KR20070111480A - Coating film for optical compensation, and optical element - Google Patents

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

Coating film and optical element for optical compensation {Coating Film for Optical Compensation, and Optical Element}

The present invention relates to an optical compensation coating film for performing optical compensation of a phase difference by a liquid crystal cell or the like, a coating liquid for forming an optical compensation coating film suitable for forming the coating film, and a method of forming the coating film for optical compensation. Furthermore, it is related with the coating film for optical compensation containing a phase difference regulator, and the phase difference regulator, and the coating liquid for coating film formation for optical compensation. Furthermore, it is related with the optical element manufactured using these, and the manufacturing method of an optical element. Furthermore, it is related with the polarizing plate and liquid crystal display device provided with an optical compensation film (retardation film) and an optical compensation film.

An optical compensation retardation film is used for a liquid crystal display device in order to compensate for the phase difference by birefringence, such as a liquid crystal cell, a polarizing plate, and other liquid crystal display component films, and to enlarge a viewing angle. As such a retardation film, for example, a polymer such as polycarbonate, polyester, polystyrene, polyamide, polyimide, polyethersulfone, etc. is a solution casting method, a uniaxial stretching method of a dried product after solution casting, a biaxial stretching of a dried product after solution casting The film formed by the stretching method, the extrusion method, the uniaxial stretching method of an extruded article, the biaxial stretching method of an extruded article, the calendering method, etc. are mentioned (for example, refer patent document 1, patent document 2). Such a retardation film is a film containing a material having a positive intrinsic birefringence value such as polycarbonate or a material having a negative intrinsic birefringence value such as polystyrene in accordance with an applied liquid crystal cell, a polarizing plate, or other liquid crystal display device composition film. Film to include is used by each of several pieces separately. In order to use these films, a complicated film-forming process is required for film formation, and also the effort of adhering these films to liquid crystal display component parts is required.

In order to solve these problems, and n _z <n _x = n _y to form the retardation layer by a thin film formation by the paste coating of the polyimide having the optical properties has been proposed (see, for example, Patent Document 3) . On the other hand, n _z > n _x ≥ n _y for the thing having an optical characteristic, that is, the value of the thickness phase difference represented by [(n _x + n _y ) / 2-n _z ] × d becomes negative, n _z Application of a compound having optical properties of> n _x = n _y is proposed. This is applied to a polymer compound solution having a functional group capable of photoisomerization, and then dried, and then irradiated with light to control the orientation of the polymer, or a liquid crystal polymer solution or a melt of a liquid crystal polymer is applied and dried and then heated to the glass transition temperature of the polymer. The treatment is performed to align the liquid crystals and to fix the alignment by cooling (see Patent Document 4, for example). However, compared with the phase difference layer formation by paste application of polyimide, when using the high molecular compound which has a functional group which can photoisomerize, it has to complicate light irradiation, and when using a liquid crystal polymer, liquid crystal is generally expensive This is a costly drawback.

By the way, in order to compensate the phase difference of the large thickness direction by birefringence, such as a liquid crystal cell, a polarizing plate, and other liquid crystal display component films, it is the opposite of the sign of the phase difference of the thickness direction, and [(n _x + n _y ) / 2- It is effective to use an optical compensation material having a large absolute value of the thickness retardation represented by n _z ] × d. In addition, it is particularly effective to form him to _{(n x + n y) /} 2-n z increases the formation material increases, the absolute value of the value represented by the following methods. This is because when the absolute value of the value represented by (n _x + n _y ) / 2-n _z is not sufficient and the film thickness needs to be increased, not only the liquid crystal display components after the coating film formation are swollen but also hollow This is because a problem such as an increase in the material cost of the film occurs.

Patent Document 1: Japanese Patent Application Laid-Open No. 3-33719

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

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

Patent Document 4: Japanese Patent Application Laid-Open No. 7-13022

An object of the present invention is to provide a coating film for optical compensation at low cost without requiring a complicated film forming step. Furthermore, an optical compensation coating film having a characteristic of [(n _x + n _y ) / 2-n _z ] × d <0 can be provided at low cost, and an optical element having the characteristics without the trouble of film adhesion or the like can be provided. will be.

Further, cellulose N- substituted carbamate, or an aromatic vinyl-based polymer containing any one of the polymer, and _{(n x + n y) /} 2-n and the value represented by _z negative, its absolute value is greater than the optical It is to provide a method of forming a compensation coating film, and to provide an optical device manufactured using the formation method.

MEANS TO SOLVE THE PROBLEM In order to solve such a subject, the present inventors earnestly researched and the said subject is made by the coating film for optical compensation characterized in that it is formed containing the polymer of either cellulose N-substituted carbamate or an aromatic vinyl type polymer. It was found that the solution to the present invention was reached.

That is, this invention relates to the coating film for optical compensation characterized by containing the polymer of any one of a cellulose N-substituted carbamate or an aromatic vinyl type polymer.

As a preferred embodiment, when it is called up to n _x, and that the least _y n, _z n the refractive index in the thickness direction, the thickness d of the refractive index in the _{plane, [(n x + n y} ) / 2- It relates to an optical compensation coating film characterized by satisfying the relationship of n _z ] × d <0.

In a preferred embodiment, in the cellulose N-substituted carbamate, at least one hydroxyl group of the cellulose is N-substituted carbamate, and at least one hydrogen atom bonded to the nitrogen atom of the cellulose carbamate is represented by the following formula (1): Substituted with a group selected from 3 to 3, the plurality of N-substituents are the same or different, and relates to a coating film for optical compensation characterized in that the compound is a group selected from the following formula (1) to (3).

In formula, R <^1> , R <^2> , R <^3> , R <^4> , R <^5> is the same or different, A hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 halogenated alkyl group, An aryl group having 6 to 20 carbon atoms, 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.

In formula, R <^6> , R <^7> , R <^8> , R <^9> , R <^10> , R <^11> and R <^12> are the same or different, A hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, C1-C1 A halogenated alkyl group of 20 to 20, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.

In formula, R <^13> , R <^14> , R <^15> , R <^16> , R <^17> , R <^18> , R <^19> is the same or different, A hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, C1-C1 A halogenated alkyl group of 20 to 20, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.

As a preferred embodiment, the aromatic vinyl polymer comprises at least one selected from poly (1-vinylnaphthalene), poly (2-vinylnaphthalene), and poly (4-vinylbiphenyl). It relates to a coating film.

As a preferable embodiment, it is related with the coating film for optical compensation characterized by including and containing a phase difference regulator.

As a preferred embodiment, a phase difference regulator for cellulose N-substituted carbamate comprising at least one selected from carbamic acid esters, N-substituted carbamic acid esters, urea, and N-substituted urea is included. It relates to a coating film.

 Preferred embodiments include ethyl carbamate, phenyl carbamate, ethyl N-phenylcarbamate, phenyl N-phenylcarbamate, ethyl N- (4-tolyl) carbamate, phenyl N- (4-tolyl) carbamate, urea , N, N'-diphenylurea, N, N'-di-p-tolylurea, N-phenyl-N '-(p-tolyl) urea The coating film for optical compensation containing the phase difference regulator for bamate is contained.

Moreover, this invention relates to the coating liquid for coating film formation for optical compensation formed containing the following (A) and (B).

(A) a polymer of any one of cellulose N-substituted carbamate or aromatic vinyl polymer,

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

As a preferable embodiment, it contains (A) and (B), and further contains (C) retardation regulator, It is related with the coating liquid for coating film formation for optical compensation characterized by the above-mentioned.

As a preferred embodiment, the (C) phase difference regulator is a phase difference regulator for cellulose N-substituted carbamate comprising at least one selected from carbamic acid ester, N-substituted carbamic acid ester, urea, and N-substituted urea. A coating liquid for forming a coating film for optical compensation.

As a preferred embodiment, the (C) phase difference modifier is ethyl carbamate, phenyl carbamate, ethyl N-phenylcarbamate, phenyl N-phenylcarbamate, ethyl N- (4-tolyl) carbamate, N- (4-tolyl Carbamic acid phenyl, at least one selected from the group of urea, N, N'-diphenylurea, N, N'-di-p-tolylurea, N-phenyl-N '-(p-tolyl) urea It is related with the coating liquid for coating film formation for optical compensation characterized by the above-mentioned phase difference regulator for cellulose N-substituted carbamate.

The present invention also relates to a retarder for cellulose N-substituted carbamate, characterized in that it comprises at least one selected from carbamic acid esters, N-substituted carbamic acid esters, urea, N-substituted urea.

Preferred embodiments include ethyl carbamate, phenyl carbamate, ethyl N-phenylcarbamate, phenyl N-phenylcarbamate, ethyl N- (4-tolyl) carbamate, phenyl N- (4-tolyl) carbamate, urea Cellulose comprising at least one selected from the group of N, N'-diphenylurea, N, N'-di-p-tolylurea and N-phenyl-N '-(p-tolyl) urea It relates to a retardation modifier for N-substituted carbamate.

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

As a preferred embodiment, the coating substrate is first dried at a temperature in the range of 0 ° C lower limit and 40 ° C upper limit, and then the coating substrate is further secondarily dried at 80 ° C lower limit and 300 ° C upper limit. It is related with the formation method of a coating film.

The present invention also relates to a method for forming an optical compensation coating film, wherein the coating solution is coated onto a substrate to form a coating substrate, and then exposed to vapor of component (B) to anneal the coating film and further dry. will be.

Moreover, this invention relates to the manufacturing method of the optical element characterized by using the said formation method.

Moreover, this invention relates to the optical element characterized by manufactured using the said manufacturing method.

The present invention also relates to an optical compensation film, which is produced using the above forming method.

Moreover, this invention relates to the polarizing plate which mounted the said optical compensation film as a polarizer protective film on at least one surface of a polarizer.

Moreover, this invention relates to the liquid crystal display device provided with the said optical compensation film.

Moreover, this invention relates to the liquid crystal display device provided with the said polarizing plate.

Effect of the Invention

Using the optical compensation coating film of this invention, an optical element can be manufactured, without the trouble of a complicated film-forming process and film adhesion | attachment, and especially [(n _x + n _y ) / 2-n _z ] The optical element which has an optical compensation layer of xd <0 can be manufactured. In addition, by using the method for forming an optical compensation coating film of the present invention, a value represented by (n _x + n _y ) / 2-n _z is negative, and an optical compensation coating film having a larger absolute value can be formed. It is very useful industrially because it can manufacture a thinner optical element.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. The present invention is an optical compensation coating film formed by containing a polymer of any one of a cellulose N-substituted carbamate or an aromatic vinyl polymer.

In the cellulose N-substituted carbamate of the present invention, at least one hydroxyl group of the cellulose is N-substituted carbamate, and at least one hydrogen atom bonded to the nitrogen atom of the cellulose carbamate is represented by the following Chemical Formulas 1 to 3 Substituted by a group selected from, a plurality of N-substituents are the same or different, and is a coating film for optical compensation, characterized in that the compound is a group selected from the following formula (1) to (3).

<Formula 1>

In formula, R <^1> , R <^2> , R <^3> , R <^4> , R <^5> is the same or different, A hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 halogenated alkyl group, An aryl group having 6 to 20 carbon atoms, 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.

<Formula 2>

In formula, R <^6> , R <^7> , R <^8> , R <^9> , R <^10> , R <^11> and R <^12> are the same or different, A hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, C1-C1 A halogenated alkyl group of 20 to 20, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.

<Formula 3>

In formula, R <^13> , R <^14> , R <^15> , R <^16> , R <^17> , R <^18> , R <^19> is the same or different, A hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, C1-C1 A halogenated alkyl group of 20 to 20, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.

The cellulose N-substituted carbamate (hereinafter, also referred to as (A) component) in the present invention is made of, for example, cellulose obtained from various wood pulp, cotton linter, cotton lint, and the like, and includes pyridine, triethylamine, and the like. It can manufacture by the well-known method of making an isocyanate type compound react in presence of the base catalyst of. 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 preferably used. In addition, an inorganic salt such as lithium chloride may be added to improve the solubility of the cellulose in the solvent. Moreover, as an example of such an isocyanate type compound, the compound represented by following formula (4)-6 is mentioned.

In formula, R <^20> , R <^21> , R <^23> and R <^24> are the same or different, A hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 halogenated alkyl group, C6-C20 An aryl group of 20, an aryloxy group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an aralkyloxy group of 7 to 20 carbon atoms, an acyloxy group of 1 to 21 carbon atoms, a halogen atom, and a nitro group.

In formula, R <^25> , R <^26> , R <^27> , R <^28> , R <^29> , R <^30> and R <^31> are the same or different, and a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, C1-C1 A halogenated alkyl group of 20 to 20, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.

In formula, R <^32> , R <^33> , R <^34> , R <^35> , R <^36> , R <^37> and R <^38> are the same or different, and are a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, C1-C1 A halogenated alkyl group of 20 to 20, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.

These isocyanate type compounds may be used independently and may use 2 or more types together.

In the present invention, from the viewpoint of availability of the isocyanate compound, R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ are the same or different, and a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, and an alkoxy 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, an aryloxy group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, an aralkyloxy group having 7 to 16 carbon atoms, and an acyl oxy group having 1 to 17 carbon atoms. It is preferable to use the cellulose N-substituted carbamate in which at least one hydroxyl group of the cellulose is N-substituted carbamate by reacting an isocyanate compound represented by the formula (4), which is a time period, a halogen atom, and a nitro group. Or R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ are the same or different and hydrogen Isocyanate compounds represented by the formulas (5) and (6) which are an 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 at least one of the hydroxyl groups of the cellulose is N-substituted carbamate. R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, and 6 to 12 carbon atoms. 12 is an aryl group, an aryloxy group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aralkyloxy group having 7 to 12 carbon atoms, an acyloxy group having 1 to 13 carbon atoms, a halogen atom, or a nitro group. It is more preferable to use the cellulose N-substituted carbamate in which at least one of the hydroxyl groups of the cellulose is N-substituted carbamate by reacting an isocyanate compound. Or R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ . R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , and R ³⁸ are the same or different and represent a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, a halogenated alkyl group of 1 to 12 carbon atoms, or 1 to 12 carbon atoms. 13 is reacted with an isocyanate compound represented by the formulas (5) and (6), which is an acyloxy group, a halogen atom, and a nitro group, wherein at least one hydroxyl group of the cellulose is N-substituted carbamate-ized N-substituted carbamate. It is more preferable to use.

Specific examples of the isocyanate compound represented by Formulas 4 to 6 include phenyl isocyanate, o-tolyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, 2-ethylphenyl isocyanate, 3-ethylphenyl isocyanate and 4-ethylphenyl Isocyanate, 2-propylphenyl isocyanate, 3-propylphenyl isocyanate, 4-propylphenyl isocyanate, 2-butylphenyl isocyanate, 3-butylphenyl isocyanate, 4-butylphenyl isocyanate, 2,3-dimethylphenyl isocyanate, 2,4- Dimethylphenyl isocyanate, 2,5-dimethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,4-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 2,3-diethylphenyl isocyanate, 2,4-di Ethylphenyl isocyanate, 2,5-diethylphenyl isocyanate, 2,6-diethylphenyl iso Anate, 3,4-diethylphenyl isocyanate, 3,5-diethylphenyl isocyanate, 2,4,6-trimethylphenyl isocyanate, 2-methoxyphenyl isocyanate, 3-methoxyphenyl isocyanate, 4-methoxyphenyl Isocyanate, 2-ethoxyphenyl isocyanate, 3-ethoxyphenyl isocyanate, 4-ethoxyphenyl isocyanate, 2- (fluoromethyl) phenyl isocyanate, 3- (fluoromethyl) phenyl isocyanate, 4- (fluoromethyl) Phenyl isocyanate, 2- (chloromethyl) phenyl isocyanate, 3- (chloromethyl) phenyl isocyanate, 4- (chloromethyl) phenyl isocyanate, 2- (bromomethyl) phenyl isocyanate, 3- (bromomethyl) phenyl isocyanate, 4- (bromomethyl) phenyl isocyanate, 2- (iodomethyl) phenyl isocyanate, 3- (iodomethyl) phenyl isocyanate, 4- (iodomethyl) phenyl isocyanate, 2- (di Fluoromethyl) phenyl isocyanate, 3- (difluoromethyl) phenyl isocyanate, 4- (difluoromethyl) phenyl isocyanate, 2- (dichloromethyl) phenyl isocyanate, 3- (dichloromethyl) phenyl isocyanate, 4- ( Dichloromethyl) phenyl isocyanate, 2- (dibromomethyl) phenyl isocyanate, 3- (dibromomethyl) phenyl isocyanate, 4- (dibromomethyl) phenyl isocyanate, 2- (diiodomethyl) phenyl isocyanate, 3- (diiodomethyl) phenyl isocyanate, 4- (diiodomethyl) phenyl isocyanate, 2- (trifluoromethyl) phenyl isocyanate, 3- (trifluoromethyl) phenyl isocyanate, 4- (trifluoro Methyl) phenyl isocyanate, 2- (trichloromethyl) phenyl isocyanate, 3- (trichloromethyl) phenyl isocyanate, 4- (trichloromethyl) phenyl isocyanate, 2- (tribromomethyl) phenyl is Soocyanate, 3- (tribromomethyl) phenyl isocyanate, 4- (tribromomethyl) phenyl isocyanate, 2- (triiodomethyl) phenyl isocyanate, 3- (triiodomethyl) phenyl isocyanate, 4- ( Triiodomethyl) phenyl isocyanate, 2-biphenylyl isocyanate, 3-biphenylyl isocyanate, 4-biphenylyl isocyanate, 2-phenoxyphenyl isocyanate, 3-phenoxyphenyl isocyanate, 4-phenoxyphenyl isocyanate, 2'-benzylphenyl isocyanate, 3'-benzylphenyl isocyanate, 4'-benzylphenyl isocyanate, 2-benzyloxyphenyl isocyanate, 3-benzyloxyphenyl isocyanate, 4-benzyloxyphenyl isocyanate, 2-acetoxyphenyl isocyanate, 3 -Acetoxyphenyl isocyanate, 4-acetoxyphenyl isocyanate, 2-fluorophenyl isocyanate, 3-fluorophenyl isocyanate , 4-fluorophenyl isocyanate, 2-chlorophenyl isocyanate, 3-chlorophenyl isocyanate, 4-chlorophenyl isocyanate, 2-bromophenyl isocyanate, 3-bromophenyl isocyanate, 4-bromophenyl isocyanate, 2-io Dophenyl isocyanate, 3-iodophenyl isocyanate, 4-iodophenyl isocyanate, 2,4-difluorophenyl isocyanate, 2,5-difluorophenyl isocyanate, 2,6-difluorophenyl isocyanate, 3, 4-difluorophenyl isocyanate, 3,5-difluorophenyl isocyanate, 2,4-dichlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, 2,6-dichlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 3,5-dichlorophenyl isocyanate, 2,4-dibromophenyl isocyanate, 2,5-dibromophenyl isocyanate, 2,6-dibromo Nyl isocyanate, 3,4-dibromophenyl isocyanate, 3,5-dibromophenyl isocyanate, 2,4-diiodophenyl isocyanate, 2,5-diiodophenyl isocyanate, 2,6-diiodo Phenyl isocyanate, 3,4-diiodophenyl isocyanate, 3,5-diiodophenyl isocyanate, 2,3,4-trifluorophenyl isocyanate, 2,3,4-trichlorophenyl isocyanate, 2,3, 4-tribromophenyl isocyanate, 2,3,4-triiodophenyl isocyanate, 2-fluoro-5-methylphenyl isocyanate, 2-fluoro-6-methylphenyl isocyanate, 3-fluoro-2-methylphenyl isocyanate, 3-fluoro-4-methylphenyl isocyanate, 4-fluoro-2-methylphenyl isocyanate, 4-fluoro-3-methylphenyl isocyanate, 5-fluoro-2-methylphenyl isocyanate, 2-chloro-5-methylphenyl isocyanate, 2 -Chloro-6-methyl Nyl isocyanate, 3-chloro-2-methylphenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, 4-chloro-2-methylphenyl isocyanate, 4-chloro-3-methylphenyl isocyanate, 5-chloro-2-methylphenyl isocyanate, 2- Bromo-5-methylphenyl isocyanate, 2-bromo-6-methylphenyl isocyanate, 3-bromo-2-methylphenyl isocyanate, 3-bromo-4-methylphenyl isocyanate, 4-bromo-2-methylphenyl isocyanate, 4- Bromo-3-methylphenyl isocyanate, 5-bromo-2-methylphenyl isocyanate, 2-iodo-5-methylphenyl isocyanate, 2-iodo-6-methylphenyl isocyanate, 3-iodo-2-methylphenyl isocyanate, 3- Iodo-4-methylphenyl isocyanate, 4-iodo-2-methylphenyl isocyanate, 4-iodo-3-methylphenyl isocyanate, 5-iodo-2-methylphenyl isocyanate, 2-nitrophenyl isocyanate Socyanate, 3-nitrophenyl isocyanate, 4-nitrophenyl isocyanate, 1-naphthyl isocyanate, 2-naphthyl isocyanate, 1-methyl-2-naphthyl isocyanate, 2-methyl-1-naphthyl isocyanate, 1-meth Methoxy-2-naphthyl isocyanate, 2-methoxy-1-naphthyl isocyanate, 1- (trifluoromethyl) -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-naphthyl isocyanate, 2- Acetoxy-1-naphthyl isocyanate, 1-fluoro-2-naphthyl isocyanate, 2- Fluoro-1-naphthyl isocyanate, 1-chloro-2-naphthyl isocyanate, 2-chloro-1-naphthyl isocyanate, 1-bromo-2-naphthyl isocyanate, 2-bromo-1-naph Methyl isocyanate, 1-iodo-2-naphthyl isocyanate, 2-iodo-1-naphthyl isocyanate, 1-nitro-2-naphthyl isocyanate, 2-nitro-1-naphthyl isocyanate and the like. The cellulose N-substituted carbamate obtained by making these and the said isocyanate type compound react may be used independently, and may use 2 or more types together.

In addition, cellulose has three hydroxyl groups per glucose residue which is the structural unit. Therefore, when substituting these hydroxyl groups, the substitution degree per glucose residue (henceforth DS) is a maximum of three. In the present invention, the lower limit of the DS is preferably 0.1, more preferably 0.5, further preferably 1, and the upper limit is preferably 3, more preferably 2.95 and even more preferably 2.9. If DS is lower than 0.1, it tends to be difficult to dissolve in a solvent. In this invention, 2 or more types of cellulose N-substituted carbamate in which DS differs may be used together, and may be used independently.

The lower limit of the number average molecular weight of the component (A) is preferably 5000, more preferably 8000, even more preferably 10000, and the upper limit is preferably 500000, more preferably 300000, even more preferably 200000. . When the number average molecular weight is less than 5000, the strength of the coating film tends to decrease, while when the number average molecular weight is larger than 500000, it tends to be difficult to dissolve in a solvent (hereinafter also referred to as component (B)). In addition, the said number average molecular weight is the value measured by the gel permeation chromatography (GPC) method. In the present invention, two or more kinds of cellulose N-substituted carbamates having different number average molecular weights may be used in combination, or may be used alone.

As the aromatic vinyl polymer (hereinafter, also referred to as component (A)) of the present invention, any one containing an aromatic vinyl unit can be used. For example, polystyrene; Poly (α-methylstyrene); Poly (2-methylstyrene), poly (3-methylstyrene), poly (4-methylstyrene), poly (2,4-dimethylstyrene), poly (2,5-dimethylstyrene), poly (3,4- Dimethylstyrene), poly (3,5-dimethylstyrene), poly (2-ethylstyrene), poly (3-ethylstyrene), poly (4-ethylstyrene), poly (2,4-diethylstyrene), poly (2,5-diethylstyrene), poly (3,4-diethylstyrene), poly (3,5-diethylstyrene), poly (2-propylstyrene), poly (3-propylstyrene), poly ( 4-propylstyrene), poly (2,4-dipropylstyrene), poly (2,5-dipropylstyrene), poly (3,4-dipropylstyrene), poly (3,5-dipropylstyrene), Poly (2-butylstyrene), poly (3-butylstyrene), poly (4-butylstyrene), poly (2,4-dibutylstyrene), poly (2,5-dibutylstyrene), poly (3, Poly (alkyl styrene) such as 4-dibutyl styrene) and poly (3.5-dibutyl 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-ethoxystyrene), poly (3-ethoxystyrene), poly (4-ethoxystyrene), poly ( 2,4-diethoxystyrene), poly (2,5-diethoxystyrene), poly (3,4-diethoxystyrene), poly (3,5-diethoxystyrene), poly (2-propoxystyrene) , Poly (3-propoxystyrene), poly (4-propoxystyrene), poly (2,4-dipropoxystyrene), poly (2,5-dipropoxystyrene), poly (3,4-diff Lopoxystyrene), poly (3,5-dipropoxystyrene), poly (2-butoxystyrene), poly (3-butoxystyrene), poly (4-butoxystyrene), poly (2,4- Poly (alkoxystyrene) such as dibutoxystyrene), poly (2,5-dibutoxystyrene), poly (3,4-dibutoxystyrene), and poly (3,5-dibutoxystyrene); Poly (2-chlorostyrene), poly (3-chlorostyrene), poly (4-chlorostyrene), poly (2,4-dichlorostyrene), poly (2,5-dichlorostyrene), poly (2,6- Dichlorostyrene), poly (3,4-dichlorostyrene), poly (2-bromostyrene), poly (3-bromostyrene), poly (4-bromostyrene), poly (2,4-dibromo Styrene), poly (2,5-dibromostyrene), poly (2,6-dibromostyrene), poly (3,4-dibromostyrene), poly (2-iodostyrene), poly ( 3-iodostyrene), poly (4-iodostyrene), poly (2,4-diiodostyrene), poly (2,5-diiodostyrene), poly (2,6-diiodostyrene) ), Poly (3,4-diiodostyrene), poly (2-fluorostyrene), poly (3-fluorostyrene), poly (4-fluorostyrene), poly (2,4-difluoro Poly (halogenated styrene) such as styrene), poly (2,5-difluorostyrene), poly (2,6-difluorostyrene), poly (3,4-difluorostyrene); Poly (2-methoxycarbonylstyrene), poly (4-methoxycarbonylstyrene), poly (2-ethoxycarbonylstyrene), poly (4-ethoxycarbonylstyrene), poly (2-propoxy Poly (vinylbenzoic acid esters) such as carbonylstyrene), poly (4-propoxycarbonylstyrene), poly (2-butoxycarbonylstyrene), and poly (4-butoxycarbonylstyrene); Poly (hydroxystyrene) such as poly (o-hydroxystyrene), poly (m-hydroxystyrene), and poly (p-hydroxystyrene); Vinyl naphthalene polymers such as poly (1-vinylnaphthalene) and poly (2-vinylnaphthalene); Poly (aryl styrene) such as poly (4-vinylbiphenyl), poly (3- (4-biphenyl) styrene), and poly (4- (4-biphenyl) styrene); Polyacenaphthylene and the like. Moreover, these 2 or more types of copolymers; The copolymer of these 1 type, or 2 or more types, and another polymer can also be used. For example, styrene- (α-methylstyrene) copolymer, styrene- (2-methylstyrene) copolymer, styrene- (3-methylstyrene) copolymer, styrene- (4-methylstyrene) copolymer, styrene- (2-methoxystyrene) copolymer, styrene- (3-methoxystyrene) copolymer, styrene- (4-methoxystyrene) copolymer, styrene- (2-chlorostyrene) copolymer, styrene- (3- Chlorostyrene) copolymer, styrene- (4-chlorostyrene) copolymer, styrene- (2-methoxycarbonylstyrene) copolymer, styrene- (4-methoxycarbonylstyrene) copolymer, styrene- (o- Hydroxystyrene) copolymer, styrene- (m-hydroxystyrene) copolymer, styrene- (p-hydroxystyrene) copolymer, styrene- (1-vinylnaphthalene) copolymer, styrene- (2-vinylnaphthalene) Copolymer, styrene- (4-vinylbiphenyl) copolymer, styrene-methyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-isoprene ball Copolymer, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, styrene-vinyl acetate copolymers such as styrene-based 2 won copolymer; (α-methylstyrene)-(2-methylstyrene) copolymer, (α-methylstyrene)-(3-methylstyrene) copolymer, (α-methylstyrene)-(4-methylstyrene) copolymer, (α -Methylstyrene)-(2-methoxystyrene) copolymer, (α-methylstyrene)-(3-methoxystyrene) copolymer, (α-methylstyrene)-(4-methoxystyrene) copolymer, ( α-methylstyrene)-(2-chlorostyrene) copolymer, (α-methylstyrene)-(3-chlorostyrene) copolymer, (α-methylstyrene)-(4-chlorostyrene) copolymer, (α- Methylstyrene)-(2-methoxycarbonylstyrene) copolymer, (α-methylstyrene)-(4-methoxycarbonylstyrene) copolymer, (α-methylstyrene)-(o-hydroxystyrene) aerial Copolymer, (α-methylstyrene)-(m-hydroxystyrene) copolymer, (α-methylstyrene)-(p-hydroxystyrene) copolymer, (α-methylstyrene)-(1-vinylnaphthalene) air Copolymer, (α-methylstyrene)-(2-vinylnaphthalene) copolymer, (α-methylstyrene)-(4-vinylbiphenyl) in air Copolymer, (α-methylstyrene) -methyl acrylate copolymer, (α-methylstyrene) -methyl methacrylate copolymer, (α-methylstyrene) -isoprene copolymer, (α-methylstyrene) -butadiene copolymer, α-methylstyrene binary copolymers such as (α-methylstyrene) -acrylonitrile copolymer, (α-methylstyrene) -maleic anhydride copolymer, and (α-methylstyrene) -vinyl acetate copolymer; Ternary copolymers, such as styrene-methyl acrylate-methyl methacrylate copolymer, a styrene-((alpha) -methylstyrene)-acrylonitrile copolymer, and styrene-((alpha) -methylstyrene) -methyl methacrylate copolymer, etc. are mentioned. Can be mentioned. These polymers may be used independently and may use 2 or more types together.

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

As the aromatic vinyl polymer, at least one selected from poly (1-vinylnaphthalene), poly (2-vinylnaphthalene), poly (4-vinylbiphenyl), or one of them is heat-resistant and easy to obtain. It is preferable at the point of view.

The lower limit of the weight average molecular weight of the aromatic vinyl polymer is preferably 10000, more preferably 20000, still more preferably 30000, and the upper limit is preferably 1000000, more preferably 800000, even more preferably 600000. . When a weight average molecular weight is less than 10000, there exists a tendency for coating film strength to fall, and when a weight average molecular weight is larger than 1 million, it will become difficult to melt | dissolve in a solvent. In addition, this weight average molecular weight is the value measured by the gel permeation chromatography (GPC) method. In the present invention, two or more kinds of polymers having different weight average molecular weights may be used in combination, or may be used alone.

Hereinafter, the coating liquid for forming a coating film for optical compensation (hereinafter also simply referred to as coating liquid) will be described. The coating solution contains a solvent in which (A) the cellulose N-substituted carbamate or the polymer of any one of the aromatic vinyl polymers and (B) (A) component can be dissolved.

The solvent for component (B) is not particularly limited as long as component (A) is soluble. Specific examples thereof include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, isopropylbenzene, and diethylbenzene. Hydrocarbon solvents such as isomer mixtures; Alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, furfuryl alcohol and benzyl alcohol; Ether solvents such as ethyl ether, isopropyl ether, 1,3-dioxolane, 1,4-dioxane, tetrahydropyran, tetrahydrofuran and 1,2-dimethoxyethane; Ketone solvents such as acetone, 2-butanone, 4-methyl-2-pentanone and cyclohexanone; Methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1, 2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1-chloropropane, 2-chloropropane, 1,1-dichloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,2 -Dichloropropane, 1,2,3-trichloropropane, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1, Halogen solvents such as 2,4-trichlorobenzene and 1,3,5-trichlorobenzene; Ester solvents such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, and ethyl cellosolve acetate; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidinone; Amine solvents, such as a pyrrolidine, a piperidine, a pyrrole, etc. are mentioned. These solvents may be used alone or in combination of two or more thereof.

In this invention, it is preferable that the solvent amount uses the ratio of (A) component with respect to the total weight of (A) component and (B) component in the range of a minimum of 1 weight% and an upper limit of 70 weight%, and a minimum of 2 weight It is more preferable to use in the range of% and an upper limit of 60 weight%, and it is still more preferable to use in the range which is a minimum of 3 weight% and an upper limit of 50 weight%. When the ratio of (A) component is smaller than 1 weight%, there exists a tendency for coating film thickness to become thin and it is difficult to obtain required film thickness, and when larger than 70 weight%, the viscosity of a coating liquid will become high and workability will fall. .

Next, the phase difference adjuster in this invention is demonstrated. The thickness retardation of the optical compensation coating film is represented by [(n _x + n _y ) / 2-n _z ] × d. In order to adjust the required thickness retardation, it is represented by (n _x + n _y ) / 2-n _z . There are a method of adjusting a value, and a method of adjusting d (film thickness). Although the method by the film thickness adjustment is simple, as described above, when the film thickness is increased to increase the thickness retardation, problems such as not only the components of the liquid crystal display device after the coating film are formed but also the material cost of the coating film are increased. do. On the contrary, when it is necessary to make film thickness small and to lower thickness phase difference, it may be restrict | limited by the point of limitation of the coating method for thin film formation with uniform thickness, the strength of a thin film, etc. Thus, by the addition of the retardation controlling agent, by adjusting the value represented by _{(n x + n y) /} 2-n z is effective to obtain a thickness retardation of interest. Retardation adjusting agent of the invention, in particular _{[(n x + n y)} / 2-n z] to obtain a coating film for optical compensation having the characteristics of a × d <0, is to adjust the thickness of the phase difference in this respect.

The phase difference regulator for cellulose N-substituted carbamate of the present invention preferably includes at least one selected from carbamic acid ester, N-substituted carbamic acid ester, urea and N-substituted urea.

The phase difference regulator for cellulose N-substituted carbamate of this invention can adjust the thickness phase difference of cellulose N-substituted carbamate in a negative direction. The carbamic acid ester can be obtained, for example, by a known method of reacting the chloroformic acid ester with ammonia, and the N-substituted carbamic acid ester can be, for example, a chloroformic acid ester to a primary amine or a secondary amine. It can manufacture by the well-known method of making it react. Further, the urea can be obtained by, for example, an industrial production method of reacting ammonia and carbon dioxide under high temperature and high pressure, and the N-substituted urea reacts an isocyanate compound with, for example, a primary amine or a secondary amine. It can be manufactured by a known method.

The carbamic acid ester of the present invention can be used as long as it contains a carbamoyloxy group (NH ₂ -CO-O-), but is preferably a compound containing 1 to 8 carbamoyloxy groups, and contains one. It is more preferable that it is a compound to make. The compound represented by following formula (7) from a viewpoint of the availability of a raw material is preferable.

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, and an aralkyl group having 7 to 20 carbon atoms.

In formula (7), R ³⁹ is more preferably 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, an aralkyl group having 7 to 16 carbon atoms, and R ³⁹ is 1 to 16 carbon atoms. It is especially preferable that they are an alkyl group of 12, a halogenated alkyl group of 1 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, and an aralkyl group of 7 to 12 carbon atoms.

The N-substituted carbamic acid esters of the present invention can be used as long as they contain N-substituted carbamoyloxy groups (R-NH-CO-O-, where R is an alkyl group, a halogenated alkyl group, an aryl group, an aralkyl group). Although it is preferable that it is a compound containing 1-8 of N-substituted carbamoyloxy groups, it is more preferable that it is a compound containing one. The compound represented by following formula (8) from a viewpoint of the availability of a raw material is preferable.

In formula, R <^40> , R <^41> is the same or different, and shows a C1-C20 alkyl group, a C1-C20 halogenated alkyl group, a C6-C20 aryl group, and a C7-C20 aralkyl group.

In formula (8), R ⁴⁰ and R ⁴¹ are the same or different, and are 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, and an aralkyl group having 7 to 16 carbon atoms. preferably, R ^40, R ⁴¹ are the same or different, particularly preferably an aralkyl group having 1 to 12 alkyl group, a C 1 -C 12 halogenated alkyl group, an aryl group having 6 to 12 carbon atoms, 7 to 12 carbon atoms in the .

Any N-substituted element of the present invention can be used as long as it contains a ureylene group (-NH-CO-NH-). The compound represented by following formula (9) is preferable from a viewpoint of the availability of a raw material.

In the formula, R ⁴² and R ⁴³ are the same or different and represent 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, and an aralkyl group having 7 to 20 carbon atoms. .

In formula (9), R ⁴² and R ⁴³ are the same or different, and are 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, and an aralkyl group having 7 to 16 carbon atoms. It is preferable that R <^42> , R <^43> is the same or different, and it is especially preferable that they are a C1-C12 alkyl group, a C1-C12 halogenated alkyl group, a C6-C12 aryl group, and a C7-C12 aralkyl group. .

As a specific example of the said carbamic acid ester, for example, methyl carbamic acid, ethyl carbamic acid, carbamic acid cyclopentyl, carbamic acid cyclohexyl, carbamic acid trichloromethyl, carbamic acid phenyl, carbamic acid 1-naphthyl, carbamic acid 2- Naphthyl, carbamic acid benzyl, ethylene glycol dicarbamate, propylene glycol dicarbamate, hydroquinone dicarbamate, pyrocatechol dicarbamate, pyrogallol tricarbamate and the like.

As a specific example of the said N-substituted carbamic acid ester, For example, N-methyl carbamic acid methyl, N-methyl carbamic acid ethyl, N-methyl carbamic acid cyclopentyl, N-methyl carbamic acid cyclohexyl, N-methyl carbamic acid triclo Romethyl, N-methylcarbamic acid phenyl, N-methylcarbamic acid 1-naphthyl, N-methylcarbamic acid 2-naphthyl, N-methylcarbamic acid benzyl, ethylene glycol bis (N-methylcarbamate), propylene Glycol bis (N-methylcarbamate), hydroquinone bis (N-methylcarbamate), pyrocatechol bis (N-methylcarbamate), pyrogallol tris (N-methylcarbamate), N-phenyl Methyl carbamic acid, ethyl N-phenylcarbamic acid, N-phenylcarbamic acid cyclopentyl, N-phenylcarbamic acid cyclohexyl, N-phenylcarbamic acid trichloromethyl, N-phenylcarbamic acid phenyl, N-phenylcarbamic acid 1- Naphthyl, N-phenylcarbamic acid 2-naphthyl, N-phenylcarbamic acid benzyl, ethylene glycol bis (N-phenylcarba ), Propylene glycol bis (N-phenylcarbamate), hydroquinone bis (N-phenylcarbamate), pyrocatechol bis (N-phenylcarbamate), pyrogallol tris (N-phenylcarbamate) , N, N'-bis (methoxycarbonyl) ethylenediamine, N, N'-bis (ethoxycarbonyl) ethylenediamine, N, N'-bis (phenoxycarbonyl) ethylenediamine, N, N ' -Bis (benzyloxycarbonyl) ethylenediamine, N, N'-bis (methoxycarbonyl) -1,2-phenylenediamine, N, N'-bis (ethoxycarbonyl) -1,2-phenyl Rendiamine, N, N'-bis (phenoxycarbonyl) -1,2-phenylenediamine, N, N'-bis (benzyloxycarbonyl) -1,2-phenylenediamine, N, N'- Bis (methoxycarbonyl) -1,3-phenylenediamine, N, N'-bis (ethoxycarbonyl) -1,3-phenylenediamine, N, N'-bis (phenoxycarbonyl)- 1,3-phenylenediamine, N, N'-bis (benzyloxycarbonyl) -1,3-phenylenediamine, N, N'-bis (methoxycarbonyl) -1,4-phenylenediamine, N, N'-bis Cycarbonyl) -1,4-phenylenediamine, N, N'-bis (phenoxycarbonyl) -1,4-phenylenediamine, N, N'-bis (benzyloxycarbonyl) -1,4 -Phenylenediamine, N- (4-tolyl) carbamic acid ethyl, N- (4-tolyl) carbamic acid phenyl, etc. are mentioned.

Specific examples of the N-substituted urea include N, N'-dimethyl urea, N, N'-diethyl urea, N, N'-dichloromethyl urea, N, N'-diphenyl urea, N, N '-Dibenzylurea, N-ethyl-N'-methylurea, N-methyl-N'-phenylurea, N-benzyl-N'-phenylurea, N, N'-di-p-tolylurea, N- Phenyl-N '-(p-tolyl) element, etc. are mentioned. These phase difference regulators for cellulose N-substituted carbamate may be used alone or in combination of two or more thereof.

Among these, in view of availability and effects, the retarder for cellulose N-substituted carbamate is ethyl carbamate, phenyl carbamate, ethyl N-phenylcarbamate, phenyl N-phenylcarbamate, N- (4-tolyl) carbate. Ethyl lactate, N- (4-tolyl) carbamic acid phenyl, urea, N, N'-diphenylelement, N, N'-di-p-tolylurea, N-phenyl-N '-(p-tolyl) Particular preference is given to at least one selected from the group of urea.

In this invention, when the total weight of the polymer which is (A) component and the phase difference regulator which is (C) component is 100 weight% in the coating liquid for optical-compensation coating film formation, the ratio of a phase difference regulator is 0.1 weight% of a minimum. It is preferable to use in the range of the upper limit of 70 weight%, It is more preferable to use in the range of the minimum of 0.2 weight% and the upper limit of 65 weight%, It is further more preferable to use in the range of the minimum of 0.3 weight% and the upper limit of 60 weight%. Do. When the ratio of the phase difference regulator is smaller than 0.1 wt%, the adjustment effect of the thickness phase difference tends to be small, and when larger than 70 wt%, it tends to bleed from the coating film for optical compensation.

Next, resin which can be added for the purpose of modifying the coating film characteristic of this invention is demonstrated. As said resin which can be added, polycarbonate resin, an acrylic resin, polyester resin, polystyrene resin, polyolefin resin, polyamide resin, polyimide resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyether sulfone resin, polyarylate Resin, an epoxy resin, a silicone resin, a phenol resin, a urethane resin, etc. are illustrated, These can be added in the range which does not impair the objective and effect of this invention.

Next, the additive which can be added in order to modify the characteristic of the coating film and coating liquid of this invention is demonstrated. As an additive, antioxidant (for example, hindered phenols, such as the Ciba specialty chemicals make, IRGANOX 1010, IRGANOX 1135, IRGANOX 1330), a processing stabilizer (for example, the Ciba specialty chemicals make, HP) -136, IRGANOX E201, IRGAFOS 168, etc.), light stabilizer (for example, hindered amines, such as those manufactured by Sanyo Lifetech, Sanol LS-765, Sanol LS-770), ultraviolet absorber (for example, Ciba specialty Benzotriazoles such as Chemicals, TINUVIN P, TINUVIN 213, TINUVIN 326, and the like, and an adhesive improving agent (for example, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, etc.) Silane coupling agent), silanol condensation catalyst (for example, aluminum tris (ethylacetoacetate) manufactured by Kawaken Fine Chemical, aluminum chelates such as aluminum chelate M), and plasticizer (for example, di2-ethylhexyl phthalate) , Diisobutyl adipate Esters), surfactants (e.g., fluorine-based compounds such as Sumitomo 3M, Fluorad FC-430, Fluorad FC-4430), antistatic agents (e.g., Ciba Specialty Chemicals, IRGASTAT P18, IRGASTAT P22 etc.) These can be mentioned, These can be added in the range which does not impair the objective and effect of this invention.

The coating liquid of this invention can be obtained, for example by mixing each said component at the temperature more than melting | fusing point of a solvent and below boiling point, and then performing stationary or stirring mixing.

Next, the board | substrate for optical elements is demonstrated. Various things can be used as a board | substrate, Especially considering a use, a transparent thing is preferable. As an example of the specific compound used for a board | substrate, Polycarbonate type polymer manufactured by polycondensation from bisphenol A and carbonyl chloride; Polyacrylic acid esters such as polymethyl acrylate and polymethyl methacrylate; Polyester polymer obtained by condensation of dibasic acids, such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and glycols, such as ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, or ring-opening polymerization of lactones ; Styrene polymers such as polystyrene and poly (α-methylstyrene); Copolymers of acrylic esters with styrene; Polyolefin polymers such as polyethylene, polynorbornene, hydrogenated polyisoprene and hydrogenated polybutadiene; Cellulose resins such as triacetyl cellulose; Polyamides such as nylon 6 and nylon 66; Polyimide; Polyamideimide; Polyvinyl alcohol; Vinyl chloride; Polyether sulfone; Epoxy resins; Silicone resins; The compound etc. which were described in international publication 01/37007 are mentioned. As a board | substrate, these polymers were film-formed by the solution casting method, the uniaxial stretching method of the dried product after solution casting, the biaxial stretching method of the dry product after solution casting, the uniaxial stretching method of an extruded product, the biaxial stretching method of an extruded product, the calendering method, etc. And a polarizing plate, a glass plate, a color filter, a liquid crystal cell, etc. which adhered these films to the polarizer as a protective film. These board | substrates can also be used as a board | substrate at the time of formation of the coating film for optical compensation.

Next, the formation method of the coating film for optical compensation of this invention is demonstrated. The coating film for optical compensation can be suitably manufactured on a board | substrate by coating the coating liquid of this invention on one side or both surfaces of the said board | substrate, and making it as a coating substrate, and drying this coated board | substrate. Gravure roll coating method, Meyer bar coating method, Doctor blade coating method, Reverse roll coating method, Immersion coating method, Air knife coating method, Calender coating method, Skids coating method, Kiss coating method, Bar coating method, Slot die coating method Coating method, spin coating method, etc. are mentioned.

As a drying method, by the method of leaving (coating) the said coating substrate in inert gas, such as air or nitrogen, the method of heat-drying in a hot air oven, an infrared heating furnace, etc., the method of drying under reduced pressure with a vacuum dryer, etc., Or a combination thereof.

As dry temperature conditions, both a constant temperature and a multistage elevated temperature can be used. In the case of constant temperature, the temperature range of lower limit -30 degreeC and an upper limit 300 degreeC is preferable, A lower limit 0 degreeC and an upper limit 280 degreeC are more preferable, A lower limit 10 degreeC and an upper limit 260 degreeC are still more preferable. If the drying temperature is lower than -30 ° C, the drying time tends to be long, and if it is higher than 300 ° C, thermal deterioration of the coating film and the substrate tends to occur. Such constant temperature drying can be used, but in order to effectively dry, it is preferable to raise the temperature in multiple stages, and from the viewpoint of economics, two stage drying of primary drying and secondary drying is particularly preferable.

In primary drying, the lower limit of 0 degreeC and the upper limit of 40 degreeC are preferable, the lower limit of 5 degreeC and the upper limit of 35 degreeC are more preferable, and the lower limit of 10 degreeC and the upper limit of 30 degreeC are more preferable. Primary drying is necessary for the formation of the foundation of the coating film internal structure necessary for making the absolute value of the value represented by (n _x + n _y ) / 2-n _x larger. If the primary drying temperature is lower than 0 ° C., the drying time required to form the foundation of the coating film internal structure tends to be long, and if it is higher than 40 ° C., the absolute value of the value expressed as (n _x + n _y ) / 2-n _x It tends to be difficult to form the foundation of the coating film internal structure necessary for making the larger.

In secondary drying, the lower limit of 80 degreeC and the upper limit of 300 degreeC are preferable, the lower limit of 90 degreeC and the upper limit of 280 degreeC are more preferable, and the lower limit of 100 degreeC and the upper limit of 260 degreeC are more preferable. Secondary drying is necessary for establishing the coating film internal structure necessary for making the absolute value of the value represented by (n _x + n _y ) / 2-n _x larger. If the secondary drying temperature is lower than 80 ° C, the establishment of the coating film internal structure tends to be insufficient. If the secondary drying temperature is higher than 300 ° C, thermal deterioration of the coating film and the substrate tends to occur. In _{addition, (n x + n y)} / 2-n when the absolute value of the value represented by _x is sufficiently large, the coating film established internal structure can be observed from the coating film cross-section such as a transmission electron microscope (TEM).

Moreover, in this invention, after coating a coating liquid on a board | substrate and making it into a coating substrate, it can also be set as the method of forming an optical compensation coating film by annealing a coating film by exposing to vapor of (B) component, and further drying.

Annealing is preferably performed for improving the leveling property of the coating film, stress relaxation, and the like, and is effective for, for example, reducing the in-plane retardation, reducing the deviation of the in-plane retardation, and the like. In the present invention, the annealing is preferably performed by standing the coating film of the coating substrate upward in a vapor of component (B). Although the temperature at the time of annealing can be set in various ways, the range of the lower limit of -30 degreeC and an upper limit [boiling point (degreeC) of (B) component] is preferable, and a lower limit of -15 degreeC and the upper limit [boiling point of (B) component- (degreeC)- 5 degreeC] is more preferable, and a minimum of 0 degreeC and an upper limit [boiling point (degreeC) -10 degreeC of (B) component] are more preferable. When the temperature at the time of annealing is lower than -30 ° C, the annealing time tends to be long, and when the temperature at the time of annealing is higher than the boiling point (° C) of the component (B), outflow tends to occur easily from the substrate of the coating film. The pressure at the time of annealing can be set in various ways, and can be performed at atmospheric pressure, under pressure, or under reduced pressure, but atmospheric pressure is preferable from the viewpoint of workability.

Next, the manufacturing method of the optical element of this invention is demonstrated. The optical element referred to here includes a substrate and a coating film for optical compensation coated on the substrate. Moreover, the element used for optical is also included after peeling the said optical compensation coating film from the said board | substrate once.

The optical element coats 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 the optical compensation coating film, followed by drying or coating described in the method for forming the optical compensation coating film. It can manufacture preferably by annealing and drying after coating using a method.

Drying can be performed suitably by using the drying method and drying temperature demonstrated by the formation method of the coating film for optical compensation.

In the optical compensation coating film of the present invention, when the largest refractive index in the plane is n _x , the smallest is n _y , and the refractive index in the thickness direction is n _z and the film thickness is d, [(n _x + n _y It is preferable to have a characteristic of) / 2-n _z ] × d <0. In the unstretched film formed into a film by the solution casting method using the solution which melt | dissolved the polymer of any one of the said cellulose N-substituted carbamate or an aromatic vinyl polymer as (B) component etc. especially _by an optical compensation coating film formed by containing any one of a cellulose N-substituted carbamate or an aromatic vinyl polymer satisfying the relationship of _x + n _y ) / 2-n _z ] × d <0. It is preferable that the said characteristic is obtained. When the thickness of the optical compensation coating film is d (nm), the in-plane retardation is represented by (n _x -n _y ) × d, and the thickness retardation is [(n _x + n _y ) / 2-n _z ] × d. Although the in-plane phase difference is measured by 590 nm light, a lower limit of 0 nm and an upper limit of 300 nm are preferable, a lower limit of 0 nm and an upper limit of 200 nm are more preferable, and a lower limit of 0 nm and an upper limit of 100 nm are more preferable. When the in-plane retardation is larger than 300 nm, compensation of the retardation due to birefringence of a liquid crystal cell or the like tends to be difficult. In addition, as for thickness phase difference, in a measurement by 590 nm light, a minimum of -1000 nm and an upper limit of -1 nm are preferable, a lower limit of -800 nm and an upper limit of -10 nm are more preferable, and a lower limit of -600 nm and an upper limit of -20 nm. More preferred. When the thickness retardation is smaller than -1000 nm, compensation of the retardation due to birefringence of a liquid crystal cell or the like tends to be difficult.

On the other hand, an optical compensation coating film that satisfies the relationship of [(n _x + n _y ) / 2-n _z ] × d ≧ 100 can be obtained by containing a cellulose derivative. A cellulose derivative can be manufactured by chemically modifying, for example, the cellulose obtained from various wood pulp, cotton linter, cotton lint, etc. as a raw material. For example, Carboxylic acid ester type | system | group derivatives, such as a cellulose formate, a cellulose diacetate, a cellulose triacetic acid, a cellulose propionate, a cellulose acetate propionate, a cellulose butyrate, a cellulose acetate butyrate, and a cellulose trifluoroacetic acid; Inorganic acid ester derivatives such as cellulose sulfate, cellulose nitrate and cellulose phosphate; And ether derivatives such as methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cyanoethyl cellulose, and carboxymethyl cellulose.

Of these, ether derivatives are preferred from the viewpoint of properties such as low hydrolysis resistance and low hygroscopicity. More preferably, at least one of the hydroxyl groups of the cellulose is an ether derivative substituted with an alkoxy group having 1 to 20 carbon atoms, and more preferably at least one of the hydroxyl groups of the cellulose is an ether derivative substituted with an alkoxy group having 1 to 10 carbon atoms.

Specific examples of preferred cellulose derivatives include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, pentyl cellulose, hexyl cellulose, heptyl cellulose, octyl cellulose, cyclopentyl cellulose, cyclohexyl cellulose, methylethyl cellulose, methylpropyl cellulose, methyl Butyl cellulose, methylpentyl cellulose, methylhexyl cellulose, methylheptyl cellulose, methyloctyl cellulose, methylcyclopentyl cellulose, methylcyclohexyl cellulose, ethyl propyl cellulose, ethyl butyl cellulose, ethyl pentyl cellulose, ethyl hexyl cellulose, ethyl heptyl cellulose, ethyl Octyl cellulose, ethylcyclopentyl cellulose, ethylcyclohexyl cellulose and the like. These cellulose derivatives may be used independently and may use 2 or more types together.

The ether derivative of the cellulose can be prepared by, for example, making an alkali cellulose with sodium hydroxide or the like, and then adding an alkyl halide such as chlorinated alkyl, followed by heating and stirring. At this time, when two or more alkyl halides are used, ether derivatives substituted with two or more alkoxy groups are obtained.

In addition, the cellulose has three hydroxyl groups per glucose residue as its structural unit, and the degree of substitution (hereinafter referred to as DS) per glucose residue is at most 3, but the lower limit of the degree of substitution is preferably 0.1, more preferably. 0.5, More preferably, the upper limit is 3, More preferably, it is 2.95, More preferably, it is 2.9. When substitution degree is lower than 0.1, it exists in the tendency which becomes difficult to melt | dissolve in a solvent. In the present invention, two or more kinds of cellulose derivatives having different degrees of substitution may be used in combination, or may be used alone.

The lower limit of the number average molecular weight of the cellulose derivative is preferably 5000, more preferably 8000, even more preferably 10000, and the upper limit is preferably 300000, more preferably 250000, still more preferably 200000. When the number average molecular weight is less than 5000, the coating film strength tends to decrease, and when the number average molecular weight is larger than 300000, it tends to be difficult to dissolve in the solvent. In addition, the said number average molecular weight is the value measured by the gel permeation chromatography (GPC) method. In the present invention, two or more kinds of cellulose derivatives having different number average molecular weights may be used in combination, or may be used alone.

Moreover, various cellulose derivatives illustrated as a cellulose derivative may be used independently, and 2 or more types may be used together.

Next, the optical compensation film (retardation film) of this invention is demonstrated. The optical compensation film (retardation film) can be preferably manufactured by forming an optical compensation layer using what was formed into a film from what was illustrated as the said optical element board | substrate, and using the formation method of the said optical compensation coating film.

Next, the polarizing plate of this invention is demonstrated. As a polarizing plate, the thing which bonded the protective film using adhesives, such as a polyester adhesive, a polyacryl adhesive, an epoxy adhesive, a cyanoacrylic adhesive, and a polyurethane adhesive, on both surfaces of a polarizer, etc. are mentioned, for example. Examples of the polarizer include dehydrochlorination of a polarizer and a polyvinyl chloride film prepared by adsorption-oriented iodine and / or dichroic dye on a hydrophilic polymer film, and a polyvinyl alcohol film prepared by dehydrating a polyvinyl alcohol-based film. To form a polyene to orientate and manufacture. Examples of the hydrophilic polymer film used for the polarizer include polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and saponified films of ethylene-vinyl acetate copolymers. As a protective film, what was filmed among the thing illustrated as the said board | substrate for optical elements, the optical compensation film (retardation film) of this invention, etc. are mentioned, What was filmed in the said board | substrate for optical elements is bonded to both surfaces of a polarizer. When making it become a polarizing plate of this invention, after manufacturing a polarizing plate, the optical compensation coating film of this invention is provided in at least one surface of the polarizing plate using the formation method of the said optical compensation coating film. When using the optical compensation film (retardation film) of this invention as a protective film, it can also be used for both surfaces of a polarizer, and the optical compensation film (retardation film) of this invention is used for one side, and the said optical element on the opposite side The film-formed thing can be used in the substrate for use. Moreover, after manufacturing the polarizing plate using the optical compensation film (retardation film) of this invention on one side, and filming in the said board | substrate for optical elements on the opposite side, the optical compensation of this invention newly on one side or both surfaces. You can also install a coating film.

Next, the liquid crystal display device of the present invention will be described. Examples of the liquid crystal display include a display device configured in the order of a light source, a light guide plate, a light diffusing film, a lens film, a brightness enhancement film, a polarizing plate, a liquid crystal cell, and a polarizing plate, and the incident light side and / or emission of the liquid crystal cell. The optical compensation film (retardation film) of the present invention is mounted (mounted) on the light side, and the liquid crystal display device of the present invention can be obtained by attaching the polarizing plate of the present invention to the polarizing plate on the incident light side and / or the outgoing light side of the liquid crystal cell. . Examples of the liquid crystal cell include a vertical alignment (VA) method, an in-plane switching (IPS) method, and an OCB (Optically Compensated Birefringence) method.

Hereinafter, although an Example is shown in order to demonstrate this invention in detail, this invention is not limited by these Examples.

Calculation of three-dimensional refractive index (n _x , n _y , n _z )

A three-dimensional refractive index was calculated by measuring with 590 nm light at 25 ° C. using an automatic birefringent meter KOBRA-WR manufactured by Oshi Keisoku Co., Ltd. The in-plane retardation from the results thus obtained was evaluated by the _{× d (n x -n y)} . In addition, thickness phase difference was _{calculated | required} by [(nx + _ny ) / 2- _nz ] xd. However, when the retardation was measured with the slow axis as the inclined central axis, when the retardation increased with the increase of the inclination angle, the following method was used in order to determine the sign of the retardation. After superimposing the λ / 4 plate made of polycarbonate on the manufactured optical element and mounting it on the automatic birefringence system KOBRA-WR such that the orientation angle of the λ / 4 plate is 0 ± 1 degree, the slow axis is used as the oblique central axis. Phase difference measurement by 590 nm light was performed at 25 degreeC. If the measurement result is higher than the phase difference of the λ / 4 plate alone, the inclination angle is increased and the phase difference of the optical element alone is also increased in the positive direction.If the measurement result is lower than the phase difference of the λ / 4 plate alone, the inclination angle is increased. In addition, it was considered that the phase difference of the optical element alone was also lowered in the negative direction, and the three-dimensional refractive index was calculated by giving a positive and negative sign to the phase difference of the optical element alone measured first. The in-plane retardation from the results thus obtained was evaluated by the _{× d (n x -n y)} . In addition, thickness phase difference was _{calculated | required} by [(nx + _ny ) / 2- _nz ] xd.

Synthesis Example 1 Synthesis of Cellulose N-phenylcarbamate (1)

1.0 g of cellulose (Asahi Kasei Chemicals, Avicel TG-F20) vacuum dried at 60 ° C. for 7 hours was added to a 500 ml four-necked flask equipped with a cooling tube, a nitrogen introduction tube, a stirrer, and a thermometer, and 100 ml of pyridine was added thereto. After making it into a suspension, 7.7 g of phenyl isocyanate (made by Tokyo Kasei Kogyo Co., Ltd.) was further added. Nitrogen was introduced and heated to 110 ° C. while stirring, followed by reaction for 7 hours. Then, after cooling to 25 degreeC, the reaction liquid was dripped in 400 ml of ethanol, and precipitation was produced | generated. After filtration and separation, 25 ml of acetone was added to the obtained polymer and dissolved therein, followed by dropwise addition in 400 ml of pure water to form a precipitate. After filtration separation, the obtained polymer was again dissolved in 30 ml of acetone, and dropped in 400 ml of pure water to form a precipitate. It washed with water after filtration separation, and it vacuum-dried at 60 degreeC for 4 hours, and obtained 2.5 g of cellulose N-phenylcarbamate (1) (henceforth a synthetic product (1)). DS of the synthetic product (1) was 3 as a result of proton NMR analysis. In addition, DS was determined by comparing the chemical shift (3.4-5.5 ppm) area of the proton derived from a cellulose backbone with the chemical shift (6.7-7.7 ppm) area of the phenyl group.

Synthesis Example 2 Synthesis of Cellulose N-phenylcarbamate (2)

1.0 g of cellulose (Asahi Kasei Chemicals, Avicel TG-F20) vacuum dried at 60 ° C. for 7 hours was added to a 500 ml four-necked flask equipped with a cooling tube, a nitrogen introduction tube, a stirrer, and a thermometer, and 100 ml of pyridine was added thereto. After making it into a suspension, 7.7 g of phenyl isocyanate (made by Tokyo Kasei Kogyo Co., Ltd.) was further added. Nitrogen was introduced and heated to 110 ° C. while stirring, followed by reaction for 7 hours. Then, after cooling to 25 degreeC, the reaction liquid was dripped in 400 ml of ethanol, and precipitation was produced | generated. After filtration and separation, 30 ml of acetone was added to the obtained polymer and dissolved therein, followed by dropwise addition in 400 ml of pure water to form a precipitate. After washing with filtration, washing with water and vacuum drying at 60 ° C. for 4 hours yielded 2.2 g of cellulose N-phenylcarbamate (2) (hereinafter also referred to as synthetic product (2)). The substitution degree DS of the synthetic product (2) was 3 as a result of proton NMR analysis. In addition, DS was determined by comparing the chemical shift (3.4-5.5 ppm) area of the proton derived from a cellulose backbone with the chemical shift (6.7-7.7 ppm) area of the phenyl group.

Synthesis Example 3 Synthesis of Cellulose N- [2- (trifluoromethyl) phenyl] carbamate (3)

1.0 g of cellulose (Asahi Kasei Chemicals, Avicel TG-F20) vacuum dried at 60 ° C. for 7 hours was added to a 500 ml four-necked flask equipped with a cooling tube, a nitrogen introduction tube, a stirrer, and a thermometer, and 100 ml of pyridine was added thereto. After the suspension, 8.7 g of 2- (trifluoromethyl) phenyl isocyanate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was further added. Nitrogen was introduced and heated to 110 ° C. while stirring, followed by reaction for 7 hours. Then, after cooling to 25 degreeC, 200 ml of ethanol were added, and the reaction liquid was dripped at 1.5 L of pure water, and precipitation was produced | generated. After filtration and separation, 100 ml of acetone was added to the obtained polymer and dissolved therein, followed by dropwise addition in 2 L of pure water to form a precipitate. After filtration and washing with water, vacuum drying at 60 ° C. for 4 hours, the polymer was placed in a soxhlet extractor. After 20 times of Soxhlet extraction with methanol, 3.4 g of cellulose N- [2- (trifluoromethyl) phenyl] carbamate (3) was obtained by vacuum drying at 25 ° C for 4 hours. 3)). DS of the synthetic product (3) was 3 as a result of proton NMR analysis. In addition, DS was determined by comparing the chemical shift (3.5-5.5 ppm) area of the proton derived from a cellulose backbone with the chemical shift (6.9-7.9 ppm) area of the proton of 2- (trifluoromethyl) phenyl group.

Experimental Example 1

4.15 g of butyl acetate was added to 0.85 g of the synthetic products (1), and the mixture was dissolved at 25 ° C. Subsequently, the coating solution was coated on a 150 μm thick glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) using a bar coater, and then dried in air at 120 ° C. for 1 minute to provide optical The device was manufactured. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result is shown in following Table 1.

Experimental Example 2

4.15 g of ethyl cellosolve acetate was added to 0.85 g of the synthetic product (1), and the mixture was dissolved at 25 ° C. Subsequently, the coating solution was coated on a glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) having a thickness of 150 μm using a bar coater, and then filled with vapor filled with ethyl cellosolve acetate. After enclosed in a container and sealed, it annealed at 25 degreeC for 24 hours. Thereafter, the coated substrate was taken out and dried in air at 120 ° C. for 1 minute to manufacture an optical element. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result was shown in Table 1.

Experimental Example 3

9.0 g of chloroform was added to 1.0 g of the synthetic product (3), and the mixture was dissolved at 25 ° C. Subsequently, the coating solution was coated on a glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) having a thickness of 150 μm using a bar coater, and then dried in air at 100 ° C. for 1 minute. An optical device was manufactured. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result was shown in Table 1.

Experimental Example 4

The optical device prepared in Experimental Example 3 was placed in a glass container filled with chloroform vapor and sealed, and then annealed at 30 ° C. for 7.5 hours. Then, the optical element was taken out and dried in air for 1 minute at 100 ° C. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result was shown in Table 1. Here, the one with smaller in-plane birefringence (n _x -n _y ) than Example 3 was obtained. In other words, the in-plane retardation was reduced by annealing.

Experimental Example 5

3.48 g of 1,2-dimethoxyethane was added to 0.52 g of the synthetic product (2), and the mixture was dissolved at 23 ° C. Subsequently, the coating liquid was coated on a glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) having a thickness of 150 µm using a bar coater to obtain a coating substrate. Thereafter, the coated substrate was dried at 23 ° C. for 44 hours in air to produce an optical element. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed. The results are shown in Table 2 below.

Experimental Example 6

To 0.5 g of Synthesis (2), 4.5 g of ethylene glycol monomethyl ether acetate was added and dissolved at 23 ° C. Subsequently, the coating liquid was coated on a glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) having a thickness of 150 µm using a bar coater to obtain a coating substrate. Then, the said coating substrate was dried in air for 1 minute at 100 degreeC, and the optical element was manufactured. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed. The results are shown in Table 2.

Experimental Example 7

To 0.5 g of Synthesis (2), 4.0 g of butyl acetate and 0.5 g of ethylene glycol monomethyl ether acetate were added and dissolved at 23 ° C. Subsequently, the coating liquid was coated on a glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) having a thickness of 150 µm using a bar coater to obtain a coating substrate. Thereafter, the coated substrate was dried at 23 ° C. for 25 minutes in air to produce an optical element. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed. The results are shown in Table 2.

Experimental Example 8

The same operation as in Example 7 was carried out except that the coated substrate was dried at 30 ° C. for 25 minutes in air to produce an optical element. The physical property measurement of the obtained optical element was performed. The results are shown in Table 2.

Experimental Example 9

The same operation as in Experiment 5 was carried out except that the coated substrate was dried at 23 ° C. for 44 hours in air, and further dried at 100 ° C. for 1 minute in air to produce an optical element. The physical property measurement of the obtained optical element was performed. The results are shown in Table 2. In 23 ℃ 44 hours, the absolute value of the value represented than only Example 5 After drying in air to a _{(n x + n y) /} 2-n z was obtained in a large optical device.

Experimental Example 10

The same operation as in Experiment 6 was carried out except that the coated substrate was dried at 23 ° C. for 19 hours in air, and further dried at 100 ° C. for 1 minute in air to produce an optical element. The physical property measurement of the obtained optical element was performed. The results are shown in Table 2. The optical element has a large absolute value of the value shown at 100 ℃ in one minute, only Experimental Example 6 than the _{(n x + n y) /} 2-n x have been dried in the air were obtained.

Experimental Example 11

The same operation as in Experiment 7 was carried out except that the coated substrate was dried in air at 23 ° C. for 25 minutes, and further dried at 250 ° C. for 1 minute in air to produce an optical element. The physical property measurement of the obtained optical element was performed. The results are shown in Table 2. 23 ℃ in the absolute value of the value represented by only Example 7 than the _{(n x + n y) /} 2-n z have dried in 25 minutes, and air was obtained a large optical element.

Experimental Example 12

The same operation as in Experiment 8 was carried out 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. The physical property measurement of the obtained optical element was performed. The results are shown in Table 2. At 30 ℃, the absolute value of the value represented by only Example 8 than the _{(n x + n y) /} 2-n z have dried in 25 minutes, and air was obtained a large optical element.

Experimental Example 13

Except for using a 40 μm-thick cellulose acetate film (in-plane retardation: 0 nm, thickness retardation: 8 nm) instead of the glass substrate and forming a coating film of 10000 nm thereon, an optical compensation film was prepared. The same operation was performed. As a result of measuring physical properties of the obtained optical compensation film, in-plane retardation was 0 nm and thickness retardation was -40 nm.

Experimental Example 14

The polarizer was produced by impregnating and extending | stretching iodine to a polyvinyl alcohol-type film. One side of this polarizer was bonded to the 80 micrometer-thick cellulose acetate film using the polyacrylic-type adhesive agent. In addition, the optical compensation film manufactured in Experimental Example 13 was bonded to the opposite surface of the polarizer using a polyacrylic adhesive so that the coating film surface was outside, and the polarizing plate which has an optical compensation layer was manufactured.

Experimental Example 15

A liquid crystal display device equipped with an IPS system liquid crystal cell was prepared, and a display device in which the optical compensation film prepared in Experimental Example 13 was superposed on the emission light side of the liquid crystal cell was manufactured. As a result of observing the display screen, the color display did not change even when viewed from the front or in an oblique direction, and a good image was obtained.

Experimental Example 16

Instead of preparing a liquid crystal display device equipped with an IPS-type liquid crystal cell and peeling off the polarizing plate on the emission light side, a display device in which the polarizing plate produced in Experimental Example 14 is bonded to the liquid crystal cell so that the coating film surface becomes the emission light side of the liquid crystal cell. Was prepared. As a result of observing the display screen, the color display did not change even when viewed from the front or in an oblique direction, and a good image was obtained.

Experimental Example 17

Operation similar to Experimental Example 15 was performed except not using the optical compensation film manufactured in Experimental Example 13. As a result, when viewed from the oblique direction, the color change was different from when viewed from the front by birefringence of the liquid crystal display constituent member.

Experimental Example 18

The same operation as in Experimental Example 16 was carried out except that the polarizing plate prepared in Experimental Example 14 was not used and the polarizing plate on the exiting light side was used as it was. As a result, when viewed from the oblique direction, the color display was different from when viewed from the front by birefringence of the liquid crystal display constituent member.

Experimental Example 19

To 12.0 g of poly (2-vinylnaphthalene) (manufactured by Aldrich, weight average molecular weight: 175000), 88.0 g of methylene chloride was added and dissolved at 25 ° C. Subsequently, the coating solution was coated on a 150 μm thick glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) using a bar coater, and then air dried at 25 ° C. for 6 hours. An optical device was manufactured. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result is shown in following Table 3. Here, an optical element of [(n _x + n _y ) / 2-n _z ] × d <0 was obtained.

Experimental Example 20

95.0 g of methylene chloride was added to 5.0 g of poly (4-vinylbiphenyl) (Aldrich, weight average molecular weight: 115000), and it melt | dissolved at 25 degreeC. Subsequently, the coating solution was coated on a 150 μm thick glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) using a bar coater, and then air dried at 25 ° C. for 6 hours. An optical device was manufactured. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result was shown in Table 3. Here, an optical element of [(n _x + n _y ) / 2-n _z ] × d <0 was obtained.

Experimental Example 21

70.0 g of chloroform was added to 30.0 g of styrene-maleic anhydride copolymer (Dykeke D332, manufactured by Nova Chemical), and dissolved at 25 ° C. Subsequently, the coating solution was coated on a glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) of 150 μm thickness using a bar coater, and then the coated substrate was filled with chloroform vapor at atmospheric pressure. After enclosed in a glass container and sealed, it annealed at 25 degreeC for 48 hours. Thereafter, the coated substrate was taken out and air dried at 25 ° C. for 6 hours to produce an optical element. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result was shown in Table 3. Here, an optical element of [(n _x + n _y ) / 2-n _z ] × d <0 was obtained.

Experimental Example 22

80.0 g of chloroform was added to 20.0 g of ethyl cellulose (DTH Chemical Co., Ltd. ETHOCEL STD-100, number average molecular weight: 63400, DS: 2.5), and it melt | dissolved at 25 degreeC. Subsequently, the coating solution was coated on a 150 μm thick glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) using a bar coater, and then air dried at 25 ° C. for 6 hours. An optical device was manufactured. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result is shown in following Table 4. Here, an optical element of [(n _x + n _y ) / 2-n _z ] × d ≧ 100 (also n _x = n _y ) was obtained.

Experimental Example 23

The coating liquid prepared in Experimental Example 22 was used, and the applied pressure of the bar coater was reduced to coat a glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) having a thickness of 150 μm, and then 25 It air-dried at 6 degreeC for 6 hours, and manufactured the optical element. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result was shown in Table 4. Here, an optical element of [(n _x + n _y ) / 2-n _z ] × d ≧ 100 (also n _x > n _y ) was obtained.

Experimental Example 24

Using the coating liquid prepared in Experimental Example 22, the applied pressure of the bar coater was reduced to coat a 150 μm thick glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm). The coated substrate was placed in a glass container filled with chloroform vapor at atmospheric pressure and sealed, and then annealed at 25 ° C. for 72 hours. Thereafter, the coated substrate was taken out and air dried at 25 ° C. for 6 hours to produce an optical element. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result was shown in Table 4. In Experimental Example 23, the thickness retardation was increased and the in-plane retardation was also increased. Here, the thickness retardation was about the same as that of Experimental Example 23, and the in-plane retardation was 0 nm, that is, [(n _x + n _y ) / 2-n _z ] x d ≥ 100 (also n _x = n _y ), an optical element was obtained, and the production of optical compensation layers having different characteristics was possible with or without annealing.

Experimental Example 25

To 20.0 g of ethyl cellulose (manufactured by Dow Chemical, ETHOCEL STD-100, number average molecular weight: 63400, DS: 2.5), 80.0 g of methylene chloride was added and dissolved at 25 ° C. Subsequently, the coating solution was coated on a 150 μm thick glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) using a bar coater, and then air dried at 25 ° C. for 6 hours. An optical device was manufactured. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result was shown in Table 4. Here, an optical element of [(n _x + n _y ) / 2-n _z ] × d ≧ 100 (also n _x > n _y ) was obtained.

Experimental Example 26

An optical device was prepared by bonding a commercially available triacetyl cellulose film having a thickness of 40 μm (= triacetic acid cellulose film) to a glass substrate having a thickness of 150 μm (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm). It was. As a result of measuring physical properties of the obtained optical element, the in-plane retardation was 0 nm, the thickness retardation was 37 nm, and it did not satisfy the relation of [(n _x + n _y ) / 2-n _z ] × d≥100 (thickness) Phase difference was low).

Experimental Example 27

An optical device was prepared by bonding a commercially available triacetyl cellulose film (= triacetic cellulose film) having a thickness of 80 µm to a glass substrate having a thickness of 150 µm (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm). It was. As a result of measuring physical properties of the obtained optical element, the in-plane retardation was 1 nm, the thickness retardation was 70 nm, and it did not satisfy the relation of [(n _x + n _y ) / 2-n _z ] × d≥100 (thickness) Phase difference was low).

Further, in Experimental Examples 26 and 27, troubles such as a complicated film forming step (substituted by purchasing a filmed one), film adhesion, and the like were required.

Synthesis Example 4 Synthesis of Cellulose N- (p-tolyl) carbamate (4)

Into a 500 ml four-necked flask equipped with a cooling tube, a nitrogen introduction tube, a stirrer, and a thermometer, 3.0 g of cellulose (Asahi Kasei Chemicals, Avicel TG-F20) dried at 60 ° C for 7 hours was added 300 ml of pyridine. After making a suspension, 22.2 g of p-tolyl isocyanate (made by Tokyo Kasei Kogyo Co., Ltd.) was further added. Nitrogen was introduced and heated to 110 ° C. while stirring, followed by reaction for 7 hours. Then, after cooling to 25 degreeC, the reaction liquid was transferred to the beaker, 600 ml of ethanol were added, and the reaction liquid was dripped at 4.5 L of pure water, and precipitation was produced | generated. After filtration and separation, 300 ml of acetone was added to the obtained polymer and dissolved therein, followed by dropwise addition to 3 L of pure water to form a precipitate. After filtration and washing with water, vacuum drying at 60 ° C. for 4 hours, the polymer was placed in a soxhlet extractor. After 20 times of Soxhlet extraction with methanol, 6.8 g of cellulose N- (p-tolyl) carbamate (4) was obtained by vacuum drying at 25 ° C for 4 hours (hereinafter also referred to as synthetic product (4)). DS of the synthetic product (4) was 3 as a result of proton NMR analysis. In addition, DS was determined by comparing the chemical shift (3.4-5.5 ppm) area of the proton derived from a cellulose backbone with the chemical shift (6.6-7.7 ppm) area of the proton of a p-tolyl group.

Experimental Example 28

To 0.48 g of Synthetic Article (4), 5.52 g of 2-butanone was added and dissolved at 25 ° C. Further, 0.32 g of ethyl N-phenylcarbamate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added thereto and dissolved at 25 ° C. Subsequently, the coating solution was coated on a glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) having a thickness of 150 μm using a bar coater, and then dried in air at 100 ° C. for 1 minute. An optical device was manufactured. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result is shown in following Table 5. In comparison with Experiment 30, in which ethyl N-phenylcarbamate was not added, an optical element having an improved thickness retardation in the negative direction was obtained.

Experimental Example 29

To 0.32 g of the synthetic product (4), 3.68 g of N, N-dimethylformamide was added and dissolved at 25 ° C. In addition, 0.48 g of N, N'-diphenylurea (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added and dissolved at 25 ° C. Subsequently, the coating solution was coated on a 150 μm thick glass substrate (average refractive index: 1.52, in-plane retardation: 0 nm, thickness retardation: 1 nm) using a bar coater, and then dried in air at 130 ° C. for 5 minutes. An optical device was manufactured. The coating film thickness (d (nm)) after drying measured the thickness of the whole optical element, and calculated | required by subtracting the thickness of a glass substrate. Next, the physical property measurement of the optical element obtained by the above was performed, and the result was shown in Table 5. In comparison with Experimental Example 31, in which no N, N'-diphenyl urea was added, an optical element having an improved thickness retardation in the negative direction was obtained.

Experimental Example 30

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

Experimental Example 31

The same operation as in Experimental Example 29 was carried out 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.

Moreover, the optical compensation coating film of this invention, this coating liquid for coating film formation for optical compensation, the optical element manufactured using these, and an optical compensation film (retardation film) are liquid crystals, such as VA system, an IPS system, and an OCB system. It can be used for expanding the viewing angle of a liquid crystal display using a cell. In order to fully exhibit the performance of the optical characteristics of the coating film for optical compensation in this invention, the IPS system is especially preferable. In addition, the optical compensation coating film, the coating liquid for forming the coating film, the optical element and the optical compensation film (retardation film) manufactured using the same, are instruments of video, cameras, portable telephones, personal computers, televisions, monitors, and automobiles. It can use suitably for liquid crystal display manufacturing components, such as a panel.

Claims (22)

An optical compensation coating film formed by containing a polymer of either cellulose N-substituted carbamate or an aromatic vinyl polymer. The method according to claim 1, wherein when the largest one among in-plane refractive indices is n _x , the smallest one is n _y , and the refractive index in the thickness direction is n _z , and the film thickness is d, [(n _x + n _y ) / 2 A coating film for optical compensation, characterized by satisfying a relationship of -n _z ] × d <0. The cellulose N-substituted carbamate of claim 1, wherein at least one of hydroxyl groups of cellulose is N-substituted carbamate, and at least one hydrogen atom bonded to a nitrogen atom of cellulose carbamate. The coating film for optical compensation characterized in that it is substituted by the group selected from the following Chemical Formulas 1 to 3, and the plurality of N-substituents are the same or different and are a group selected from the following Chemical Formulas 1 to 3. <Formula 1>

In formula, R <^1> , R <^2> , R <^3> , R <^4> , R <^5> is the same or different, A hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 halogenated alkyl group, An aryl group having 6 to 20 carbon atoms, 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. <Formula 2>

In formula, R <^6> , R <^7> , R <^8> , R <^9> , R <^10> , R <^11> and R <^12> are the same or different, A hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, C1-C1 A halogenated alkyl group of 20 to 20, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group. <Formula 3>

In formula, R <^13> , R <^14> , R <^15> , R <^16> , R <^17> , R <^18> , R <^19> is the same or different, and is a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, carbon number A halogenated alkyl group of 1 to 20, an acyloxy group of 1 to 21 carbon atoms, a halogen atom and a nitro group are shown. The method of claim 1 or 2, wherein the aromatic vinyl polymer comprises at least one selected from poly (1-vinylnaphthalene), poly (2-vinylnaphthalene), and poly (4-vinylbiphenyl). An optical compensation coating film. The coating film for optical compensation as described in any one of Claims 1-4 containing a phase difference regulator. The optical compensation according to claim 5, comprising a retarder for cellulose N-substituted carbamate comprising at least one selected from carbamic acid esters, N-substituted carbamic acid esters, urea, N-substituted urea. Coating film for use. Ethyl carbamate, phenyl carbamic acid, ethyl N-phenylcarbamic acid, phenyl N-phenylcarbamic acid, ethyl N- (4-tolyl) carbamic acid, N- (4-tolyl) carbamic acid phenyl; Cellulose N-substituted including at least one selected from the group of urea, N, N'-diphenylurea, N, N'-di-p-tolylurea, N-phenyl-N '-(p-tolyl) urea A coating film for optical compensation, comprising a phase difference regulator for carbamate. (A), (B), i.e. (A) any one of the cellulose N-substituted carbamate or aromatic vinyl polymer of any one of Claims 1-4, (B) A solvent in which (A) component is soluble Coating liquid for coating film formation for optical compensation containing containing. The coating liquid for coating film formation for optical compensation of Claim 8 containing (A) and (B), and further containing (C) retardation regulator. (C) The phase difference regulator is a phase difference regulator for cellulose N-substituted carbamate comprising at least one selected from carbamic acid ester, N-substituted carbamic acid ester, urea and N-substituted urea. Coating liquid for coating film formation for optical compensation. The method of claim 10, wherein (C) retardation agent is ethyl carbamate, phenyl carbamate, ethyl N-phenylcarbamate, phenyl N-phenylcarbamate, ethyl N- (4-tolyl) carbamate, N- (4- At least one selected from the group of tolyl) carbamic acid phenyl, urea, N, N'-diphenylurea, N, N'-di-p-tolylurea, N-phenyl-N '-(p-tolyl) urea It is a phase difference regulator for cellulose N-substituted carbamate containing, The coating liquid for coating film formation for optical compensation characterized by the above-mentioned. A phase difference regulator for cellulose N-substituted carbamate, comprising at least one selected from carbamic acid ester, N-substituted carbamic acid ester, urea and N-substituted urea. 13. The process of claim 12 wherein ethyl carbamate, phenyl carbamic acid, ethyl N-phenylcarbamic acid, phenyl N-phenylcarbamic acid, ethyl N- (4-tolyl) carbamic acid, N- (4-tolyl) carbamic acid phenyl, At least one selected from the group consisting of urea, N, N'-diphenylurea, N, N'-di-p-tolylurea and N-phenyl-N '-(p-tolyl) urea. Phase difference modifier for cellulose N-substituted carbamate. A coating method for forming an optical compensation coating film, which is dried after coating the coating liquid according to any one of claims 8 to 11 to a substrate to form a coating substrate. 15. The optical compensation according to claim 14, wherein the coated substrate is first dried at a temperature in the range of 0 ° C lower limit and 40 ° C upper limit, followed by further drying the coating substrate at 80 ° C lower limit and 300 ° C upper limit. Method of forming a coating film for use. After coating the coating liquid as described in any one of Claims 8-11 to a board | substrate to make a coating board, it exposes to the vapor of (B) component, anneals a coating film, and further dries, The optical compensation characterized by the above-mentioned. Method of forming a coating film for use. The formation method in any one of Claims 14-16 was used. The manufacturing method of the optical element characterized by the above-mentioned. It manufactured using the manufacturing method of Claim 17, The optical element characterized by the above-mentioned. It produced using the formation method of Claims 14-16, The optical compensation film characterized by the above-mentioned. The optical compensation film of Claim 19 was attached to at least one surface of the polarizer as a polarizer protective film, The polarizing plate characterized by the above-mentioned. The liquid crystal display device provided with the optical compensation film of Claim 19. The liquid crystal display device provided with the polarizing plate of Claim 20.