WO2006085449A1

WO2006085449A1 - Coating film for optical compensation, and optical element

Info

Publication number: WO2006085449A1
Application number: PCT/JP2006/301496
Authority: WO
Inventors: Michinori Tsukamoto; Yasuhiro Sekiguchi; Tomoki Hiiro; Sadao Fujii
Original assignee: Kaneka Corporation
Priority date: 2005-02-14
Filing date: 2006-01-31
Publication date: 2006-08-17
Also published as: KR20070111480A; TW200634108A

Abstract

This invention provides a coating film for optical compensation at low cost without providing a troublesome film forming step, and an optical element having the same properties as attained by the provision of film application step despite the fact that any troublesome work of film application and the like is not required. There is also provided a method for the formation of a coating film for optical compensation. In the coating film, the value obtained by (nx + ny)/2 - nz is negative, and the absolute value is larger. In the equation, nx represents the maximum in-plane refractive index, ny represents the minimum in-plane refractive index, nz represents the refractive index in thickness-wise direction, and d represents the film thickness. An optical element may be produced by using the method for the formation of a coating film. The coating film for optical compensation is characterized by comprising any polymer of cellulose N-substituted carbamate or an aromatic vinyl polymer.

Description

Specification

Optical compensation coating film and optical element

Technical field

[0001] The present invention relates to an optical compensation coating film for performing optical compensation of retardation by a liquid crystal cell or the like, an optical compensation coating film-forming coating solution suitable for forming the coating film, and the optical compensation The present invention relates to a method for forming a coating film. Furthermore, the present invention relates to a retardation adjusting agent, an optical compensation coating film containing the retardation adjusting agent, and a coating liquid for forming the optical compensation coating film. Furthermore, the present invention relates to an optical element manufactured using them and a method for manufacturing the optical element. Furthermore, the present invention relates to an optical compensation film (retardation film), a polarizing plate provided with the optical compensation film, and a liquid crystal display device.

Background art

In a liquid crystal display device, a phase difference film for optical compensation is used in order to increase the viewing angle by compensating for the phase difference due to birefringence of a liquid crystal cell, a polarizing plate, and other liquid crystal display device constituent films. ing. As such a retardation film, for example, a polymer such as polycarbonate, polyester, polystyrene, polyamide, polyimide, and polyethersulfone is subjected to a solution casting method, a uniaxial stretching method after a solution casting, and a drying after solution casting. And a biaxial stretching method, extrusion method, uniaxial stretching method of extruded product, biaxial stretching method of extruded product, calendar method, etc. (see, for example, Patent Document 1 and Patent Document 2). ) ₀ Such a retardation film is a film having a positive intrinsic birefringence value such as polycarbonate, polystyrene, etc. according to the applied liquid crystal cell, polarizing plate, other liquid crystal display device constituting film, etc. One to several films with material strength having a negative intrinsic birefringence value such as the above are used separately. In order to use these films, first, a complicated film forming process is required for film formation, and it is also necessary to attach these films to liquid crystal display device components.

[0003] In order to solve these problems, the pace z X y of polyimide having optical characteristics of n <n = n

The formation of a retardation layer has been proposed by forming a thin film by coating (for example, see Patent Document 3). On the other hand, those having optical properties of n> n≥n, in other words, (( _n + n) / 2-nzxvxyz For those in which the thickness retardation value represented as X d is negative, coating of compounds having optical properties of n> n = n has been proposed. This can be achieved by applying a solution of a polymer compound having a functional group capable of photoisomerization, drying, and then irradiating light to control the orientation of the polymer, or a liquid crystal polymer solution or a liquid crystal polymer melt. coating, dried, and heat treated at the glass transition temperature of the polymer one to orient the liquid crystal, it is intended to fix I spoon alignment by cooling (for example, see Patent Document 4.) with ₀ tooth force, polyimide Compared to the formation of a retardation layer by applying a paste, the use of a polymer compound having a functional group capable of photoisomerization has the complication of having to irradiate light, and the use of a liquid crystal polymer is generally expensive. There is a disadvantage that the cost is high.

[0004] By the way, in order to compensate for a large thickness direction retardation due to birefringence of a liquid crystal cell, a polarizing plate, and other liquid crystal display device constituent films, the sign of the thickness direction retardation is opposite, n + n) / 2-n] It is effective to use an optical compensation material having a large absolute value of the thickness retardation represented by Xd. For this purpose, it is particularly effective to form a material with a large absolute value of the value represented by (n + n) / 2-n by a large forming method. This is because if the absolute value of the value represented by (n + n) / 2−n is not sufficient and the film thickness needs to be increased, the liquid crystal display component parts after the coating film is formed only become bulky. This is a force that causes problems such as an increase in the material cost of the coating film.

Patent Document 1: JP-A-3-33719

Patent Document 2: Japanese Patent Laid-Open No. 11-248939

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-290023

Patent Document 4: JP-A-7-13022

Disclosure of the invention

Problems to be solved by the invention

[0005] An object of the present invention is to provide an optical compensation coating film at low cost without requiring a complicated film forming step. Furthermore, it provides an optical compensation coating film having the characteristics of [(n + n) / 2−n] X d 0 at low cost, and has the characteristics without the need for film sticking or the like. It is to provide an optical element.

[0006] Furthermore, either cellulose N-substituted carbamate or aromatic bulle polymer And a method of forming an optical compensation coating film having a larger absolute value, the value represented by (n + n) / 2-n being negative. It is to provide an optical element manufactured using the same.

Means for solving the problem

[0007] In order to solve such problems, the present inventors have intensively studied and formed a cellulose N-substituted carbamate or any one of aromatic vinyl polymers. The present inventors have found that the above-mentioned problems can be solved by an optical compensation coating film characterized by the above, and have reached the present invention.

[0008] That is, the present invention relates to a coating film for optical compensation characterized by comprising a polymer of either cellulose N-substituted carbamate or aromatic bulle polymer.

[0009] In a preferred embodiment, when the maximum refractive index in the plane is n, the minimum refractive index is n, the refractive index in the thickness direction is n, and the film thickness is d, [(n + n) / 2-n] (1 <0) The present invention relates to a coating film for optical compensation characterized by satisfying the relationship 1 <0.

In a preferred embodiment, in the cellulose N-substituted carbamate, at least one of hydroxyl groups of cellulose is N-substituted carbamate, and at least one of hydrogen atoms bonded to a nitrogen atom of the cellulose strength carbamate is It is substituted with a group selected from the following general formulas (1) to (3), and the plurality of N-substituents are the same or different and are the following general formulas (1) to (3) The present invention relates to a coating film for optical compensation, which is a compound.

[0011] [Chemical 1]

R ⁴ and R ⁵ are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or carbon. C 6-20 aralkyl group, C 6-20 aralkyl group, C 7-20 aralkyl group, C 7-20 aralkyl group, C 1-21 syloxy group, halogen atom, nitro Represents a group. )

[0013] [Chemical 2]

(Wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^1Q , R ^U , R ¹² are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. An alkoxy group, a halogenated alkyl group having 1 to 20 carbon atoms, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.

[0015] [Chemical 3]

(In the formula, R ¹³ , R ″, R ¹⁵ , R ^ln , R ″, R ¹⁸ , R ¹⁹ are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.

[0017] Preferably, the embodiment contains at least one selected from the group consisting of aromatic vinyl polymers such as poly (1-burnaphthalene), poly (2-burnaphthalene) and poly (4-birubiphthal). It is related with the coating film for optical compensation characterized by these.

[0018] Preferred embodiment is characterized in that it is formed containing a phase difference adjusting agent. The present invention relates to a coating film for optical compensation.

[0019] Preferably, the embodiment contains a phase difference adjusting agent for cellulose N-substituted carmate comprising at least one selected from force rubamic acid ester, N-substituted force rubamic acid ester, urea, and N-substituted urea force. The present invention relates to an optical compensation coating film.

[0020] Preferred embodiments include ethyl carnomate, phenyl carnomate, N-phenyl carbamate, N phenyl carbamate, N- (4-tolyl) carbamate, N— (4-Tolyl) strength rubamate, urea, N, N, —diphenyl urea, N, N, —di-p-trilylurea, N—phenol—N '-(p-tolyl) The present invention relates to a coating film for optical compensation, comprising a retardation adjusting agent for cellulose N-substituted carnomate, which has at least one force selected from the group of urea.

Furthermore, the present invention relates to a coating solution for forming an optical compensation coating film formed by containing the following (A) and (B).

[0022] (A) a polymer of any one of cellulose N-substituted carbamate and aromatic bur polymer;

(B) A solvent in which component (A) is soluble and soluble.

As a preferred embodiment, the coating film for forming an optical compensation coating film is characterized by comprising (A) and (B), and further comprising (C) a retardation adjusting agent. Concerning the working fluid.

[0024] As a preferred embodiment, (C) phase difference adjusting agent strength rubamic acid ester, N-substituted carbamic acid ester, urea, cellulose-substituted N-substituted carbamate consisting of at least one selected from N-substituted urea. The present invention relates to a coating solution for forming a coating film for optical compensation, which is a phase difference adjusting agent for use in optical compensation.

[0025] Preferred embodiments include: (C) Retardation adjusting agent strength rubyl ethamine, force rubamate phenyl, N-phenol carbamic acid, N-phenol carbamic acid, N- ( 4-tolyl) -force rubamate, N— (4-tolyl) -force rubamate, urea, N, N, -diphenylurea, N, N, —di-p-tolylurea, N—phenol-N The present invention relates to a coating solution for forming an optical compensation coating film, which is a retardation adjusting agent for cellulose N-substituted carbamate, comprising at least one selected from the group of, (p-tri) urea.

[0026] Further, the present invention provides a rubamic acid ester, N-substituted rubamic acid ester, urea, N The present invention relates to a retardation adjusting agent for cellulose N-substituted carbamate, characterized by comprising at least one selected from substituted urea.

[0027] Preferred embodiments include ethyl carnomate, phenyl carnomate, N-phenyl carbamate, N phenol carbamate, N- (4-tolyl) carbamate, N- Of (4-tolyl) force rubamate, urea, N, N, —diphenyl urea, N, N, —di-p-tolylurea, N—phenol—N ′-(ptolyl) urea The present invention relates to a phase difference adjusting agent for cellulose N-substituted carnomate characterized by having at least one force selected from the group.

[0028] Further, the present invention relates to a method for forming an optical compensation coating film, wherein the coating liquid is coated on a substrate to form a coated substrate, and then the coated substrate is dried.

[0029] As a preferred embodiment, the above-mentioned coated substrate is first dried at a temperature in the range of a lower limit of 0 ° C and an upper limit of 40 ° C, and then the coated substrate is further reduced to a lower limit of 80 ° C and an upper limit of 300 The present invention relates to a method for forming a coating film for optical compensation, characterized by secondary drying at ° C.

[0030] Further, the present invention is characterized in that after the coating liquid is applied to a substrate to form a coated substrate, the coating film is annealed by exposure to the vapor of component (B) and further dried. The present invention relates to a method for forming an optical compensation coating film.

Furthermore, the present invention relates to a method for manufacturing an optical element characterized by using the above-described forming method.

Furthermore, the present invention relates to an optical element manufactured using the above manufacturing method.

[0033] Further, the present invention relates to an optical compensation film manufactured using the above-described forming method.

Furthermore, the present invention relates to a polarizing plate characterized in that the above optical compensation film is mounted as a polarizer protective film on at least one surface of a polarizer.

Furthermore, the present invention relates to a liquid crystal display device provided with the above optical compensation film.

Furthermore, the present invention relates to a liquid crystal display device provided with the above polarizing plate.

The invention's effect

[0037] When the optical compensation coating film of the present invention is used, a complicated film forming process or film pasting is performed. In particular, an optical element having an optical compensation layer of [(n + 11) 72-11] (1 <0 can be produced. Using the method of forming a film, the value represented by (n + n) / 2-n is negative, and a coating film for optical compensation having a larger absolute value can be formed. Since the device can be manufactured, it is extremely useful industrially.

BEST MODE FOR CARRYING OUT THE INVENTION

[0038] Hereinafter, the present invention will be described in detail. The present invention is a coating film for optical compensation characterized by comprising a polymer of cellulose N-substituted carbamate or an aromatic vinyl polymer.

[0039] In the cellulose N-substituted carbamate of the present invention, at least one hydroxyl group of cellulose is N-substituted carbamate, and at least one hydrogen atom bonded to a nitrogen atom of the cellulose carbamate is represented by the following general formula. It is a compound that is substituted with a group selected from (1) to (3), and a plurality of N-substituents are the same or different and have the following general formulas (1) to (3) An optical compensation coating film characterized by

[0040] [Chemical 4]

[0041]

R ⁵ is the same or different and is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents an aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group. )

[0042] [Chemical 5]

[0044] [Chemical 6]

(In the formula, R ¹³ , R ″, R ¹⁵ , R ^ln , R ″, R ¹⁸ and R ¹⁹ are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.

[0046] The cellulose N-substituted carbamate in the present invention (hereinafter sometimes referred to as component (A)) is, for example, cellulose obtained from various wood pulp, cotton linter, cotton lint, etc. It can be produced by a known method of reacting an isocyanate compound in the presence of a base catalyst such as triethylamine. The base catalyst can also be used as a solvent. As other solvents, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide can be suitably used. Furthermore, an inorganic salt such as lithium chloride can be added to improve the solubility of cellulose in a solvent. Examples of such isocyanate compounds include the following general formulas (4) to (4) The compound represented by (6) is mentioned.

[0047] [Chemical 7]

[0048] (In the formula, R ° and R ^z R ^z R ^z are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Alkyl halide group, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, and acyloxy group having 1 to 21 carbon atoms Represents a halogen atom or a nitro group.

[0049] [Chemical 8]

[0050] (wherein R ²⁵ ,

R ² °, R ²⁹ , R ³ °, ¹ are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl halide having 1 to 20 carbon atoms. Group, a C1-C21 acyloxy group, a halogen atom, and a nitro group. )

[0051] [Chemical 9]

[0052] (wherein R ³² , R ³³ , R ³⁴ , R ³⁵ ,

R ³⁷ and R ³⁸ are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 1 to 21 carbon atoms. Represents an acyloxy group, a halogen atom or a nitro group. )

These isocyanate compounds may be used alone or in combination of two or more.

In the present invention, from the viewpoint of availability of the above isocyanate compound, R ² °, R ²¹ , R ²² , R ²³ , R ²⁴ may be the same or different and each is a hydrogen atom or an alkyl having 1 to 16 carbon atoms. Group, alkoxy group having 1 to 16 carbon atoms, halogenated alkyl group having 1 to 16 carbon atoms, aryl group having 6 to 16 carbon atoms, aryloxy group having 6 to 16 carbon atoms, aralkyl group having 7 to 16 carbon atoms, carbon An isocyanate compound represented by the general formula (4), which is an aralkyloxy group having 7 to 16 carbon atoms, an acyloxy group having 1 to 17 carbon atoms, a halogen atom, or a nitro group, is reacted, and at least one hydroxyl group of the cellulose is N-substituted carbamate cellulose N-substituted carbamate is preferably used. Or R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³ °, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ are the same or different, A hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, a halogenated alkyl group having 1 to 16 carbon atoms, an acyloxy group having 1 to 17 carbon atoms, a halogen atom, and a nitro group. It is preferable to use cellulose N-substituted carbamate in which isocyanate compounds represented by the general formulas (5) and (6) are reacted and at least one of hydroxyl groups of the cellulose is N-substituted carbamate. R 2 °, R ²¹ , R ²² , R ²³ , R ²⁴ are the same or different and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen having 1 to 12 carbon atoms. Alkyl group, aryl group having 6 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, aralkyl group having 7 to 12 carbon atoms, aralkyloxy group having 7 to 12 carbon atoms, acyloxy group having 1 to 13 carbon atoms, halogen It is more preferable to use a cellulose N-substituted carbamate in which an isocyanate compound represented by the general formula (4), which is an atom or a nitro group, is reacted and at least one hydroxyl group of the cellulose is N-substituted carbamate. Or R ²⁵ , R ²⁶ ,

R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ are the same or different and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms. An isocyanate compound represented by the general formulas (5) and (6), which is an alkoxy group of 1 to 12, a halogenated alkyl group of 1 to 12 carbon atoms, an acyloxy group of 1 to 13 carbon atoms, a halogen atom, or a nitro group. It is more preferable to use cellulose N-substituted carbamate which is reacted and at least one of the hydroxyl groups of cellulose is N-substituted carbamate.

Specific examples of the isocyanate compounds represented by the general formulas (4) to (6) include phenyl isocyanate, o tolyl isocyanate, m-tolyl isocyanate, p tolyl isocyanate, 2 ethyl phenyl isocyanate, 3 Ethyl phenyl isocyanate, 4 Ethyl phenyl isocyanate, 2 Propyl phenol isocyanate, 3 Propyl phenyl isocyanate, 4 Propyl phenyl isocyanate, 2 Butyl phenyl isocyanate, 3 Butyl phenyl isocyanate, 4 Butyl phenyl isocyanate, 4 Butyl phenyl isocyanate Dimethylphenol isocyanate, 2,5-Dimethylphenol isocyanate, 2,6 Dimethylphenol isocyanate, 3,4 Dimethylphenol isocyanate, 3,5 Dimethylphenol isocyanate, 2, 3 Jetyl phenyl isocyanate, 2, 4-Jetyl phenyl isocyanate, 2, 5 Jetyl phenyl isocyanate, 2, 6 Jetyl phenyl isocyanate, 3, 4-Jetyl phenol engineering, 3, 5 Jetyl phenol isocyanate, 2, 4, 6 Trimethyl Phenolate isocyanate, 2-methoxyphenolate isocyanate, 3-methoxyphenolate isocyanate, 4-methoxyphenylisocyanate, 2 ethoxyphenylisocyanate, 3 ethoxyphenylisocyanate, 4 ethoxyphenylisocyanate, 2 (fluoromethyl) phenol Ruisocyanate, 3- (Fluoromethyl) phenyl isocyanate, 4 (Fluoromethyl) phenol isocyanate, 2- (Chloromethyl) phenol isocyanate, 3- (Chloromethyl) phenol isocyanate 4- (chloromethyl) phenyl isocyanate, 2- (bromomethyl) phenyl isocyanate, 3- (bromomethyl) phenyl isocyanate 4- (bromomethyl) phenol isocyanate, 2- (iodomethyl) phenol isocyanate, 3— (odomethyl) phenol isocyanate, 4 (odomethyl) phenol isocyanate, 2- (difluoromethyl) phenol isocyanate, 3— (Difluoromethyl) phenylisocyanate, 4- (Difluoromethyl) phenylisocyanate, 2- (Dichloromethyl) phenylisocyanate, 3- (Dichloromethyl) phenylisocyanate, 4— (Dichloromethyl) phenylisocyanate, 2 (Dibromo Methyl) phenol isocyanate, 3 (dibromomethyl) phenol isocyanate, 4 (dibromomethyl) phenol isocyanate, 2- (jodomethyl) phenol isocyanate, 3— (jointmethyl) phenol isocyanate, 4 (Jodome L) Phenyl isocyanate, 2- (trifluoromethyl) phenyl isocyanate, 3— (trifluoromethyl) phenyl isocyanate, 4— (trifluoromethyl) phenyl isocyanate, 2— (trichloromethyl) phenyl isocyanate , 3- (trichloromethyl) phenol isocyanate, 4- (trichloromethyl) phenol isocyanate, 2- (tribromomethyl) phenol isocyanate, 3- (tribromomethyl) phenol isocyanate, 4 (tribromo) Methyl) phenyl isocyanate, 2- (triiodomethyl) phenyl isocyanate, 3- (triiodomethyl) phenol isocyanate, 4 (triiodomethyl) phenyl isocyanate, 2 biphenyl-isocyanate, 3 biphenyl -Lyl isocyanate, 4-biphenylyl isocyanate 2 Phenyloxyisocyanate, 3—Phenoxyphene-isocyanate, 4 Phenoxyphenol-isocyanate, 2′-Benzylphenolisocyanate, 3,1-Benzylphenolisocyanate, 4,1-Benzylphenol-isoleocyanate, 2-Benzyloxyphene -Ruisocyanate, 3-benzyloxyphenol-isocyanate, 4 benzyloxyphenol-isoleocyanate, 2-acetoxyphenyl isocyanate, 3-acetoxyphenyl isocyanate, 4-acetoxyphenyl isocyanate, 2 fluorophenol isocyanate, 2 fluorophenol isocyanate Ruisocyanate, 4 Fluorophenol isocyanate, 2 Chlorophenyl isocyanate, 3 Chlorophenolate isocyanate, 4 Chlorophenolate isocyanate, 2 Bromophenolate Isocyanate, 3 Bromophenylenoisocyanate, 4 Bromophenylenoisocyanate, 2 Phodophenylisocyanate, 3—Phodophenylisocyanate, 4 Phodophenylisocyanate, 2, 4 Difluorophenol isocyanate, 2, 5 Difluorophene Ruisocyanate, 2,6 Difluorophenyl isocyanate, 3,4 Difluorophenyl isocyanate, 3,5 Difluorophenyl isocyanate, 2,4 Dichlorophenyl isocyanate, 2,5 Dichlorodiphenyl isocyanate, 2, 6 Dichlorodiphenyl isocyanate 3,4-dichroic phenylisocyanate, 3,5-diclonal phenylisocyanate, 2,4 dibromophenenoisocyanate, 2,5 dibromopheninoisocyanate, 2,6 dibromophenolisocyanate 3,4 dibromophenylisocyanate, 3,5 dibromophenylisocyanate, 2,4-jodophenylisocyanate, 2,5-jodephenylisocyanate, 2,6 jodophenylisocyanate, 3,4-jodophenylisocyanate, 3, 5 Jo Douphenyl isocyanate, 2, 3, 4 Trifluorophenol isocyanate, 2, 3, 4 Trichlorophenol isocyanate, 2, 3, 4— Tribromophenol isocyanate, 2, 3, 4 Triophenol isocyanate, 2 Fluoro 5 methyl phenol Ruisocyanate, 2-Fluoro 6-methyl phenol isocyanate, 3 Fluoro 2-Methyl phenol isocyanate, 3 Fluoro 4-Methyl phenol isocyanate, 4 Fluoro 2-methyl phenol isocyanate, 4 Fluoro 3 Methyl phenol isocyanate, 5-Fluoro 2 methyl -Luocyanate, 2 Black Mouth 5—Methylphenol isocyanate, 2 Black Mouth 6—Methylphenolic isocyanate, 3 Black Mouth 2—Methylphenol isocyanate, 3 Black Mouth 4—Methylphenol isocyanate, 4 Black Mouth one 2—Methylphenol isocyanate 3—Methylphenol isocyanate 3—Methylphenol 2—Methylphenol isocyanate 2—Methylphenol isocyanate 5—Bromo 6—Methylphenol isocyanate 3 Bromo 2—Methylphenol -Luisocyanate, 3 bromo-4 methylphenol isocyanate, 4-bromo-2 methylphenylisocyanate, 4-bromo-3-methylphenylisocyanate, 5 bromo-2-methylphenolisocyanate, 2 jorde —5-methylphenolisocyanate, 2 pheode 6-methyl Ruisocyanate, 3 iodine 2-methyl phenol isocyanate, 3 iodine 4-methyl phenol isocyanate, 4 iodine 2-methyl phenyl isocyanate, 4 iodine 3-methyl phenol isocyanate, 5 iodine 2 Chirufue two Ruisoshianeto, 2 two Torofue two Ruisoshianeto, 3 two Torofue two Ruisoshianeto, 4 twelve Torofue two Ruisoshianeto 1-naphthynoleisocyanate, 2-naphthinoreisocyanate, 1-methylenole 2-naphthylisocyanate, 2-methyl-1 naphthylisocyanate, 1-methoxy-2-naphthylisocyanate, 2-methoxy-1-naphthylisocyanate, 1- (Trifluoromethyl) -1-2-naphthyl isocyanate, 2- (trifluoromethyl) 1-naphthyl isocyanate, 1 (trichloromethyl) 2-naphthyl isocyanate, 2- (trichloromethyl) 1 Naphthyl isocyanate, 1 (Tribromomethyl) 2-Naphthyl isocyanate, 2- (Tribromomethyl) 1 Naphthyl isocyanate, 1 (Triiodomethyl) 2-Naphthyl isocyanate, 2- (Triiodomethyl) 1 Naphthyl isocyanate, 1-acetoxy 2-Naphthyno isocyanate, 2-acet Xy 1 Naphthinoreisocyanate, 1-Fluoro 2-Naphtyl isocyanate, 2-Fluoro-1 Naphthyl isocyanate, 1 Chloro 2-Naphthinoreisocyanate, 2-Chloro 1 Naphthinoreisocyanate, 1 Bromo 2-Naphthinoisocyanate, 2-Bromo-1 Naphthinoisocyanate, 1 ododo 2-Naphthylisocyanate, 2- odoid-1 naphthylisocyanate, 1 12 tallow 2-Naphthinoreisocyanate, 2— -Trow 1 Naphthinoreisocyanate. Cellulose N-substituted carbamates obtained by reacting these and the isocyanate compounds may be used alone or in combination of two or more.

[0055] Cellulose has three hydroxyl groups per glucose residue, which is a structural unit. Therefore, when these hydroxyl groups are substituted, the degree of substitution per glucose residue (hereinafter referred to as DS) is a maximum of 3. In the present invention, the lower limit of DS is preferably 0.1, more preferably 0.5, more preferably 1, and the upper limit is preferably 3, more preferably 2.95, and even more preferably 2.9. . When DS is lower than 0.1, it tends to be difficult to dissolve in a solvent. In the present invention, two or more cellulose N-substituted carbamates having different DSs may be used in combination, or may be used alone.

[0056] Further, the lower limit of the number average molecular weight of component (A) is preferably 5000, more preferably 8000, more preferably <10,000, and the upper limit is preferably <500,000, more preferably <300000, Preferably it is 200,000. If the number average molecular weight is less than 5,000, the coating film strength tends to decrease, and if the number average molecular weight is more than 500,000, it tends to be difficult to dissolve in a solvent (sometimes referred to as component (B)). The number average molecular weight is determined by gel permeation chromatography. It is a value measured by the graphic (GPC) method. In the present invention, two or more types of cellulose N-substituted carnomates having different number average molecular weights may be used in combination, or may be used alone. Any aromatic vinyl polymer of the present invention (hereinafter sometimes referred to as component (A)) may be used as long as it contains an aromatic bulule unit. For example, polystyrene; poly (α-methylenostyrene); poly (2-methylstyrene), poly (3-methylstyrene), poly (4-methylstyrene), poly (2, 4 dimethylstyrene), poly (2, 5 Dimethyl styrene), poly (3,4 dimethyl styrene), poly (3,5 dimethyl styrene), poly (2 ethyn styrene), poly (3 eth styrene), poly (4 ethyn styrene), poly (2, 4 Methinostyrene), poly (2,5 dimethyl styrene), poly (3,4 methyl styrene), poly (3,5 dimethyl styrene), poly (2 propyl styrene), poly (3 propino styrene), Poly (4 propinole styrene), poly (2, 4 dipropyl styrene), poly (2, 5 dipropyl styrene), poly (3,4-dipropyl styrene), poly (3, 5-dipropyl styrene) , Po Li (2 Buchi Honoré styrene), poly (3-butyl styrene), poly (4-butyl Honoré styrene), poly (

2,4 dibutyl styrene), poly (2,5 dibutyl styrene), poly (3,4 dibutinoles styrene), poly (3,5 dibutyl styrene) and other poly (alkyl styrene); poly (2-methoxystyrene), poly (3-methoxystyrene), poly (4-methoxystyrene), poly (2,4 dimethoxystyrene), poly (2,5 dimethoxystyrene), poly (3,4 dimethoxystyrene), poly (3,5 dimethoxystyrene) ), Poly (2 ethoxy styrene), poly (3 ethoxy styrene), poly (4 ethoxy styrene), poly (2, 4 ethoxy styrene), poly (2, 5 diethoxy styrene), poly (3,4-jet) Toxistyrene), poly (3,5-ethoxystyrene), poly (2 propoxystyrene), poly (3 propoxystyrene), poly (4 propoxystyrene), poly (2, 4 Propoxy styrene), poly (2, 5-di-propoxy styrene), poly (

3,4-dipropoxystyrene), poly (3,5 dipropoxystyrene), poly (2 butoxystyrene), poly (3 butoxystyrene), poly (4-butoxystyrene), poly (2,4 dibutoxystyrene) , Poly (2,5 dibutoxystyrene), poly (3,4 dibutoxystyrene), poly (3,5 dibutoxystyrene) and other poly (alkoxystyrene); poly (2 chlorostyrene), poly (3 chlorostyrene) ), Poly (4 chlorostyrene), poly (2, 4 dichlorostyrene), poly (2, 5 dichlorostyrene), poly (2, 6 dichlorostyrene), poly (3,4 dichloro) Styrene), poly (2 bromostyrene), poly (3 bromostyrene), poly (4-bromostyrene), poly (2,4 dib-mouthed styrene), poly (2,5 dib-headed styrene), poly (2, 6— Jib mouth styrene), poly (3,4 dip styrene), poly (2 styrene), poly (3 styrene), poly (4 styrene), poly (2,4 styrene), poly (2,5 styrene) , Poly (2,6 jodostyrene), poly (3,4 jodostyrene), poly (2 fluorostyrene), poly (3 fluorostyrene), poly (4 fluorostyrene), poly (2,4 difluorostyrene), poly (2,5-difluorostyrene), poly (2,6-difluorostyrene), poly (3,4-difluorostyrene) and other poly (norogenated styrene); poly (2-methoxy (Carbon Styrene), Poly (4-Methoxy Carbon Styrene), Poly (2 Ethoxy Carbon Styrene), Poly (4 Ethoxy Carbon Styrene), Poly (2 Propoxy Carbon Styrene), Poly (4 Propoxy Carbon Styrene), Poly (bi-benzoic acid ester) such as poly (2-butoxycarbostyrene), poly (4-butoxycarbostyrene); poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene) Poly (hydroxystyrene) such as poly (1-vininolenaphthalene), poly (2 bulennaphthalene) and other urnaphthalene-based polymers; poly (4 bulbifene), poly (3- (4-biphen-) ) Styrene), poly (4 (4-bi) -styrene) and other poly (aryl styrene); polyacenaphthylene, etc. It is below. In addition, a copolymer of two or more of these; a copolymer of one or two or more of these with another polymer can also be used. For example, styrene mono (α-methyl styrene) copolymer, styrene mono (2-methyl styrene) copolymer, styrene mono (3-methyl styrene) copolymer, styrene mono (4-methyl styrene) copolymer, styrene Mono (2-methoxystyrene) copolymer, styrene mono (3-methoxystyrene) copolymer, styrene- (4-methoxystyrene) copolymer, styrene- (2 chlorostyrene) copolymer, styrene mono (3 Chlorostyrene) copolymer, styrene- (4-chlorostyrene) copolymer, styrene mono (2-methoxycarbostyrene) copolymer, styrene mono (4-methoxycarbostyrene) copolymer, styrene mono ( ο Hydroxystyrene) copolymer, styrene mono (m-hydroxystyrene) copolymer, styrene mono (p hydroxystyrene) copolymer, styrene mono 1 Bulle naphthalene) copolymer, styrene Ren one (2 Bulle naphthalene) copolymer, styrene i (4-bi - Rubifue - Le) copolymer Styrene Methyl Acrylate Copolymer, Styrene-Methyl Methacrylate Copolymer, Styrene Isoprene Copolymer, Styrene Butadiene Copolymer, Styrene One Attorney Nitryl Copolymer, Styrene Maleic Anhydride Copolymer, Styrene Styrene binary copolymers such as butyl acetate copolymer; (a-methylstyrene) -one (2-methylstyrene) copolymer, ((-methylstyrene) -one (3-methylstyrene) copolymer, (a-methylstyrene) Mono (4-methylstyrene) copolymer, (a-methylstyrene)-(2-methoxystyrene) copolymer, (a-methylstyrene)-(3-methoxystyrene) copolymer, (a-methylstyrene) )-(4-methoxystyrene) copolymer, (α-methylstyrene)-(2 chlorostyrene) copolymer, (a-methylstyrene)-(3-chloro Tylene) copolymer, (a-methylenostyrene)-(4 chlorostyrene) copolymer, (a-methylenostyrene)-(2-methoxycarbonyl styrene) copolymer, (a-methylstyrene)- (4-Methoxycarbon styrene) copolymer, (a-methylstyrene) mono (o-hydroxystyrene) copolymer, (a-methylstyrene)-(m-hydroxystyrene) copolymer, (a-methylstyrene) -(p -hydroxystyrene) copolymer, (a-methylstyrene)-(1-Burnaphthalene) copolymer, ((X-Methylstyrene)-(2-Burnaphthalene) copolymer, (a-Methyls Tylene) One (4-Birbiphenyl) Copolymer, (a-Methylstyrene) Methyl Acrylate Copolymer, (a-Methylstyrene) -Methyl Methacrylate Copolymer, (Ex-Methylstyrene) One Isopre Copolymer, (a-methylstyrene) monobutadiene copolymer, (α-methylstyrene) monoacrylonitrile copolymer, (α-methylstyrene) monomaleic anhydride copolymer, (-methylstyrene) vinyl acetate copolymer Such as at-methylstyrene binary copolymer; styrene methyl acrylate, methyl methacrylate copolymer, styrene- (a-methylstyrene) -acrylonitrile copolymer, styrene- (α-methylstyrene) -methyl methacrylate copolymer And the like, and the like. These polymers may be used alone or in combination of two or more.

[0058] The polymer can be produced by polymerizing a single monomer or two or more monomers in the presence of a radical polymerization initiator, a cation polymerization initiator, or a cationic polymerization initiator.

[0059] As the aromatic bur polymer, poly (1 urnaphthalene), poly (2 It is preferable from the viewpoint of heat resistance and availability that it contains at least one selected from di (l-naphthalene) and poly (4-birubiphenol).

[0060] Further, the lower limit of the weight average molecular weight of the aromatic vinyl polymer is preferably 10,000, more preferably 20000, still more preferably 30000, and the upper limit is preferably 1000000, more preferably <ί or 800,000, and even more preferably. Mas <ί until 600000. If the weight average molecular weight force is less than S 10000, the coating film strength tends to decrease, and if the weight average molecular weight is more than 1000000, it tends to be difficult to dissolve in the solvent. The weight average molecular weight is a value measured by gel permeation chromatography (GPC). In the present invention, two or more polymers having different weight average molecular weights may be used in combination, or may be used alone!

[0061] Hereinafter, a coating solution for forming an optical compensation coating film (hereinafter sometimes simply referred to as a coating solution) will be described. The coating liquid contains (i) a polymer selected from the above-mentioned cellulose, a substituted carnomate, and an aromatic vinyl polymer, and (ii) a solvent in which the component (ii) is soluble and soluble.

[0062] The solvent of component (Β) is not particularly limited as long as component (Α) is soluble. Specific examples include benzene, toluene, ο-xylene, m-xylene, p Hydrocarbon solvents such as xylene, ethylbenzene, isopropylbenzene, and jetylbenzene isomer mixtures; methanol, ethanol, 1 propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1 propanol, furfuryl Alcohol solvents such as alcohol and benzyl alcohol; ether solvents such as ethyl ether, isopropyl ether, 1,3 dioxolane, 1,4 dioxane, tetrahydropyran, tetrahydrofuran, 1,2-dimethoxyethane; acetone, 2 butanone, Ketone solvents such as 4-methyl-2-pentanone and cyclohexanone; Len, black mouth form, carbon tetrachloride, 1, 2-dichloro mouth ethane, 1, 1, 1 trichrome mouth ethane, 1, 1, 2—triclo mouth ethane, 1, 1, 1, 2—tetrachloro mouth ethane, 1 , 1, 2, 2-tetrachloroethane, pentachloroethane, hexachloroethane, 1-clopronone, 2-clopronone, 1,1-dichloropronone, 1,2-dichloromethane. Ronon, 1,3 dichlorof. Ronon, 2, 2 dichlorof. Ronone, 1, 2, 3 Trichloropronone, Black benzene, 1, 2 Dichloro benzene, 1, 3 Dichloro benzene, 1, 4 Dichlorobenzene, 1, 2, 3 Trichloro benzene, 1, 2, 4 Trichome benzene, 1, Halogen-based solvents such as 3,5-trichlorodiethylbenzene; ester-based solvents such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethyl acetate sorb acetate; N, Amide solvents such as N-dimethylformamide, N, N-dimethylacetamide, and 1-methyl-2-pyrrolidinone; amine solvents such as pyrrolidine, piperidine, and pyrrole. These solvents may be used alone or in combination of two or more.

[0063] In the present invention, the amount of the solvent is preferably a lower limit that the ratio of the component (A) to the total weight of the component (A) and the component (B) is 1% by weight as the lower limit and 70% by weight as the upper limit. More preferably, the lower limit is 3% by weight, and the upper limit is 50% by weight. When the proportion of component (A) is less than 1% by weight, the coating film thickness tends to be thin, and the required film thickness tends to be difficult to obtain. When it exceeds 70% by weight, the viscosity of the coating liquid is high. Therefore, workability tends to be inferior.

[0064] Next, the phase difference adjusting agent in the present invention will be described. The thickness retardation of the coating film for optical compensation is the force expressed by [(n + n) / 2-n] X d. In order to adjust to the required thickness retardation, (n + n) Z2— There are a method of adjusting the value represented by n and a method of adjusting d (film thickness). The method of adjusting the film thickness is simple, but as mentioned earlier, increasing the film thickness and increasing the thickness phase difference only increases the bulk of the liquid crystal display device components after the coating film is formed. There arises a problem that the material cost of the film increases. Conversely, when it is necessary to reduce the thickness phase difference by reducing the film thickness, there are cases where there are restrictions on the limitations of the coating method for forming a thin film having a uniform thickness, the strength of the thin film, and the like. Therefore, it is effective to adjust the value represented by (n + n) Z2−n by adding a phase difference adjusting agent to obtain a target thickness phase difference. In order to obtain an optical compensation coating film having the characteristics of ((n + n) / 2-n] (1 <0), the retardation adjusting agent of the present invention is particularly suitable for such a thickness retardation. It's no surprise that you can adjust it.

[0065] The retardation adjusting agent for cellulose N-substituted carbamate of the present invention is preferably composed of at least one selected from strength rubamate ester, N-substitution strength rubamate ester, urea, and N-substituted urea. ! /

[0066] The retardation adjusting agent for cellulose N-substituted carbamate of the present invention is cellulose N- The thickness phase difference of the substituted carbamate can be adjusted in the negative direction. The strong rubamic acid ester can be obtained by, for example, a known method of reacting ammonia with a chloroformate, and the N-substituted rubamic acid ester can be obtained by, for example, forming a primary amine or a secondary amine with a chloroformate. It can be produced by a known method of reacting. The urea can be obtained, for example, by an industrial production method in which ammonia and carbon dioxide are reacted under high temperature and high pressure. The N-substituted urea is obtained by reacting, for example, an isocyanate compound with a primary amine or a secondary amine. It can be produced by a known method.

[0067] The strength rubamic acid ester of the present invention contains a strength rubamoyloxy group (NH—CO—O—).

2

Any compound having 1 to 8 powerful rubamoyloxy groups that can be used is preferred. A compound containing 1 is more preferred. From the viewpoint of availability of raw materials, a compound represented by the following general formula (7) is preferred.

[0068] [Chemical 10]

NH ₂ -C-0-R ³⁹ (7)

0

(In the formula, R ³⁹ represents an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. ;).

[0070] In the general formula (7), R ³⁹ is an alkyl group having 1 to 16 carbon atoms, a halogenated alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or an alkyl group having 7 to 16 carbon atoms. R ³⁹ is more preferably an aralkyl group. R ³⁹ is an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Particularly preferred is a group.

[0071] The N-substituted rubamic acid ester of the present invention contains an N-substituted rubamoyloxy group (R-NH-CO-O-, R is an alkyl group, a halogenated alkyl group, an aryl group, an aralkyl group). Any of them can be used. N—Substitution power A compound containing 1 to 8 rubamoyloxy groups is preferred. A compound containing 1 is more preferred. Viewpoint of availability of raw materials Compounds represented by the following general formula (8) are preferred. Yes.

[0072] [Chemical 11]

R ⁴⁰ -NH-COR ⁴¹ (8)

O

[In the formula, R ^4Q and R ⁴¹ are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents ~ 20 aralkyl groups).

[0074] In the general formula (8), R ^4Q and R ⁴¹ are the same or different and each represents an alkyl group having 1 to 16 carbon atoms, a halogenated alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R ^4Q and R ⁴¹ are more preferably an aralkyl group having 7 to 16 carbon atoms, the same or different, and an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, Particularly preferred are aryl groups having 6 to 12 carbon atoms and aralkyl groups having 7 to 12 carbon atoms.

[0075] The N-substituted urea of the present invention can be used as long as it contains a ureylene group (one NH—CO—NH—). A compound represented by the following general formula (9) is also preferable from the viewpoint of availability of raw materials.

[0076] [Chemical 12]

R ⁴² -NH-C-NH— ⁴³ (Ο

II)

o

[In the formula, R ⁴² and R ⁴³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Represents a 7-20 aralkyl group having carbon atoms).

In General Formula (9), R ⁴² and R ⁴³ are the same or different and each represents an alkyl group having 1 to 16 carbon atoms, a halogenated alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R ⁴² and R ⁴³ are more preferably an aralkyl group having 7 to 16 carbon atoms, the same or different, and an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, Carbon number 6-12 Particularly preferably an aryl group, an aralkyl group having 7 to 12 carbon atoms.

[0079] Specific examples of the above carnomate ester include, for example, methyl carnomate, ethyl rubamate, cyclopentyl rubamate, cyclohexyl rubamate, trichloromethyl rubamate, ferro-carbamate fe- , Naphthyl chloride, naphthyl chloride, benzyl carbamate, ethylene glycol dicarbamate, propylene glycol dicarbamate, hydroquinone dicarbamate, pyrocatechol dicarbamate, pyrogallol tricarbamate and the like.

[0080] Specific examples of the N-substituted rubamic acid ester include, for example, methyl N-methylcarbamate, ethyl N-methylcarbamate, cyclopentyl N-methylcarbamate, cyclohexyl N-methylcarbamate, and trichloro N-methylcarbamate. Methyl, phenyl N-methylcarbamate, 1-naphthyl N-methylcarbamate, 2-naphthyl N-methylcarbamate, benzyl N-methylcarbamate, ethylene glycol bis (N-methylcarbamate), propylene glycol bis (N-methylcarbamate), Hydroquinone bis (N-methinorecarbamate), pyro-teconolebis (N-methinorecarbamate), pyrogallol tris (N-methylcarbamate), methyl N-phenol carbamate, ethyl N-phenol carbamate, N-phenylcarbamate cyclopentyl, N-phenylcarbamate cyclohexyl, N-phenylcarbamate trichloromethyl, N-phenolcarbamate phenol, N-phenylcarbamate 1-naphthyl, N-phenol 2-Naphthyl rubamate, benzyl N phenolcarbamate, ethylene glycol bis (N phenol carbamate), propylene glycol bis (N phenol carbamate) ゝ hydroquinone bis (N phenol carbamate), pyrotechnic les bis ( N phenol-carbamate), pyrogallol tris (N-phenol carbamate), N, N, bis (methoxycarbol) ethylenediamine, N, N, bis (ethoxycarbole) ethylenediamine, N, N, I Bis (phenoxycarbol) ethylenediamine, N, N, monobis (benzyloxyca) (Polyol) ethylenediamine, N, N, —bis (methoxycarbol) — 1, 2—phenolene diamine, N, N, monobis (ethoxycanoleboninole) 1, 2—phenylenediamine, N, N, 1 bis (phenoxycanoleboninole) 1,2-Fenylene diamine, N, N, 1 bis (penzinoreoxycarbole) —1,2,2-phenolic diamine, N, N, —bis (methoxycarbo-) Le) — 1 , 3 Phenylenediamine, N, N, One bis (ethoxycarbon) 1, 1, 3 Phenylenediamine, N, N, One bis (Phenoxycanoleboninole) 1, 3 Phenylenediamine, N, N , -Bis (benzyloxycarbol) 1,3 phenylenediamine, N, Ν'-bis (methoxycarbol) -1,4 phenylenediamine, Ν, Ν, bis (ethoxycarbo-) 1), 1, 4—Phenoldiamine, Ν, Ν, and bis (phenoxycarbol) -1, 4, Phenoldiamine, Ν, Ν, and bis (Penzinoreoxycanoleboninole), 1, 4, Hue -Rangeamine, Ν— (4 tolyl) carnomate ethyl, Ν— (4-tolyl) carnomate phenol, etc.

[0081] Specific examples of Ν-substituted urea include 、, N'-dimethylurea, Ν, N'-diethylurea, Ν, Ν, -dichloromethylurea, Ν, Ν, -diphenolurea. , Ν, Ν, -dibenzylurea, Νethyl-Ν, monomethylurea, Ν-methyl-Ν, one-phenolurea, Ν-benzyl Ν, -phenolurea, Ν, Ν, —di-ρ-tolyl Urea, Ν ferrule Ν,-(Ρ-tolyl) urea, and the like. These retardation agents for cellulose Ν-substituted carbamates may be used alone or in combination of two or more.

[0082] Among these, from the viewpoint of availability and effects, the retardation adjusting agent for cellulose Ν substituted carnomates is carnomate ethyl, carnomate phenol, Ν-carcarnomate ethyl, Ν-phenol. -Lucarbamate phenol, Ν— (4-Tolyl) strength ethyl rubamate, Ν mono (4-tolyl) strength rubamate phenol, urea, Ν, Ν, diphenylurea, Ν, Ν, ジー Ρ Tolyl It is particularly preferable that at least one selected from the group strength of urea, Νphenol Ν, and-(ρtolyl) urea.

In the present invention, in the coating solution for forming an optical compensation coating film, the total weight of the polymer as component (i) and the phase difference adjusting agent as component (C) is 100% by weight. %, It is preferable to use the lower limit of 0.1% by weight and the upper limit of 70% by weight. The lower limit of 0.2% by weight and the upper limit of 65% by weight are preferred. More preferably, the lower limit is 0.3% by weight, and the upper limit is 60% by weight. When the ratio of the phase difference adjusting agent is less than 0.1% by weight, the effect of adjusting the thickness phase difference tends to be small, and when it is larger than 70% by weight, it tends to bleed from the coating film for optical compensation. is there.

[0084] Next, a description will be given of the resin that can be added for the purpose of modifying the properties of the coating film of the present invention. I will explain. Examples of the resin that can be added include polycarbonate resin, talyl resin, polyester resin, polystyrene resin, polyolefin resin, polyamide resin, polyimide resin, polyvinyl alcohol resin, polybuta resin. Examples include settal resin, polyether sulfone resin, polyarylate resin, epoxy resin, silicone resin, phenol resin, urethane resin, and the like.て can be added.

[0085] Next, an additive agent that can be added for the purpose of modifying the properties of the coating film and coating solution of the present invention will be described. Additives include antioxidants (eg, Hindu phenols such as IRGANOX 1010, IRGANOX 1135, IRGANOX 1330, etc. manufactured by Ciba 'Specialty' Chemicals), processing stabilizers (eg, HP-136, IRGANOX manufactured by Ciba 'Specialty' Chemicals) E201, IRGAFOS 168, etc.), light stabilizers (for example, hindered amines such as Sanol LS-765, Sanol LS-770 from Sankyo Lifetech), UV absorbers (for example, TINUVIN P, TINUVIN made by Chinoku 'Specialty' Chemicals) 213, benzotriazoles such as TINUVIN 326), adhesion improvers (eg, silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane), silanol condensation catalysts (eg, rivers) Such as aluminum tris (ethyl acetate acetate), aluminum chelate M, etc. Luminium chelates), plasticizers (for example, esters such as di-2-ethylhexyl phthalate and diisobutyl adipate), surfactants (for example, fluorine compounds such as Fluorad FC-430 and Fluorad FC-4430 manufactured by Sumitomo 3EM) And antistatic agents (for example, IRG ASTAT P18, IRGASTAT P22, etc. manufactured by Ciba Specialty Chemicals) and the like, and these can be added within a range without impairing the object and effect of the present invention.

[0086] The coating liquid of the present invention can be obtained, for example, by mixing the above-mentioned components at a temperature not lower than the melting point of the solvent and not higher than the boiling point, or after being mixed or stirred.

Next, the optical element substrate will be described. As the substrate, it is preferable to be transparent in view of the power with which various types of substrates can be used, particularly the application power. Examples of specific compounds used for the substrate include polycarbonate polymers produced by polycondensation of bisphenol A and salty carbon; polymethyl acrylate, polymethyl methacrylate, etc. Poly Acrylic acid ester; Condensation of dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid and the like, and ring opening of latatones with ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, neopentyl darlicol, etc. Polyester polymers obtained by polymerization; styrene polymers such as polystyrene and poly (-methylstyrene); copolymers of acrylic acid esters and styrene; hydrogenated products of polyethylene, polynorbornene and polyisoprene, Polyolefin-based polymers such as hydrogenated polybutadienes; Cellulose-based resins such as triacetyl cellulose; Polyamides such as nylon 6 and nylon 66; Polyimides; Polyamide imides; Polybulal alcohol; Butyl chloride; Polyethersulfone; Examples thereof include xylose resin; silicone resin; compounds described in International Publication No. 01Z37007 pamphlet. As a substrate, these polymers can be used as a solution casting method, a uniaxial stretching method of a dried product after solution casting, a biaxial stretching method of a dried product after solution casting, an extrusion method, a uniaxial stretching method of extrusion, and a biaxial stretching method of an extruded product. Examples of the film formed by an axial stretching method, a calendar method, and the like, and a polarizing plate, a glass plate, a color filter, a liquid crystal cell, and the like, which are attached to a polarizer as a protective film. These substrates can also be used as substrates for forming an optical compensation coating film.

Next, a method for forming the optical compensation coating film of the present invention will be described. The coating film for optical compensation can be suitably prepared on a substrate by applying the coating liquid of the present invention on one or both sides of the substrate to form a coated substrate, and then drying the coated substrate. The coating methods include gravure roll coating method, Mayer bar coating method, doctor blade coating method, linole roll coating method, dip coating method, air knife coating method, calendar coating method, squeeze coating method, kiss coating method, bar coating method. Slot die coating method, spin coating method and the like.

[0089] As the drying method, for example, a method of leaving the coated substrate in air or an inert gas such as nitrogen (air drying), a method of heating and drying in a hot air oven, an infrared heating furnace, or the like, a vacuum dryer, or the like Can be carried out by a method of drying under reduced pressure, etc., or a combination thereof.

[0090] As the drying temperature condition, constant temperature, multi-step temperature increase! /, Or deviation can be used. For constant temperature, the lower limit is 30 ° C, the upper limit is 300 ° C. The lower limit is 0 ° C and the upper limit is 280 ° C. The preferred lower limit is 10 ° C and the upper limit is 260 ° C. When the drying temperature is lower than -30 ° C, the drying time tends to be longer. When the drying temperature is higher than 300 ° C, the coating film or the substrate tends to be thermally deteriorated. Although such constant temperature drying can be used, primary drying and secondary drying are particularly preferable from the economical viewpoint that it is preferable to increase the temperature in multiple stages in order to effectively dry.

[0091] In primary drying, the lower limit is 5 ° C, the lower limit is 0 ° C, the upper limit is 40 ° C, and the upper limit is 35 ° C. The lower limit is 10 ° C, and the upper limit is 30 ° C. preferable. Primary drying is (n + n)

Z2— Necessary for forming the foundation of the internal structure of the coating film necessary to increase the absolute value of n. When the primary drying temperature is lower than o ° c, the drying time required for the basic formation of the inner structure of the coating film tends to be longer, and when it is higher than 40 ° C, it is expressed by (n + n) / 2-n There is a tendency that it is difficult to form the foundation of the internal structure of the coating film necessary to increase the absolute value of the value to be increased.

[0092] In secondary drying, the lower limit of 80 ° C and the upper limit of 300 ° C are preferable lower limit of 90 ° C, and the upper limit of 280 ° C is more preferable lower limit of 100 ° C and upper limit of 260 ° C. preferable. Secondary drying is necessary to establish the coating film internal structure necessary to increase the absolute value of the value represented by (n + n) / 2-n. When the secondary drying temperature is lower than 80 ° C, the internal structure of the coating film tends to be insufficiently established, and when it is higher than 300 ° C, the coating film and the substrate tend to be thermally deteriorated. When the absolute value of (n + n) Z2−n is sufficiently large, the established internal structure of the coating film is observed with a transmission electron microscope (TEM) or the like. can do.

[0093] Further, the present invention provides a coating for optical compensation by applying a coating solution to a substrate to form a coated substrate, then exposing the coating film to the vapor of component (B), and further drying. This is the method of forming a film.

[0094] Annealing is preferably performed for improving the leveling property of the coating film, stress relaxation, and the like, and is effective, for example, for reducing in-plane retardation and reducing in-plane retardation fluctuation. In the present invention, the annealing is preferably performed in the vapor of the component (B) by standing still horizontally with the coating film of the coated substrate facing upward. The temperature during annealing can be set in various ways. Lower limit 30 ° C, upper limit (boiling point of component (B)) is preferred Lower limit 15 ° C, upper limit (component (B) boiling point (° C) -5 ° C] is more preferred lower limit 0 ° C, and upper limit [(B) component boiling point (° C) -10 ° C] is more preferred. If the temperature during annealing is lower than 30 ° C, the annealing time tends to be longer, and if the temperature during annealing is higher than the boiling point (° C) of component (B), the coating film tends to flow out from the substrate. Tend to be. Various pressures can be set during annealing, and atmospheric pressure, increased pressure, or reduced pressure can be used, but atmospheric pressure is preferable in terms of workability.

Next, a method for manufacturing the optical element of the present invention will be described. The optical element here is composed of a substrate and an optical compensation coating film coated on the substrate. Also included is an element used for optical use after the substrate force is once peeled off from the coating film for optical compensation.

[0096] The optical element is coated with the coating liquid of the present invention on one or both surfaces of the substrate using the coating method described in the method for forming a coating film for optical compensation, and then dried or optically compensated. After coating using the coating method described in the method for forming a coating film for coating, it can be suitably produced by annealing and drying.

Drying can be suitably performed by using the drying method and the drying temperature described in the method for forming the optical compensation coating film.

[0098] The coating film for optical compensation of the present invention has a maximum refractive index n in the plane, n is the minimum refractive index, n is the refractive index in the thickness direction, and d is the film thickness. [(N + n) / 2-n] It is preferable to have the characteristic of Xd <0. In particular, an unstretched film formed by a solution casting method using a solution in which any one of the above cellulose N-substituted carbamates or aromatic vinyl polymers is dissolved in a solvent exemplified as the component (B). In the membrane [(n + n) / 2-n]

It is preferable that the above-mentioned properties are obtained by a coating film for optical compensation formed by containing any one of cellulose N-substituted carbamates satisfying the relationship of X d and 0 or an aromatic bur polymer. When the thickness of the optical compensation coating film is d (nm), the in-plane retardation is expressed by (nn) X d, and the thickness retardation is [(n + n) / 2−n] X d. The expressed in-plane phase difference is preferably lower limit Onm and upper limit 200 nm force, preferably lower limit Onm and upper limit 300 nm, more preferably lower limit Onm and upper limit lOOnm, when measured with 590 nm light. If the in-plane retardation is larger than 300 nm, it tends to be difficult to compensate for the retardation due to birefringence in a liquid crystal cell or the like. Also, the thickness retardation is 590 nm, and the lower limit—1000 ηm, the upper limit—lnm is the lower limit of 800 nm, and the upper limit—lOnm is the lower limit—60 Onm, an upper limit of 20 nm is more preferable. If the thickness retardation is smaller than lOOOnm, it tends to be difficult to compensate for the retardation due to birefringence of liquid crystal cells.

[0099] On the other hand, a coating film for optical compensation satisfying the relationship of [(n + n) / 2-n] Xd≥100 used in another application can be obtained by containing a cellulose derivative. . Cellulose derivatives can be produced, for example, by chemically modifying cellulose obtained from various wood pulps, cotton linters, cotton lint and the like as raw materials. For example, carboxylic acid ester derivatives such as cellulose formate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose butyrate, cellulose acetate butyrate, cellulose trifluoroacetate; cellulose sulfate, cellulose nitrate, cellulose phosphate, etc. Inorganic acid ester derivatives of the following: ether derivatives such as methylcellulose, ethylcellulose, propylcellulose, butinoresenorelose, hydroxyethinoresenorelose, hydroxypropinoresenorelose, cyanoethylcellulose, carboxymethylcellulose, etc. It is done.

[0100] Of these, ether derivatives are preferred from the standpoint of physical properties such as low hydrolyzability and low hygroscopicity. More preferably, it is an ether derivative in which at least one hydroxyl group of cellulose is substituted with an alkoxy group having 1 to 20 carbon atoms, and more preferably, at least one of hydroxyl groups of cellulose is substituted with an alkoxy group having 1 to 10 carbon atoms. It is an ether derivative.

[0101] Preferable examples of the preferred! / 誘導体 cellulose derivatives are methylcellulose, ethyl cellulose, propinoresenorelose, butinoresenorelose, pentinoresenorelose, hexinoresenorelose, heptinoresenorelose, tasty cutinore Senorelose, Cyclopentino Resenellose, Succeed Hexino Resenorelose, Methinore Ethino Resenorelose, Methinorepropino Resenorelose, Methinore Butino Resenorelose, Methino Resentino Resenorelose, Methino Resenorelose , Methinoles, petitenoresenorelose, methinoreoctinoresenorelose, methinorecyclopentinoresenolesose, methinorecyclohexenoresenorelose, ethinorepropinoresenorelose, ethinorebutinoresenorerose, ethinorepenti Norecenorelose, ethenorehexenoresenorellose, ethenoreheptinoresenorose, ethinore-skilled cutinorecenorelose, ethenorecyclopentenoresenellose, ethinorecyclohexylcellulose and the like. These cellulose derivatives can be used alone 2 or more types may be used in combination.

[0102] The above ether-based derivative of cellulose can be produced, for example, by converting it to alkaline cellulose with sodium hydroxide or the like, and then adding and heating and stirring an alkyl halide such as chlorinated alkyl. At this time, when two or more alkyl halides are used, an ether derivative substituted with two or more alkoxy groups can be obtained.

[0103] Cellulose has three hydroxyl groups per glucose residue as its structural unit, and the degree of substitution per glucose residue (hereinafter sometimes referred to as DS) is 3 at maximum. The lower limit is preferably 0.1, more preferably 0.5, even more preferably 1, and the upper limit is preferably 3, more preferably 2.95, and even more preferably 2.9. If the degree of substitution is lower than 0.1, it tends to be difficult to dissolve in a solvent. In the present invention, two or more cellulose derivatives having different degrees of substitution may be used in combination, or may be used alone!

[0104] Further, the lower limit of the number average molecular weight of the cellulose derivative is preferably 5000, more preferably 8000, still more preferably 10000, and the upper limit is preferably 300000, more preferably 250000, and even more preferably 200000. If the number average molecular weight is less than 5,000, the coating film strength tends to decrease, and if the number average molecular weight is more than 300,000, it tends to be difficult to dissolve in a solvent. The number average molecular weight is a value measured by gel permeation chromatography (GPC). In the present invention, two or more cellulose derivatives having different number average molecular weights may be used in combination, or may be used alone.

[0105] Further, various cellulose derivatives exemplified as the cellulose derivative may be used alone, or two or more kinds may be used in combination.

[0106] Next, the optical compensation film (retardation film) of the present invention will be described. As the optical compensation film (retardation film), a film formed from those exemplified as the substrate for the optical element is used, and the optical compensation layer is formed by using the method for forming the optical compensation coating film. It can be suitably manufactured.

[0107] Next, the polarizing plate of the present invention will be described. As a polarizing plate, for example, a protective film is attached to both surfaces of a polarizer using an adhesive such as a polyester-based adhesive, a polyacrylic adhesive, an epoxy-based adhesive, a cyanacrylic adhesive, or a polyurethane-based adhesive. A combination of these can be listed. Examples of polarizers include iodine and Z or Z Is a polarizer produced by adsorbing and orienting a dichroic dye, a polybulualcohol-based film is dehydrated to form a polyene, and a polarizer and polysalt hybrid film produced by orienting are dehydrochlorinated. Examples include those prepared by forming and orienting polyene. Examples of the hydrophilic polymer film used for the polarizer include a polybulal alcohol film, a partially formalized polybulal alcohol film, and a saponified film of an ethylene acetate butyl copolymer. Examples of the protective film include those exemplified as the substrate for the optical element, those formed into a film, and the optical compensation film (retardation film) of the present invention. Among the substrates for the optical element, When the film is pasted on both sides of the polarizer, the optical compensation coating film of the present invention is formed on at least one side of the polarizing plate using the method for forming an optical compensation coating film after preparing the polarizing plate. By providing, it can be set as the polarizing plate of this invention. When the optical compensation film (retardation film) of the present invention is used as a protective film, it can be used on both sides of a polarizer, or the optical compensation film (retardation film) of the present invention is used on one side and the opposite. It is also possible to use a film made of the optical element substrate on the surface. Also, after producing a polarizing plate using the optical compensation film (retardation film) of the present invention on one side and a film formed on the opposite side of the substrate for the optical element, a new polarizing plate is prepared on one side or both sides. The optical compensation coating film of the present invention can also be provided.

[0108] Next, the liquid crystal display device of the present invention will be described. As a liquid crystal display device, for example,

, Light source Z light guide plate Z light diffusing film Z lens film Z brightness enhancement film Z polarizing plate Z liquid crystal cell display device configured in the order of Z polarizing plate, the incident light side of the liquid crystal cell and the Z or outgoing light side The liquid crystal of the present invention is mounted by mounting the optical compensation film (retardation film) of the present invention on the polarizing plate of the incident light side and the Z or outgoing light side of the Z or liquid crystal cell. It can be a display device. Examples of the liquid crystal cell method include a VA (Vertical Alignment) method, an IPS (In-Plane Switching) method, and an OCB (Optically Compensated Birefringence) method.

Example

[0109] Examples are given below to describe the present invention in more detail, but the present invention is not limited to these examples. [0110] Calculation of three-dimensional refractive index (n, n, n)

Using an automatic birefringence meter, KOBRA-WR, manufactured by Oji Scientific Instruments, measurement was performed at 590 nm under 25 ° C, and the three-dimensional refractive index was calculated. From the obtained results, the in-plane retardation is calculated as (n -n)

Obtained by Xd. Further, the thickness phase difference was determined by [(n + n) / 2-n] Xd. However, when the phase difference was measured with the slow axis as the tilt center axis, if the phase difference increased as the tilt angle increased!], The following method was also used to determine the sign of the phase difference. Overlay the polycarbonate λ 4 plate on the manufactured optical element, and attach it to the automatic birefringence meter KOBRA-WR so that the orientation angle force of the λ 4 plate is 0 ± 1 degree. 2 The phase difference was measured with 590nm light at 5 ° C. When the measurement result is higher than the phase difference of λ Ζ4 plate alone, it is considered that the phase difference of the optical element alone is also rising in the positive direction as the tilt angle is increased, and when it is lower than the phase difference of λ Ζ4 plate alone Considers that the phase difference of the single optical element decreases in the negative direction as the tilt angle increases, and adds a positive or negative sign to the phase difference of the single optical element measured earlier to calculate the three-dimensional refractive index. did. From the obtained results, the in-plane phase difference was determined by (η−n) Xd. Also, the thickness phase difference is expressed as [(n + n) / 2-n

It was determined by Xd.

[0111] (Synthesis Example 1) Synthesis of cellulose N-phenylcarbamate (1)

Cellulose (Avicel TG-F20 from Asahi Kasei Chemicals) vacuum dried for 7 hours at 60 ° C in a 500 ml 4-neck flask equipped with a condenser, nitrogen inlet, stirrer, and thermometer. Was added to form a suspension, and then 7.7 g of phenol isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Nitrogen was introduced, and the temperature was raised to 110 ° C. with stirring, followed by reaction for 7 hours. Then, after cooling to 25 ° C, the reaction solution was dropped into 400 ml of ethanol to form a precipitate. After separation by filtration, the resulting polymer was dissolved by adding 25 ml of acetone, and then dropped into 400 ml of pure water to cause precipitation. After separation by filtration, the obtained polymer was again dissolved in 30 ml of acetone and dropped into 400 ml of pure water to form a precipitate. After separation by filtration and washing with water and vacuum drying at 60 ° C for 4 hours, 2.5 g of cellulose N-ferrugerbamate (1) was obtained (hereinafter sometimes referred to as synthetic product (1)). O) DS of synthetic product (1) was 3 as a result of proton NMR analysis. DS is the chemical shift area (3.4 to 5.5 ppm) of protons derived from the cellulose skeleton and the chemical shift area (6.7 to 7.8 ppm) of protons in the phenolic group. Was determined by comparing.

[0112] (Synthesis Example 2) Synthesis of cellulose N-phenylcarbamate (2)

Cellulose (Avicel TG-F20 from Asahi Kasei Chemicals) vacuum dried for 7 hours at 60 ° C in a 500 ml 4-neck flask equipped with a condenser, nitrogen inlet, stirrer, and thermometer. Was added to form a suspension, and then 7.7 g of phenol isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Nitrogen was introduced, and the temperature was raised to 110 ° C. with stirring, followed by reaction for 7 hours. Then, after cooling to 25 ° C, the reaction solution was dropped into 400 ml of ethanol to form a precipitate. After separation by filtration, the resulting polymer was dissolved by adding 30 ml of acetone, and then dropped into 400 ml of pure water to cause precipitation. After filtration, washing with water and vacuum drying at 60 ° C for 4 hours, 2.2 g of cellulose N-phenol carbamate (2) was obtained (hereinafter sometimes referred to as synthetic product (2)). _The degree of substitution DS of synthetic product (2) was 3 as a result of proton NMR analysis. DS is obtained by comparing the chemical shift area (3.4 to 5.5 ppm) of protons derived from the cellulose skeleton with the chemical shift area (6.7 to 7.8 ppm) of protons in the phenolic group. Were determined.

[0113] (Synthesis Example 3) Synthesis of Cellulose N— [2- (Trifluoromethyl) phenyl] carbamate (3)

Cellulose (Avicel TG-F20 from Asahi Kasei Chemicals) vacuum dried for 7 hours at 60 ° C in a 500 ml 4-neck flask equipped with a condenser, nitrogen inlet, stirrer, and thermometer. Then, 8.7 g of 2- (trifluoromethyl) phenol isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Nitrogen was introduced, and the temperature was raised to 110 ° C. with stirring, followed by reaction for 7 hours. Thereafter, after cooling to 25 ° C., 200 ml of ethanol was added, and the reaction solution was dropped into 1.5 L of pure water to form a precipitate. After separation by filtration, 100 ml of acetone was added to the obtained polymer and dissolved, and then dropped into 2 L of pure water to cause precipitation. After filtration, washing with water and vacuum drying at 60 ° C for 4 hours, the polymer was put into a Soxhlet extractor. After 20 Soxhlet extractions with methanol and vacuum drying at 25 ° C for 4 hours, 3.4 g of cellulose N— [2- (trifluoromethyl) phenol] force permeate (3) Obtained (hereinafter sometimes referred to as synthetic product (3).) ₀ DS of synthetic product (3) was 3 as a result of proton NMR analysis. DS is the conversion of protons derived from the cellulose skeleton. The chemical shift (3.5-5.5 ppm) area was compared with the proton chemical shift (6.9-7.9 ppm) area of the 2- (trifluoromethyl) phenol group.

[0114] (Experiment 1)

Synthetic product (1) 4.85 g of butyl acetate was added to 0.85 g and dissolved at 25 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane phase difference: Onm, thickness phase difference: lnm) using a bar coater, and then 120 ° An optical element was fabricated by drying in air for 1 minute at C. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained as described above were measured, and the results are shown in Table 1.

[0115] (Experiment 2)

Synthetic product (1) 4.85 g of ethyl acetate sorb acetate was added to 0.85 g and dissolved at 25 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater, It was placed in a glass container filled with solvacetate vapor, sealed, and then annealed at 25 ° C for 24 hours. Thereafter, the coated substrate was taken out and dried in air at 120 ° C for 1 minute to produce an optical element. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, the physical properties of the optical element obtained as described above were measured, and the results are shown in Table 1.

[0116] (Experiment 3)

Synthetic product (3) 1. Black mouth form 9. Og was added to Og and dissolved at 25 ° C. Next, this coating solution was applied to a 150 / zm-thick glass substrate (average refractive index: 1.52, in-plane phase difference: Onm, thickness phase difference: lnm) using a bar coater. The optical device was fabricated by drying in air for 1 minute at ° C. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, the physical properties of the optical element obtained above were measured, and the results are shown in Table 1.

[0117] (Experiment 4)

The optical element produced in Experimental Example 3 was placed in a glass container filled with Kuroguchi-form vapor, sealed, and then annealed at 30 ° C for 7.5 hours. Then remove the optical element and Dry in air for 1 minute. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained as described above were measured, and the results are shown in Table 1. Here, an in-plane birefringence (n−n) smaller than that in Experimental Example 3 was obtained. In other words, the in-plane retardation can be reduced by annealing.

[0118] (Experiment 5)

Synthetic product (2) To 0.52 g, 3.48 g of 1,2-dimethoxyethane was added and dissolved at 23 ° C. Next, this coating solution is applied onto a 150 m thick glass substrate (average refractive index: 1.5, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater. It was. Thereafter, the coated substrate was dried in air at 23 ° C. for 44 hours to produce an optical element. The coating film thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained as described above were measured. The results are shown in Table 2.

[0119] (Experimental example 6)

4.5 g of ethylene glycol monomethyl ether acetate was added to 0.5 g of the synthetic product (2) and dissolved at 23 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater, and coated substrate It was. The coated substrate was then dried in air at 100 ° C for 1 minute to produce an optical element. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained as described above were measured. The results are shown in Table 2.

[0120] (Experimental example 7)

Synthetic product (2) 0.5 g of butyl acetate 4. Og and ethylene glycol monomethyl etherate 0.5 g were added and dissolved at 23 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: 1 nm) using a bar coater. It was. Thereafter, this coated substrate was dried in air at 23 ° C. for 25 minutes to produce an optical element. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Then obtained by above The physical properties of the optical element were measured. The results are shown in Table 2.

[0121] (Experiment 8)

The same procedure as in Experimental Example 7 was performed, except that the coated substrate was dried in air at 30 ° C. for 25 minutes to produce an optical element. The physical properties of the obtained optical element were measured. The results are shown in Table 2.

[0122] (Experiment 9)

The same procedure as in Example 5 was performed, except that the coated substrate was dried in air at 23 ° C for 44 hours and further dried in air at 100 ° C for 1 minute to produce an optical element. It was. The physical properties of the obtained optical element were measured. The results are shown in Table 2. An optical element in which the absolute value of (n + n) / 2−n is larger than that in Experimental Example 5, which was simply dried in air at 23 ° C. for 44 hours, was obtained.

[0123] (Experiment 10)

The same procedure as in Experimental Example 6 was performed, except that the coated substrate was dried in air at 23 ° C for 19 hours and further dried in air at 100 ° C for 1 minute to produce an optical element. It was. The physical properties of the obtained optical element were measured. The results are shown in Table 2. An optical element having a larger absolute value represented by (n + n) / 2−n than that obtained in Experimental Example 6 which was simply dried in air at 100 ° C. for 1 minute was obtained.

[0124] (Experiment 11)

Except that the coated substrate was dried in air at 23 ° C for 25 minutes and further dried in air at 250 ° C for 1 minute, the same procedure as in Experimental Example 7 was performed. It was. The physical properties of the obtained optical element were measured. The results are shown in Table 2. An optical element with a larger absolute value of (n + n) / 2-n than in Experiment 7 was obtained, which was only dried in air at 23 ° C for 25 minutes.

[0125] (Experiment 12)

The same procedure as in Experimental Example 8 was performed, except that the coated substrate was dried in air at 30 ° C for 25 minutes and further dried in air at 250 ° C for 1 minute to produce an optical element. It was. The physical properties of the obtained optical element were measured. The results are shown in Table 2. Optical element with a larger absolute value of (n + n) / 2-n than Experimental Example 8 which was dried in air for 25 minutes at 30 ° C Is obtained.

[0126] [Table 1]

[0127] [Table 2]

(Experimental example 13)

40 μm thick cellulose acetate film instead of glass substrate (in-plane retardation: On m, thickness retardation: 8 nm), and an optical compensation film was prepared by forming a coating film of lOOOOnm thereon, and the same operation as in Experimental Example 10 was performed. As a result of measuring the physical properties of the obtained optical compensation film, the in-plane retardation was Onm and the thickness retardation was 40 nm.

[0129] (Experiment 14)

A polyvinyl alcohol film was impregnated with iodine and stretched to produce a polarizer. An 80 m thick cellulose acetate film was bonded to one side of this polarizer using a polyacrylic adhesive. Furthermore, the optical compensation film produced in Experimental Example 13 was bonded to the opposite surface of the polarizer using a polyacrylic adhesive so that the coating film surface was on the outside, and a polarizing plate having an optical compensation layer was produced. .

[0130] (Experiment 15)

A liquid crystal display device equipped with an IPS liquid crystal cell was prepared, and a display device was produced in which the optical compensation film produced in Experimental Example 13 was superimposed on the outgoing light side of the liquid crystal cell. As a result of observing the display screen, a good image was obtained in which the color display did not change when looking at the front force or the oblique direction force.

[0131] (Experiment 16)

Prepare a liquid crystal display equipped with an IPS liquid crystal cell, remove the polarizing plate on the outgoing light side, and replace the polarizing plate prepared in Experimental Example 14 with the coating film surface facing the outgoing light side of the liquid crystal cell. A display device bonded to a liquid crystal cell was prepared. As a result of observing the display screen, a good image was obtained in which the color display did not change whether viewed from the front or obliquely.

[0132] (Experimental example 17)

The same operation as in Experimental Example 15 was performed, except that the optical compensation film prepared in Experimental Example 13 was not used. As a result, when viewed from an oblique direction, the color display was different from that when the front force was also seen due to the birefringence of the liquid crystal display device constituent members.

[0133] (Experiment 18)

The same operation as in Experimental Example 16 was performed, except that the polarizing plate prepared in Experimental Example 14 was not used and the polarizing plate on the outgoing light side was used as it was. As a result, when viewed from an oblique direction, the color display was different from that when viewing the front force due to the birefringence of the liquid crystal display device constituent members. [Experiment 19]

Poly (2 binaphthalene) (manufactured by Aldrich, weight average molecular weight: 175000) 12. Methylene chloride (88. Og) was added to Og and dissolved at 25 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater, and then 25 ° The optical element was fabricated by air drying in air for 6 hours at C. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained as described above were measured, and the results are shown in Table 3. Here, an optical element of [(n + n) / 2-n] Xd <0 was obtained.

[0135] (Experiment 20)

Poly (4-vinyl biphenyl) (Aldrich, weight average molecular weight: 115000) 5. 95.0 g of methylene chloride was added to Og and dissolved at 25 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater, and then 25 ° The optical element was fabricated by air drying in air for 6 hours at C. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained as described above were measured, and the results are shown in Table 3. Here, an optical element of [(n + n) / 2-n] Xd <0 was obtained.

[0136] (Experimental example 21)

Styrene Maleic anhydride copolymer (Dylark D332 from Nova Chemical) 30. Og was added with 70.0 g of chloroform and dissolved at 25 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater, and this coating was applied. The substrate was placed in a glass container filled with black mouth form vapor at atmospheric pressure, sealed, and then annealed at 25 ° C for 48 hours. Then, the coated substrate was taken out and air-dried at 25 ° C for 6 hours to produce an optical element. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained above were measured, and the results are shown in Table 3. Here, an optical element of [(n + n) Z2-n] Xd <0 was obtained.

[0137] [Table 3] Coating thickness: dn _y z In-plane retardation: Thickness retardation:

(m) (n _x — n _v X d 〔(n _x 10 n _y ) Z2― n JX d

(n m) (n m)

Experimental example 1 9 9800 1. 6779 1. 67 78 1. 6843 1-63

Experimental example 20 4700 1. 6472 1. 64 72 1. 6555 0-39

Experimental example 2 1 46 500 1. 5690 1. 56 90 1. 5720 0-140

[0138] (Experimental example 22)

Ethylcellulose (ETHOCEL STD-100, manufactured by Dow Chemical, number average molecular weight: 634 00, DS: 2.5) 20. Og Dissolved under C. Next, apply this coating solution to a 150 m thick glass substrate (average refractive index: 1.52, in-plane phase difference: Onm, thickness phase difference: Inm) using a bar coater, then 25 The optical element was fabricated by air drying in air for 6 hours at ° C. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained above were measured, and the results are shown in Table 4. Here, [(n + n) / 2-n] X d≥l

An optical element of 00 (where n = n) was obtained.

[0139] (Experimental example 23)

150 m thick glass substrate by reducing the applied pressure of the bar coater using the coating solution prepared in Example 22 (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: Inm) After coating, an optical element was produced by air drying in air at 25 ° C for 6 hours. The coating thickness after drying (d (nm)) was obtained by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained as described above were measured, and the results are shown in Table 4. Here, an optical element of [(n + n) / 2−n] Xd≥100 (where n> n) was obtained.

[0140] (Experimental example 24)

150 m thick glass substrate by reducing the applied pressure of the bar coater using the coating solution prepared in Example 22 (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: Inm) After coating, the coated substrate was placed in a glass container filled with black mouth form vapor at atmospheric pressure, sealed, and then annealed at 25 ° C. for 72 hours. Thereafter, the coated substrate was taken out and air-dried in air at 25 ° C for 6 hours to produce an optical element. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained above were measured, and the results are shown in Table 4. In Experimental Example 23, the in-plane retardation also increased at the same time as the thickness retardation increased. However, here, the in-plane retardation is Onm, that is, the same thickness retardation as in Experimental Example 23, that is, [(n + n) / 2-n] X d≥

100 optical elements (where n = n) were obtained, and the characteristics of the optical elements were determined by the presence or absence of annealing. It was possible to produce different optical compensation layers.

[0141] (Experiment 25)

Ethylcellulose (ETHOCEL STD-100, manufactured by Dow Chemical, number average molecular weight: 634 00, DS: 2.5) 20. Dissolved under C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater. The optical element was fabricated by air-drying in air for 6 hours at ° C. The coating thickness after drying (d (nm)) was obtained by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, the physical properties of the optical element obtained above were measured, and the results are shown in Table 4. Here, [(n + n) / 2-n] X d

An optical element of ≥100 (where n> n) was obtained.

[0142] (Experiment 26)

A commercially available 40 μm-thick triacetyl cellulose film (= cellulose triacetate film) is attached to a 150 m-thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) By attaching, an optical element was produced. As a result of measuring the physical properties of the obtained optical element, the in-plane retardation force S0 nm and the thickness retardation were 37 nm, and [(n + n) / 2−n

] It did not satisfy the relationship of X d≥100 (thickness phase difference was low).

[0143] (Experiment 27)

A commercially available 80 μm thick triacetyl cellulose film (= cellulose triacetate film) is pasted on a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) By attaching, an optical element was produced. As a result of measuring the physical properties of the obtained optical element, the in-plane retardation was 1 nm and the thickness retardation was 70 nm, and [(n + n) / 2-n

[0144] In Experimental Examples 26 and 27, troublesome film forming steps (replaced by purchasing the film) and film sticking were required.

[0145] [Table 4] Coating thickness: dn _{y In-} plane retardation: Thickness retardation:

(nm (n _x -n _y ) X d ((n _x + n _y ) / 2-n JX d

(nm) (nm)

Experimental example 22 1 3000 1. 4727 1. 4727 1. 4646 0 105

Experimental example 23 43000 1. 4727 1. 4724 1. 4649 1 3 329

Experimental example 24 4 1300 1. 4723 1. 4723 1. 4654 0 285

Experimental example 25 1 8400 1. 4732 1. 4731 1. 4637 2 174

[Synthesis Example ⁴ ] Synthesis of cellulose N- (p-tolyl) carbamate ( ⁴ )

Cellulose (Avicel TG-F20 from Asahi Kasei Chemicals) vacuum dried for 7 hours at 60 ° C in a 500 ml four-necked flask equipped with a condenser, nitrogen inlet, stirrer, and thermometer. Then, 22.2 g of p-tolyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Nitrogen was introduced, the temperature was raised to 110 ° C with stirring, and the reaction was carried out for 7 hours. Thereafter, after cooling to 25 ° C., the reaction solution was transferred to a beaker, 600 ml of ethanol was added, and the reaction solution was dropped into 4.5 L of pure water to form a precipitate. After separation by filtration, the obtained polymer was dissolved by adding 300 ml of acetone, and then dropped into 3 L of pure water to cause precipitation. After filtration and washing with water and vacuum drying at 60 ° C for 4 hours, the polymer was put into a Soxhlet extractor. After performing Soxhlet extraction with methanol 20 times and vacuum drying at 25 ° C for 4 hours, 6.8 g of cellulose N- (p-tolyl) carbamate (4) was obtained (hereinafter referred to as synthetic product (4) may be called.) ₀ DS of synthetic (4) is the result of proton NMR analysis, it was 3. The DS is obtained by comparing the chemical shift area (3.4 to 5.5 ppm) of protons derived from the cellulose skeleton with the chemical shift area (6.6 to 7.7 ppm) of protons in the p-tolyl group. Were determined.

[0147] (Experimental example 28)

Synthetic product (4) To 0.58 g of 2-butanone 5.52 g was added and dissolved at 25 ° C. Further, 0.32 g of N-phenylcarbamate ethyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and dissolved at 25 ° C. Next, this coating solution was applied to a 150 m-thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater, and then 100 ° The optical element was fabricated by drying in air for 1 minute at C. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained above were measured, and the results are shown in Table 5. Compared with Experimental Example 30 in which N-phenylcarbamate ethyl was not added, an optical element having an improved thickness retardation in the negative direction was obtained.

[0148] (Experimental example 29)

3. 68 g of N, N-dimethylformamide was added to 0.32 g of the synthesized product (4) and dissolved at 25 ° C. Add 0.48 g of N, N, -diphenylurea (Tokyo Chemical Industry Co., Ltd.) and dissolve at 25 ° C. I understood. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater, and then 130 ° C. And dried in air for 5 minutes to produce an optical element. The coating thickness after drying (d (nm)) was obtained by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained above were measured, and the results are shown in Table 5. Compared with Experimental Example 31 in which N, N'-diphenylurea was not added, an optical element having an improved thickness retardation in the negative direction was obtained.

[0149] (Experiment 30)

The same operation as in Experimental Example 28 was carried out except that N-phenylcarbamate was not added. The physical properties of the obtained optical element were measured, and the results are shown in Table 6.

[0150] (Experimental example 31)

The same operation as in Experimental Example 29 was performed except that N, N′-diphenylurea was not added. The physical properties of the obtained optical element were measured, and the results are shown in Table 6.

[0151] [Table 5] Coating film thickness: d In-plane position ffl difference: Thickness phase difference:

(nm) (n _x — n _y ) X d ((n _x + n _y ) / 2— n JX d

(n m) (n m)

Experimental example 28 10 200 1-95 Experimental example 29 10 300 3-16

[0152] [Table 6] Coating film thickness: d Surface defect phase difference: Thickness phase difference:

(nm) (n _x — n _y ) X d C (n _x + n _y ) / 2-n JX d

(nm) (n m)

Experimental example 30 10800 0 19 Experimental example 31 10700 1 6 Industrial applicability

The coating film for optical compensation of the present invention, the coating liquid for forming the coating film for optical compensation, the optical element produced using them, and the optical compensation film (retardation film) are VA system, It can be used to expand the viewing angle of liquid crystal display devices using liquid crystal cells such as IPS and OCB. The IPS method is particularly preferable in order to sufficiently exhibit the performance of the optical properties of the coating film for optical compensation in the present invention. In addition, the optical compensation coating film, the coating film forming coating liquid, the optical element and the optical compensation film (retardation film) produced using the coating film, video, camera, mobile phone, laptop computer, It can be suitably used for liquid crystal display device production parts such as televisions, monitors, and instrument panels of automobiles.

Claims

Claims [1] A coating film for optical compensation, comprising a polymer of any one of cellulose N-substituted carbamate and aromatic bulle polymer. [2] When the maximum refractive index in the plane is n, the minimum refractive index is n, the refractive index in the thickness direction is n, and the film thickness is d, [(n + n) / 2-n] 2. The optical compensation coating film according to claim 1, wherein X d satisfies the relationship of 0. [3] In the cellulose N-substituted carbamate, at least one hydroxyl group of cellulose is N-substituted carbamate, and at least one hydrogen atom bonded to a nitrogen atom of the cellulose carbamate is represented by the following general formula (1): The compound is substituted with a group selected from (3), and a plurality of N-substituents are the same or different and are compounds selected from the following general formulas (1) to (3). 3. The coating film for optical compensation according to claim 1, wherein the coating film is for optical compensation.

[Chemical 1]

R ⁴ and R ⁵ are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group. )

[Chemical 2]

(In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^1Q , R ^U , R ¹² are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Represents a halogenated alkyl group having 1 to 20 carbon atoms, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, or a nitro group.

[Chemical 3]

(In the formula, R ¹³ , R ″, R ¹⁵ , R ^ln , R ″, R ¹⁸ , R ¹⁹ are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Represents a halogenated alkyl group having 1 to 20 carbon atoms, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, or a nitro group.

[4] Aromatic Bulle Polymer Strength Poly (1-Burnaphthalene), Poly (2-Burnaphthalene), Poly (4-Vinyl Vinyl) Force Contains at least one selected Item 3. The coating film for optical compensation according to Item 1 or Item 2.

[5] The optical compensation coating film according to any one of [1] to [4], wherein the optical compensation coating film is formed containing a phase difference adjusting agent.

[6] The cellulose N-substituted carnomate phase difference adjusting agent having at least one force selected from strong rubamic acid ester, N-substituted rubamic acid ester, urea, and N-substituted urea. 5. An optical compensation coating film according to 5.

[7] strength rubamate ethyl, strength rubamate phenyl, N-phenylcarbamate ethyl, N Phenylcarbamate phenol, N— (4-Tolyl) strength rubamate ethyl, N— (4 Tolyl) strength rubamate phenol, urea, N, N, diphenol urea, N, N, 7. A group strength of di-p-tolyl urea and N ferrue N ′-(p tolyl) urea, comprising at least one force selected, a retardation adjusting agent for cellulose N-substituted carbamate, Optical compensation coating film.

[8] A coating solution for forming an optical compensation coating film, which comprises the following (A) and (B).

(A) Any one of the cellulose N-substituted carbamates according to claims 1 to 4 or the aromatic bulle polymer,

(B) A solvent in which component (A) is soluble and soluble.

[9] The coating for forming an optical compensation coating film according to claim 8, characterized in that it comprises (A) and (B), and further comprises (C) a retardation adjusting agent. liquid.

[10] (C) The phase difference adjusting agent is a phase difference adjusting agent for cellulose N-substituted carbamate comprising at least one selected from force rubamic acid ester, N-substituted force rubamic acid ester, urea, and N-substituted urea. 10. The coating solution for forming an optical compensation coating film according to claim 9, wherein the coating solution is for optical compensation.

[11] (C) Retardation adjuster is ethyl carnomate, vinyl carnomate, N-phenyl carbamate, N-phenyl carbamate, N- (4-tolyl) force Rutile ethyl, N— (4-tolyl) strength rubamate, urea, N, N, diphenylurea, N, N, —di-p-tolylurea, N—phenol N,-(p 11. The coating solution for forming a coating film for optical compensation according to claim 10, wherein the coating solution is a retardation adjusting agent for cellulose N-substituted carnomate selected from the group of (tolyl) urea.

[12] A retardation adjusting agent for cellulose N-substituted carnomate, characterized in that it also has at least one force selected from rubamic acid ester, N-substituted rubamic acid ester, urea, and N-substituted urea.

[13] hard rubamate, strong rubamate, N-phenyl carbamate, N

Phenylcarbamate phenol, N— (4-Tolyl) strength rubamate ethyl, N— (4 Tolyl) strength rubamate phenol, urea, N, N, diphenol urea, N, N, Di-p-tolyl urea, N ferrue N '-(p tolyl) urea group power at least one force selected The retardation adjusting agent for cellulose N-substituted carbamate according to claim 12,

[14] A method for forming an optical compensation coating film, comprising: coating a substrate with the coating liquid according to claims 8 to 11 to obtain a coated substrate; and drying the coated substrate. .

[15] The coated substrate is primarily dried at a temperature in the range of 0 ° C at the lower limit and 40 ° C at the upper limit, and further dried at the lower limit of 80 ° C and the upper limit of 300 ° C. 15. The method for forming a coating film for optical compensation according to claim 14, wherein:

[16] The coating liquid according to claim 8 to claim 11 is applied to a substrate to form a coated substrate, and then the coating film is annealed by exposure to the vapor of component (B) and further dried. A method for forming a coating film for optical compensation.

[17] A method for manufacturing an optical element, wherein the forming method according to any one of claims 14 to 16 is used.

18. An optical element manufactured using the manufacturing method according to claim 17.

[19] An optical compensation film produced by using the forming method according to any one of claims 14 to 16.

[20] A polarizing plate, wherein the optical compensation film according to claim 19 is mounted as a polarizer protective film on at least one surface of the polarizer.

21. A liquid crystal display device comprising the optical compensation film according to claim 19.

22. A liquid crystal display device comprising the polarizing plate according to claim 20.