TWI398665B - Optical film and process for producing the same - Google Patents

Description

Optical film and its preparation method

The present invention relates to optical films for optical components. More specifically, it relates to an optical film used for polarization control in the field of optics such as displays, optoelectronics, and the like.

Conventionally, in the field of optics such as displays and optoelectronics, optical films such as phase difference plates and viewing angle-improving films have been used. These optical films have various uses, and in recent years, in particular, they are mostly used for polarization control of liquid crystal display elements.

When a phase difference plate, that is, a linearly polarized light that vibrates in a mutually perpendicular direction passes through a plate, a birefringent plate having a set optical path difference therebetween is provided. The retardation plate to be used generally has a type of one-fourth of a-half, one-wavelength plate, and the like according to the ratio of the obtained optical path difference to the wavelength of light used in vacuum.

Such a phase difference plate has conventionally used a thin plate in which muscovite is cleaved at an appropriate thickness, or a synthetic resin sheet in which molecules are aligned in a single direction. However, if the phase difference plate obtained by muscovite is opened, there will be a problem that a large area cannot be obtained. Further, a phase difference plate composed of a synthetic resin sheet which is aligned in a single direction has a problem that its optical characteristics are not sufficiently uniform in the plane. Further, the phase difference plate obtained by the above method has the same continuous optical characteristics, and cannot provide different optical characteristics in the in-plane plural domain.

In another method of producing a phase difference plate, a method in which a resin film which is not stretched is uniformly aligned on a rubbed polymer film to uniformly align the liquid crystal is known (see Patent Documents 1 and 2). According to this method, a phase difference plate having uniform optical characteristics in the plane can be obtained. However, even in the case of using this method, in order to obtain an optical film having different optical characteristics in the in-plane complex domain, the so-called complicated process system in which the protective layer is provided by the lens and rubbed is necessary.

In order to solve such problems, Patent Document 3 discloses that a photosensitive film formed on a substrate is formed by irradiating polarized or unpolarized radiation to form a liquid crystal alignment film, and then, by using the optical film on the alignment film The functional liquid crystal material is aligned to form a layer having the desired optical properties, and in addition, the layer is cured to form an optical functional layer.

However, in such a method using an alignment film, the coating step of the alignment film, the alignment treatment step, the step of matching the liquid crystal material, and the like, and the production steps are still complicated, and thus there is a problem that the production cost is high.

The viewing angle-improved film is used for the purpose of improving the viewing angle of the liquid crystal display element, and the refractive characteristics of the liquid crystal display element have appropriately compensated refractive properties. As described above, in order to improve the appropriate refractive characteristics of the film at the viewing angle, the refractive index round body has a shape and a tilt.

In the conventional method, a method of curing the disc-shaped liquid crystal after oblique alignment of the polymer film on the alignment treatment is known (see Patent Document 4). However, in this method, the coating step of the alignment film, the alignment treatment step, the alignment step of the liquid crystal material, and the like are complicated, and thus the production cost of the optical film is high. Further, if this method is to be used to obtain an optical film having various optical characteristics in the in-plane plural domain, it is necessary to provide a so-called complicated process system in which a protective layer is provided by a lens and rubbed.

[Patent Document 1] JP-A-2001-129927 (Patent Document 3) Japanese Patent Publication No. 2002-172111 [Patent Document 4] Japanese Patent Publication No. Hei 7-98411

A first object of the present invention is to provide an optical film useful for optical field control such as a display or photovoltaic.

A second object of the present invention is to provide an optical film for polarization control of a refractive index round body having an arbitrary shape which is arbitrarily inclined.

A third object of the present invention is to provide an optical film for polarization control having different optical characteristics in a plurality of fields in the plane.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are achieved by forming an optical film characterized by an optically anisotropic layer by irradiating polarized light or unpolarized radiation in a photosensitive film.

According to the present invention, an optical film excellent in in-plane uniformity can be easily obtained, and when it is combined with a liquid crystal cell, light control can be effected, and thus a liquid crystal element having excellent electrooptical characteristics can be produced. Further, according to the present invention, since an optical film having a refractive index round body having an arbitrary inclination and an arbitrary shape can be easily obtained, when it is combined with a liquid crystal cell, the most appropriate optical correction can be performed, and the production is excellent. A liquid crystal element having a viewing angle characteristic.

Further, according to the present invention, since optical films having different optical characteristics in the in-plane plural domain can be easily obtained, different optical designs can be performed in various fields in the in-plane of the electro-optical elements using the same.

Therefore, the optical film of the present invention can be effectively used in various devices such as display elements which can be used locally for desktop computers, watches, clocks, coefficient display panels, word processors, personal computers, liquid crystal televisions and the like.

Further, an optical film having different optical characteristics in the in-plane plural domain is useful even in the case of constituting an optical element using polarized holography, and can be suitably used, for example, in a device such as a light emitter.

[Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail.

Photosensitive polymer

The photosensitive film used in the present invention is advantageous in that it contains a photosensitive polymer having an induction radiation structure. Here, "induction" means that when radiation is received, the energy level is raised by the photoexcitation reaction, and then the energy is released to return to the stable state.

These structures are exemplified by a conjugated ketene structure (hereinafter also referred to as "specific structure") represented by the following formulas (I), (II), and (III).

-P ¹ -CR ¹ =CR ² -CO-Q ¹ - (I)P ² -CR ³ =CR ⁴ -CO-Q ² - (II)-P ³ -CR ⁵ =CR ⁶ -CO-Q ³ ( In the formula III), P ¹ , P ³ , Q ¹ , and Q ² each independently have a divalent organic group of an aromatic ring, and P ² and Q ³ independently have a monovalent organic group of an aromatic ring, and R ¹ And R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group.

In the above formulas (I), (II) and (III), P ¹ , P ³ , Q ¹ and Q ² have a divalent organic group of an aromatic ring, and P ² and Q ³ have a monovalent organic group of an aromatic ring. base. P ¹ , P ² , P ³ , Q ¹ , Q ² and Q ³ are preferably an organic group having an aromatic ring having 6 to 20 carbon atoms which may be substituted by a halogen atom.

Specific examples of the monovalent organic group (P ² , Q ³ ) having an aromatic ring include a phenyl group, a 4-methoxyphenyl group, a 4-pentylphenyl group, a 4-octylphenyl group, and a 4-fluoro group. Phenyl, 3-methoxyphenyl, 3-pentylphenyl, 3-octylphenyl, 3-fluorophenyl, 3,4-difluorophenyl, 3,4,5-trifluoro Phenyl, 4-trifluoromethylphenyl, 3-trifluoromethylphenyl, biphenyl, 4-pentylbiphenyl, 4-octylbiphenyl, 4-fluorobiphenyl, 3 ,4-difluorobiphenyl, 3,4,5-trifluorobiphenyl, 1-naphthyl, 4-octyl-1-naphthyl, 5-pentyl-1-naphthyl, 2-naphthalene Base, 6-octyl-2-naphthyl, 9-fluorenyl, 10-octyl-9-fluorenyl, 10-pentyl-9-fluorenyl. They may be the same or different from each other.

Further, the divalent organic group (P ¹ , P ³ , Q ¹ , Q ² ) having an aromatic ring may, for example, be a 1,2-phenylene group or a 3-fluoro-1,2-phenylene group. 4-fluoro-1,2-phenylene, 3-methoxy-1,2-phenylene, 4-methoxy-1,2-phenylene, 3-methyl-1,2- Phenyl, 4-methyl-1,2-phenylene, 1,3-phenylene, 2-fluoro-1,3-phenylene, 4-fluoro-1,3-phenylene , 5-fluoro-1,3-phenylene, 2-methoxy-1,3-phenylene, 4-methoxy-1,3-phenylene, 5-methoxy-1, 3-phenylene, 2-methyl-1,3-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 1,4-stretch Phenyl, 2-fluoro-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-methyl-1,4-phenylene, 4,4'-extension Phenyl, 3,4'-extended biphenyl, 3,3'-extended biphenyl, and the like. They may be the same or different from each other.

Further, in the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably hydrogen. atom. These alkyl groups may be linear or branched, and may be the same or different from each other.

The photosensitive polymer used in the present invention may, for example, have the above specific structure in the main chain or the side chain. Since the obtained optical directionality is large, it is preferable that the side chain has the above specific structure. The skeleton of the above-mentioned photosensitive polymer is not particularly limited, and specific examples thereof include (1) polyphthalate (2) polystyrene derivative, and (3) poly(styrene-co-phenyl horse). An acetal imide derivative, and (4) a poly(meth) acrylate derivative. Among these, from the viewpoint of heat resistance, (1) polyphthalate (2) polystyrene derivative, and (3) poly(styrene-co-phenylmaleic anhydride) Amine derivatives are preferred.

Among the above-mentioned photosensitive polymers, the ratio of the repeating unit having a specific structure is preferably from 10 to 100%, particularly preferably from 50 to 90%, in the total repeating unit.

Further, the photosensitive polymer is preferably an organic group represented by the following formula (IV) (hereinafter also referred to as "specific mesogens") to increase the optical anisotropy.

-P ⁴ -T ⁴ -Q ⁴ - (IV) In the formula, P ⁴ and Q ⁴ represent a divalent aromatic ring, a heterocyclic ring or an alicyclic ring, and then T ⁴ represents a single bond or a divalent bonded group.

Specific examples of the divalent aromatic ring, heterocyclic ring or alicyclic ring (P ⁴ , Q ⁴ ) include 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methoxy -1,4-phenylene, 2-methyl-1,4-phenylene, 4,4'-extended biphenyl, 2,6-naphthylene, 2,6-anthracene, 1, 3-cyclobutenyl, 1,4-cyclohexyl, 1,2,3,4-tetrahydro-2,6-naphthylene, 1,2,3,4-tetrahydro-2,6- Naphthylene, 1,2,3,4,5,6,7,8,9,10-decahydro-2,6-naphthylene and the like. They may be the same or different from each other.

Specific examples of the divalent binding group represented by T ⁴ include a keto group, an ether bond, an ester bond, a guanamine bond, a urethane bond, a urea bond, a vinylidene group, an ethynyl group, an azo group, and an even group. The nitroxide group, the methylenimine group, the methylene chain having 1 to 10 carbon atoms, and the bonding group are selected from the group consisting of two or more groups in which the above-mentioned bonding groups are the same or different. Among these, -O- (wherein an ester bond, a guanamine bond, a methylene chain of 2 carbon atoms, and a bond of an ether bond to a methylene chain of 2 carbon atoms) The group represented by CH ₂ ) ₂ -O- is preferred.

The specific mesogen may be introduced into the main chain and/or the side chain of the above-mentioned photosensitive polymer. Since the obtained optical anisotropy is large, it is preferred to introduce into the side chain. When the specific mesogen is introduced into the side chain of the photosensitive polymer, it may coexist in the same side chain as the specific structure described above, or may coexist in a side chain not containing the specific structure. Further, it may be combined with a side chain in which a specific structure coexists with a specific mesogen, a side chain containing only a specific structure, and/or a side chain containing only a specific mesogen. Further, the side chain in which the specific structure coexists with the specific mesogen may be a position close to the main chain bonding site in any one of the specific structure and the specific mesogen.

Further, in the case where a specific structure and a specific mesogen coexist in the main chain or in the side chain, the organic groups P ¹ , P ³ , Q ¹ and Q ^{2 in the} specific structures (I) to (III), With respect to the organic group P ⁴ or Q ⁴ in the specific meso form (IV), a part or all of its structure may be shared.

The polyperurethane is a polyamic acid obtained by polycondensing (a) a tetracarboxylic dianhydride represented by the following (V) with (b) a diamine compound represented by the following (VI). It is obtained by reacting with (c) a halide having a specific structure, an alcohol having a specific structure, or a phenol having a specific structure.

In the formula, S ⁵ is a tetravalent organic group.

In the formula of H ₂ N-T ⁶ -NH ₂ (VI), T ⁶ is a divalent organic group.

The tetracarboxylic dianhydride (A) represented by the above formula (V) used in the synthesis of the polyphthalate may, for example, be butane tetracarboxylic dianhydride or 1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3', 4, 4,-cyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4, 5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxy-3-furanyl)-naphthalene [1,2-c ]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5(tetrahydro-2,5-dioxy-3-furanyl)- Naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5(tetrahydro-2,5-dioxy -3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3 ,3a,4,5,9b-hexahydro-7-methyl-5(tetrahydro-2,5-dioxy-3-furanyl)-naphthalene[1,2-c]-furan-1,3 -dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5(tetrahydro-2,5-dioxy-3-furanyl)-naphthalene [1,2-c ]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5(tetrahydro-2,5-dioxy-3-furanyl)- Naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,45,9b-hexahydro-8-ethyl-5(tetrahydro-2,5-dioxy-3 -furyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5(tetrahydrogen) -2,5-dioxy-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 5-(2,5-dioxytetrahydrofuran)-3-methyl -3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, diamine diamine Acetic acid dianhydride, 3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-tetrahydrofuran-2,5'-dione, and the following formula (VII) And an aliphatic or alicyclic tetracarboxylic dianhydride of a compound represented by (VIII);

(wherein R ⁷ and R ⁹ represent a divalent organic group having an aromatic ring, R ⁸ and R ^{1 0} are a hydrogen atom or an alkyl group, and the plural R ⁸ and R ^{1 0} groups may be the same or different) Pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,4 , 5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ',4,4'-diphenylmethanetetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenyldecanetetracarboxylic dianhydride, 3,3',4,4'- Tetraphenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulphuric anhydride, 4 , 4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3 ',4,4'-Perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide Di-anhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl-bis(triphenylphthalic acid) dianhydride, bis(triphenylbenzenedioic acid) )-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(1,2,4-benzene tris) Anhydride), propylene glycol-bis(1,2,4-benzenetricarboxylic anhydride), 1,4-butanediol-bis(1,2,4-benzenetricarboxylic anhydride), 1,6-hexanediol-double (1) , 2,4-benzenetricarboxylic anhydride), 1,8-octanediol-bis(1,2,4-benzenetricarboxylic anhydride), 2,2-bis(4-hydroxyphenyl)propane-bis (1,2 , 4-benzenetricarboxylic anhydride), 2,3,4,5-pyridinetetracarboxylic dianhydride, and 2,6-bis(3,4-dicarboxyphenyl)pyridine dianhydride, the following formula (1)~ (18) An aromatic or heterocyclic tetracarboxylic dianhydride such as a compound represented by the above. They may be used alone or in combination of two or more.

Among these, for example, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,3-dimethyl-1,2,3,4-ring may be mentioned. Butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxy Tetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di Oxy-3-furanyl)-naphthalene[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(four Hydrogen-2,5-dioxy-3-furanyl)-naphthalene[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5, 8-Dimethyl-5-(tetrahydro-2,5-dioxy-3-furanyl)-naphthalene [1,2-c]furan-1,3-dione, bicyclo[2,2, 2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenylindole tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and the following formula (19) among the compounds represented by the above formula (VII) a compound represented by ~(21) and represented by the above formula (VIII) Among the compound of the following formula the compound (22) represented by the better. Further, particularly preferred are 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride. 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy-3-furanyl)- Naphthalene [1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxy -3-furyl)-naphthalene [1,2-c]furan-1,3-dione, pyromellitic dianhydride, and a compound represented by the following formula (19).

They may be used alone or in combination of two or more.

Further, as the (di)diamine compound used in the synthesis of the polyphthalate, for example, p-phenylenediamine, meta-phenylenediamine, 4,4'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylphosphonium, 3,3'-dimethyl-4, 4'-Diaminobiphenyl, 4,4'-diaminophenylguanamine benzene, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3-di Methyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1 -(4'-aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ketone, 3 , 4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 - bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4 -aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-double (3-Aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroxyindenyl, 2,7-diaminopurine, 9,9-bis(4-amino Phenyl) fluorene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4,-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl,3,3'-dimethoxy-4,4'-diaminobiphenyl, 1, 4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylphenylidene)diphenylamine, 2,2'-bis[4-(4-amino group -2-trifluoromethylphenethyl)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-double [(4-Amino-2-trifluoromethyl)phenethyl]-octafluorobiphenyl, 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy -2,4-diaminobenzene, 1-pentadecanyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy Base-2,4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, 1 (4,4- Dimethyl-choline nest 2,4-en-3-yloxy)-2,4-diaminobenzene, 1(4,4-dimethyl-cholest-5,24-dien-3-yloxy)-2 , 4-diaminobenzene, dodecyloxy (3,5-diaminobenzimidyl), tetradecyloxy (3,5-diaminobenzimidyl), pentadecyloxy (3,5-diaminobenzimidyl),hexadecanyloxy (3,5-diaminobenzimidyl), octadecyloxy (3,5-diaminobenzimidamide) Base), cholestyloxy (3,5-diaminobenzimidyl), cholestyloxy (3,5-diaminobenzimidyl), 4,4-dimethyl-cholesteryl -24-dien-3-yloxy (3,5-diaminobenzimidyl), 4,4-dimethyl-cholest-5,24-dien-3-yloxy (3 ,5-diaminobenzimidyl), (2,4-diaminophenethyl)palmitate, (2,4-diaminophenethyl) stearate, (2,4- An aromatic diamine such as a diaminophenethyl)-4-trifluoromethylbenzoate or a compound represented by the following formulas (23) to (24);

M-xylylenediamine, diamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, seven Methyldiamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecyldiamine, dodecamethylenediamine, 4,4-diamine-7 Methylene diamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-bis(aminomethyl) ring Hexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, tetrahydrobicyclopentadiene diamine, six Hydrogen-4,7-methanol is extended to succinyldimethylenediamine, tricyclo[6.2.1.0 ^{2 , 7} ]-undecene dimethyldiamine, bis(4-aminocyclohexyl)methane, Bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(2-aminoethyl)ether, bis(3-amine Propyl)ether, 1,2-bis(2-aminoethoxy)ethane, 1,3-bis(2-aminoethoxy)propane, 1,4-bis(2-aminoethoxy) Butane, 1,4-double ( 2-aminoethoxy)butane, 1,5-bis(2-aminoethoxy)pentane, 1,6-bis(2-aminoethoxy)hexane, 1,2-double (3-Aminopropoxy)ethane, 1,3-bis(3-aminopropoxy)propane, 1,4-bis(3-aminopropoxy)butane, 1,4-double Aliphatic groups such as (3-aminopropoxy)butane, 1,5-bis(3-aminopropoxy)pentane, and 1,6-bis(3-aminopropoxy)hexane And alicyclic diamine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino -2,3-dicyanopyridine ,5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-three 1,4-bis(3-aminopropyl)per 2,4-Diamino-6-isopropoxy-1,3,5-three 2,4-diamino-6-methoxy-1,3,5-three 2,4-diamino-6-phenyl-1,3,5-three 2,4-diamino-6-methyl-5-three 2,4-diamino-1,3,5-three 4,6-diamino-2-vinyl-5-three , 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-diamine Piper 1,4-bis(2-aminoethyl)perazine 1,4-bis(3-aminopropyl)per And 3,6-diamino acridine, bis(4-aminophenyl)phenylamine, and a compound represented by the following formula (IX) to (X), and having two primary amines in the molecule; a diamine having a nitrogen atom other than the amine group of the first stage;

Wherein R ^{1 1} represents a ring having a nitrogen-containing atom and is selected from the group consisting of pyridine, pyrimidine, and tri Piperidine and piperazine a monovalent organic group, X ¹ represents a divalent organic group)

Wherein X ² represents a ring having a nitrogen-containing atom and is selected from the group consisting of pyridine, pyrimidine, and tri Piperidine and piperazine Divalent organic group, R ^{1 2} denotes a divalent organic group-based, and the two siloxane diamino silicones represented by X ² may be the same or different) by the following formula (XI);

(Wherein, R ^{1 3} lines represents a hydrocarbon group having 1 to 12, there is a plurality of R ^{1 3} may be the same or different, q is an integer of 1 to 3, r is an integer of 1 to 20) may be exemplified by the following formula ( 25) The compound shown in ~(26). These diamine compounds may be used alone or in combination of two or more.

(wherein, y is an integer of 2 to 12, and z is an integer of 1 to 5) among these, P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,7-diaminoguanidine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-( 4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylphenyldiisopropylidene)diphenylamine, 4,4'-(m-stretch Phenyldiisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, a compound represented by the above formula (23) to (24), 2 , 6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, the compound represented by the above formula (IX): 27) The compound represented by the above formula (X), the following formula (2) 8) The compound represented by the above formula and the compound represented by the above formula (XI) are preferably 1,3-bis(3-aminopropyl)tetramethyldioxane.

They may be used alone or in combination of two or more.

Further, a diamine compound having a specific mesogen may, for example, be 4-(4-trans-n-heptylcyclohexylphenoxy)-1,3-diaminobenzene or 4-(4-trans-heptane). Cyclohexylphenoxy)-1,3-diaminobenzene, 4-trans-pentyldicyclohexyl-3,5-diaminobenzoate, 4-[3-(4-biphenyl) Oxy)propoxy]-1,3-diaminobenzene, 4-[8-(4-biphenyloxy)octyloxy]-1,3-diaminobenzene, 4-[3- (4-cyanobiphenyl-4'-oxy)propoxy]-1,3-diaminobenzene, 4-[12-(4-cyanobiphenyl-4'-oxy)-10 Dialkoxy]-1,3-diaminobenzene, 4-[6-(4-methoxybiphenyl-4'-oxy)hexyloxy]-1,3-diaminobenzene, 4-[12-(4-methoxybiphenyl-4'-oxy)dodecyloxy]-1,3-diaminobenzene, 4-[3-(4-fluorobiphenyl) -4'-oxy)propoxy]-1,3-diaminobenzene, 4-[3-(4-trifluoromethoxybiphenyl-4'-oxy)propoxy]-1 , 3-diaminobenzene, and 5-[6-(4-cyanobiphenyl-4'-oxy)hexyl]-3,5 Diamino benzoate. They may be used alone or in combination of two or more.

Further, a halide having a specific structure of (C) used in the synthesis of polyphthalate is specifically, for example, 1-bromo-3-(4-carbonyloxy)propane or 1-bromo-3. -(4'-carbonyloxy)propane, 1-bromo-4-(4-carbonyloxy)butane, 1-bromo-4-(4'-carbonyloxy)butane, 1-bromo -6-(4-carbonyloxy)hexane, 1-bromo-6-(4'-carbonyloxy)hexane, 1-bromo-8-(4-carbonyloxy)octane, 1- Bromo-8-(4'-carbonyloxy)octane, 1-bromo-3-(4'-fluoro-4-carbonyloxy)propane, 1-bromo-3-(4-fluoro) -4'-carbonyloxy)propane, 1-bromo-4-(4'-fluoro-4-carbonyloxy)butane, 1-bromo-4-(4-fluoro-4'-carbonyl Oxy)butane, 1-bromo-6-(4'-fluoro-4-carbonyloxy)hexane, 1-bromo-6-(4-fluoro-4'-carbonyloxy) Alkane, 1-bromo-8-(4'-fluoro-4-carbonyloxy)octane, 1-bromo-8-(4-fluoro-4'-carbonyloxy)octane, 1- Bromo-3-(4'-A 4-carbonyloxy)propane, 1-bromo-3-(4-methoxy-4'-carbonyloxy)propane, 1-bromo-4-(4'-methoxy-4- Carbonyloxy)butane, 1-bromo-4-(4-methoxy-4'-carbonyloxy)butane, 1-bromo-6-(4'-methoxy-4-carbonyloxy a bromide such as hexane or 1-bromo-6-(4-methoxy-4'-carbonyloxy)hexane, and a bromine atom of the above bromide is substituted by a fluorine atom, a chlorine atom or an iodine atom. Compound. They may be used alone or in combination of two or more. Among these, in order to improve the reactivity and ease of synthesis, bromide is preferred, especially 1-bromo-6-(4-carbonyloxy)hexane, 1-bromo-6-(4' -carbonyloxy)hexane, 1-bromo-8-(4-carbonyloxy)octane, 1-bromo-8-(4'-carbonyloxy)octane, 1-bromo-6- (4'-Methoxy-4-carbonyloxy)hexane, 1-bromo-6-(4-methoxy-4'-carbonyloxy)hexane, 1-bromo-8-(4 '-Methoxy-4-carbonyloxy)octane and 1-bromo-8-(4-methoxy-4'-carbonyloxy)octane are particularly preferred.

Further, a halide having a specific structure and a specific mesogen may, for example, be 1-bromo-6-(4'-phenyl-4-carbonyloxy)hexane or 1-bromo-6-( 4-phenyl-4'-carbonyloxy)hexane, 1-bromo-8-(4'-phenyl-4-carbonyloxy)octane, 1-bromo-8-(4-phenyl -4'-carbonyloxy)octane, 1-bromo-6-(4'-(2-phenoxyethoxy)-4-carbonyloxy)hexane, 1-bromo-6-( 4-(2-phenoxyethoxy)-4'-carbonyloxy)hexane, 1-bromo-8-(4'-(2-phenoxyethoxy)-4-carbonyloxy Octane, 1-bromo-8-(4-(2-phenoxyethoxy)-4'-carbonyloxy)octane, 1-bromo-6-(4'-(2-benzene) Ethyl)-4-carbonyloxy)hexane, 1-bromo 6-(4-(2-phenylethyl)-4'-carbonyloxy)hexane, 1-bromo-8-(4' -(2-Phenylethyl)-4-carbonyloxy)octane, 1-bromo-8-(4-(2-phenylethyl)-4'-carbonyloxy)octane, 1-bromo -6-(4'-cyclohexyl-4-carbonyloxy Hexane, 1-bromo-6-(4-cyclohexyl-4'-carbonyloxy)hexane, 1-bromo-8-(4'-cyclohexyl-4-carbonyloxy)octane, 1 -bromo-8-(4-cyclohexyl-4'-carbonyloxy)octane, 1-bromo-6-(4'-(2-(cyclohexyloxy)ethoxy)-4-carbonyl Oxy)hexane, 1-bromo-6-(4-(2-(cyclohexyloxy)ethoxy)-4'-carbonyloxy)hexane, 1-bromo-8-(4' -(2-(cyclohexyloxy)ethoxy)-4-carbonyloxy)octane, 1-bromo-8-(4-(2-(cyclohexyloxy)ethoxy)-4' -carbonyloxy)octane, 1-bromo-6-(4'-(2-cyclohexylethyl)-4-carbonyloxy)hexane, 1-bromo-6-(4-(2- Cyclohexylethyl)-4'-carbonyloxy)hexane, 1-bromo-8-(4'-(2-cyclohexylethyl)-4-carbonyloxy)octane, 1-bromo- 8-(4-(2-Cyclohexylethyl)-4'-carbonyloxy)octane, 1-bromo-6-(4-(4-carbonyl)phenoxy)hexane, 1-bromo -6-(4-(4'-carbonyl)benzene Hexyl, 1-bromo-8-(4-(4-carbonyl)phenoxy)octane, 1-bromo-8-(4-(4'-carbonyl)phenoxy)octane, 1-bromo-6-(4-(4'-methoxy-4-carbonyl)phenoxy)hexane, 1-bromo-6-(4-(4-methoxy-4'-carbonyl) Phenoxy)hexane, 1-bromo-8-(4-(4'-methoxy-4-carbonyl)phenoxy)octane, 1-bromo-8-(4-(4- Methoxy-4'-carbonyl)phenoxy)octane, 1-bromo-6-(4-(4-carbonyl)cyclohexyloxy)hexane, 1-bromo-6-(4-( 4'-carbonyl)cyclohexyloxy)hexane, 1-bromo-8-(4-(4-carbonyl)cyclohexyloxy)octane, 1-bromo-8-(4-(4'- Carbonyl)cyclohexyloxy)octane, 1-bromo-6-(4-(4'-methoxy-4-carbonyl)cyclohexyloxy)hexane, 1-bromo-6-(4- (4-methoxy-4'-carbonyl)cyclohexyloxy)hexane, 1-bromo-8-(4-(4'-methoxy-4-carbonyl)cyclohexyloxy)octane, And 1-bromo-8-(4- 4-methoxy-4'-carbonyl) cyclohexyloxy) octane. They may be used alone or in combination of two or more.

(丁) An alcohol having a specific structure, and examples thereof include 4-(4-carbonyl)cyclohexanol, 4-(4'-carbonyl)cyclohexanol, and a halogen atom of the above (propyl) halide is substituted with a hydroxyl group. Compound. They may be used alone or in combination of two or more. Among these, 6-(4-carbonyloxy)-1-hexanol, 6-(4'-fluoro-4-carbonyloxy)-1-hexanol, 8-(4-carbonyloxy) 1-octanol and 8-(4'-fluoro-4-carbonyloxy)-1-octanol are preferred.

(e) a phenol having a specific structure, and examples thereof include 4-hydroxychalcone, 4'-hydroxychalcone, 4'-hydroxyfluoro-4-chalcone, 4-fluoro-4'-hydroxyl group Chalcone, 4-(4-carbonyl)phenol, 4-(4'-carbonyl)phenol, and the like. They may be used alone or in combination of two or more.

In the synthesis of the above polyglycolate, in order to improve the properties thereof and to increase the optical anisotropy, a halide having a specific structure, an alcohol or a phenol, or a specific one may be used. The halide of the structure, (D) does not contain a specific structure of alcohol or (pent') does not contain a specific structure of phenols.

The (c') does not contain a halide of a specific structure, and examples thereof include hexadecyl hexadecane, bromostyrene decane, methyl bromide, ethyl bromide, bromopropane, chlorohexadecane, chlorostearyl decane, methyl chloride, Ethyl chloride, chloropropane, 1,1,1-trifluoro-2-iodoethane, and the like. Further, a halide having no specific structure and containing a specific mesogen may, for example, be 1-bromo-3-(4-biphenyloxy)propane or 1-bromo-3-(4-cyclohexylbenzene). Oxy)propane, 1-bromo-4-(4-biphenyloxy)butane, 1-bromo-4-(4-cyclohexylphenoxy)butane, 1-bromo-6-( 4-biphenyl)hexane, 1-bromo-6-(4-cyclohexylphenoxy)hexane, 1-bromo-8-(4-biphenyloxy)octane, and 1-bromo Ben-8-(4-cyclohexylphenoxy)octane.

Further, (d) is an alcohol having no specific structure, and examples thereof include a compound in which the above-mentioned (c')-containing halogen atom of a halide having a specific structure is substituted with a hydroxyl group.

(pent') a phenol having no specific structure, and examples thereof include phenol, 4-cyclohexyl phenol, bisphenol, cresol, 4-hexadecyloxyphenol, 4-hexadecylphenol, and 4-stearyl ester. Alkyl phenol, 4-stearyl phenol and 4-trifluoromethyl phenol.

They may be used alone or in combination of two or more.

The polylysine may be obtained by polycondensing the above-mentioned (meth)tetracarboxylic dianhydride component with a (di)diamine component to obtain a polylysine, and in the presence of a catalytically desirable catalyst, It is obtained by reacting a halide having a specific structure, an alcohol having a specific structure, or a phenol having a specific structure. Further, depending on the case, in order to improve heat resistance, the residual polyaminic acid structure may be dehydrated and closed to form a quinone imine structure.

Examples of the catalyst used in the reaction of the polyamic acid with a halide having a specific structure include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium methoxide, and potassium. Alkaline catalysts such as methoxide, sodium ethoxide, potassium ethoxide, sodium propoxide, potassium propoxide, sodium butoxide, potassium butoxide, trimethylamine, triethylamine and pyridine.

Examples of the catalyst used in the reaction of polyamic acid with an alcohol or a phenol having a specific structure include dehydration catalysts such as dicyclohexylcarbodiimide and methyl chloroformate. These dehydration catalysts may be used in combination with an auxiliary catalyst such as dimethylaminopyridine.

The dehydration ring closure reaction of the poly-proline structure remaining in the polyphthalate is carried out by heating the polyphthalate or by dissolving the polyamine in N-methyl-2-pyrrole Iridone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylhydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphine triammonium Or an aprotic organic solvent such as 1,3-dimethylimidazolidone, adding a dehydrating agent such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride to the solution, and pyridine, zirconia, and lutidine. A dehydration ring-closing catalyst such as triethylamine can be carried out by heating as needed.

Further, the above polystyrene derivative (2) or poly(styrene-phenyl maleic anhydride imide derivative (3) may be substituted by a hydroxyl group-substituted polystyrene polymer or substituted by a hydroxyl group. A styrene-phenyl maleic anhydride imide polymer and a (c) halide having a specific structure are obtained by reacting in the presence of a catalyst.

The above hydroxy-substituted polystyrene polymer and hydroxy-substituted styrene-phenyl maleic anhydride imide polymer are hydroxystyrene derivatives and/or hydroxyphenyl maleic anhydride imide The derivative may be polymerized in the presence of a catalyst such as an azo compound such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide, or may be added by adding water under acidic or basic conditions. Decomposed to get.

The above hydroxystyrene derivative may, for example, be 4-ethenyloxystyrene, 3-acetoxystyrene, 4-tert-butoxystyrene, 3-tert-butoxystyrene, and 4 - Hydroxy-α-methylstyrene. Further, the above-mentioned hydroxyphenylmaleic anhydride imide derivative may, for example, be 4-ethenyloxyphenylmaleic acid imide, 3-ethyloxyphenyl maleic anhydride, or 4-hydroxyl Phenyl maleic anhydride imide, 3-hydroxyphenyl maleic anhydride imide 4-tert-butoxyphenyl maleic anhydride imide, and 3-tert-butoxyphenyl maleic anhydride Imine.

Further, in order to improve the obtained polystyrene derivative or poly(styrene-phenyl group) when synthesizing the above-mentioned hydroxy-substituted polystyrene polymer and hydroxy-substituted styrene-phenyl maleic anhydride imide polymer The properties of the maleic anhydride imide derivative and the increase of the optical anisotropy obtained can be used as a copolymerization component in combination with other radical polymerizable monomers.

(Other) other radical polymerizable monomer, for example, having, for example, 4-(4-(4-biphenyloxy)butoxy)styrene, 4-(6-(4-biphenyloxy)) Hexyloxy)styrene, 4-(8-(4-biphenyloxy)octyloxy)styrene, 4-(4-(4-biphenyloxy)butoxy)phenylmaleic anhydride Imine, 4-(6-(4-biphenyloxy)hexyloxy)phenylmaleic anhydride imide, and 4-(8-(4-biphenyloxy)octyloxy)phenyl horse a monomer of a specific mesogen such as an imide amide; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) enoate, 1-(meth) acrylate Butyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, polyethylene glycol mono(meth)acrylate An aliphatic (meth) acrylate compound such as an ester or trimethylolpropane tris(meth)acrylate; tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) Acrylic glycam An alicyclic ester of an oil ester, dicyclopentadienyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tricyclodecyl (meth)acrylate, isobornyl (meth)acrylate, etc. Acrylate compound; benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, bis(2-hydroxyethyl)trimeric isocyanate tri(meth)acrylic acid An aromatic (meth) acrylate compound such as an ester; ethylene, propylene, butylene, styrene, p-methyl styrene, p-trifluoromethyl styrene, α-methyl styrene, p-trifluoromethyl- Α-methylstyrene, 4-(4-trifluoromethylbenzyloxy)styrene, p-hexadecyloxystyrene, p-palmityloxystyrene, 4-trifluoromethylphenyl -3-(4-vinylphenyl)propionate, 4-hexadecyl-3-(4-vinylphenyl)propionate, 4-stearylmethyl-3-(4-vinylbenzene Ethylene compound of propionate, vinyl chloride, vinyl acetate, acrylonitrile, etc.; maleic anhydride, phenyl maleic anhydride, imine, 4-fluorophenyl horse Anhydride imide, 3,5-difluorophenylmaleic anhydride imide, 4-(trifluoromethyl)phenylmaleic anhydride imide, 4-(hexadecyloxy)phenyl Maleic acid derivatives such as maleic acid imide, 4-(palmitoyloxy)phenyl maleic acid imide, and the like; and dienes such as butadiene, isobutylene, and chlorobutene.

The halide used in the synthesis of the above polystyrene derivative or poly(styrene-phenylmaleic anhydride imide) derivative may, for example, be the same halogen as the previously described (c) halide having a specific structure. Compound.

In the synthesis of the above polystyrene derivative or poly(styrene-phenylmaleic anhydride imide) derivative, in order to improve the properties thereof and to increase the optical anisotropy obtained, the specific structure may be used simultaneously. Halides and halides without specific structures. Here, the halide of a specific configuration is not contained, and may be, for example, the same halogen compound as the previously mentioned (c') halide having no specific structure.

The hydroxy-substituted polystyrene polymer or the hydroxy-substituted styrene-phenyl maleic anhydride imide polymer, and the catalyst used in the reaction with the organic halide, for example, lithium hydroxide or hydroxide Sodium, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium propoxide, potassium propoxide, sodium butoxide, potassium butoxide An alkaline catalyst such as trimethylamine, triethylamine or pyridine.

Further, the above polystyrene derivative or poly(styrene-phenylmaleic anhydride imide) derivative may have a specific structure by a styrene derivative having a specific structure in a side chain and/or a side chain. The phenylmaleic anhydride imide derivative can be obtained by polymerization in the presence of a catalyst such as an azo compound such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide.

The poly(meth) acrylate derivative may be an azo compound such as azobisisobutyronitrile or a benzoyl sulfonyl group, etc., which may have a specific structure (meth) acrylate compound. It is obtained by carrying out polymerization in the presence of a catalyst such as a peroxide. Specific examples of the (meth) acrylate compound include a compound having a specific structure of a (meth) acrylate compound, for example, in JP-A-H09-335092 and JP-A-10-321617. Among these, the compound exemplified in Japanese Laid-Open Patent Publication No. Hei 10-321617 is preferable because the optical anisotropy of the obtained optical material is large.

Further, in the case of synthesizing the above poly(meth) acrylate derivative, in order to improve the properties of the obtained poly(meth) acrylate derivative, and to increase the optical anisotropy, the specific structure may be used in combination. A acrylate compound and other radical polymerizable monomers. Here, the other radical polymerizable single system is exemplified by the same compounds as the other radical polymerizable monomers previously mentioned.

These photosensitive polymers may be used singly or in combination of two or more kinds.

Photosensitive film additive

The photosensitive film used in the present invention contains the above-mentioned photosensitive polymer and various low molecular or high molecular additives in order to increase and stabilize the optical anisotropy.

The additive for the anisotropy increase of the obtained optical material may, for example, be a low molecular or high molecular weight liquid crystal compound.

The low molecular liquid crystal compound may, for example, form a Schiff base liquid crystal, a oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or an ester liquid crystal having a nematic phase, a cholesterol phase, and a smectic layer. A triphenylene liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like.

Among these, a low molecular liquid crystal compound which forms a nematic phase is preferred. More specifically, a biphenyl liquid crystal such as 4-cyano-4'-pentylbiphenyl and 4-cyano-4'-hexylbiphenyl may be exemplified.

The above molecular liquid crystal compound may also be a liquid crystal monomer having radical polymerizability. Specifically, the liquid crystal monomer may, for example, be a monoacrylate having a structure represented by the following formulas (29) to (32), or a diacrylate having a structure represented by the following formulas (33) to (37), and having A triacrylate having the structure shown by the following formulas (38) to (40).

These liquid crystal monomers can be used singly or in combination. From the viewpoint of heat resistance and transparency of the obtained optical functional layer, it is preferred to use a combination of a monoacrylate, a diacrylate or a triacrylate.

In addition, in the case where the liquid crystal monomer is contained in the photosensitive film, it is preferable to use a photoradical initiator such as benzoin for the purpose of promoting the polymerization reaction in the radiation irradiation step. For example, the polymer liquid crystals of the main chain type and the side chain type are more specifically, for example, the polymer compounds represented by the following formulas (41) to (45).

The photosensitive film used in the present invention may contain a thermosetting crosslinking agent in order to stabilize the optical anisotropy of the obtained optical film. The thermosetting crosslinking agent is effective as a compound containing a polyfunctional epoxy, and specific examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and the like. Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-di Bromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m- Xylylenediamine, 1,3-bis(N,N-diglycidylaminemethyl)cyclohexane, and N,N'N',N',-tetraglycidyl-4,4'-di Aminodiphenylmethane and the like.

Further, the thermosetting crosslinking agent is a polymer compound having a thermosetting group in a side chain. Examples of the polymer compound include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic acid. 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, α-ethyl Glycidyl-containing, such as 6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether ester, m-vinylbenzyl glycidyl ether ester, p-vinylbenzyl glycidyl ether ester, etc. A free radical polymer of a vinyl monomer. These monomers may be used alone or in combination of two or more.

The radical polymer may be used in combination with other radical polymerizable monomers to the extent that the effects of the present invention are not impaired. Here, the other radical polymerizable monomer may be exemplified by other radical polymerizable monomers as previously mentioned. Among these, styrene-p-methylstyrene and α-methylstyrene are preferred. They may be used alone or in combination of two or more.

In addition, as another example of the polymer compound having a thermosetting group in the side chain, an epoxy resin represented by the following formula (i) such as a bisphenol A epoxy resin or a bisphenol P epoxy resin; An epoxy resin represented by the following formula (ii) such as a novolac type epoxy resin or a cresol novolac type epoxy resin; or an epoxy resin represented by the following formula (iii) such as a polyfunctional epoxy resin .

(In the formula, X is a methylene group, an alkylene group having 2 to 6 carbon atoms, a fluorine-based alkyl group having 2 to 6 carbon atoms or a divalent organic group having an alicyclic skeleton, and R is a carbon atom An alkyl group of 1 to 3, Y is a p-valent organic group, m is an integer of 0 to 4, m' is an integer of 0 to 3, and n and p are 2 to 20) which are commercially available. For example, the bisphenol A type epoxy resin is Epikote 828, the same 1001, the same 1002, the same 1003, the same 1004, the same 1007, the same 1009, the same 1010 (above, the oily shell epoxy (manufactured by the company)). The bisphenol F type epoxy resin is Epikote 807, the same 834 (above, oiled shell epoxy (manufactured by the company)), the novolac type epoxy resin is Epikote 152, the same 154, the same 157H65 (above, the oiled shell ring) Oxygen (share) system, EPPN201, the same 202 (above, Nippon Chemical Co., Ltd.), etc. , cresol varnish type epoxy resin is EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.), Epikote 180S75 (oiled shell) Epoxy (stock), etc., other, ring-type aliphatic epoxy resin is Araldit CY175, same as CY177, same as CY179 (above, Chiba. SPECIALITY. Chemical), ERL-4234, ERL-4299, ERL -4221, ERL-4206 (above, UCB), Showdin 509 (Showa Productions), Araldit CY-182, CY-192, and CY-184 (above, Chiba. SPECIALITY. Chemicals) System), Epichloron 200, same 400 (above, Dainippon Ink Industry Co., Ltd.), Epikote 871, 872, EP1032H60 (above, oiled shell epoxy (manufactured by the company)), ED-5661, ED-5662 ( In the above, Salis coating (manufactured by the company), the aliphatic polyglycidyl ether is Epikote 190P, and the same 191P (above, manufactured by Oiled Shell Epoxy Co., Ltd.) Eponlite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) Epilon TMP (made by Nippon Oil & Fat Co., Ltd.).

Further, when the above polyfunctional epoxy-containing compound is used, an alkaline catalyst such as 1-benzyl-2-methylimidazole may be added for the purpose of producing a more efficient crosslinking reaction.

Further, the photo-alignment film used in the present invention may contain a compound containing a functional decane for the purpose of improving adhesion to a substrate. The compound containing a functional decane may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropylpropane Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Decane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl- 3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1 , 4,7-trioxane, 10-triethoxydecyl-1,4,7-trioxane, 9-trimethoxydecyl-3,6-tridecyl acetate, 9 -triethoxydecyl-3,6-trimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxy Decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3 Aminopropyltriethoxydecane, N-bis(hydroxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(hydroxyvinyl)-3-aminopropyltriethoxydecane For example, a reaction product of a tetracarboxylic dianhydride and an amine group-containing decane compound described in JP-A-63-291922, and the like can be mentioned.

Substrate

Examples of the substrate used in the production of the optical film of the present invention include glass such as float glass and soda glass, cellulose acetate, polyethylene terephthalate, polybutylene terephthalate, and polysulfur. Polycarbonate, polyarylate resin film. When the substrate is used as a protective layer of an optical film, it is preferably transparent and has a small birefringence.

Photosensitive film

The photosensitive film used in the present invention can be advantageously produced by, for example, the method shown below.

First, the above-mentioned photosensitive polymer and the above-mentioned additives as needed are dissolved in a solvent to prepare a photosensitive varnish. The solvent to be used at this time is not particularly limited as long as it is an organic solvent capable of dissolving the polymer. Such solvents are exemplified by, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylammonium, γ-butane An aprotic polar solvent such as ester, tetramethylurea, 1,3-dimethylimidazolium or hexamethylphosphine trisamine; phenol such as phosphocresol, xylenol, phenol or halogenated phenol a solvent; a halogenated solvent such as chloroform, dichloroethane or tetrachloroethane; a ketone solvent such as cyclohexanone. They may be used alone or in combination of two or more. Further, the solvent may be used in combination with a poor solvent of the polymer to be used insofar as the polymer is not precipitated.

Next, the photosensitive varnish is applied onto the substrate by a roll coating method, a spin coating method, a printing method, or the like, and is heated at a temperature of 40 to 200 ° C to form a coating film. The solid fraction of the coating film thickness is preferably from 0.1 to 100 μm, more preferably from 1 to 10 μm. When the photosensitive varnish is applied, in order to improve the adhesion between the substrate and the coating film, a compound containing a functional decane, a titanate or the like may be applied to the substrate in advance.

Optical function layer

The substrate is irradiated with radiation having no linearly polarized or partially polarized light or radiation without polarization, and is heated at a temperature of 150 to 250 ° C as appropriate to impart an optical directionality to form an optical functional layer. . For the radiation, ultraviolet rays and visible light having a wavelength of 150 nm to 800 nm can be used. It is preferred to use ultraviolet rays having a wavelength of from 320 nm to 450 nm. Further, in order to improve the obtained optical anisotropy, the substrate can be heated and irradiated at 50 to 250 °C. Further, the irradiation of the radiation may be performed in a direction perpendicular to the substrate surface or in an oblique direction, or may be performed in combination.

The refractive properties imparted by the optical film of the present invention can be controlled by the above-described radiation irradiation step. When the film is irradiated with linearly polarized radiation, in the obtained optical functional layer, the electric vector of the radiation is regarded as a rotation axis to form a flat long refractive index round body. On the other hand, when the film is irradiated with radiation having no polarization, the refractive index circle system forms the flat shape by using the optical axis of the radiation as a rotation axis. Further, in the case of using partially polarized radiation, an intermediate result of the linearly polarized light and the unpolarized light is given depending on the degree of polarization thereof.

For this reason, when irradiated with radiation, it is possible to obtain various appropriate optical films and arbitrarily inclined and arbitrary shapes by using radiations having different directions, optical axis directions, and/or polarization degrees depending on the need to combine electrical vectors. The optically anisotropic layer of the refractive index 楕 round body.

Further, when the radiation is irradiated with the above-mentioned radiation, the objective is to produce an optical member having different optical characteristics in different fields, and it is possible to irradiate various fields in the surface with radiation having different polarization states, optical axis directions, and energies. The method of irradiating the coating film by light, for example, by changing the light intensity, the incident angle, and the like, depending on the method of changing the intensity of the radiation, the direction of the optical axis, and the method of changing the energy in the plane. . These methods can be used alone or in combination. Further, when one or two of these methods are used, it is possible to combine the total irradiation of the entire substrate. A particularly preferred method is to impart a first alignment to a portion of the substrate by irradiation through the reticle, and then to provide a second alignment of the residual portion by comprehensively exposing the substrate.

As the light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, a heavy water lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The above-mentioned ultraviolet light in a preferred wavelength range can be obtained by a method in which a filter, a folded lattice, and the like are used in combination with the above-mentioned light source. In short, a PYREX (registered trademark) glass polarizing plate or the like which is a polarizing plate cannot be permeable. The above-mentioned light source can be used at the same time as the ultraviolet light having a shorter wavelength than 320 nm.

Optical film

Next, an appropriate protective layer as needed may be added to the above optical functional layer to obtain the optical film of the present invention. In this case, the substrate used in the production of the optical functional layer can be removed by peeling or the like, and the body can also be used as a protective layer of the optical functional layer.

The above additional protective layer may, for example, be a resin layer of cellulose acetate, polycarbonate, polysulfide or polyarylate. These protective layers may optionally contain a UV absorber, a plasticizer, an antioxidant, and the like. Moreover, these protective layers are preferably transparent and have a small birefringence.

effect

According to the present invention, it is possible to provide an optical film for polarization control which is produced in a simple step and which has high in-plane uniformity of optical characteristics. In addition, according to the present invention, it is possible to provide a step in forming an optical functional layer, and to produce different opticals in a plurality of in-plane fields by irradiating a polarized state, an optical axis direction, or a radiation having different energies in different fields. Characteristic optical film. Further, according to the present invention, when the optical functional layer is formed, radiation having different directions of the electric vector, the optical axis direction, and/or the polarization degree can be used arbitrarily, and the optical refractive index can be arbitrarily obtained in various optical films. The optical isotropic layer of the body.

In the following, the present invention is more specifically described by the examples, but the present invention is not limited by the examples.

Synthesis Example 1 Synthesis of hexastyrene-phenylmaleic anhydride imine polymer substituted by hydroxy group

4-Ethyloxystyrene 0.05 mol (8.1 g), N-(4-acetoxyphenyl)maleic anhydride imamine 0.05 mol (11.6 g), and α,α'-couple 0.1 g of nitrogen bisisobutyronitrile was dissolved in 80 ml of N,N-dimethylacetamide, and reacted at 80 ° C for 8 hours under a nitrogen atmosphere. Next, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product.

The reaction product was washed with methanol, and then heated to reflux for 4 hours in 400 ml of ethanol containing 40 ml of concentrated hydrochloric acid. The resulting viscous solution is poured into a large amount of excess water to cause the reaction product to settle. The slab was washed with water and dried at 40 ° C for 15 hours under reduced pressure to obtain 13.4 g of a hydroxy-substituted styrene-phenyl maleic acid imide polymer (hereinafter referred to as "polymer 1a"). ).

Synthesis of poly(styrene-phenylmaleic anhydride imide) derivatives with specific structure

In 3.1 g of the polymer 1a, 80 ml of N,N-dimethylacetamide, 9.7 g of 1-(4-carbonyloxy)-6-brominated hexane, 5.6 g of potassium carbonate, and 0.2 g of potassium iodide were added. The reaction was carried out at 85 ° C for 12 hours under a nitrogen atmosphere.

In addition, the reaction mixture is poured into a large amount of excess water to cause the reaction product to settle. The reaction product was washed successively with water and ethanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 7.0 g of a poly(styrene-phenylmaleic anhydride imide) derivative having a specific structure (hereinafter , called "polymer 1b").

Synthesis Example 2 Polymerization of polylysine

0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 0.1 mol (0.18 g) of p-phenylenediamine, dissolved in N-methyl-2-pyrrolidone 300 In gram, the reaction was carried out at 60 ° C for 6 hours.

Next, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. The reactive product was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 27.4 g of polylysine (hereinafter referred to as "polymer 2a").

Synthesis of polyamines with specific structure

In 16.6 g of synthetic polymer 2a having a specific structure of polyperurethane, 350 g of N-methyl-2-pyrrolidone and 1-bromo-6-(4-carbonyloxy)hexane 38.7 were added. Gram and potassium carbonate 13.8 g were reacted at 120 ° C for 4 hours.

Next, the reaction mixture was poured into water to precipitate a reaction product. The obtained precipitate was washed with water and dried under reduced pressure for 15 hours to obtain 35.4 g of a polyamine (hereinafter referred to as "polymer 2b").

Synthesis Example 3 Synthesis of polymethacrylate derivatives with specific structure

18.2 g of 4-(2-methylpropenoxime hydroxyethyl)chalcone carboxylate, 14.1 g of 4-(2-(methacryloxy)ethoxy)biphenyl, and azobis 0.5 g of isobutyronitrile was dissolved in 100 ml of tetrahydrofuran, and heated under reflux for 10 hours under a nitrogen atmosphere. The viscous reaction mixture was poured into methanol to precipitate the polymer, and dried to obtain 32 g of polymethacrylate (hereinafter referred to as "polymer 3b").

Comparative synthesis Ruthenium iodide

To 20.0 g of the polymer 2a, 380 g of N-methyl-2-pyrrolidone, 9.5 g of pyridine, and 12.3 g of acetic anhydride were added, and the oxime imidization reaction was carried out at 120 ° C for 4 hours.

Next, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. This reactive organism was washed with methanol and dried under reduced pressure for 15 hours to obtain 15.3 g of polyimine (hereinafter referred to as "polymer Ab").

Example 1 Phase difference plate

The polymer 1b obtained in Synthesis Example 1 was dissolved in γ-butyrolactone to form a solution having a solid concentration of 10% by weight, and the solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent solution. This solution was applied onto a PYREX (registered trademark) glass substrate by a spin coater to a film thickness of 7.5 μm, and dried at 180 ° C for 1 hour to form a film. Next, using a UV-polarized exposure apparatus LPU-2000S manufactured by Lataku Konica Saskatchewan, the linearly polarized ultraviolet light of 365 nm wavelength is 10 J/cm ² to illuminate the film from the normal direction to impart optical anisotropy. A phase difference plate is formed.

The retardation axis direction of the obtained phase difference plate was the same direction as the polarization direction of the ultraviolet ray, and had a hysteresis value of 0.317 μm having a wavelength of 633 nm. In addition, the delayed axis vector and the hysteresis value are in-plane uniform.

Example 2~3 Production of phase difference plate

The polymer 1b obtained in Synthesis Example 1 was replaced with the polymer 2b to 3b obtained in Synthesis Examples 2 to 3, and the thickness of the photosensitive film was as shown in Table 1, and a phase difference plate was tried in the same manner as in Example 1. . The orientation of the delayed phase axis of the obtained phase difference plate is also in the same direction as the polarization direction of the ultraviolet ray irradiation in any of the embodiments. The resulting hysteresis values are shown in Table 1. Even in either embodiment, the late axis vector and the hysteresis value are phase in-plane uniform.

Comparative example Production of phase difference plate

A phase difference plate was attempted in the same manner as in Example 1 except that the polymer 1b obtained in Synthesis Example 1 was substituted and the polymer Ab obtained in Comparative Synthesis Example was used. The obtained optical film could not exhibit intentional optical anisotropy and did not have a function as a phase difference plate.

Claims (2)

An optical film comprising an optically anisotropic layer formed by irradiating a polarizing film or a non-polarizing radiation on a photosensitive film, wherein the photosensitive film comprises a film selected from the group consisting of a polymer of at least one structure of the group of structures shown in I), (II), and (III), -P ¹ -CR ¹ =CR ² -CO-Q ¹ - (I) P ² -CR ³ =CR ⁴ -CO-Q ² - (II) -P ³ -CR ⁵ =CR ⁶ -CO-Q ³ (III) where P ¹ , P ³ , Q ¹ , and Q ² are mutual a divalent organic group independently having an aromatic ring, and P ² and Q ³ are a monovalent organic group having an aromatic ring independently of each other, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are Hydrogen atoms or alkyl groups independent of each other. A method of producing an optical film according to the first aspect of the invention, characterized in that the photosensitive film is irradiated with polarized or unpolarized radiation.