclooctyloxycarbonyl group, 1- (iso ) Octylcyclodecyloxycarbonyl group, and the like.

The group containing the t-butylester structure of the said 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 formula (C), T is group or t-butoxycarbonyl group represented by any of said formula (C-1)-(C-6). For n and R, n is 2 and R is a single bond or n is an integer of 2 to 10, and R is a group or carbon number obtained by removing n hydrogens from a heterocyclic compound having 3 to 10 carbon atoms. It is a 1-18 n-valent hydrocarbon group.

As n, 2 or 3 is preferable.

As n in the said Formula (C), when n is 2, it is a single bond, a C1-C12 alkanediyl group, a 1, 2- phenylene group, a 1, 3- phenylene group, a 1, 4- phenylene group, 2,6-naphthalenyl group, 5-sodium sulfo-1,3-phenylene group, 5-tetrabutyl phosphonium sulfo-1,3-phenylene group, etc. are mentioned.

In the case where n is 3, the group represented by the following formula, benzene-1,3,5-triyl group, etc. are mentioned as said R.

As said alkanediyl group, linear is preferable.

[C] ester structure containing compound represented by said formula (C) can be synthesize | combined by the normal method of organic chemistry, or by combining suitably the conventional method of organic chemistry.

For example, the compound in which T in said Formula (C) is group represented by said Formula (C-1) (except the case where R <^23> is a phenyl group), Preferably it is compound R- in presence of a phosphoric acid catalyst. (COOH) _n (wherein R and n each have the same meaning as in Formula (C)) and Compound R ²⁴ -O-CH = R ^{23 '} (wherein R ²⁴ is the same as in Formula (C-1)) R ^{23 '} can be synthesized by adding a group obtained by removing a hydrogen atom from the first carbon of R ²³ in the formula (C-1).

The compound in which T in said Formula (C) is represented by said Formula (C-2) adds the compound R- (COOH) _n and the compound represented by following formula preferably in presence of a p-toluenesulfonic acid catalyst. It can synthesize | combine by making it. However, R and n are synonymous with the said Formula (C).

In said formula, n1 is synonymous with said formula (C-2).

Although it will not specifically limit as content of the [C] ester structure containing compound in the said liquid crystal aligning agent for retardation films in consideration of required heat resistance, etc., but [C] ester structure containing compound 0.1 with respect to 100 mass parts of [A] cellulose. Mass parts-50 mass parts are preferable, 1 mass part-20 mass parts are more preferable, 2 mass parts-10 mass parts are more preferable.

In addition, a [C] ester structure containing compound can be synthesize | combined by a well-known method.

<Other optional components>

The said liquid crystal aligning agent for retardation films is a compound which has at least 1 epoxy group in a molecule | numerator in the range which does not impair the effect of this invention other than the radiation sensitive polymers, such as the above (henceforth "epoxy compound"). , Functional silane compounds, surfactants, photosensitizers and the like. Hereinafter, these other arbitrary components are explained in full detail. Moreover, these arbitrary components may be used 1 type or in mixture of 2 or more types, and 1 type (s) or 2 or more types can also be used also for each arbitrary component.

[Epoxy Compound]

An epoxy compound can be contained in the said liquid crystal aligning agent for retardation films in order to improve the adhesiveness to the board | substrate surface of the liquid crystal aligning film formed further.

As an 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-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl -Aminomethylcyclohexane, etc. are mentioned.

As a content rate of an epoxy compound, 40 mass parts or less are preferable with respect to a total of 100 mass parts of [A] cellulose and the [B] other polymer arbitrarily contained, and 0.1 mass part-30 mass parts are more preferable. Moreover, when the said liquid crystal aligning agent for retardation films contains an epoxy compound, you may use together base catalysts, such as 1-benzyl- 2-methylimidazole, in order to raise | generate a crosslinking reaction efficiently.

[Functional silane compound]

The said functional silane compound can be used for the purpose of improving the adhesiveness with respect to the board | substrate surface of the liquid crystal aligning film formed.

As a functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, 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 Silylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3, 6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminoprop Triethoxysilane, N-phenyl-3-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 In addition to the reactant with the silane compound which has an amino group, etc., the reactant with tetracarboxylic dianhydride and the silane compound which has an amino group, etc. which are described in Unexamined-Japanese-Patent No. 63-291922 are mentioned.

As a content rate of a functional silane compound, 50 mass parts or less are preferable with respect to a total of 100 mass parts of [A] cellulose and the [B] other polymer arbitrarily contained, and 20 mass parts or less are more preferable.

[Surfactants]

As surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant etc. are mentioned, for example.

As a use ratio of surfactant, 10 mass parts or less are preferable with respect to 100 mass parts of whole liquid crystal aligning agents for said retardation films, and 1 mass part or less is more preferable.

[Photosensitizer]

The photosensitizer which may be contained in the liquid crystal aligning agent for retardation film includes a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH ₂ and a compound having a group and a photomultiplier sensitivity of the structure at least one member selected from the group consisting of SO ₂ Cl. The cellulose contained in the liquid crystal aligning agent for the retardation film is reacted with a cellulose such as HE-cellulose and a mixture of a specific cinnamic acid derivative and a photosensitizer to provide a photosensitive structure derived from a specific cinnamic acid derivative. Namsan structure) and a photosensitive structure derived from a photosensitizer. This photosensitive structure is excited by irradiation of light and has a function of imparting this excitation energy to the photosensitive structure which is proximate in the polymer. This excited state may be a singlet or a triplet, but is preferably a triplet in view of long life and efficient energy transfer. It is preferable that the light which the said photosensitive structure absorbs is an ultraviolet-ray or visible light of the wavelength of 150 nm-600 nm. Since the light whose wavelength is shorter than the said lower limit cannot be handled by a normal optical system, it cannot use suitably for the optical orientation method. On the other hand, light having a wavelength longer than the upper limit is small in energy and hardly causes an excited state of the photosensitive structure.

As such a photosensitive structure, for example, 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, an acridine structure, an indole A structure etc. can be mentioned, These can be used individually or in combination of 2 or more types. These photosensitive structures are each 1-4 hydrogen atoms from acetophenone, benzophenone, anthraquinone, biphenyl, carbazole, nitrobenzene or dinitrobenzene, naphthalene, fluorene, anthracene, acridine or indole, respectively. The structure which consists of group obtained by removing the is called. Here, each of the acetophenone structure, the carbazole structure and the indole structure is preferably a structure composed of a group obtained by removing 1-4 of the hydrogen atoms of the benzene ring of acetophenone, carbazole or indole. It is preferable that it is at least 1 sort (s) chosen from the group which consists of an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, and a naphthalene structure among these photosensitive structures, and is an acetophenone structure and a benzo. It is especially preferable that it is at least 1 sort (s) chosen from the group which consists of a phenone structure and a nitroaryl structure.

As a photosensitizer, it is preferable that it is a compound which has a carboxyl group and a photosensitizer structure, and as a more preferable compound, the compound etc. which are represented by following formula (H-1)? (H-10) are mentioned, for example.

In said formula, q is an integer of 1-6.

As the usage-amount of a photosensitizer, 0.0001 mol-0.5 mol are preferable with respect to 1 mol of hydroxyl groups which a cellulose has, 0.0005 mol-0.2 mol are more preferable, 0.001 mol-0.1 mol are especially preferable.

<Preparation of the liquid crystal aligning agent for retardation film>

As above-mentioned, the liquid crystal aligning agent for retardation films of this invention contains [A] cellulose as an essential component, and contains a [B] polymer, a [C] ester structure containing compound, and other arbitrary components as needed. Although preferably, each component is prepared as a solution composition dissolved in an organic solvent.

As an organic solvent, it is preferable to melt | dissolve [A] cellulose and other components used arbitrarily, and to not react with these. As an organic solvent which can be used suitably for the said liquid crystal aligning agent for retardation films, it changes with the kind of other polymer contained arbitrarily.

As a preferable organic solvent in the case where the said liquid crystal aligning agent for retardation films contains [A] cellulose and a [B] polymer, the organic solvent illustrated as what is used for the synthesis | combination of polyamic acid is mentioned. These organic solvents can be used individually or in combination of 2 or more types.

The preferable solvent used for preparation of the said liquid crystal aligning agent for retardation films can be obtained combining the 1 type (s) or 2 or more types of said organic solvent according to the presence or absence of the use of another polymer, and its kind. In such a solvent, each component contained in the liquid crystal aligning agent for retardation films does not precipitate in the following preferable solid content concentration, and the surface tension of the liquid crystal aligning agent for retardation films becomes 25 mN / m-40 mN / m.

Solid content concentration of the liquid crystal aligning agent for retardation films of this invention, ie, the ratio which the mass of all components other than the solvent in the liquid crystal aligning agent for retardation films occupies in the total mass of the liquid crystal aligning agent for retardation films considers viscosity, volatility, etc. Although selected, it is 1 mass%-10 mass% preferably. When solid content concentration is less than 1 mass%, the film thickness of the liquid crystal aligning film formed from the liquid crystal aligning agent for retardation films may become small, and a favorable liquid crystal aligning film may not be obtained. On the other hand, when solid content concentration exceeds 10 mass%, the film thickness of a coating film may become excessive and a favorable liquid crystal aligning film may not be obtained, and the viscosity of the liquid crystal aligning agent for retardation films may increase, and coating characteristics may be inadequate. have. The range of preferable solid content concentration changes with the method employ | adopted when apply | coating the liquid crystal aligning agent for retardation films on a board | substrate. For example, as a range of solid content concentration in the case of the spinner method, 1.5 mass%-4.5 mass% are preferable. In the printing method, the solid content concentration is preferably in the range of 3% by mass to 9% by mass, and the solution viscosity is preferably in the range of 12 mPa · s to 50 mPa · s. When using the inkjet method, it is preferable to make solid content concentration into the range of 1 mass%-5 mass%, and to make solution viscosity into the range of 3 mPa * s-15 mPa * s.

As temperature at the time of preparing the liquid crystal aligning agent for retardation films of this invention, 0 degreeC-200 degreeC is preferable, and 0 degreeC-40 degreeC is more preferable.

<Liquid crystal aligning film for retardation film and its formation method>

 The said liquid crystal aligning agent for retardation films can be used suitably in order to form the liquid crystal aligning film, especially the liquid crystal aligning film used for retardation film manufacture by the photo-alignment method.

As a method of forming the liquid crystal aligning film for retardation films, the method of forming a coating film of a liquid crystal aligning film on a board | substrate, and then providing a liquid crystal aligning ability to this coating film by the photo-alignment method is mentioned, for example.

The liquid crystal aligning film for retardation films using the liquid crystal aligning agent for retardation films can be manufactured by the following method, for example. The liquid crystal aligning agent for retardation film is apply | coated to a board | substrate by suitable coating methods, such as a roll coater method, a spinner method, the printing method, and the inkjet method, for example. Next, a coating film is formed by preheating (prebaking) the said coating surface and then postbaking. As prebaking conditions, they are 0.1 minutes-5 minutes at 40 degreeC-120 degreeC, for example. As postbaking conditions, 100 degreeC-300 degreeC is preferable, 110 degreeC-250 degreeC is more preferable, 1 minute-200 minutes are preferable, and 5 minutes-100 minutes are more preferable. The film thickness of the coating film after postbaking becomes like this. Preferably it is 0.001 micrometer-1 micrometer, More preferably, it is 0.005 micrometer-0.5 micrometer.

Examples of the substrate include glass substrates such as float glass and soda glass, triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyamide, polyimide, and polymethyl methacrylate. And transparent substrates containing plastic substrates such as polycarbonate. In particular, TAC is generally used as a protective layer of a polarizing film that bears an important function in LCD. In most cases, the retardation film is used in combination with a polarizing film. The retardation film needs to be precisely controlled and bonded at an angle capable of exhibiting desired optical characteristics with respect to the polarization axis of the polarizing film. Therefore, if the retardation film which formed the liquid crystal aligning film which can orientate a liquid crystal in arbitrary directions by a photo-alignment method on a TAC film, and formed and apply | coated and hardened the polymeric liquid crystal so that the desired optical characteristic may be exhibited, The bonding process of the conventional polarizing film and retardation film can be skipped, and it contributes to productivity improvement. In addition, it contributes to miniaturization and weight reduction of LCD materials, and can be applied to flexible displays and the like. However, the TAC film is characterized by poor solvent resistance, so that the solvent that can be used for forming the alignment film is limited, and a high solubility solvent such as NMP cannot be used. In addition, the TAC film is low in heat resistance and is characterized by being unable to be processed at high temperature for formation of the alignment film.

In addition, the said liquid crystal aligning agent for retardation films is apply | coated on the LCD structural member called a color filter, the polarizing plate, and the optical film containing a retardation film, for example, and can be used as a liquid crystal aligning film through the radiation irradiation process mentioned later. Moreover, the liquid crystal aligning agent for retardation films is apply | coated on the retardation film manufactured using the said liquid crystal aligning agent for retardation films, and can also be used as a liquid crystal aligning film through the same process.

At the time of application | coating of the said liquid crystal aligning agent for retardation films, in order to make adhesiveness of a board | substrate and a coating film more favorable, you may apply | coat a functional silane compound, titanate, etc. on a board | substrate previously.

Subsequently, the liquid crystal aligning ability is provided by irradiating linearly or partially polarized radiation or unpolarized radiation to the said coating film. As the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. When the radiation to be used is linearly polarized or partially polarized, irradiation may be performed in a direction perpendicular to the substrate surface, or may be performed from an inclined direction in order to give a pretilt angle, or may be performed in combination. In the case of irradiating non-polarized radiation, the direction of irradiation needs to be inclined direction. In addition, the "pretilt angle" in this specification means the angle of the inclination of the liquid crystal molecule from the direction parallel to a board | substrate surface.

Examples of the light source to be used include low pressure mercury lamps, high pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer-laser mercury-xenon lamps (Hg-Xe lamps), and the like. Ultraviolet rays in the above preferred wavelength region can be obtained by means of using the light source together with a filter, a diffraction grating, or the like, for example.

As an irradiation amount of radiation, 1J / m <2> or more and less than 10,000J / m <2> are preferable, and 10J / m <2> -3,000J / m <2> is more preferable. In addition, when providing the liquid-crystal orientation ability by the photo-alignment method to the coating film formed with the liquid crystal aligning agent conventionally known, when the radiation dose of 10,000 J / m <2> or more is needed, when the said liquid crystal aligning agent for retardation films is used, Even if the irradiation amount of 3,000 J / m <2> or less and 1,000 J / m <2> or less can provide favorable liquid-crystal orientation ability, it helps to reduce the manufacturing cost of a liquid crystal display element.

<Retardation film and its manufacturing method>

The retardation film provided with the liquid crystal aligning film for retardation films is also contained suitably in this invention. The retardation film formed using the liquid crystal aligning agent for retardation films can be manufactured as follows, for example. The formation method of the retardation film contained in this invention,

(1) Process of forming a coating film on the board | substrate by application | coating of the said liquid crystal aligning agent for retardation films,

(2) Process of forming liquid crystal aligning film for retardation films by irradiation of radiation to the said coating film,

(3) It has the process of forming a polymeric liquid crystal layer by application | coating of the polymeric liquid crystal to at least one part of the said liquid crystal aligning film for retardation films.

In process (1) and (2), it operates similarly to the formation method of the liquid crystal aligning film for retardation films mentioned above, and forms the liquid crystal aligning film for retardation films on a board | substrate. In a process (3), a polymeric liquid crystal is apply | coated to at least one part of the formed liquid crystal aligning film for retardation films. As a method of apply | coating a polymeric liquid crystal, the appropriate coating methods, such as a roll coater method, a spinner method, the printing method, the inkjet method, are mentioned, for example. Then, the solvent contained in the polymerizable liquid crystal is dried by heating and / or unbiased radiation irradiation, and the polymerizable liquid crystal is cured to form a polymerizable liquid crystal layer. In addition, this polymerization process may be performed in air, may be performed in inert gas atmosphere, such as nitrogen, and suitable conditions can be selected according to the polymeric group and initiator of the polymeric liquid crystal to be used. The film thus obtained can fix the polymerizable liquid crystal in the intended alignment state and can be used as a retardation film.

It will not specifically limit, if it is a compound which can superpose | polymerize by heating or radiation irradiation as said polymeric liquid crystal. For example, the nematic liquid crystal compound described in UV curable liquid crystal and its application (refer to page 34-page 42 of Liquid Crystal Vol. 3, No. 1 1999) may be sufficient, or a mixture with some compound may be sufficient as it. Moreover, the well-known photoinitiator or the thermal-polymerization initiator may be included. These polymerizable liquid crystal compounds and mixtures thereof can be dissolved in an appropriate solvent and used. Further, by adding a chiral agent or the like, a liquid crystal or a cholesteric liquid crystal that has a twisted nematic orientation twisted in the vertical direction to the substrate may be used, or a discotic liquid crystal may be used.

The film thickness of a polymerizable liquid crystal selects the film thickness from which desired optical characteristic is obtained. For example, when manufacturing a 1/2 wavelength plate in visible light with a wavelength of 540 nm, the film thickness whose phase difference of the formed retardation film is 240 nm-300 nm is selected, for example, if it is a 1/4 wavelength plate, phase difference Selects a film thickness of 120 nm to 150 nm. The film thickness from which the target phase difference is obtained differs depending on the optical properties of the polymerizable liquid crystal to be used. For example, when the mercury polymerizable liquid crystal (RMS03-013C) is used, it is selected in the range of 0.6 micrometer-1.5 micrometers as a film thickness for manufacturing a quarter wave plate.

As temperature in the case of heating a polymeric liquid crystal, the temperature which can obtain favorable orientation is selected. For example, when using the mercury polymerizable liquid crystal and RMS03-013C, it is selected in the range of 40 to 80 degreeC.

As radiation in the case of irradiating radiation, unbiased ultraviolet rays etc. are mentioned, for example. As irradiation amount of radiation, less than 1,000 J / m <2> -100,000 J / m <2> is preferable, and 10,000 J / m <2> -50,000 J / m <2> is more preferable.

<The manufacturing method of the retardation film containing 2 or more types of area | regions from which a liquid crystal orientation direction differs>

Moreover, the manufacturing method of the retardation film containing 2 or more types of regions from which a liquid crystal aligning direction differs in 3D image use etc. is also suitably included in this invention. The retardation film which has a region from which the liquid crystal aligning direction differs in the 3D image use formed using the said liquid crystal aligning agent for retardation films can be manufactured as follows, for example. The manufacturing method of the said retardation film,

The step (2),

(2-1) Process of providing the liquid-crystal orientation ability of a 1st direction by irradiation of the radiation of the 1st direction to the said coating film, and

(2-2) It has the process of providing a liquid crystal aligning ability of a 2nd direction further by irradiation of the radiation of a 2nd direction different from a 1st direction to a part of said coating film.

In addition, as another manufacturing method,

The step (2),

(2-1 ') Process of providing the liquid-crystal orientation ability of a 1st direction by irradiation of the radiation of a 1st direction to the said coating film, and

(2-2 ') It has the process of providing the liquid crystal aligning ability of a 2nd direction by irradiation of the radiation of the 2nd direction different from a 1st direction to the part to which the radiation of the said coating film was not irradiated.

Here, "direction" means the incident direction or the polarization direction of radiation. As a 2nd direction in a process (2-2) and (2-2 '), it differs from the 1st direction which provided the liquid-crystal orientation ability by radiation irradiation in a process (2-1) or (2-1'). Although it will not specifically limit if it rotates, 70 degrees-110 degrees are preferable, and the rotation direction of polarization is more preferable, 85 degrees-95 degrees, and 90 degrees is the most preferable. As a means to irradiate in a different direction, the method of irradiating a radiation through a mask is mentioned. Moreover, as a mask, what was patterned in the unitary shape so that a permeation | transmission part and a light shielding part may be alternately lined up is preferable.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples. In addition, the required amount of the raw material compound and the polymer used in the following Examples was ensured by repeating synthesis | combination of the raw material compound and a polymer in the synthesis scale shown to the following synthesis example as needed.

<Synthesis of Specific Cinnamic Acid Derivatives>

All the synthesis reactions of specific cinnamic acid derivatives were performed in inert atmosphere.

Synthesis Example 1

To 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, acrylic acid was added to 7g mixed solution with a syringe, and it stirred. The mixed solution was further heated and stirred at 120 ° C for 3 hours. After confirming completion | finish of reaction 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. 8.4g of compounds (specific cinnamic acid derivative (K-1)) represented by following formula (K-1) were obtained by recrystallizing these deposits with the 1: 1 (mass ratio) solution of ethyl acetate and hexane.

[Synthesis Example 2]

Into a 300 mL three-necked flask equipped with a cooling tube, 6.5 g of 4-fluorophenylboronic acid, 10 g of 4-bromocinnamic acid, 2.7 g of tetrakistriphenylphosphine palladium, 4 g of sodium carbonate, 80 mL of tetrahydrofuran, and 39 mL of pure water were added. Mixed. Subsequently, the reaction solution was heated and stirred at 80 ° C. for 8 hours, and 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 separated by filtration. The obtained solid was dissolved in ethyl acetate, and liquid-liquid separation was performed in order of 100 mL of 1N hydrochloric acid aqueous solution, 100 mL of pure water, and 100 mL of saturated saline solution. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained solid was dried in vacuo to obtain 9 g of a compound (specific cinnamic acid derivative (K-2)) represented by the following Formula (K-2).

[Synthesis Example 3]

In a 200 mL three-necked flask equipped with a cooling tube, 3.6 g of 4-fluorostyrene, 6 g of 4-bromocinnamic acid, 0.059 g of palladium acetate, 0.32 g of tris (2-tolyl) phosphine, 11 g of triethylamine, and dimethylacetate 50 mL of amide was mixed. After stirring this solution at 120 degreeC for 3 hours, and confirming completion | finish of reaction 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 with ethyl acetate to obtain 4.1 g of a compound (specific cinnamic acid derivative (K-3)) represented by the following formula (K-3).

[Synthesis Example 4]

In a 200 mL three-necked flask equipped with a cooling tube, 9.5 g of 4-vinyl biphenyl, 10 g of 4-bromocinnamic acid, 0.099 g of palladium acetate, 0.54 g of tris (2-tolyl) phosphine, 18 g of triethylamine, and dimethylacetamide 80 mL was mixed. After stirring this solution at 120 degreeC for 3 hours, and confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The precipitate was collected by filtration, and the filtrate was poured into 500 mL of 1N hydrochloric acid aqueous solution to recover the precipitate. 11 g of compounds (specific cinnamic acid derivatives (K-4)) represented by the following formula (K-4) were obtained by recrystallizing these precipitates with a dimethylacetamide and ethanol 1: 1 solution.

Synthesis Example 5

47.8 g of 4-bromophenylcyclohexane, 0.9 g of palladium acetate, and 4.9 g of tri (o-tolyl) phosphine were added to a 500 mL three-necked flask equipped with a cooling tube. Removed it. Next, 350 mL of dehydrated DMAc, 110 mL of triethylamine, and 16.5 mL of acrylic acid were added and reacted at 90 ° C. for 4 hours. After the completion of the reaction, the mixture was cooled to room temperature, and 600 mL of ethyl acetate was added. The mixture was washed once with 600 mL of 1 M hydrochloric acid and twice with 400 mL of water, and then filtered through Celite. Subsequently, 24.0 g of compounds (specific cinnamic acid derivatives (K-5)) represented by the following formula (K-5) were obtained by adding hexane, concentrating and recovering the precipitated crystals.

<Synthesis of [A] Cellulose>

[Synthesis Example 6]

0.05 mol of acid chloride of a specific cinnamic acid derivative (K-1) (prepared by mixing a specific cinnamic acid derivative (K-1) obtained in Synthesis Example 1, excess thionyl chloride and dimethylformamide), and hydroxyethyl cellulose ( HE-cellulose) 0.01 mol and 0.06 mol of pyridine were placed in 20 mL of nitrobenzene and heated at 80 ° C. for 24 hours. Then, it cooled and diluted with methanol. The reaction product was filtered, washed with methanol and water, dried in vacuo, and then pulverized with a vibration mill to obtain [A] cellulose (cellulose cinnamate A-1). The yield of cellulose cinnamate was about 65%-92%. Thin layer chromatography (TLC) confirmed that no cinnamic acid remained in the reaction product.

[Synthesis Example 7]

Instead of the specific cinnamic acid derivative (K-1), an acid chloride of 0.05 mol (cinnamic acid derivative (K-2), excess thionyl chloride and dimethylformamide) of the specific cinnamic acid derivative (K-2) obtained in Synthesis Example 2 was used. A white powder of [A] cellulose (cellulose cinnamate A-2) was obtained in the same manner as in Synthesis example 6, except that the mixture was prepared).

[Synthesis Example 8]

Instead of the specific cinnamic acid derivative (K-1), an acid chloride of 0.05 mol (cinnamic acid derivative (K-3), excess thionyl chloride and dimethylformamide) of the specific cinnamic acid derivative (K-3) obtained in Synthesis Example 3 was used. A white powder of [A] cellulose (cellulose cinnamate A-3) was obtained in the same manner as in Synthesis example 6 except that the mixture was prepared).

Synthesis Example 9

Instead of the specific cinnamic acid derivative (K-1), an acid chloride of 0.05 mol (cinnamic acid derivative (K-4), excess thionyl chloride and dimethylformamide) of the specific cinnamic acid derivative (K-4) obtained in Synthesis Example 4 was used. A white powder of [A] cellulose (cellulose cinnamate A-4) was obtained in the same manner as in Synthesis example 6 except that the mixture was prepared).

Synthesis Example 10

Instead of the specific cinnamic acid derivative (K-1), an acid chloride of 0.05 mol (specific cinnamic acid derivative (K-5), excess thionyl chloride and dimethylformamide) of the specific cinnamic acid derivative (K-5) obtained in Synthesis Example 5 Was prepared in the same manner as in Synthesis Example 6 to obtain a white powder of [A] cellulose (cellulose cinnamate A-5).

Synthesis Example 11

In the same manner as in Synthesis Example 6, except that 0.03 mol of the acid chloride and 0.02 mol of the acryloyl chloride of the specific cinnamic acid derivative (K-5) obtained in Synthesis Example 5 were used instead of the specific cinnamic acid derivative (K-1), [A] White powder of cellulose (cellulose cinnamate A-6) was obtained.

[Synthesis Example 12]

Instead of the specific cinnamic acid derivative (K-1), 0.04 mol of the acid chloride of the specific cinnamic acid derivative (K-5) obtained in Synthesis Example 5 and 0.01 mol of the compound represented by the following Formula (a) were used. The white powder of [A] cellulose (cellulose cinnamate A-7) was obtained by operation.

[Synthesis Example 13]

Instead of the specific cinnamic acid derivative (K-1), the same as in Synthesis Example 6 except that 0.03 mol of an acid chloride of the specific cinnamic acid derivative (K-5) obtained in Synthesis Example 5 and 0.02 mol of the compound represented by the following Formula (b) were used: It operated so that white powder of [A] cellulose (cellulose cinnamate A-8) was obtained.

<Synthesis of Polymer [B]>

[Synthesis Example 14]

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

Synthesis Example 15

22.4 g (0.1 mol) of 2,3,5-tricarboxy cyclopentyl acetic anhydride and 14.23 g (0.1 mol) of cyclohexanebis (methylamine) were dissolved in 329.3 g of NMP, and reacted at 60 ° C for 6 hours. The reaction mixture was then poured into excess methanol to precipitate the reaction product. 32g of polyamic acid (PA-2) was obtained by wash | cleaning a deposit with methanol and drying at 40 degreeC under reduced pressure for 15 hours.

Synthesis Example 16

17.5g of polyamic acid (PA-2) obtained by the synthesis example 15 was taken, NMP232.5g, pyridine 3.8g, and acetic anhydride 4.9g were added, it was made to react at 120 degreeC for 4 hours, and imidation was performed. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. 15g of polyimide (PI-1) was obtained by wash | cleaning a deposit with methanol and drying under reduced pressure for 15 hours.

Synthesis Example 17

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 methylethyl ether (DEGME) were placed. Subsequently, 40 mass parts of glycidyl methacrylate, 10 mass parts of styrene, 30 mass parts of methacrylic acid, and 20 mass parts of cyclohexyl maleimide were put, and it substituted nitrogen, and started stirring gently. The solution temperature was raised to 70 degreeC, this temperature was preserve | saved for 5 hours, and the polymer solution containing the copolymer (MA-1) of poly (meth) acrylate was obtained. Solid content concentration of the obtained polymer solution was 33.1 mass%. The weight average molecular weight Mw of the obtained polymer was 7,000.

Synthesis Example 18

A white powder of cellulose (cellulose cinnamate CE-1) was obtained in the same manner as in Synthesis Example 6 except that 0.05 mol of the compound represented by the formula (a) was used instead of the specific cinnamic acid derivative (K-1).

<Synthesis of [C] ester structure-containing compound>

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

Synthesis Example 19

Into a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, 21 g of trimesic acid, 60 g of n-butyl vinyl ether, and 0.09 g of phosphoric acid were added, and the reaction was carried out at 50 ° C under stirring for 30 hours. After completion of the reaction, the organic layer obtained by adding 500 mL of hexane to the reaction mixture was separated and washed two times with 1 M aqueous sodium hydroxide solution and three times with water in that order. Thereafter, the solvent was distilled off from the organic layer to obtain 50 g of an ester structure-containing compound (C-1-1) as a colorless transparent liquid.

<Preparation of the liquid crystal aligning agent for retardation film>

Example 1

[B] A solution containing polyamic acid (PA-1) as the polymer was converted to polyamic acid (PA-1) contained therein to take an amount equivalent to 1,000 parts by mass, and the [A] cellulose (A -1) 100 mass parts was added, and NMP and ethylene glycol monobutyl ether (EGMB) were further mixed, and the solvent composition was set as NMP: EGMB = 50: 50 (mass ratio), and solid content concentration was 4.0 mass% of the solution. The liquid crystal aligning agent for retardation films (S-1) was prepared by filtering this solution with the filter of 1 micrometer of pore diameters.

[Examples 2 to 11]

[A]-[C] component and the solvent of the kind and quantity shown in following Table 1 were added, and it operated like Example 1, and the liquid crystal aligning agent for retardation films (S-2)? (S-11) (each Solid content concentration prepared 4.0 mass%). In addition, in Table 1, DEGME is diethylene glycol monoethyl ether in the solvent used by Examples 2, 3, and 7-11.

[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 to this, and it stirred for 8 hours. The reaction mixture was diluted with NMP, added to methanol, and the precipitate was washed with water sufficiently and dried to obtain 25 g of a polymer. NMP and ethylene glycol monobutyl ether were added to this, and the solvent composition set it as the solution of NMP: EGMB = 50: 50 (mass ratio) and solid content concentration of 4.0 mass%. The composition (CS-1) was prepared by filtering this solution with the filter of 1 micrometer of pore diameters.

[Reference Example 2]

1.00 g of 4- (2-methacryloyloxyethoxy) azobenzene, 0.01 g of 2,2'-azobis (isobutyronitrile), and 2.00 g of dry benzene were added to an ampoule, degassed, and sealed. It poured in and obtained the precipitate of a high molecular compound. After filtration, the precipitate was dissolved in benzene again, reprecipitated with methanol, and filtered twice. NMP and EGMB were added to this, and the solvent composition made NMP: EGMB = 50: 50 (mass ratio), and solid content concentration into the solution of 4.0 mass%. The composition (CS-2) was prepared by filtering this solution with the filter of 1 micrometer of pore diameters.

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

After apply | coating the liquid crystal aligning agent for retardation films adjusted in Examples 1-11 and Reference Examples 1-2 to the one surface of a TAC film using a spinner, and prebaking for 1 minute on 80 degreeC hotplate, in-tube Was post-baked at 100 ° C. for 10 minutes in an oven substituted with nitrogen to form a coating film having a film thickness of 0.1 μm. In that case, when melt | dissolution was not seen in a TAC film, TAC coatability was made favorable and the case where melt | dissolution was seen was made into defect. As for TAC coating property, the surface of this coating film was irradiated with a polarized ultraviolet ray of 300 J / m 2 containing a 313 nm bright line perpendicularly from the substrate normal to the surface of the coating film using a Hg-Xe lamp and a glan taylor prism, to form a liquid crystal alignment film for a retardation film. Was manufactured and evaluation of the liquid-crystal orientation mentioned later was performed. The results are shown in Table 1 below.

[Evaluation of adhesion]

After apply | coating the liquid crystal aligning agent for retardation films prepared in Examples 1-11 and Reference Examples 1-2, to one surface of a TAC film using a spinner, and prebaking for 1 minute on an 80 degreeC hotplate, It was post-baked at 100 degreeC for 10 minutes in oven which carried out the nitrogen substitution, and formed the coating film of 0.1 micrometer in film thickness. About the obtained coating film, the 8.5.3 adhesive crosscut tape method of JISK-5400-1990 was performed, the number of the remaining crosscuts in 100 crosscuts was calculated | required, and the adhesiveness of the coating film was evaluated. When the number of remaining crosscuts out of 100 crosscuts is 80 or more, it can be said that adhesiveness is favorable.

<Manufacture of liquid crystal aligning film for retardation film>

[Example 12]

After apply | coating the liquid crystal aligning agent for phase difference films (S-1) prepared in Example 1 to the one surface of a transparent glass substrate using a spinner, and prebaking for 1 minute on an 80 degreeC hotplate, nitrogen inside the tube was substituted. In one oven, it post-baked at 200 degreeC for 1 hour, and formed the coating film of 0.1 micrometer in film thickness. Subsequently, the polarizing ultraviolet-ray 300J / m <2> containing 313 nm bright line was irradiated perpendicularly from the board | substrate normal line on the surface of this coating film using the Hg-Xe lamp and the Glen Taylor prism, and the liquid crystal aligning film for retardation films was produced.

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

The liquid crystal aligning film for retardation films was produced like Example 12 except having used the said ultraviolet-ray of a predetermined irradiation amount using the liquid crystal aligning agent for retardation films shown in Table 2.

<Production of retardation film>

Examples 23 to 33 and Comparative Examples 1 to 3

After polymerizable liquid crystal (Merck, RMS03-013C) was filtered with a filter having a pore diameter of 0.2 μm on the surface on which the liquid crystal alignment film for retardation film prepared in Examples 12 to 22 and Reference Examples 3 to 5 was formed, After coating and baking for 1 minute on a hot plate at 60 ℃, using a Hg-Xe lamp was irradiated with a polymerizable liquid crystal coating surface by irradiating 30,000 J / ㎡ of unpolarized ultraviolet light containing 365 nm bright line to produce a retardation film The following evaluation was performed. The results are shown in Table 3.

[Evaluation of Liquid Crystal Orientation]

About the retardation film manufactured in Examples 23-33 and Comparative Examples 1-3, the presence or absence of an abnormal domain is observed with a polarizing microscope, and the case where an abnormal domain is not observed is made into liquid crystal aligning "A", The case where the abnormal domain was observed was evaluated as liquid crystal alignment property "B".

[Evaluation of Thermal Stability]

After making the liquid crystal aligning film for retardation films on the irradiation conditions for which liquid-crystal orientation becomes "A", it operated similarly to the above except having heated at 150 degreeC for 1 hour before polymeric liquid crystal coating, and manufacturing a retardation film, the said The liquid crystal orientation evaluation similar to the above was performed, the case where an abnormal domain was not observed was made into thermal stability "A", and the case where an abnormal domain was observed was made into thermal stability "B".

As is apparent from the results in Table 3, the amount of light irradiation required for optical alignment when the liquid crystal alignment film for retardation film is produced using the liquid crystal aligning agent for retardation film is very low, and the retardation film provided with the liquid crystal alignment film for retardation film. It turned out that it has the outstanding liquid-crystal orientation and heat resistance.

<Manufacture of retardation film containing the area from which liquid crystal orientation direction differs>

Example 34

After forming the liquid crystal aligning film for retardation films on the board | substrate similarly to Example 12, in the polarization direction rotated 90 degrees from the original polarization ultraviolet-ray, through the mask patterned in strip shape so that the permeation | transmission part and the light shielding part may alternately line up, The first polarized ultraviolet ray (polarized ultraviolet ray 300J / m 2 including bright lines of 313 nm obtained using an Hg-Xe lamp and a glan taylor prism) was irradiated. Next, after polymerizable liquid crystal (Merck, RMS03-013C) was filtered with the filter of 0.2 micrometer of pore size on the surface in which the liquid crystal aligning film for retardation films was formed, it apply | coats using a spinner, and it uses it for 60 minutes by a 60 degreeC hotplate. After baking, 30,000 J / m <2> of non-polarization | polarized-light containing a 365 nm bright line was irradiated to the polymeric liquid crystal coating surface using the Hg-Xe lamp, and the retardation film containing the area from which a liquid-crystal orientation direction differs was manufactured.

[Example 35]

After applying the liquid crystal aligning agent for retardation film on the board | substrate similarly to Example 12, in the state which light-shielded half of the board | substrate, the 313 nm bright line obtained using the first polarized ultraviolet-ray (Hg-Xe lamp and a gran taylor prism) was taken out. Containing polarized ultraviolet ray 300J / m 2). Next, in the polarization direction rotated by 90 ° from the first polarized ultraviolet light, the first exposed light is shielded, and the polarized ultraviolet light is irradiated to the unexposed part, and the second polarized ultraviolet light irradiation (Hg-Xe lamp and the glan taylor prism) is performed. Polarized ultraviolet light 300 J / m 2) containing 313 nm bright lines were used. Next, after polymerizable liquid crystal (Merck, RMS03-013C) was filtered with the filter of 0.2 micrometer of pore size on the surface in which the liquid crystal aligning film for retardation films was formed, it apply | coats using a spinner, and it uses it for 60 minutes by a 60 degreeC hotplate. After baking, 30,000 J / m <2> of non-polarization | polarized-light containing a 365 nm bright line was irradiated to the polymeric liquid crystal coating surface using the Hg-Xe lamp, and the retardation film containing the area from which a liquid-crystal orientation direction differs was manufactured.

[Evaluation of Retardation Film Including Regions with Different Liquid Crystal Orientation Directions]

When the retardation film obtained in Example 34 was arrange | positioned between the polarizing plates arrange | positioned on cross nicol condition, and it observed using the transmitted light from an observation side and the reverse direction, when it arrange | positions so that it may become parallel or perpendicular to the polarization direction of the irradiated polarized ultraviolet-ray. In total, the whole surface was dark regardless of patterning. On the other hand, when retardation film was rotated 45 degrees in the plane, the whole surface became bright and had birefringence regardless of patterning.

When the retardation film obtained in Example 35 was observed similarly to the above, when arrange | positioning so that it might become parallel or perpendicular to the polarization direction of the irradiated polarized ultraviolet-ray, the whole surface was dark regardless of the polarization direction of the irradiated polarized ultraviolet ray. On the other hand, when retardation film was rotated 45 degrees in the plane, the whole surface became bright regardless of the polarization direction of the irradiated polarized ultraviolet-ray, and showed that it had birefringence.

Moreover, using the retardation film manufactured and operated similarly to Example 23, of the retardation film containing the area from which the polarization direction of the irradiated polarized ultraviolet-ray and the 2 types of liquid crystal aligning directions obtained in the said Example 34 and 35 differed When arrange | positioning so that the polarization direction of the irradiated-polarized ultraviolet-ray might become parallel or perpendicular | vertical, and observed on the cross nicol condition, it was confirmed that the external shape was divided | segmented by the edge which the pattern which becomes bright and the pattern which becomes dark become clear.

ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal aligning agent which can form the liquid crystal aligning film for retardation films which can be photo-aligned also by a small amount of radiation irradiation, and the heating process during and after irradiation is unnecessary, and this liquid crystal aligning film for retardation films is provided, And a retardation film excellent in thermal stability and a method of manufacturing the same.

Claims (12)

(A) Liquid crystal aligning agent for retardation films containing cellulose containing group which has cinnamic-acid structure. The method of claim 1,
[A] Liquid crystal aligning agent for retardation films in which cellulose is represented by following formula (1):

(In formula (1), R <^1> -R <^6> is respectively independently a hydrogen atom or a monovalent organic group, and at least 1 is a group which has a cinnamic acid structure; X is an oxygen atom or a sulfur atom; m is an integer of 10-10,000. The method of claim 2,
[A] Liquid crystal aligning agent for retardation films in which cellulose is represented by following formula (1-1):

(In formula (1-1), R <^1> -R <^6> , X and m are synonymous with said Formula (1).). The method of claim 1,
The liquid crystal aligning agent for retardation films whose group which has the said cinnamic acid structure originate in at least 1 sort (s) of compound chosen from the group which consists of a compound represented by following formula (2) and a compound represented by following formula (3):

(In formula (2), R <^7> is a phenylene group, a biphenylene group, a terphenylene group, or a cyclohexylene group; a part of hydrogen atoms of this phenylene group, biphenylene group, terphenylene group, or cyclohexylene group, or All may be substituted by a C1-C10 alkyl group, a C1-C10 alkoxy group which may have a fluorine atom, a fluorine atom, or a cyano group; R <^8> is a single bond and a C1-C3 alkanediyl group , An oxygen atom, a sulfur atom, -CH = CH-, -NH-, -COO- or -OCO-; a is an integer of 0 to 3, provided that a is a plurality of R ⁷ and R ⁸ may be the same or different, respectively; R ⁹ is a fluorine atom or a cyano group; b is an integer of 0 to 4; provided that when b is 2 or more, a plurality of R ⁹ may be the same or different; ;
In formula (3), R <^10> is a phenylene group or a cyclohexylene group; Some or all of the hydrogen atoms of this phenylene group or cyclohexylene group may be substituted with a C1-C10 linear or cyclic alkyl group, a C1-C10 chain or cyclic alkoxy group, a fluorine atom, or a cyano group. ; R ¹¹ is a single bond, an alkylene 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, a plurality of R ¹⁰ And R ¹¹ may be the same or different, respectively; R ¹² is a fluorine atom or a cyano group; d is an integer of 0-4; However, when d is two or more, some R <^12> may be same or different; R ¹³ is an oxygen atom, -COO- or -OCO-; R ¹⁴ is an aromatic group, alicyclic group, heterocyclic group or condensed cyclic group; R ¹⁵ is a single bond, -OCO- (CH ₂ ) _f- * or -O (CH ₂ ) _g- *; With the proviso that * is a moiety that binds to the carboxyl group; f and g are each an integer of 1-10; e is an integer of 0 to 3; However, when e is two or more, some R <^13> and R <^14> may be same or different, respectively). The method of claim 2,
In the formula (1), at least one of R ^{1 to} R ⁶ is a group represented by the following formula (5), and the liquid crystal aligning agent for retardation film:

(In Formula (5), R <^19> is a hydrogen atom or a methyl group; h is an integer of 1-10; However, when h is two or more, some R <^19> may be same or different; R <^20> , A single bond or a (h + 1) valent hydrocarbon group having 1 to 20 carbon atoms; R ²¹ is a single bond, -COO- or -OCO-; i is an integer of 0 to 10; j is 0 or 1 R ²² is a methylene group, a C 2-10 alkylene group, a phenylene group, or a cyclohexylene group; k is 0 or 1). The method according to any one of claims 1 to 5,
[B] [A] Polymers other than cellulose
Further contains,
The liquid crystal aligning agent for retardation films whose said [B] polymer contains group represented by said formula (5). The liquid crystal aligning film for retardation films formed with the liquid crystal aligning agent for retardation films of any one of Claims 1-5. The method of claim 7, wherein
The liquid crystal aligning film for retardation films containing 2 or more types of area | regions from which a liquid crystal aligning direction differs. The retardation film provided with the liquid crystal aligning film for retardation films of Claim 7, and a polymeric liquid crystal layer. (1) Process of forming a coating film on the board | substrate by application | coating of the liquid crystal aligning agent for retardation films of any one of Claims 1-5,
(2) Process of forming liquid crystal aligning film for retardation films by irradiation of radiation to the said coating film,
(3) Process of forming polymeric liquid crystal layer by application | coating of polymeric liquid crystal to at least one part of said liquid crystal aligning film for retardation films
The manufacturing method of retardation film which has. The method of claim 10,
The step (2),
(2-1) Process of providing the liquid-crystal orientation ability of a 1st direction by irradiation of the radiation of the 1st direction to the said coating film, and
(2-2) Process of providing the liquid crystal aligning ability of a 2nd direction further by irradiation of the radiation of a 2nd direction different from a 1st direction to a part of said coating film
The manufacturing method of retardation film which has. The method of claim 10,
The step (2),
(2-1 ') Process of providing the liquid-crystal orientation ability of a 1st direction by irradiation of the radiation of a 1st direction to the said coating film, and
(2-2 ') Production of retardation film which has a process of providing the liquid-crystal orientation ability of a 2nd direction by irradiation of the radiation of the 2nd direction different from a 1st direction to the part to which the radiation of the said coating film was not irradiated. Way.