KR20090116797A - Optical film - Google Patents

Abstract

Disclosed is an optical film (20) comprising an alignment film (10) and a coating layer (11) formed on the alignment film (10). The alignment film (10) contains a polymer having a structural unit derived from a polyvalent amine compound having at least two amino groups and at least one olefinically unsaturated bond. The coating layer (11) is a birefringent layer containing a structural unit derived from a polymerizable liquid crystal compound.

Description

Optical film {OPTICAL FILM}

This invention relates to the manufacturing method of an optical film, a flat panel display device, and an optical film.

Compared with CRTs, flat panel displays (FPDs), such as liquid crystal displays (LCDs) and organic electroluminescence (EL), which are space-saving or low-power consumption, are used for screens of computers, televisions, mobile phones, car navigation systems or portable information terminals. It is widely spread as. Various optical films are used for FPD for antireflection, viewing angle expansion, etc. As the optical film, for example, an anti-reflection film such as an anti-reflection (AR) film which reduces the reflectance of the surface by multilayering an optical thin film layer having different refractive indices, and transmits only light in a specific vibration direction and other light The retardation film which optically color-compensates interference color of LCDs, such as a polarizing film to block, an STN system, and a TN system, an ellipse polarizing film which integrated the polarizing film and retardation film, and the viewing angle expansion film which enlarges the viewing angle of LCD.

As one type of optical film, λ / 4 plate is known. As a manufacturing method, the method of extending | stretching the film which consists of polyvinyl alcohol, a polycarbonate, or a cycloolefin type polymer is common.

On the other hand, as an optical film which provides optical compensability different from a stretched film, it superposes | polymerizes after apply | coating polymeric liquid crystal molecule on the orientation film obtained by rubbing process films, such as alkyl modified polyvinyl alcohol and a polyimide, for example. The optical film with a coating layer which shows birefringence is known (refer patent document 1, nonpatent literature 1).

Patent Document 1: Japanese Unexamined Patent Publication No. 2003-114330

Non-Patent Document: Jpn. J. Appl. Phys., Vol. 32, 1993, pp. L1242-1244

Disclosure of Invention

Problems to be Solved by the Invention

Usually, an optical film is included and used in a polarizing plate, and the polarizing plate is affixed on the glass surface of a liquid crystal panel. At this time, when a problem such as an angle shift or wrinkles occurs, it is necessary to peel off the adhered polarizing plate from the glass surface of the liquid crystal panel and attach the other polarizing plate and the liquid crystal panel again.

As a result of examining the optical film which the present inventors coat | covered and polymerized a polymeric liquid crystal molecule to the orientation film formed by rubbing a polyamic acid or a polyimide, and formed the coating layer, it became clear that adhesiveness between an orientation film and a coating layer is not enough. . When using the polarizing plate containing the optical film with insufficient adhesiveness of an orientation film and a coating layer, there exists a tendency which is difficult to peel the polarizing plate which the problem mentioned above generate | occur | produced from the glass surface of a liquid crystal panel.

Then, the objective of this invention is providing the optical film in which the adhesive film between an orientation film and a coating layer fully improved in the optical film provided with the orientation film and the coating layer containing the liquid crystalline polymer formed on the orientation film.

Means to solve the problem

The present invention is an optical film having an alignment film and a coating layer formed on the alignment film, the alignment film contains a polymer containing a structural unit derived from a polyvalent amine compound having at least two amino groups and at least one olefinically unsaturated bond, The coating layer contains the liquid crystalline polymer containing the structural unit derived from a polymeric liquid crystal compound, and provides the optical film which is a layer which shows birefringence.

By providing the said structure, the optical film of this invention can fully improve the adhesiveness between an oriented film and a coating layer.

It is preferable that the said polyhydric amine compound is a compound represented with the following general formula (I) and / or (II). The orientation film containing the polymer containing the structural unit derived from such a polyhydric amine compound improves adhesiveness with a coating layer further.

[Formula 1]

In formulas (I) and (II), R ¹ represents a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and a1 represents a trivalent aromatic group having 5 to 14 carbon atoms. Provided that the carbon atom contained in a1 may be substituted with a nitrogen atom, an oxygen atom, a sulfur atom or a sulfonyl group (-SO _2- ), and the hydrogen atom contained in a1 may be a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyl group. And a C 1-6 alkoxy group, carboxyl group, acryloyl group or methacroyl group may be substituted. In formula (I), a2 represents a C1-C20 alkylene group, a divalent cyclic hydrocarbon group or a single bond which may be branched. B is -C≡C-, -CH = CH-, -O-, -S-, -C (= O)-, -C (= O) -O-, -OC (= O)-,- OC (= O) -O-, -C (= S)-, -C (= S) -O-, -OC (= S)-, -OC (= S) -O-, -CH = N- , -N = CH-, -N = N-, -N (→ O) = N-, -N = N (→ O)-, -C (= O) -NR-, -NR-C (= O )-, -NR-, -CH ₂ O-, -SCH _2- , -CH ₂ S-, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH- The divalent group shown or a single bond is shown. R represents a hydrogen atom or an alkyl group.

In the optical film of the present invention, it is preferable that the alignment film contains a polymer of the polyvalent amine compound and an acid dianhydride. Thereby, the effect of this invention that the adhesiveness of an orientation film and a coating layer is excellent can be exhibited more effectively and reliably.

From a viewpoint of further improving the adhesiveness of an orientation film and a coating layer, it is preferable that a coating layer is a layer which can apply | coat the solution containing a polymeric liquid crystal compound to an orientation film, and can polymerize and form a polymeric liquid crystal compound.

If the said polymeric liquid crystal compound is a compound represented by following General formula (1), the adhesiveness of an oriented film and a coating layer will further improve.

P1-E1-B1-A1-B2-A2-B3-A3-B4-E2-P2 (1)

In formula (1), A1, A2 and A3 are each independently a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylenephenylene group, an oxyphenylene group or a thiophenylene group (however, in these groups, an alkyl group, an alkoxy group or A halogen atom may be bonded). In addition, B1, B2, B3 and B4 are each independently -C≡C-, -CH = CH-, -O-, -S-, -C (= O)-, -C (= O) -O- , -OC (= O)-, -OC (= O) -O-, -C (= S)-, -C (= S) -O-, -OC (= S)-, -OC (= S ) -O-, -CH = N-, -N = CH-, -N = N-, -N (→ O) = N-, -N = N (→ O)-, -C (= O)- NR—, —NR—C (═O) —, —NR—, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O— or —OC The bivalent group represented by (= O) -CH = CH- or a single bond is shown. In addition, R represents a hydrogen atom or an alkyl group. E1 and E2 each independently represent an alkylene group having 2 to 25 carbon atoms (however, an alkyl group, an alkoxy group or a halogen atom may be bonded). P1 and P2 each independently represent a hydrogen atom or a polymerizable group (wherein at least one of P1 and P2 is a polymerizable group).

In the optical film of the present invention, the coating layer is represented by the following formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1 -7), a structure derived from a polymerizable liquid crystal compound represented by (1-8), (1-9) or (1-10) (hereinafter abbreviated as formula (1-1) to (1-10)) It is preferable to include a unit. Thereby, the adhesiveness of a coating layer and an oriented film further improves.

[Formula 2]

Moreover, this invention provides the flat panel display device provided with the said optical film. Since such a flat panel display device is provided with a layer showing birefringence, that is, a retardation plate, the flat panel display device is excellent in viewing angle characteristics and has good color reproducibility. Moreover, since the said flat panel display apparatus is excellent in the adhesiveness of a coating layer and an oriented film, it is excellent in environmental tolerance than the conventional flat panel display apparatus.

The present invention also provides a process for preparing a polymer composition containing a polyhydric amine compound having at least two amino groups and at least one olefinically unsaturated bond, a polymer of an acid dianhydride, and applying and drying the polymer composition on a supporting substrate. The manufacturing method of the optical film provided with the process of carrying out the orientation process of the film | membrane obtained and forming an orientation film, and the process of apply | coating the solution containing a polymeric liquid crystal compound on an orientation film, and superposing | polymerizing a polymeric liquid crystal compound and forming a coating layer are provided.

By providing such a process, the optical film with sufficiently improved adhesiveness between an orientation film and a coating layer can be manufactured.

Effects of the Invention

According to the present invention, it is possible to provide an optical film excellent in adhesiveness between the alignment film and the coating layer while exhibiting excellent birefringence.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows preferable embodiment of the optical film of this invention.

2 is a schematic diagram relating to an apparatus of a rubbing process.

It is a schematic diagram of the index ellipsoid which shows the optical characteristic of a coating layer.

Explanation of the sign

One… Roller, 2... Cloth, 3... Table, 4... Membrane-shaped polymer, 5... Rotational direction of the roller, 6... Indentation, 7.. Table moving direction, 10... Alignment layer, 11? Coating layer, 12.. Index ellipsoid, 13... Tilt angle, 14... Vertical ellipsoid, 20... Optical film.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail, referring drawings as needed. In addition, the same code | symbol is attached | subjected to the same element in the figure, and the overlapping description is abbreviate | omitted. In addition, unless otherwise indicated, positional relationship of up, down, left, right, etc. shall be based on the positional relationship shown in drawing. In addition, the dimension ratio of drawing is not limited to the ratio shown.

[Optical film]

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows preferable embodiment of the optical film of this invention. As shown in FIG. 1, the optical film 20 of this invention is equipped with the orientation film 10 and the coating layer 11 formed on the orientation film 10. As shown in FIG.

The optical film 20 of the present invention is a process for preparing a polymer composition containing a polymer of a polyhydric amine compound having at least two amino groups and at least one olefinically unsaturated bond, a polymer of an acid dianhydride, and a polymer composition on a supporting substrate. To a step of forming an alignment film 10 by coating the film obtained by drying the film, and drying the coating film 11 by coating a solution containing a polymerizable liquid crystal compound on the alignment film 10 to polymerize the polymerizable liquid crystal compound. It can manufacture by the manufacturing method provided with the process of forming.

First, the alignment film 10 which comprises the optical film 20 is demonstrated. The alignment film 10 contains a polymer containing a structural unit derived from a polyvalent amine compound (hereinafter referred to as "the present polyvalent amine") having at least two amino groups and at least one olefinically unsaturated bond.

The orientation film 10 is manufactured by orientation-processing the film | membrane containing the polymer synthesize | combined with this polyhydric amine and acid dianhydride normally as mentioned later. The polymer is usually a polyamic acid, and a part or all of the polyamic acid may be subjected to dehydration ring closure reaction (imidization) to form an imide ring.

As this polyhydric amine, the steroid skeleton which the olefinic unsaturated group like the compound represented by Formula (15) and (16) couple | bonded, and the polyhydric amine compound which has at least 2 amino group can be illustrated. Since the synthesis | combination of this polyhydric amine is easy, it is preferable to use the compound represented by said Formula (I) and / or Formula (II) as this polyhydric amine.

[Formula 3]

In formulas (I) and (II), R ¹ represents a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and is preferably a methyl group or a hydrogen atom. a1 is a carbon which represents a trivalent aromatic of 5 to 14 carbon atoms, an aromatic group configuration is a nitrogen atom, an oxygen atom, a sulfur atom or a sulfonyl group (-SO ₂ -) may be substituted with.

Specific examples of a1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and phenylene ring, furan ring, thiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, quinoxaline ring and quina. The group derived from aromatic hetero rings, such as a sleepy ring, a phenazine ring, a benzofuran ring, and a thianaphthene ring, is mentioned. In view of easy synthesis of the present polyvalent amine, a1 is preferably a group derived from a benzene ring and a pyrimidine ring, and more preferably a group derived from a benzene ring. Hydrogen contained in a1 may be a halogen atom such as fluorine, chlorine or bromine; Alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, isopropyl group and t-butyl group; Hydroxyl group; C1-C6 alkoxy groups, such as a methoxy group, an ethoxy group, and t-butoxy group; Carboxyl group; Acryloyl group; It may be substituted by the methacryloyl group.

b is -C≡C-, -CH = CH-, -O-, -S-, -C (= O)-, -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -C (= S)-, -C (= S) -O-, -OC (= S)-, -OC (= S) -O-, -CH = N-, -N = CH-, -N = N-, -N (→ O) = N-, -N = N (→ O)-, -C (= O) -NR-, -NR-C (= O) -, -NR-, -CH ₂ O-, -SCH _2- , -CH ₂ S-, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH- A divalent group or a single bond is shown. Especially, it is preferable that b is -C (= O) -O-, -O-, or a single bond from the point which the synthesis | combination of this polyhydric amine is easy.

a2 represents a linear or branched C1-C20 alkylene group, a C5-C20 bivalent cyclic hydrocarbon group, or a single bond. From a viewpoint of the ease of synthesis of the polyhydric amine compound represented by Formula (I), as a2, it is preferable that it is a C1-C10 alkylene group, and it is more preferable that it is a methylene group, an ethylene group, or a propylene group.

Further, b, and means that a2 is engaged when a single bond, in formula (I), a1 and -OC (= O) -C (R 1) = CH 2 directly.

As a bivalent cyclic hydrocarbon group, it is preferable that the aromatic group which may have a substituent, or the alicyclic group which may have a substituent is preferable. As a specific example of a bivalent aromatic group, group represented by following formula (i)-(iv) is mentioned.

[Formula 4]

Moreover, as a bivalent alicyclic group, group represented by following formula (ix)-(xi) is mentioned, for example.

[Formula 5]

As this polyhydric amine represented by Formula (I), 2, 3- diamino- methacryloxybenzene, 2, 4- diamino- methacryloxybenzene, 2, 5- diamino- methacryloxy, for example. Benzene, 2,6-diamino-methacryloxybenzene, 2,3-diamino-acryloxybenzene, 2,4-diamino-acryloxybenzene, 2,5-diamino-acryloxybenzene, 2,6 -Diamino-acryloxybenzene, 2,3-diamino-1,4-dimethacryloxybenzene, 2,5-diamino-1,4-dimethacryloxybenzene, 2,3-diamino-1 And benzene derivatives substituted with a plurality of amino groups such as, 4-diacryloxybenzene and 2,5-diamino-1,4-diacryloxybenzene and a (meth) acryloyl group.

Moreover, as this polyhydric amine, 2, 3- diamino-1- methacryloxy naphthalene, 2, 4- diamino-1- methacryloxy naphthalene, 2, 5- diamino-1- methacryloxy naphthalene, 2 , 6-diamino-1-methacryloxynaphthalene, 2,7-diamino-1-methacryloxynaphthalene, 2,8-diamino-1-methacryloxynaphthalene, 3,4-diamino-1- Methacryloxynaphthalene, 3,5-diamino-1-methacryloxynaphthalene, 3,6-diamino-1-methacryloxynaphthalene, 3,7-diamino-1-methacryloxynaphthalene, 3,8 -Diamino-1-methacryloxynaphthalene, 4,5-diamino-1-methacryloxynaphthalene, 4,6-diamino-1-methacryloxynaphthalene, 4,7-diamino-1-methacryl Oxynaphthalene, 4,8-diamino-1-methacryloxynaphthalene, 5,6-diamino-1-methacryloxynaphthalene, 5,7-diamino-1-methacryloxynaphthalene, 5,8-dia Mino-1-methacryloxy naphthalene, 6,7-diamino-1-methacryloxynaphthal , 6,8-diamino-1-methacryloxynaphthalene, 7,8-diamino-1-methacryloxynaphthalene, 1,3-diamino-2-methacryloxynaphthalene, 1,4-diamino- 2-methacryloxynaphthalene, 1,5-diamino-2-methacryloxynaphthalene, 1,6-diamino-2-methacryloxynaphthalene, 1,7-diamino-2-methacryloxynaphthalene, 1 , 8-diamino-2-methacryloxynaphthalene, 3,4-diamino-2-methacryloxynaphthalene, 3,5-diamino-2-methacryloxynaphthalene, 3,6-diamino-2- Methacryloxynaphthalene, 3,7-diamino-2-methacryloxynaphthalene, 3,8-diamino-2-methacryloxynaphthalene, 4,5-diamino-2-methacryloxynaphthalene, 4,6 -Diamino-2-methacryloxynaphthalene, 4,7-diamino-2-methacryloxynaphthalene, 4,8-diamino-2-methacryloxynaphthalene, 5,6-diamino-2-methacryl Oxynaphthalene, 5,7-diamino-2-methacryloxynaphthalene, 5,8-diamino-2-methac Ryloxynaphthalene, 6,7-diamino-2-methacryloxynaphthalene, 6,8-diamino-2-methacryloxynaphthalene, 7,8-diamino-2-methacryloxynaphthalene, 2,3- Diamino-1-acryloxynaphthalene, 2,4-diamino-1-acryloxynaphthalene, 2,5-diamino-1-acryloxynaphthalene, 2,6-diamino-1-acryloxynaphthalene, 2, 7-diamino-1-acryloxynaphthalene, 2,8-diamino-1-acryloxynaphthalene, 3,4-diamino-1-acryloxynaphthalene, 3,5-diamino-1-acryloxynaphthalene, 3,6-diamino-1-acryloxynaphthalene, 3,7-diamino-1-acryloxynaphthalene, 3,8-diamino-1-acryloxynaphthalene, 4,5-diamino-1-acryloxy Naphthalene, 4,6-diamino-1-acryloxynaphthalene, 4,7-diamino-1-acryloxynaphthalene, 4,8-diamino-1-acryloxynaphthalene, 5,6-diamino-1- Acryloxynaphthalene, 5,7-diamino-1-acryloxynaphthalene, 5,8-di Mino-1-acryloxynaphthalene, 6,7-diamino-1-acryloxynaphthalene, 6,8-diamino-1-acryloxynaphthalene, 7,8-diamino-1-acryloxynaphthalene, 1,3 -Diamino-2-acryloxynaphthalene, 1,4-diamino-2-acryloxynaphthalene, 1,5-diamino-2-acryloxynaphthalene, 1,6-diamino-2-acryloxynaphthalene, 1 , 7-diamino-2-acryloxynaphthalene, 1,8-diamino-2-acryloxynaphthalene, 3,4-diamino-2-acryloxynaphthalene, 3,5-diamino-2-acryloxynaphthalene , 3,6-diamino-2-acryloxynaphthalene, 3,7-diamino-2-acryloxynaphthalene, 3,8-diamino-2-acryloxynaphthalene, 4,5-diamino-2-acrylic Oxynaphthalene, 4,6-diamino-2-acryloxynaphthalene, 4,7-diamino-2-acryloxynaphthalene, 4,8-diamino-2-acryloxynaphthalene, 5,6-diamino-2 -Acryloxynaphthalene, 5,7-diamino-2-acryloxynaphthalene, 5,8-diamino-2-acryloxynaphthalene, 6,7-diamino-2-acryloxynaphthalene, 6,8-diamino-2-acryloxynaphthalene, 7,8-diamino-2-acryloxy And naphthalene derivatives substituted with a plurality of amino groups such as naphthalene and a (meth) acryloyl group.

Moreover, as this polyhydric amine, 2, 3- diamino- (2-methacryloxyethyl) oxybenzene, 2, 4- diamino- (2-methacryloxy ethyl) oxybenzene, 2, 5- diamino- ( 2-methacryloxyethyl) oxybenzene, 2,6-diamino- (2-methacryloxyethyl) oxybenzene, 2,3-diamino- (2-acryloxyethyl) oxybenzene, 2,4-dia Mino- (2-acryloxyethyl) oxybenzene, 2,5-diamino- (2-acryloxyethyl) oxybenzene, 2,6-diamino- (2-acryloxyethyl) oxybenzene, 2,3- Diamino-1,4-di (2-methacryloxyethyl) oxybenzene, 2,5-diamino-1,4-di (2-methacryloxyethyl) oxybenzene, 2,3-diamino-1 , 4-di (2-acryloxyethyl) oxybenzene, 2,5-diamino-1,4-di (2-acryloxyethyl) oxybenzene, 2,3-diamino- (3-methacryloxypropyl ) Oxybenzene, 2,4-diamino- (3-methacryloxypropyl) oxybenzene, 2,5-diamino- (3-methacryloxypropyl) oxybenzene, 2,6-diamino- (3- Methacryloxypropyl) oxybenzene , 2,3-diamino- (3-acryloxypropyl) oxybenzene, 2,4-diamino- (3-acryloxypropyl) oxybenzene, 2,5-diamino- (3-acryloxypropyl) oxy Benzene, 2,6-diamino- (3-acryloxypropyl) oxybenzene, 2,3-diamino-1,4-di (3-methacryloxypropyl) oxybenzene, 2,5-diamino-1 , 4-di (3-methacryloxypropyl) oxybenzene, 2,3-diamino-1,4-di (3-acryloxypropyl) oxybenzene, 2,5-diamino-1,4-di ( 3-acryloxypropyl) oxybenzene, 2,3-diamino- (4-methacryloxybutyl) oxybenzene, 2,4-diamino- (4-methacryloxybutyl) oxybenzene, 2,5-dia Mino- (4-methacryloxybutyl) oxybenzene, 2,6-diamino- (4-methacryloxybutyl) oxybenzene, 2,3-diamino- (4-acryloxybutyl) oxybenzene, 2, 4-diamino- (4-acryloxybutyl) oxybenzene, 2,5-diamino- (4-acryloxybutyl) oxybenzene, 2,6-diamino- (4-acryloxybutyl) oxybenzene, 2 , 3-diamino-1,4-di (4-meth Krilloxybutyl) oxybenzene, 2,5-diamino-1,4-di (4-methacryloxybutyl) oxybenzene, 2,3-diamino-1,4-di (4-acryloxybutyl) oxy Benzene, 2,5-diamino-1,4-di (4-acryloxybutyl) oxybenzene, 2,3-diamino- (4-methacryloxycyclohexyl) oxybenzene, 2,4-diamino- (4-methacryloxycyclohexyl) oxybenzene, 2,5-diamino- (4-methacryloxycyclohexyl) oxybenzene, 2,6-diamino- (4-methacryloxycyclohexyl) oxybenzene, 2,3-diamino- (4-acryloxycyclohexyl) oxybenzene, 2,4-diamino- (4-acryloxycyclohexyl) oxybenzene, 2,5-diamino- (4-acryloxycyclohexyl ) Oxybenzene, 2,6-diamino- (4-acryloxycyclohexyl) oxybenzene, 2,3-diamino-1,4-di (4-methacryloxy cyclohexyl) oxybenzene, 2,5- Diamino-1,4-di (4-methacryloxycyclohexyl) oxybenzene, 2,3-diamino-1,4-di (4-acryloxycyclohexyl) oxybenzene, 2,5-diamino- One, And benzene derivatives in which a plurality of amino groups such as 4-di (4-acryloxycyclohexyl) oxybenzene and the (meth) acryloyl group are bonded via an ether group.

As the present polyvalent amine, 2- (methacryloyloxy) methyl-2,3-diaminobenzoate, 2- (methacryloyloxy) methyl-2,4-diaminobenzoate, 2- (methacryl) Royloxy) methyl-2,5-diaminobenzoate, 2- (methacryloyloxy) methyl-2,6-diaminobenzoate, 2- (methacryloyloxy) methyl-3,4- Diaminobenzoate, 2- (methacryloyloxy) methyl-3,5-diaminobenzoate, 2- (methacryloyloxy) methyl-3,6-diaminobenzoate, 2- (acrylo Yloxy) methyl-2,3-diaminobenzoate, 2- (acryloyloxy) methyl-2,4-diaminobenzoate, 2- (acryloyloxy) methyl-2,5-diaminobenzo 8, 2- (acryloyloxy) methyl-2,6-diaminobenzoate, 2- (acryloyloxy) methyl-3,4-diaminobenzoate, 2- (acryloyloxy) methyl- 3,5-diaminobenzoate, 2- (acryloyloxy) methyl-3,6-diaminobenzoate, 2- (methacryloyloxy) ethyl-2,3- Aminobenzoate, 2- (methacryloyloxy) ethyl-2,4-diaminobenzoate, 2- (methacryloyloxy) ethyl-2,5-diaminobenzoate, 2- (methacrylo) Yloxy) ethyl-2,6-diaminobenzoate, 2- (methacryloyloxy) ethyl-3,4-diaminobenzoate, 2- (methacryloyloxy) ethyl-3,5-dia Minobenzoate, 2- (methacryloyloxy) ethyl-3,6-diaminobenzoate, 2- (acryloyloxy) ethyl-2,3-diaminobenzoate, 2- (acryloyloxy ) Ethyl-2,4-diaminobenzoate, 2- (acryloyloxy) ethyl-2,5-diaminobenzoate, 2- (acryloyloxy) ethyl-2,6-diaminobenzoate, 2- (acryloyloxy) ethyl-3,4-diaminobenzoate, 2- (acryloyloxy) ethyl-3,5-diaminobenzoate, 2- (acryloyloxy) ethyl-3, 6-diaminobenzoate, 2- (methacryloyloxy) propyl-2,3-diaminobenzoate, 2- (methacryloyloxy) propyl- 2,4-diaminobenzoate, 2- (methacryloyloxy) propyl-2,5-diaminobenzoate, 2- (methacryloyloxy) propyl-2,6-diaminobenzoate, 2 -(Methacryloyloxy) propyl-3,4-diaminobenzoate, 2- (methacryloyloxy) propyl-3,5-diaminobenzoate, 2- (methacryloyloxy) propyl- 3,6-diaminobenzoate, 2- (acryloyloxy) propyl-2,3-diaminobenzoate, 2- (acryloyloxy) propyl-2,4-diaminobenzoate, 2- ( Acryloyloxy) propyl-2,5-diaminobenzoate, 2- (acryloyloxy) propyl-2,6-diaminobenzoate, 2- (acryloyloxy) propyl-3,4-dia Minobenzoate, 2- (acryloyloxy) propyl-3,5-diaminobenzoate, 2- (acryloyloxy) propyl-3,6-diaminobenzoate, 3- (methacryloyloxy ) Propyl-2,3-diaminobenzoate, 3- (methacryloyloxy) propyl-2,4-diaminobenzo , 3- (methacryloyloxy) propyl-2,5-diaminobenzoate, 3- (methacryloyloxy) propyl-2,6-diaminobenzoate, 3- (methacryloyloxy ) Propyl-3,4-diaminobenzoate, 3- (methacryloyloxy) propyl-3,5-diaminobenzoate, 3- (methacryloyloxy) propyl-3,6-diaminobenzo 8, 3- (acryloyloxy) propyl-2,3-diaminobenzoate, 3- (acryloyloxy) propyl-2,4-diaminobenzoate, 3- (acryloyloxy) propyl- 2,5-diaminobenzoate, 3- (acryloyloxy) propyl-2,6-diaminobenzoate, 3- (acryloyloxy) propyl-3,4-diaminobenzoate, 3- ( Acryloyloxy) propyl-3,5-diaminobenzoate, 3- (acryloyloxy) propyl-3,6-diaminobenzoate, 4- (methacryloyloxy) butyl-2,3- Diaminobenzoate, 4- (methacryloyloxy) butyl-2,4-diaminobenzoate, 4- (methacryloyl jade ) Butyl-2,5-diaminobenzoate, 4- (methacryloyloxy) butyl-2,6-diaminobenzoate, 4- (methacryloyloxy) butyl-3,4-diaminobenzo 8- (methacryloyloxy) butyl-3,5-diaminobenzoate, 4- (methacryloyloxy) butyl-3,6-diaminobenzoate, 4- (acryloyloxy) Butyl-2,3-diaminobenzoate, 4- (acryloyloxy) butyl-2,4-diaminobenzoate, 4- (acryloyloxy) butyl-2,5-diaminobenzoate, 4 -(Acryloyloxy) butyl-2,6-diaminobenzoate, 4- (acryloyloxy) butyl-3,4-diaminobenzoate, 4- (acryloyloxy) butyl-3,5 -Diaminobenzoate, 4- (acryloyloxy) butyl-3,6-diaminobenzoate, 6- (methacryloyloxy) hexyl-2,3-diaminobenzoate, 6- (methacryl Royloxy) hexyl-2,4-diaminobenzoate, 6- (methacryloyloxy) hexyl-2,5-diaminobenzoate, 6- (methacryloyloxy ) Hexyl-2,6-diaminobenzoate, 6- (methacryloyloxy) hexyl-3,4-diaminobenzoate, 6- (methacryloyloxy) hexyl-3,5-diaminobenzo 8- (methacryloyloxy) hexyl-3,6-diaminobenzoate, 6- (acryloyloxy) hexyl-2,3-diaminobenzoate, 6- (acryloyloxy) hexyl -2,4-diaminobenzoate, 6- (acryloyloxy) hexyl-2,5-diaminobenzoate, 6- (acryloyloxy) hexyl-2,6-diaminobenzoate, 6- (Acryloyloxy) hexyl-3,4-diaminobenzoate, 6- (acryloyloxy) hexyl-3,5-diaminobenzoate, 6- (acryloyloxy) hexyl-3,6- Diaminobenzoate, 4- (methacryloyloxy) cyclohexyl-2,3-diaminobenzoate, 4- (methacryloyloxy) cyclohexyl-2,4-diaminobenzoate, 4- ( Methacryloyloxy) cyclohexyl-2,5-diaminobenzoate, 4- (methacryloyloxy) cyclohexyl-2,6-diaminobenzo Yit, 4- (methacryloyloxy) cyclohexyl-3,4-diaminobenzoate, 4- (methacryloyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (methacrylo) Yloxy) cyclohexyl-3,6-diaminobenzoate, 4- (acryloyloxy) cyclohexyl-2,3-diaminobenzoate, 4- (acryloyloxy) cyclohexyl-2,4- Diaminobenzoate, 4- (acryloyloxy) cyclohexyl-2,5-diaminobenzoate, 4- (acryloyloxy) cyclohexyl-2,6-diaminobenzoate, 4- (acrylo Yloxy) cyclohexyl-3,4-diaminobenzoate, 4- (acryloyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (acryloyloxy) cyclohexyl-3,6- The benzoate derivative which has several amino groups and (meth) acryloyl groups, such as diamino benzoate, is mentioned.

As the present polyhydric amine, 2-methacryloyloxyethyl-3,5-diaminotriazine, 2-acryloyloxyethyl-3,5-diaminotriazine, 3-methacryloyloxypropyl-3 , 5-diaminotriazine, 3-acryloyloxypropyl-3,5-diaminotriazine, 4-methacryloyloxybutyl-3,5-diaminotriazine, 4-acryloyloxybutyl -3,5-diaminotriazine, 4-methacryloyloxycyclohexyl-3,5-diaminotriazine, 4-acryloyloxycyclohexyl-3,5-diaminotriazine, 6-meta Triazine derivatives having a plurality of amino groups and (meth) acryloyl groups, such as chryloyloxyhexyl-3,5-diaminotriazine and 6-acryloyloxyhexyl-3,5-diaminotriazine Can be.

As the present polyvalent amine, 3,5-diamino-2-fluoroacid-2- (methacryloyloxy) ethyl ester, 3,5-diamino-2-flooxyacid-2- (acryloyloxy ) Ethyl ester, 3,5-diamino-1-naphthoic acid-2- (methacryloyloxy) ethyl ester, 3,6-diamino-1-naphthoic acid-2- (methacryloyl jade) Ethyl ester, 3,7-diamino-1-naphthoic acid-2- (methacryloyloxy) ethyl ester, 3,8-diamino-1-naphthoic acid-2- (methacryloyl jade) Ethyl ester, 3,5-diamino-1-naphthoic acid-2- (acryloyloxy) ethyl ester, 3,6-diamino-1-naphthoic acid-2- (acryloyloxy) Ethyl ester, 3,7-diamino-1-naphthoic acid-2- (acryloyloxy) ethyl ester, 3,8-diamino-1-naphthoic acid-2- (acryloyloxy) ethyl ester , 2-methacryloyloxy-4,4'-diaminobiphenyl, 3-methacryloyloxy-4,4'-diamino Phenyl, 2-acryloyloxy-4,4'-diaminobiphenyl, 3-acryloyloxy-4,4'-diaminobiphenyl, 2,2'-dimethacryloyloxy-4, 4'-diaminobiphenyl, 3,3'-dimethacryloyloxy-4,4'-diaminobiphenyl, 2,2'-diacryloyloxy-4,4'-diaminobiphenyl And 3,3'-diacryloyloxy-4,4'-diaminobiphenyl.

Among the above-mentioned, as this polyhydric amine represented by Formula (I), the compound represented by following formula (I-a), (I-b), (I-c), and (I-d) is easy to obtain, and is preferable.

[Formula 6]

-메틸스티렌, 2,4-디아미노-

-메틸스티렌, 2,5-디아미노-

-메틸스티렌, 2,6-디아미노-

-메틸스티렌, 3,4-디아미노-

-메틸스티렌, 3,5-디아미노-

-메틸스티렌, 3,6-디아미노-

-메틸스티렌 등의 복수의 아미노기와 스티렌 골격을 갖는 화합물, 1,2-디아미노-9-비닐카르바졸, 1,3-디아미노-9-비닐카르바졸, 1,4-디아미노-9-비닐카르바졸, 1,5-디아미노-9-비닐카르바졸, 1,6-디아미노-9-비닐카르바졸, 1,7-디아미노-9-비닐카르바졸, 1,8-디아미노-9-비닐카르바졸, 2,3-디아미노-9-비닐카르바졸, 2,4-디아미노-9-비닐카르바졸, 2,5- 디아미노-9-비닐카르바졸, 2,6-디아미노-9-비닐카르바졸, 2,7-디아미노-9-비닐카르바졸, 3,4-디아미노-9-비닐카르바졸, 3,5-디아미노-9-비닐카르바졸, 3,6-디아미노-9-비닐카르바졸, 4,5-디아미노-9-비닐카르바졸 등의 비닐카르바졸 유도체를 들 수 있다. As this polyhydric amine represented by Formula (II), it is 2, 3- diamino styrene, 2, 4- diamino styrene, 2, 5- diamino styrene, 2, 6- diamino styrene, 3, 4-diaminostyrene, 3,5-diaminostyrene, 3,6-diaminostyrene, 2,3-diamino-1,4divinylbenzene, 2,5-diamino-1,4divinylbenzene, 2,3-diamino-

-Methyl styrene, 2,4-diamino-

-Methyl styrene, 2,5-diamino-

-Methyl styrene, 2,6-diamino-

-Methylstyrene, 3,4-diamino-

-Methyl styrene, 3,5-diamino-

-Methylstyrene, 3,6-diamino-

Compounds having a plurality of amino groups such as methyl styrene and a styrene skeleton, 1,2-diamino-9-vinylcarbazole, 1,3-diamino-9-vinylcarbazole, 1,4-diamino-9- Vinylcarbazole, 1,5-diamino-9-vinylcarbazole, 1,6-diamino-9-vinylcarbazole, 1,7-diamino-9-vinylcarbazole, 1,8-diamino- 9-vinylcarbazole, 2,3-diamino-9-vinylcarbazole, 2,4-diamino-9-vinylcarbazole, 2,5-diamino-9-vinylcarbazole, 2,6-dia Mino-9-vinylcarbazole, 2,7-diamino-9-vinylcarbazole, 3,4-diamino-9-vinylcarbazole, 3,5-diamino-9-vinylcarbazole, 3,6 Vinylcarbazole derivatives such as -diamino-9-vinylcarbazole and 4,5-diamino-9-vinylcarbazole.

The polymer can contain the structural unit derived from polyhydric amines (henceforth "other polyhydric amine") other than the said polyhydric amine in the range which does not inhibit the effect of this invention.

However, it is preferable that content of the structural unit derived from this polyhydric amine is 10 mol% or more with respect to the structural unit derived from all the polyhydric amine which comprises the orientation film 10 normally, and it is more preferable that it is 30-100 mol%. . When this content is less than 10 mol%, there exists a tendency for the adhesiveness of the orientation film obtained and a coating layer to fall.

-아미노톨루엔, 3-아미노-

-아미노톨루엔, 4-(2-아미노에틸)아닐린, 3-(2-아미노에틸)아닐린, 4-(3-아미노프로필)아닐린, 3-(3-아미노프로필)아닐린, 1,1-디(4-아미노페닐)에탄, 1,2-디(4-아미노페닐)에탄, 1,2-디(4-아미노페닐)에틸렌, 1,2-디(4-아미노페닐)아세틸렌, 1,1-디(3-아미노페닐)에탄, 1,2-디(3-아미노페닐)에탄, 1,2-디(3-아미노페닐)에틸렌, 1,2-디(3-아미노페닐)아세틸렌, 1,1-디(2-아미노페닐)에탄, 1,2-디(2-아미노페닐)에탄, 1,2-디(2-아미노페닐)에틸렌, 1,2-디(2-아미노페닐)아세틸렌, 디(4-아미노페닐)메탄, 디(4-아미노페닐)에테르, 디(4-아미노페닐)술피드, 디(4-아미노페닐)술폰, 디(4-아미노페닐)아민, 4,4'-디아미노벤조페논, 디(3-아미노페닐)메탄, 디(3-아미노페닐)에테르, 디(3-아미노페닐)술피드, 디(3-아미노페닐)술폰, 디(3-아미노페닐)아민, 3,3'-디아미노벤조페논, 디(2-아미노페닐) 메탄, 디(2-아미노페닐)에테르, 디(2-아미노페닐)술피드, 디(2-아미노페닐)술폰, 디(2-아미노페닐)아민, 2,2'-디아미노벤조페논, 2,2-디(4-아미노페닐)프로판, 1,1-디(4-아미노페닐)시클로헥산, 2,2-디(4-아미노페닐)헥사플루오로프로판, 2,2-디(3-아미노페닐)프로판, 1,1-디(3-아미노페닐)시클로헥산, 2,2-디(3-아미노페닐)헥사플루오로프로판, 2,2-디(2-아미노페닐)프로판, 1,1-디(2-아미노페닐)시클로헥산, 2,2-디(2-아미노페닐)헥사플루오로프로판, 2,2-디(4-아미노-3-메틸페닐)프로판, 1,1-디(4-아미노-3-메틸페닐)시클로헥산, 2,2-디(4-아미노-3-메틸페닐)헥사플루오로프로판, 4,4'-디아미노비페닐, 3,3'-디아미노비페닐, 2,2'-디아미노비페닐, 3,3'-디메틸-4,4'-디아미노비페닐, 2,2'-디메틸-4,4'-디아미노비페닐, 3,3'-디트리플루오로메틸-4,4'-디아미노비페닐, 2,2'-디트리플루오로메틸-4,4'-디아미노비페닐, 3,3'-디메톡시-4,4'-디아미노비페닐, 2,2'-디메톡시-4,4'-디아미노비페닐, 2,2'-디클로로-4,4'-디아미노-5,5'-디메톡시비페닐, 1,5-디아미노나프탈렌, 1,8-디아미노나프탈렌, 1,4-디아미노나프탈렌, 2,3-디아미노나프탈렌, 2,6-디아미노나프탈렌, 2,7-디아미노나프탈렌, 1,8-디아미노플루오렌, 2,7-디아미노플루오렌, 3,6-디아미노플루오렌, 4,5-디아미노플루오렌, 1,8-디아미노카르바졸, 2,7-디아미노카르바졸, 3,6-디아미노카르바졸, 4,5-디아미노카르바졸, 1,8-디아미노크산톤, 2,7-디아미노크산톤, 3,6-디아미노크산톤, 4,5-디아미노크산톤, 1,8-디아미노크산텐, 2,7-디아미노크산텐, 3,6-디아미노크산텐, 4,5-디아미노크산텐, 1,8-디아미노안트론, 2,7-디아미노안트론, 3,6-디아미노안트론, 4,5-디아미노안트론, 1,8-디아미노안트라센, 2,7-디아미노안트라센, 3,6-디아미노안트라센, 4,5-디아미노안트라센, 9,10-디아미노안트라센, 1,5-디아미노안트라센, 2,6-디아미노안트라센, 1,8-디아미노안트라퀴논, 2,7-디아미노안트라퀴논, 1,5-디아미노안트라퀴논, 2,6-디아미노안트라퀴논, 4-아미노벤조산-4-아미노페닐에스테르, 3-아미노벤조산-4-아미노페닐에스테르, 2-아미노벤조산-4-아미노페닐에스테르, 4-아미노벤조산-3-아미노페닐에스테르, 4-아미노벤조산-2-아미노페닐에스테르, 4-아미노벤조산-4-아미노페닐아미드, 3-아미노벤조산-4-아미노페닐아미드, 2-아미노벤조산-4-아미노페닐아미드, 4-아미노벤조산-3-아미노페닐아미드, 4-아미노벤조산-2-아미노페닐아미드, 1,4-비스(4-아미노페닐)벤젠, 1,3-비스(4-아미노페닐)벤젠, 1,2-비스(4-아미노페닐)벤젠, 1,4-비스(3-아미노페닐)벤젠, 1,3-비스(3-아미노페닐)벤젠, 1,2-비스(3-아미노페닐)벤젠, 1,4-비스(2-아미노페닐)벤젠, 1,3-비스(2-아미노페닐)벤젠, 1,2-비스(2-아미노페닐)벤젠, 2,2-비스[4-(4-아미노페녹시)페닐]프로판, 2,2-비스[4-(4-아미노-3트리플루오로메틸페녹시)페닐]프로판, 2,2-비스[4-(4-아미노페녹시)페닐]헥사플루오로프로판, 2,2-비스[4-(4-아미노-3트리플루오로메틸페녹시)페닐]헥사플루오로프로판, 2,2-비스[4-(4-아미노페녹시)페닐]시클로헥산, 2,2-비스[4-(4-아미노-3트리플루오로메틸페녹시)페닐]시클로헥산, 2,2-비스[4-(4-아미노페녹시)페닐]술폰, 2,2-비스[4-(4-아미노페녹시)페닐]술피드, 2,2-비스[4-(4-아미노페녹시)페닐]에테르, 2,2-비스[4-(4-아미노페녹시)페닐]아민, 2,2-비스[4-(3-아미노페녹시)페닐]프로판, 2,2-비스[4-(3-아미노페녹시)페닐]헥사플루오로프로판, 2,2-비스[4-(3-아미노페녹시)페닐]시클로헥산, 2,2-비스[4-(3-아미노페녹시)페닐술폰, 2,2-비스[4-(3-아미노페녹시)페닐]술피드, 2,2-비스[4-(3-아미노페녹시)페닐]에테르, 2,2-비스[4-(3-아 미노페녹시)페닐]아민, 9,9-비스(4-아미노페닐)플루오렌, 9,9-비스(3-아미노페닐)플루오렌, 9,9-비스(2-아미노페닐)플루오렌, 9,9-비스(4-아미노페닐)-10-히드로안트라센, 9,9-비스(3-아미노페닐)-10-히드로안트라센, 9,9-비스(2-아미노페닐)-10-히드로안트라센, 2,2',5,5'-테트라클로로-4,4'-디아미노비페닐, 옥타플루오로-4,4'-디아미노비페닐, 4,4'-비스[(4-아미노페녹시)-옥타플루오로비페닐, 4,4'-비스[(4-아미노-2-트리플루오로메틸)페녹시]-옥타플루오로비페닐, 1,4-비스(4-아미노페녹시)벤젠, 1,3-비스(4-아미노페녹시)벤젠, 1,2-비스(4-아미노페녹시)벤젠, 1,4-비스(3-아미노페녹시)벤젠, 1,3-비스(3-아미노페녹시)벤젠, 1,2-비스(3-아미노페녹시)벤젠, 1,4-비스(2-아미노페녹시)벤젠, 1,3-비스(2-아미노페녹시)벤젠, 1,2-비스(2-아미노페녹시)벤젠, 4,4'-비스(4-아미노페녹시)비페닐, 1,1'-비스(4-아미노페녹시)비페닐, 2,2'-비스(4-아미노페녹시)비페닐, 3,3'-비스(4-아미노페녹시)비페닐, 1,4-비스(4-아미노페녹시)비페닐, 2,3-비스(4-아미노페녹시)비페닐, 2,4-비스(4-아미노페녹시)비페닐, 1,5-비스(4-아미노페녹시)비페닐, 4,4'-비스(3-아미노페녹시)비페닐, 4,4'-비스(2-아미노페녹시)비페닐, 1,3-비스(4-아미노페녹시)-2,2-디메틸프로판, 1,3-비스(3-아미노페녹시)-2,2-디메틸프로판, 1,2-비스(3-아미노페녹시)-2,2-디메틸프로판, 5-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단, 6-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단, 4,4'-메틸렌-비스(2-클로로아닐린), 2,3-디아미노피리딘, 2,6-디아미노피리딘, 2,5-디아미노피리딘, 2,4-디아미노피리미딘, 3,4-디아미노피리딘, 3,5-디아미노피리딘, 5,6-디아미노-2,3-디시아노피라진, 2,6-디아미노-3,5-디시아노피라진, 5,6-디아미노-2,4-디히드록시피리미딘, 2,6-디아미노-3,4-디히드록시피리미딘, 2,4-디아미노-6-디메틸아미노-1,3,5-트리아진, 1,4-비스(3-아미노프로필)피페라진, 2,4-디아미노-6-이소프로폭시-1,3,5-트리아진, 2,4-디아미노-6-메톡시-1,3,5-트리아진, 2,4-디아미노-6-페닐-1,3,5-트리아진, 2,4-디아미노-6-메틸-1,3,5-트리아진, 2,4-디아미노-1,3,5-트리아진, 4,6-디아미노-2-비닐-1,3,5-트리아진, 2,4-디아미노-5-페닐티아졸, 2,6-디아미노푸린, 5,6-디아미노-1,3-디메틸우라실, 3,5-디아미노-1,2,4-트리아졸, 6,9-디아미노-2-에톡시아크리딘락테이트, 3,8-디아미노-6-페닐페난트리딘, 1,4-디아미노피페라진, 3,6-디아미노아크리딘, 비스(4-아미노페닐)페닐아민, 1,1-메타자일릴렌디아민, 메틸렌디아민, 에틸렌디아민을 들 수 있다. As another polyvalent amine, aromatic diamine and non-aromatic diamine can be used, for example. As aromatic diamine, for example, o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 1, 4- diamino-3-methylbenzene, 1, 3- diamino-4-methylbenzene , 1,3-diamino-2-methylbenzene, 1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-2,4-dimethylbenzene, 1,4-diamino-2, 5-dimethylbenzene, 1,4-diamino-3-methoxybenzene, 1,3-diamino-4-methoxybenzene, 1,4-diamino-3-ethoxybenzene, 1,3-diamino 4-ethoxybenzene, 1,4-diamino-3-isopropylbenzene, 1,3-diamino-4-isopropylbenzene, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3 , 5-diaminobenzoic acid, methyl 2,4-diaminobenzoic acid, methyl 2,5-diaminobenzoic acid, methyl 3,5-diaminobenzoic acid, ethyl 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid Ethyl, 3,5-diaminobenzoate, 1,4-diamino-3-chlorobenzene, 1,3-diamino-4-chlorobenzene, 1,3-diamino-2-chlorobenzene, 1,4 -Diamino-2,6-dichlorobenzene, 1,4-diamino-2, 4-dichlorobenzene, 1,4-diamino-2,5-dichlorobenzene, N, N-dimethyl-2,4-diaminoaniline, N, N-dimethyl-2,5-diaminoaniline, N, N -Dimethyl-3,5-diaminoaniline, N, N-diethyl-2,4-diaminoaniline, N, N-diethyl-2,5-diaminoaniline, N, N-diethyl-3, 5-diaminoaniline, N, N-dipropyl-2,4-diaminoaniline, N, N-dipropyl-2,5-diaminoaniline, N, N-dipropyl-3,5-diaminoaniline , N, N-dipropyl-2,4-diaminoaniline, N, N-dipropyl-2,5-diaminoaniline, N, N-dipropyl-3,5-diaminoaniline, N, N- Diphenyl-2,4-diaminoaniline, N, N-diphenyl-2,5-diaminoaniline, N, N-diphenyl-3,5-diaminoaniline, N-phenyl-2,4-dia Minoaniline, N-phenyl-2,5-diaminoaniline, N-phenyl-3,5-diaminoaniline, 4-amino-

-Aminotoluene, 3-amino-

-Aminotoluene, 4- (2-aminoethyl) aniline, 3- (2-aminoethyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-aminopropyl) aniline, 1,1-di ( 4-aminophenyl) ethane, 1,2-di (4-aminophenyl) ethane, 1,2-di (4-aminophenyl) ethylene, 1,2-di (4-aminophenyl) acetylene, 1,1- Di (3-aminophenyl) ethane, 1,2-di (3-aminophenyl) ethane, 1,2-di (3-aminophenyl) ethylene, 1,2-di (3-aminophenyl) acetylene, 1, 1-di (2-aminophenyl) ethane, 1,2-di (2-aminophenyl) ethane, 1,2-di (2-aminophenyl) ethylene, 1,2-di (2-aminophenyl) acetylene, Di (4-aminophenyl) methane, di (4-aminophenyl) ether, di (4-aminophenyl) sulfide, di (4-aminophenyl) sulfone, di (4-aminophenyl) amine, 4,4 ' Diaminobenzophenone, di (3-aminophenyl) methane, di (3-aminophenyl) ether, di (3-aminophenyl) sulfide, di (3-aminophenyl) sulfone, di (3-aminophenyl) Amine, 3,3'-diaminobenzophenone, di (2-aminophenyl) methane, di (2 -Aminophenyl) ether, di (2-aminophenyl) sulfide, di (2-aminophenyl) sulfone, di (2-aminophenyl) amine, 2,2'-diaminobenzophenone, 2,2-di ( 4-aminophenyl) propane, 1,1-di (4-aminophenyl) cyclohexane, 2,2-di (4-aminophenyl) hexafluoropropane, 2,2-di (3-aminophenyl) propane, 1,1-di (3-aminophenyl) cyclohexane, 2,2-di (3-aminophenyl) hexafluoropropane, 2,2-di (2-aminophenyl) propane, 1,1-di (2 -Aminophenyl) cyclohexane, 2,2-di (2-aminophenyl) hexafluoropropane, 2,2-di (4-amino-3-methylphenyl) propane, 1,1-di (4-amino-3 -Methylphenyl) cyclohexane, 2,2-di (4-amino-3-methylphenyl) hexafluoropropane, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'- Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl- 4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diamino Biphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4 '-Diamino-5,5'-dimethoxybiphenyl, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 1,4-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6- Diaminonaphthalene, 2,7-diaminonaphthalene, 1,8-diaminofluorene, 2,7-diaminofluorene, 3,6-diaminofluorene, 4,5-diaminofluorene, 1, 8-diaminocarbazole, 2,7-diaminocarbazole, 3,6-diaminocarbazole, 4,5-diaminocarbazole, 1,8-diaminoxanthone, 2,7-diaminok Santone, 3,6-diaminoxanthone, 4,5-diaminoxanthone, 1,8-diaminoxanthene, 2,7-diaminoxanthene, 3,6-diaminoxanthene, 4,5 Diaminoxanthene, 1,8-diaminoanthrone, 2,7-diaminoanthrone, 3,6-diaminoanthrone, 4,5-diaminoanthrone, 1,8-diaminoanthracene, 2,7-diaminoanthracene, 3,6-diaminoanthracene, 4,5-diaminoanthracene, 9,10-diaminoanthracene, 1,5-diaminoanthracene, 2,6-diaminoanthracene, 1,8-diaminoanthraquinone, 2,7-diaminoanthraquinone, 1,5-diaminoanthraquinone, 2,6-diaminoanthraquinone, 4-aminobenzoic acid-4-aminophenyl ester, 3-aminobenzoic acid-4-aminophenyl ester, 2-aminobenzoic acid-4-aminophenyl ester , 4-aminobenzoic acid-3-aminophenyl ester, 4-aminobenzoic acid-2-aminophenyl ester, 4-aminobenzoic acid-4-aminophenylamide, 3-aminobenzoic acid-4-aminophenylamide, 2-aminobenzoic acid- 4-aminophenylamide, 4-aminobenzoic acid-3-aminophenylamide, 4-aminobenzoic acid-2-aminophenylamide, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-amino Phenyl) benzene, 1,2-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,3-bis (3-aminophenyl) benzene, 1,2-bis (3 -Aminophenyl) benzene, 1,4-bis (2-ami Nophenyl) benzene, 1,3-bis (2-aminophenyl) benzene, 1,2-bis (2-aminophenyl) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3trifluoromethylphenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-amino-3trifluoromethylphenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 2,2-bis [4- (4-amino-3trifluoromethylphenoxy) phenyl] cyclohexane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulphone, 2,2-bis [4- (4 -Aminophenoxy) phenyl] sulfide, 2,2-bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (4-aminophenoxy) phenyl] amine, 2, 2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3- Aminophenoxy) phenyl] cyclohexane, 2,2-bis [4- (3-aminophenoxy) phenylsulfone, 2,2-bis [4- (3-amino Oxy) phenyl] sulfide, 2,2-bis [4- (3-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] amine, 9,9- Bis (4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (2-aminophenyl) fluorene, 9,9-bis (4-aminophenyl)- 10-hydroanthracene, 9,9-bis (3-aminophenyl) -10-hydroanthracene, 9,9-bis (2-aminophenyl) -10-hydroanthracene, 2,2 ', 5,5'-tetra Chloro-4,4'-diaminobiphenyl, octafluoro-4,4'-diaminobiphenyl, 4,4'-bis [(4-aminophenoxy) -octafluorobiphenyl, 4,4 ' -Bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) Benzene, 1,2-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,2-bis ( 3-aminophenoxy) benzene, 1,4-bis (2-aminophenoxy) benzene, 1,3-bis (2-aminophenoxy) Benzene, 1,2-bis (2-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 1,1'-bis (4-aminophenoxy) biphenyl, 2, 2'-bis (4-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) biphenyl, 2,3-bis (4-aminophenoxy) biphenyl, 2,4-bis (4-aminophenoxy) biphenyl, 1,5-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-amino Phenoxy) biphenyl, 4,4'-bis (2-aminophenoxy) biphenyl, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,3-bis (3- Aminophenoxy) -2,2-dimethylpropane, 1,2-bis (3-aminophenoxy) -2,2-dimethylpropane, 5-amino-1- (4'-aminophenyl) -1,3, 3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 4,4'-methylene-bis (2-chloroaniline), 2,3-diaminopyridine , 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminopyrimidine, 3,4-diaminopyridine, 3,5-diaminopyridine, 5,6-diami No-2,3-dicyanopyrazine, 2,6-diamino-3,5-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,6-diamino-3 , 4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino -6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1, 3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino- 2-vinyl-1,3,5-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3, 5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopipe Razine, 3, 6- diamino acridine, bis (4-aminophenyl) phenylamine, 1, 1- methaxylylene diamine, methylene diamine, ethylene diamine is mentioned.

Moreover, as another polyhydric amine, the compound which has a steroid skeleton or a phenylenediamine skeleton represented by following formula (13), (14), (17) or (18) can be used.

[Formula 7]

Moreover, as another polyhydric amine, the compound which has a steroid skeleton and an aniline skeleton represented by following formula (19)-(21) can also be used.

[Formula 8]

Moreover, as another polyhydric amine, the compound which has a phenylenediamine skeleton represented by following formula (22), or the compound which has two aniline skeletons in the molecule | numerator represented by following formula (23) can be used.

[Formula 9]

In formula (22), R ⁷ represents a monovalent group having a ring structure containing a nitrogen atom derived from pyridine, pyrimidine, triazine, piperidine, piperazine, and the like, X is -CH _2- , -C≡C -, -CH = CH-, -CH ₂ -CH _2- , -O-, -S-, -C (= O)-, -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -CH = N-, -N = CH-, -N = N-, -N (→ O) = N-, -N = N (→ O)-, -C (= O) -NR'-, -NR'- C (= O) -, -OCH 2 -, -NR'-, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CH = The divalent group or single bond represented by CH-C (= O) -O- or -OC (= O) -CH = CH- is represented. R 'represents a hydrogen atom or an alkyl group

[Formula 10]

In formula (23), R <^8> represents the bivalent group which has a ring structure containing the nitrogen atom derived from pyridine, pyrimidine, triazine, piperidine, piperazine, etc., and X is synonymous with the above.

As a specific example of a compound represented by Formula (22), the compound represented by Formula (27) and (28) is mentioned.

[Formula 11]

As a specific example of a compound represented by Formula (23), the compound represented by following formula (25) and (26) is mentioned.

[Formula 12]

In formula (25), y represents the integer of 2-12, and z shows the integer of 1-5 in formula (26).

Examples of the non-aromatic diamine include 1,2-ethylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4, 4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] ^{-undecylenedimethyldiamine} , 4,4'-methylenebis (cyclohexylamine) di (4-aminocyclohexyl) methane, 2,2'-di (4-aminocyclohexyl) propane, di (4 -Amino-3-methylcyclohexyl) methane, 2,2'-di (4-amino-3-methylcyclohexyl) propane, di (3-amino-4-methylcyclohexyl) methane, 2,2'-di Aliphatic and alicyclic diamines such as (3-amino-4-methylcyclohexyl) propane; Alicyclic skeletons derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane and cyclodecane; Steroid skeletons such as cholesterol and cholestanol; The diamine which has alicyclic skeletons, such as a norbornene skeleton and an adamantane skeleton, and the diamino organosiloxane represented by following formula (24) are mentioned.

[Formula 13]

In formula (24), R <^9> respectively independently represents a C1-C12 alkyl group or a C1-C12 alkoxy group, p is an integer of 1-3, q shows the integer of 0-20.

As other polyhydric amine, p-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl sulfide, 1, 5- diamino naphthalene, 2,7- dia, among others Minofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2, 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) Bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-amino Phenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, the compound represented by said formula (19)-(21), the compound represented by said formula (25)-(28), 2,6 -Diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine are preferred.

As said acid dianhydride, it is 1,2,3,4-cyclobutane tetracarboxylic dianhydride, a 1,2-dimethyl- 1,2,3,4- cyclobutane tetracarboxylic dianhydride, for example. , 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 , 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1, 5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane- 2: 3,5: 6-di anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetra Dro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1, 3,3a, 4,5,9b-hexahydro-7-ethyl-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, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -octo-7-ene2,3,5,6-tetracarboxylic dianhydride, the following formula (3) and ( Aliphatic and alicyclic tetracarboxylic dianhydrides, such as a compound represented by 4), can be used.

[Formula 14]

In formulas (3) and (4), R ³ and R ⁵ each independently represent a divalent organic group having an aromatic ring, and R ⁴ and R ⁶ each independently represent a hydrogen atom or an alkyl group, and a plurality of R ^{4 's are} present; And R ⁶ may be the same as or different from each other.

Moreover, pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic acid 2 as acid 2 anhydride Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic Acid dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2, 3,4-furantetetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy ) Diphenylsulfone anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane 2 anhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene-bis (triphenylphthal 2) anhydride, m-phenylene-bis (triphenylphthalic acid) 2 anhydride, bis (triphenylphthalic acid) -4,4'-diphenylether 2 anhydride, bis (triphenylphthalic acid) -4,4'-diphenyl Methane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimelitate), 1,4-butanediol-bis (anhydrotrimelitate), 1,6-hexanediol- Bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), the following formula Aromatic tetracarboxylic dianhydride, such as the compound represented by (5)-(8), can also be used.

[Formula 15]

As an acid 2 anhydride, a 1,2,3,4-cyclobutane tetracarboxylic dianhydride, a 1,2,3,4- cyclopentane tetracarboxylic dianhydride, 2,3,5- especially Tricarboxycyclopentyl acetic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, cis-3,7-dibutyl Cycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-di Anhydride, 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, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxylic acid 2 anhydride, pyromellitic acid 2 Anhydride, 3,3 ', 4,4'-benzo Nontetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the following formula (9), The compound represented by (10), (11) and (12) is preferable from a viewpoint which can express favorable liquid crystal alignability.

[Formula 16]

Moreover, as acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1, 3- dimethyl- 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2, 3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] furan-1,3-dione, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6 -Tricarbonyl-2-carboxynorbornane-2: 3,5: 6-di anhydride, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2, Particularly preferred is 5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, pyromellitic dianhydride or the compound represented by the formula (9).

The polymer may contain the silane coupling agent in order to improve the adhesiveness of the oriented film to a board | substrate in the range which does not impair the effect of this invention. Moreover, you may mix | blend additives, such as a crosslinking agent, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, and an inorganic filler.

When mix | blending the amino organosiloxane represented by following formula (25) as a silane coupling agent, lifting, peeling, foaming in an alignment film between the obtained orientation film and a support base material can be suppressed, and it may be excellent in rework property.

[Formula 17]

In formula (25), R <^10> represents a C1-C12 alkyl group or a C1-C12 alkoxy group. Two or more R <^10> may be same or different, respectively. In addition, p 'represents the integer of 1-3 and q' represents the integer of 0-20.

Moreover, in order to adjust the molecular weight of a polymer, you may use the acid monoanhydride, a monoamine compound, and a monoisocyanate compound which are monofunctional components as a molecular weight modifier.

Examples of the acid 1 anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride and n-hexadecylsuccinic anhydride. have. As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decyl Amines, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine is mentioned. As a monoisocyanate compound, phenyl isocyanate and naphthyl isocyanate are mentioned, for example.

The polymer is generally synthesized by reacting a solution composed of the present polyhydric amine, acid dianhydride, organic solvent, other polyhydric amine, molecular weight modifier, and additive contained as necessary at -20 ° C to 150 ° C, preferably 0 to 100 ° C. do. Although a polymer normally has a polyamic acid as a main component, some or all may be imidized by dehydration ring-closure reaction.

The content ratio of the acid dianhydride, the present polyvalent amine, and other polyvalent amines provided to synthesize the polymer is such that the carboxyl group of the acid dianhydride is 0.2 to 1.2 moles with respect to 1 mole of the total amino groups contained in the present polyvalent amine and the polyvalent amine. It is preferable and it is more preferable that it becomes 0.8-1.2 mol. Here, the molecular weight of a polymer becomes large, so that the molar ratio of an amino group and a carboxyl group is closer to 1: 1. From the viewpoint of handling the polymer, the molar ratio can be appropriately adjusted so that the weight average molecular weight of the polymer is 2000 to 200000.

The ratio of the imide ring contained in a polymer, ie, the imidation ratio (%) can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time in a dehydration ring-closure reaction (imidization reaction).

Specifically as the method of imidization, a dehydrating agent and a dehydrating ring-closure catalyst are added to the method of (i) heating the polymer composition which has a polyamic acid as a main component, and (ii) the polymer composition which has a polyamic acid as a main component. Thus a method of heating is illustrated. In the imidation reaction, the higher the heating temperature, the longer the reaction time, and the larger the amount of the catalyst, the more the imidation ratio tends to be improved.

It is preferable that method (i) is normally performed at 50-250 degreeC, and is performed at 60-200 degreeC. If the reaction temperature is 50 ° C. or higher, the molecular weight of the polymer tends to increase. If the reaction temperature is 200 ° C. or lower, the dehydration ring closure reaction proceeds quickly, which is preferable.

In the method (ii), for example, acetic anhydride, propionic anhydride, trifluoroacetic anhydride and pyromellitic anhydride can be used as the dehydrating agent. The usage-amount of a dehydrating agent is 0.01-30 mol with respect to 1 mol of structural units containing an amic acid normally.

As the dehydration ring closure catalyst, for example, a third amine having no active hydrogen such as pyridine, collidine, lutidine, triethylamine, trimethylamine, tributylamine and trioctylamine can be used. The use amount of the dehydration ring-closure catalyst is usually from 0.01 to 30 moles per 1 mole of the dehydrating agent used.

The reaction temperature in method (ii) is 0-250 degreeC normally, Preferably it is 10-200 degreeC. If reaction temperature is 0 degreeC or more, the molecular weight of the polymer obtained tends to become large, and when reaction temperature is 200 degrees C or less, it is preferable at the point which dehydration ring-closure reaction advances rapidly.

) 은 통상적으로 본 다가 아민 및 다른 다가 아민 그리고 산 무수물의 합계량 (β) 이 (α+β) 에 대해 0.1 ∼ 30 중량 % 가 되는 양인 것이 바람직하다. As an organic solvent used for preparation of a polymer and dehydration ring-closure reaction, if a polyamic acid can be melt | dissolved, it will not specifically limit. As the organic solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylcaprolactam, dimethyl sulfoxide, γ-butyrolactone, Aprotic polar solvents such as tetramethylurea, pyridine, picoline, dimethyl sulfone and hexamethylphosphortriamide; Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, can be used. The amount of organic solvent used (

) Is usually an amount such that the total amount (β) of the present polyvalent amine and other polyvalent amines and acid anhydrides is 0.1 to 30% by weight relative to (α + β).

In the organic solvent, for example, an empty solvent such as alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like can be used in combination without causing the polymer to be precipitated. Specific examples of the empty solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol and triethylene Glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propio Nate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol Dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol dieth ether, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monophenyl ether, propylene glycol Monoacetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorbenzene, o-di Chlorbenzene, hexane, heptane, octane, benzene, toluene, xylene.

In the above-mentioned preparation method of the polymer, a large amount of empty solvent is poured into a polymer solution containing polyamic acid as a main component to precipitate the polyamic acid, and the purified polyamic acid is isolated by drying the precipitated polyamic acid under reduced pressure. The method of dissolving this polyamic acid in an organic solvent again and adjusting the polymer composition which has a polyamic acid as a main component is mentioned. Furthermore, you may mix separately the polyamic acid prepared or multiple types of its solution, and may prepare the polymer composition which has a polyamic acid as a main component.

The polymer having a high imidation ratio was also subjected to the same operation as described above to isolate a polymer having a high imidation ratio, and then dissolved in the organic solvent to give a polymer having a high imidation ratio as a main component. It can be used as a composition.

As a method of shape | molding a polymer in a film form, the method of forming into a film by apply | coating a polymer composition on a support base material by a well-known method, and then heating 50-200 degreeC, Preferably 80-180 degreeC is mentioned. As a coating method, the method of coating using a dip coater, a bar coater, a spin coater, etc., the extrusion coating method, the direct gravure coating method, the reverse gravure coating method, the CAP coating method, the die coating method etc. Can be used. Moreover, it is preferable that it is 0.001-10 micrometers, and, as for the film thickness of the polymer shape | molded in a film form, it is more preferable that it is 0.01-1 micrometer.

As a support base material, glass, a plastic sheet, a plastic film, and a translucent film are mentioned, for example. As said translucent film, For example, polyolefin film, such as polyethylene, a polypropylene, norbornene-type polymer, a polyvinyl alcohol film, a polyethylene terephthalate film, a polymethacrylic acid ester film, a polyacrylic acid ester film, a cellulose ester film, Polyethylene naphthalate film, polycarbonate film, polysulfone film, polyether sulfone film, polyether ketone film, polyphenylene sulfide film, polyphenylene oxide film is mentioned. By forming the alignment film on the support substrate, the mechanical strength of the alignment film formed is improved. In addition, a support base material may peel immediately after formation of the film containing the said polymer, may peel after an orientation process, and may peel after manufacturing an optical film.

In order to improve the adhesiveness of a support base material and a polymer, you may apply previously a functional silane containing compound and a functional titanium containing compound to the surface which contact | connects the polymer of a support base material.

Subsequently, orientation property is provided to the obtained film-form polymer, and the orientation film 10 used for this invention is formed.

As a method of providing orientation to the alignment film 10, for example, partially irradiated with ultraviolet rays described in rubbing treatment, JP-A-6-222366 and JP-A-6-281937 described later. The resist film is formed by partially forming a resist film on the surface of the film subjected to the treatment of changing the pretilt angle and the rubbing treatment described in JP-A-5-107544, and subjected to a rubbing treatment in a direction different from that of the rubbing treatment. The process of removing and changing the orientation ability of an oriented film is mentioned.

The rubbing process will be described in detail. The rubbing treatment refers to a treatment of rubbing a polymer in a film form with a cloth. It is a schematic diagram which shows the apparatus of a rubbing process. The rubbing processing apparatus is provided with the roller 1 and the table 3. When rubbing the membrane-shaped polymer 4, the membrane-shaped polymer 4 is mounted on the table 3, and the table 3 moves in the direction of the arrow 7. In addition, on the table 3, the film-form polymer 4 formed on the support base material may be mounted. The cloth 2 is wound around the outer periphery of the roller 1, the table 3 moves to the rotating roller 1, and the film-like polymer 4 and the cloth 2 are contacted and rubbed. And film-form polymer (4) is oriented and the oriented film (10) is obtained.

When using the rubbing processing apparatus shown in FIG. 2, as a parameter of friction strength, it is called the rotation speed of the roller 1, the space | interval of the roller 1, and the table 3 (henceforth "indentation amount"); 6), the feeding speed of the film for alignment film (speed that the table 3 is sent to the roller 1), and the number of times that the table 3 passes below the roller 1 (hereinafter, referred to as "rubbing times"). For example, when the table 3 passes once under the rotating roller 1, it will be said that the number of rubbings is 1 time.) And the properties of the cloth 2 are mentioned.

When the rotation speed of the roller 1 becomes large, the contact frequency of the cloth 2 and the membrane-shaped polymer 4 will increase, and frictional strength will increase. Moreover, when the indentation amount 6 becomes small, the cloth 2 and the membrane-shaped polymer 4 will contact strongly, and frictional strength will become large. In addition, when the delivery speed of the film-like polymer 4 decreases, the frictional time with the roller 1 increases, so that the frictional strength increases, and when the number of rubbing times is increased, the frictional strength increases.

For the fabric 2 used for the rubbing treatment, for example, artificial fiber cloths such as natural fiber cloths such as hemp, silk, cotton, and wool, silk, polyamide, and polyimide can be used. As for the surface of the cloth 2, it is usually used that is velvet.

Next, the coating layer 11 is formed in the orientation film 10 manufactured as mentioned above. The coating layer 11 is a layer which shows birefringence containing the structural unit derived from a polymeric liquid crystal compound.

As a method of forming the coating layer 11 on the oriented film 10, the method of melt | melting the liquid crystalline polymer obtained by superposing | polymerizing a polymeric liquid crystal compound, and apply | coating on the oriented film 10, a polymeric liquid crystal compound, for example The method of apply | coating the solution (henceforth "liquid crystal composition") which melt | dissolved in the organic solvent on the oriented film 10, and polymerizing a polymeric liquid crystal compound is mentioned. Among them, the latter method is preferable because the viscosity of the liquid crystal composition is low, the handling is easy, the coating layer excellent in the smoothness can be formed, and the formation process of the coating layer can be performed at a relatively low temperature.

The formation method of the coating layer 11 by a liquid crystal composition is demonstrated in more detail. First, a nonpolymerizable liquid crystalline polymer, a polymerization initiator, a polymerization inhibitor, a photosensitizer, a crosslinking agent and a leveling agent are added to the solution which consists of a polymeric liquid crystal compound and an organic solvent as needed, and a liquid crystal composition is prepared.

As the polymerizable liquid crystal compound, three molecules structure and liquid crystalline, 3.2 non-chiral rod-shaped liquid crystal molecules, 3.3 chiral rod-shaped liquid crystals of the liquid crystal handbook (Liquid Crystal Handbook Editing Committee Editing, Maruzen Co., Ltd., issued October 30, 2000) The compound which has a polymeric group is mentioned in the compound described in liquid crystal molecule. In the layer showing birefringence, the polymerizable liquid crystal compound is preferably a rod-shaped polymerizable liquid crystal compound from the viewpoint of obtaining a desired phase difference value from the thin film. You may use a polymeric liquid crystal compound individually by 1 type or in mixture of 2 or more types.

It is preferable to use the compound represented by following formula (1) as a polymeric liquid crystal compound.

P1-E1-B1-A1-B2-A2--B3-A3-B4-E2-P2 (1)

In formula (1), A1, A2 and A3 are respectively independently a C5-20 divalent cyclic hydrocarbon group, a bivalent heterocyclic group which is a 5-12 membered ring, a methylene phenylene group, an oxyphenylene group, or a thiophenylene group. Indicates. Al <1>, A <2> and A <3> are C1-C4 alkyl groups, such as a methyl group, an ethyl group, i-propyl group, t-butyl group; C1-C4 alkoxy groups, such as a methoxy group and an ethoxy group; Trifluoromethyl group; Trifluoromethyloxy group; Nitrile group; Nitro group; Halogen atoms, such as a fluorine atom, a chlorine atom, and an iodine atom, may be substituted. As a bivalent cyclic hydrocarbon group, the same group as what was illustrated as a bivalent cyclic hydrocarbon group contained in Formula (1) is illustrated.

As a heterocyclic group, group represented by a following formula (xii)-(xxii) formula is mentioned, for example.

[Formula 18]

Among the groups A1, A2 and A3, all of the same kinds of groups are preferred in terms of ease of production, and in particular, 1,4-phenylene group or 1,4-cyclohexylene group is easy to manufacture. desirable.

B1, B2, B3 and B4 (hereinafter abbreviated as "B1 to B4") in the formula (1) are each independently -CH _2- , -C≡C-, -CH = CH-, -CH ₂ -CH _2- , -O-, -S-, -C (= O)-, -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -CH = N-, -N = CH-, -N = N-, -N (→ O) = N-, -N = N (→ O)-, -C (= O) -NR-, -NR-C ( _{= O) -, -OCH 2 -} , -NR-, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CH = CH-C (= O) -O-, -OC (= O ) -CH = CH- represents a divalent group or a single bond. Here, R 'represents a hydrogen atom or an alkyl group. Especially, as B1-B4, they are each independently a single bond, -C≡C-, -O-, -OC (= O) -O-, -OC (= O)-, -OC (= O) -O -Is preferable in view of easy synthesis of the compound represented by the formula (1) and excellent in birefringence. Moreover, since B1-B4 is the same kind of bivalent group or single bond, since the synthesis | combination of the compound represented by Formula (1) becomes easier, it is preferable.

In formula (1), E1 and E2 represent a C2-C25 alkylene group each independently, Preferably, a C4-C10 alkylene group is shown. Although the hydrogen atom of E1 and E2 may be substituted by the alkyl group, the alkoxy group, the trifluoromethyl group, the trifluoromethyloxy group, the nitrile group, the nitro group, and the halogen atom, it is preferable that it is a hydrogen atom. E1 and E2 are preferable at the point which is easy in the synthesis | combination of the compound represented by Formula (1) as it is an alkylene group of the same kind.

In Formula (1), P1 and P2 represent a hydrogen atom or a polymeric group, and at least one of P1 and P2 is a polymeric group.

Here, a polymerizable group is a substituent which can superpose | polymerize a polymerizable liquid crystal compound, Specifically, a vinyl group, p-stilbene group, acryloyl group, methacroyl group, a carboxyl group, methylcarbonyl group, a hydroxyl group, an amide group, carbon number 1-4 alkylamino group, amino group, epoxy group, oxetanyl group, aldehyde group, isocyanate group, thioisocyanate group are illustrated. The polymerizable group may contain the groups illustrated in B1 and B2 in order to connect the groups exemplified above with E1 and E2.

Especially, since the handling at the time of photopolymerization is easy, and the synthesis | combination of the compound represented by Formula (1) is easy, it is preferable that a polymeric group is acryloyl group or a methacroyl group, and it is more preferable that it is acryloyl group.

When both of P1 and P2 are polymerizable groups, the film hardness of the optical film obtained tends to be improved, which is preferable.

Especially as a polymeric liquid crystal compound, the compound represented by said Formula (1-1)-(1-10) is preferable at the point which can be obtained easily. As the polymerizable liquid crystal compound, for example, a polymerizable liquid crystal compound (trade name "RMS03-001", manufactured by Merck Co., Ltd.) used in Examples described later can be obtained.

As a nonpolymerizable liquid crystal compound, the compound which does not have a polymeric group can be mentioned among the compound of the three-part molecular structure and liquid crystalline 3.2 nonchiral rod-like liquid crystal molecule and 3.3 chiral rod-like liquid crystal molecule of the said liquid crystal handbook. As a specific example of a nonpolymerizable liquid crystal compound, the compound represented by following formula (30)-(35) is mentioned.

[Formula 19]

-히드록시케톤류,

-아미노케톤류, 요오드늄염, 술포늄염을 들 수 있다. 중합 개시제는 시판품으로서 입수할 수 있고, 예를 들어, 이르가큐어 907, 이르가큐어 184, 이르가큐어 651, 이르가큐어 250, 및 이르가큐어 369 (이상, 모두 치바 스페셜티 케미컬즈사 제조), 세이크올 BZ, 세이크올 Z, 세이크올 BEE (이상, 모두 세이코 화학사 제조), 카야큐어 BP100 (닛폰 화약사 제조), 카야큐어 UVI-6992 (다우사 제조), 아데카 옵트마 SP-152, 아데카 옵트마 SP-170 (이상, 모두 아사히 덴카 제조) 등의 광중합 개시제를 들 수 있다. As a polymerization initiator, For example, benzoin, benzophenones, benzyl ketals,

Hydroxyketones,

Amino ketones, an iodonium salt, and a sulfonium salt are mentioned. A polymerization initiator can be obtained as a commercial item, For example, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 250, and Irgacure 369 (all are the Chiba Specialty Chemicals make), Sheikhol BZ, Sheikhol Z, Sheikhol BEE (above, all manufactured by Seiko Chemical Co., Ltd.), Kayakure BP100 (made by Nippon Kayaku Co., Ltd.), Kayakure UVI-6992 (manufactured by Dausa), Adeka Optma SP-152, Ah And photopolymerization initiators such as Deca Optma SP-170 (all manufactured by Asahi Denka).

By using the said photoinitiator, a polymeric liquid crystal compound can be photopolymerized. In addition, even if content of a polymerization initiator does not disturb the orientation of a liquid crystal polymer, it is preferable that it is 10 weight% or less with respect to content of a polymeric liquid crystal compound.

As a photosensitizer, xanthones, such as xanthone and thioxanthone, anthracene which has substituents, such as anthracene and an alkyl ether, phenothiazine, and rubrene, are mentioned, for example. By using a photosensitizer, the sensitivity of a polymeric liquid crystal compound can be improved.

As a leveling agent, the additive for radiation hardening paints (Bik Chemical Co., Ltd. make, brand names "BYK-352", "BYK-353", "BYK-361N"), a paint additive (made by Torre Dow Corning Corporation, brand name) "SH28PA", "DC11PA", "ST80PA"), and a paint additive (Shin-Etsu Silicone Co., Ltd. make, brand names "KP321", "KP323", "X22-161A", "KF-6001") can be used. By using a leveling agent, the coating layer obtained can be smoothed.

As an organic solvent, it is preferable to dissolve a polymeric liquid crystal compound and a nonpolymerizable liquid crystal compound. Specifically, Alcohol solvent, such as methanol, ethanol, ethylene glycol, propylene glycol; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, and propylene glycol methyl ether acetate; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Hydrocarbon solvents, such as pentane, hexane, heptane, toluene, xylene, are illustrated. You may use an organic solvent individually by 1 type or in mixture of 2 or more types.

The liquid crystal composition is usually adjusted to 10 Pa · s or less, preferably 0.1 mPa · s to 7 Pa · s so as to be easy to coat.

Subsequently, the adjusted liquid crystal composition is coated on the alignment film 10, dried and polymerized to form a coating layer 11 on the alignment film 10.

As a method of coating a liquid crystal composition to the oriented film 11, the extrusion coating method, the direct gravure coating method, the reverse gravure coating method, the CAP coating method, and the die coating method are mentioned, for example. Moreover, you may use the method of coating using coaters, such as a dip coater, a bar coater, and a spin coater.

The polymerizable liquid crystal compound can be polymerized by irradiating visible light, ultraviolet light or laser light as long as the polymerizable group is photopolymerizable, and can be polymerized by heating as long as the polymerizable group is thermally polymerizable. From the viewpoint of film formability, photopolymerization is preferable, and from the viewpoint of handleability, polymerization with ultraviolet light is more preferable.

In the case of photopolymerization, the solvent is preferably dried almost before the photopolymerization in order to improve the film formability. In the case of thermal polymerization, polymerization usually proceeds with drying, and preferably, most of the solvents are dried prior to polymerization, whereby the film formability tends to be excellent. As a drying method of a solvent, natural drying, ventilation drying, reduced pressure drying is mentioned, for example.

The coating layer 11 formed on the alignment film 10 has birefringence. Here, birefringence means that either one of a tilt angle and an in-plane phase difference value represents a non-zero value.

Based on FIG. 3, birefringence is demonstrated. 3 is a schematic diagram of the refractive index ellipsoid 12 showing the optical properties of the coating layer 11. In the refractive index ellipsoid 12, three-dimensional main refractive indexes na, nb, nc are defined. The angle (13) formed between the Z axis and the principal refractive index nc is defined by the tilt angle, and the long axis ny and the short axis nx of the vertical ellipsoid 14 formed on the coating film when viewed in the Z direction are defined, and ny and nx of The product of the difference and the film thickness d, that is, (ny-nx) · d is defined as the in-plane retardation value.

As a measuring method of in-plane phase difference value, an ellipsometer measurement is mentioned, for example. As a measurement method of the tilt angle, for example, in the measurement of the in-plane retardation value, the incident angle dependence of light is measured and calculated from curve fitting using a calculated value of the change due to the incident angle dependence of the phase difference value of the ideal refractive index ellipsoid. How to do this.

The relationship between in-plane retardation value (retardation value) and wavelength (DELTA) n ((lambda)) of an optical film can be represented by Formula (2).

Re (λ) = d × Δn (λ) (2)

In Formula (2), Re ((lambda)) shows the phase difference value in wavelength (lambda) mn, d shows a film thickness, (DELTA) n ((lambda)) shows the refractive index anisotropy in wavelength (lambda) mn.

The optical film of this invention can be used as an antireflection film, a retardation film, a viewing angle expansion film, and an optical compensation film as it is.

Moreover, the optical film of this invention can also be used in combination with another film. Specifically, the elliptically polarizing plate which affixed the optical film of this invention to the polarizing film, and the wide area | region circular polarizing plate which attached the optical film of this invention as a wide band (lambda) / 4 plate further to this elliptically polarizing plate are mentioned. have.

(Flat panel display)

The present invention can provide a flat panel display device (FPD) including the optical film. Specifically, a liquid crystal material is sandwiched between two transparent substrates on which an electrode and an alignment film are formed, and a voltage is applied to drive the liquid crystal molecules, thereby including the optical film of the present invention in a liquid crystal display element having an optical shutter effect. Liquid crystal display device (LCD) formed by attaching a polarizing plate; The light emitting layer which consists of at least 1 layer of electroconductive organic compound is formed between the transparent substrate in which an electrode was formed, and the electrode of gold, silver, aluminum, platinum, an alloy, etc., and the wide area | region containing an optical film of this invention on a transparent substrate. Organic electroluminescent (organic EL) which has a circular polarizing plate is mentioned.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to this.

Example

EMBODIMENT OF THE INVENTION Although this invention is demonstrated concretely based on an Example below, this invention is not limited to this.

<Measurement of imidation ratio>

The imidation ratio of the polymer was measured as follows. 20 mg of polymer powder is placed in an NMR sample tube (Kusano Scientific, NMR Sampling Tube Standard, φ 5 mm), 0.53 ml of deuterated dimethylsulfoxide (DMSO-d ₆ , 0.05% TMS blend) is added, and ultrasonic waves are applied. And completely dissolved. Proton NMR of 500 MHz was measured for this solution by the NMR measuring apparatus (JNM-ECP500) by the Nippon Electronics Corporation. The imidation ratio is based on the proton derived from the structure which does not change before and after imidization as a reference proton, using the peak integration value of this proton and the proton peak integration value derived from the NH group of the amic acid which appears in 10.0 ppm vicinity. It calculated | required by the following formula.

·x/y)×100Imidization ratio (%) = (1-

X / y) × 100

는 폴리아믹산 (이미드화율이 0 %) 인 경우에 있어서의 아믹산의 NH 기 프로톤 1 개에 대한 기준 프로톤의 개수 비율이다. In the above formula, x is the proton peak integration value derived from the NH group of amic acid, y is the peak integration value of a reference proton,

Is the number ratio of the reference protons to one NH group proton of the amic acid in the case of polyamic acid (imidation ratio of 0%).

<Molecular weight measurement>

The molecular weight of the polymer was measured under the conditions shown below.

Gel permeation chromatography apparatus: Shodex GPC-101 (manufactured by Showa Denko Co., Ltd.) Column: Shodex KD-803 and KD-805 (manufactured by Showa Denko Co., Ltd.), temperature 50 ° C., flow rate 1 ml / min.

Eluent: N, N-dimethylformamide (containing 30 mmol / L lithium bromide monohydrate, 30 mmol / L phosphoric anhydride crystal and 30 mmol / L tetrahydrofuran)

Standard sample for preparing molecular weight calibration curve: TSK standard polyethylene oxide (molecular weight 900000, 150000, 100000, 30000, manufactured by Toso Corporation) and polyethylene oxide (molecular weight 12000, 4000, 1000, manufactured by Polymer Laboratories)

<Adhesiveness>

According to JIS K5600, the cross cut test of the obtained optical film was performed and the adhesiveness of an orientation film and a coating layer was evaluated.

(Example 1)

Synthesis of Polymer

19.22 g (0.098 mol) of "AN1" represented by a following formula as an acid dianhydride, and 26.43 g (0.1 mol) of "DA1" represented by a following formula as this polyhydric amine in 259 g of N-methylpyrrolidone (NMP) It was made to react at room temperature for 5 hours, and the polymer solution which has a polyamic acid as a main component was prepared. This polymer had a number average molecular weight of about 17000 and a weight average molecular weight of about 47000. NMP and butyl cellosolve are added and stirred to 40 g of the polymer solution containing polyamic acid as a main component, and the polymer is prepared so as to be 6% by weight, 74% by weight of NMP, and 20% by weight of butyl cellosolve, and then It filtered under pressure with the membrane filter of 1 micrometer in diameter, and obtained the solution containing a polymer.

[Formula 20]

<Method for Producing Alignment Film>

1 weight part of aminoorganosiloxane ("ADD1") represented by a following formula was mixed with the solution containing the said polymer with respect to a total of 100 weight part of acid anhydride and diamine, and the polymer composition for oriented film formation was prepared.

[Formula 21]

Subsequently, the said polymer composition was spin-coated to the glass substrate of thickness 0.7mm, it dried at 120 degreeC for 1 minute at 50 degreeC for 1 minute, and formed the polymer of 107 nm. Next, the polymer of the film shape is rubbed at a time of rayon (manufactured by Yoshikawa Chemical Co., Ltd., brand name `` YA-20-R '') once at a rotational speed of 500 rpm, an indentation amount of 0.15 mm, and a stage speed of 16.7 mm / sec. Was prepared.

<Optical film>

On the said orientation film A, the composition (henceforth "liquid crystal composition A") containing a polymeric liquid crystal compound (rod-shaped polymeric liquid crystal compound), a polymerization initiator, and an organic solvent shown in Table 1 is spin-coated, and 55 degreeC It dried for 1 minute, and formed the liquid crystal compound containing layer. It was confirmed that this liquid crystal compound containing layer was a monodomain by polarizing microscope observation. Subsequently, ultraviolet rays were irradiated to polymerize the polymerizable liquid crystal compound to obtain an optical film having a coating layer (film thickness 796 nm) on the alignment film. Table 3 shows the evaluation results of the obtained optical film. The front retardation value of the coating layer was measured by a measuring instrument (KOBRA-WR, manufactured by Oji Instrument Co., Ltd.), and the birefringence was 126 mn. As a result of evaluating adhesiveness, peeling was not confirmed between the alignment film and the coating layer. Here, in Table 3, 0/25 means that zero peeling was confirmed among 25 test pieces.

(Example 2)

<Optical film>

An optical film was produced in the same manner as in Example 1 except that the coating layer was formed on the alignment film A using the composition shown in Table 2 (hereinafter, referred to as "liquid crystal composition B") instead of the liquid crystal composition A. . Table 3 shows the results of the evaluation.

(Example 3)

<Preparation of mixed solution containing a polymer>

30.03 g (0.1 mol) of "AN2" represented by the following formula as an acid dianhydride, 7.93 g (0.03 mol) of "DA1" as this polyhydric amine, and 13.88 g (0.07 mol) of "DA2" represented by the following formula as another polyhydric amine ) Was reacted at 50 ° C. for 24 hours in NMP 294 g to prepare a polymer solution containing polyamic acid as a main component. This polymer solution was diluted to 5 weight% with NMP, 47.5 g of pyridine and 102.1 g of acetic anhydride were added as imidation catalyst, and it was made to react at 40 degreeC for 3 hours. The solution was poured into 4.2 L of methanol, and the obtained precipitate was separated by filtration and dried to obtain a white powder. The obtained powder was a polymer whose number average molecular weight is about 9000, the weight average molecular weight is about 46000, and the imidation ratio is 80%. 34.5 g of (gamma) -butyrolactone was added to 3 g of the said powders, and it stirred for 20 hours and made it melt | dissolve at 50 degreeC. (Gamma) -butyrolactone and dipropylene glycol monomethyl ether are added to this solution, and the mixture is stirred, so that the powder is 6% by weight, 79% by weight of -butyrolactone and 15% by weight of dipropylene glycol monomethyl ether. After the preparation, the mixture was filtered under pressure with a membrane filter having a pore diameter of 1 μm, and aminoorganosiloxane (ADD2) was added to prepare a polymer composition for forming an alignment film.

[Formula 22]

<Method for Producing Alignment Film>

The polymer composition was applied and dried in the same manner as in Example 1 to form a 100 nm film-like polymer. Next, the film-like polymer was rubbed in the same manner as in Example 1 to obtain an alignment film B.

<Optical film>

On the said oriented film B, operation similar to Example 1 was performed using liquid crystal composition A, and the optical film was manufactured by forming a coating layer.

(Examples 4-11, Comparative Examples 1 and 2)

An optical film was produced in accordance with Example 1 except that the conditions of the alignment film and the coating layer were changed as shown in Table 3.

As can be seen from Table 3, according to the optical film of the present invention, it was confirmed that the adhesion between the alignment film and the coating layer was very good.

The optical film of this invention is excellent in the adhesiveness of an orientation film and a coating layer sufficiently, and can be used for antireflection films, such as an anti-reflection (AR) film, a polarizing film, retardation film, an elliptical polarizing film, and a viewing angle expansion film. Moreover, the optical film of this invention can be used for flat panel display devices (FPD), such as a liquid crystal display device (LCD) and organic electro luminescence (EL).

Claims (9)

As an optical film provided with an orientation film and the coating layer formed on this orientation film, The alignment film contains a polymer comprising a structural unit derived from a polyvalent amine compound having at least two amino groups and at least one olefinically unsaturated bond, The said coating layer is an optical film which is a layer which shows birefringence containing the structural unit derived from a polymeric liquid crystal compound. The method of claim 1, The optical film whose said polyhydric amine compound is a compound represented with the following general formula (I). [Formula 1]

[In formula (I), R <^1> represents a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, a1 represents a C5-14 trivalent aromatic group, and a2 represents a C1-C20 alkyl which may be branched. A benzene group, a divalent cyclic hydrocarbon group or a single bond, b represents -C≡C-, -CH = CH-, -O-, -S-, -C (= O)-, -C (= O ) -O-, -OC (= O)-, -OC (= O) -O-, -C (= S)-, -C (= S) -O-, -OC (= S)-,- OC (= S) -O-, -CH = N-, -N = CH-, -N = N-, -N (→ O) = N-, -N = N (→ O)-, -C ( = O) -NR-, -NR-C (= O)-, -NR-, -CH ₂ O-, -SCH _2- , -CH ₂ S-, -CH = CH-C (= O) -O Or a divalent group or a single bond represented by -OC (= O) -CH = CH-, and each R independently represents a hydrogen atom or an alkyl group. Provided that the carbon atom contained in a1 may be substituted with a nitrogen atom, an oxygen atom, a sulfur atom or a sulfonyl group (-SO _2- ), and the hydrogen atom contained in a1 may be a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyl group. And a C 1-6 alkoxy group, carboxyl group, acryloyl group or methacroyl group may be substituted.] The method of claim 1, The optical film whose said polyhydric amine compound is a compound represented by the following general formula (II). [Formula 2]

[In formula (II), R <^1> represents a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, a1 represents a C5-C14 trivalent aromatic group, However, a carbon atom contained in a1 represents a nitrogen atom, An oxygen atom, a sulfur atom or a sulfonyl group (-SO _2- ) may be substituted, and the hydrogen atom contained in a1 may be a halogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, or an acryl. Or may be substituted with a royl group or a methacroyl group.] The method of claim 1, The optical film in which the said oriented film contains the polymer of the said polyhydric amine compound and an acid dianhydride. The method of claim 1, The optical film which is a layer which the said coating layer apply | coats the solution containing the said polymeric liquid crystal compound on the said oriented film, and can polymerize and form the said polymeric liquid crystal compound. The method of claim 1, The optical film whose said polymeric liquid crystal compound is a compound represented by following General formula (1). P1-E1-B1-A1-B2-A2-B3-A3-B4-E2-P2 (1) In formula (1), A1, A2 and A3 are each independently a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylenephenylene group, an oxyphenylene group or a thiophenylene group (however, in these groups, an alkyl group, an alkoxy group or Halogen atoms may be bonded to each other. -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -C (= S)-, -C (= S) -O-, -OC (= S)-, -OC (= S) -O-, -CH = N-, -N = CH-, -N = N-, -N (→ O) = N-, -N = N (→ O) -, -C (= 0) -NR-, -NR-C (= 0)-, -NR-, -CH ₂ O-, -SCH _2- , -CH ₂ S-, -CH = CH-C ( Represents a divalent group or a single bond represented by = O) -O- or -OC (= O) -CH = CH-, each R independently represents a hydrogen atom or an alkyl group, and each of E1 and E2 independently represents carbon number; 2-25 alkylene groups (however, an alkyl group, an alkoxy group, or a halogen atom may be bonded) are represented, and P1 and P2 are each independently a hydrogen atom or a polymerizable property. (Where, P1 is a group and at least one is a polymerization of the property P2) it shows a.; The method of claim 1, The polymerizable liquid crystal compound is represented by the following formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), The optical film which is a compound represented by (1-8), (1-9) or (1-10). [Formula 3]

The flat panel display device provided with the optical film as described in any one of Claims 1-7. A process for preparing a polymer composition containing a polymer of a polyhydric amine compound having at least two amino groups and at least one olefinically unsaturated bond, and an acid dianhydride; Applying the polymer composition onto a support base material and subjecting the film obtained by drying to form an alignment film; The manufacturing method of the optical film provided with the process of apply | coating the solution containing a polymeric liquid crystal compound on the said oriented film, and superposing | polymerizing the said polymeric liquid crystal compound to form a coating layer.

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