JP2005062424A - Manufacturing method for retardation plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a retardation plate which realize superior adhesion between a substrate and an optical anisotropic layer and has high manufacturing efficiency. <P>SOLUTION: The retardation plate is obtained by coating a transparent substrate 10 with silane coupling agent or the like, to form a surface-improved layer 11. Then, the surface-improved layer 11 is coated with a liquid crystal compound, contacted with an aligned substrate to regularly align the liquid crystal compound and the alignment condition is fixed to form an optically anisotropic layer 14. Since the surface-improved layer 11 is provided for the retardation plate, adhesion between the transparent substrate 10 and the optically anisotropic layer 14 is increased, and the manufacturing efficiency is also improved. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method of manufacturing a retardation plate that is preferably used in an image display device such as a liquid crystal display device (LCD).

  The retardation plate is an important member that realizes an improvement in contrast and an expansion of the viewing angle range in an image display device such as a liquid crystal display device by optical compensation. There are retardation plates obtained by stretching a polymer film to impart optical anisotropy, and those obtained by coating an optically anisotropic layer containing a liquid crystal compound on a substrate such as glass or a polymer film. . In particular, the latter has attracted attention with the recent thinning of liquid crystal display devices.

  In the production of a phase difference plate, in order to form an optically anisotropic layer containing a liquid crystal compound, the orientation direction of the whole liquid crystal compound molecule or the mesogen portion exhibiting liquid crystallinity is changed in a constant direction or continuously. It is necessary to orient regularly. As a method therefor, for example, there is a method of forming an alignment film on a substrate, further forming a liquid crystal compound-containing layer thereon, aligning the liquid crystal compound, and forming the optically anisotropic layer (for example, Patent Document 1). Further, there is a method in which another alignment layer is formed on a substrate and the liquid crystal compound is aligned between the alignment layer formation surfaces of the two substrates (for example, see Patent Document 2). .

  One of the important elements in the thus produced retardation plate is the adhesion between each layer, for example, the transparent base material and the optically anisotropic layer. For example, the retardation plate is often used by bonding an optical element to a polarizing plate or the like, and further bonding the optical element to a glass surface of a liquid crystal cell. In the process of bonding such an optical element to the glass surface, reworkability of the optical element may be required. However, since the optical element has a multilayer structure, if the adhesiveness is low at any layer interface, for example, the interface between the transparent substrate and the optically anisotropic layer, there is a possibility that peeling occurs from the interface during rework. is there.

There is known a method of providing an adhesion improving layer in order to improve the adhesion between the layers in the retardation plate. For example, an adhesion improving layer is formed on a transparent substrate made of a polymer film, an alignment film is formed thereon, and a discotic compound is applied thereon to form an optically anisotropic layer, thereby forming a retardation. A method of manufacturing a plate is known (see, for example, Patent Document 3). However, this method has a problem in terms of production efficiency because it is necessary to form at least three layers of an adhesion improving layer, an alignment film, and an optically anisotropic layer on a transparent substrate.
JP 2002-14233 A Japanese Patent Laid-Open No. 9-281480 JP-A-7-333433

  Therefore, an object of this invention is to provide the manufacturing method of the phase difference plate which is excellent in the adhesiveness of a transparent base material and an optically anisotropic layer, and is excellent also in manufacturing efficiency.

The present invention is a method for producing a retardation plate in which an optically anisotropic layer is laminated on a transparent substrate,
It is a manufacturing method characterized by including the process of following (1)-(5).
(1) A step of forming a surface modification layer on the transparent substrate having liquid crystal alignment regulating power.
(2) A step of forming a liquid crystal compound-containing layer on the transparent substrate via the surface modification layer.
(3) A step of bringing an alignment substrate having a liquid crystal alignment regulating force into contact with the liquid crystal compound-containing layer, and regularly aligning the liquid crystal compound of the liquid crystal compound-containing layer with the alignment substrate.
(4) A step of fixing the alignment state of the liquid crystal compound in the liquid crystal compound-containing layer to form an optically anisotropic layer.
(5) A step of removing the alignment substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the phase difference plate which is excellent in the adhesiveness of a base material and an optical anisotropic layer, and is excellent also in manufacturing efficiency can be provided.

  The present inventors are retardation plates including an optically anisotropic layer on a transparent substrate, wherein the optically anisotropic layer is disposed on the transparent substrate via a surface modification layer, and the optical It has been found that a retardation plate having a liquid crystal compound in which an anisotropic layer is aligned is excellent in adhesion between the transparent substrate and the optically anisotropic layer, and a patent application has been filed separately. Furthermore, the present inventors have conceived that in forming the optically anisotropic layer, the liquid crystal compound is aligned by both the alignment substrate and the transparent substrate in contact with an alignment substrate having a liquid crystal alignment regulating force. And it came to the manufacturing method of the phase difference plate of this invention.

  In the present invention, the transparent substrate may be a substrate obtained by directly rubbing the polymer film surface. This polymer film is preferably formed from a cellulose derivative.

  In this invention, it is preferable to include the process of making a hydrophilic group express on the surface in which the said surface modification layer of the said transparent base material is formed prior to the said process (1).

  In the present invention, the surface modified layer preferably contains an organosilicon compound.

  In the step (1) of the present invention, the method for forming the surface modified layer includes immersing the transparent substrate in a silane coupling agent solution, or silane coupling agent solution on the surface of the transparent substrate. It is preferable that the silane coupling agent solution is dried after that.

  In the present invention, the silane coupling agent preferably contains a compound represented by the following general formula (I).

前記式（Ｉ）において、Ｘは、ハロアルキル基、メルカプト基、アルキルスルファニル基、アミノ基、イソシアネート基、ウレイド基、下記一般式（ａ）で示される基、下記一般式（ｂ）で示される基、エチレン骨格、およびエポキシ基からなる群から選択される基を示し、
Ｒ¹、Ｒ²およびＲ³は、同一または異なって、水酸基の保護基またはアルキル基を示し、
ｎは、１〜１０の整数を示す。
ただし、Ｒ¹、Ｒ²およびＲ³の少なくとも１つは、水酸基の保護基を示す。

In the formula (I), X represents a haloalkyl group, a mercapto group, an alkylsulfanyl group, an amino group, an isocyanate group, a ureido group, a group represented by the following general formula (a), or a group represented by the following general formula (b). , An ethylene skeleton, and a group selected from the group consisting of epoxy groups,
R ¹ , R ² and R ³ are the same or different and each represents a hydroxyl-protecting group or an alkyl group;
n represents an integer of 1 to 10.
However, at least one of R ¹ , R ² and R ³ represents a hydroxyl-protecting group.

前記式（ａ）において、Ｙ¹、Ｙ²およびＹ³は、同一または異なって、水素原子、アルキル基およびアリール基からなる群から選択される原子または基を示し、
前記式（ａ）において、Ｚ¹は、結合手、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−および−Ｃ（＝Ｏ）−からなる群から選択される基を示し、
前記式（ｂ）において、Ｙ⁴、Ｙ⁵およびＹ⁶は、同一または異なって、水素原子、アルキル基およびアリール基からなる群から選択される原子または基を示し、
前記式（ｂ）において、Ｚ²は、結合手、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−および−Ｃ（＝Ｏ）−からなる群から選択される基を示す。

In the formula (a), Y ¹ , Y ² and Y ³ are the same or different and represent an atom or group selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group,
In the formula (a), Z ¹ represents a group selected from the group consisting of a bond, —C (═O) —O—, —O—C (═O) — and —C (═O) —. Show
In the formula (b), Y ⁴ , Y ⁵ and Y ⁶ are the same or different and represent an atom or group selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group,
In the formula (b), Z ² represents a group selected from the group consisting of a bond, —C (═O) —O—, —O—C (═O) — and —C (═O) —. Show.

  In the step (2) of the present invention, the method for forming the liquid crystal compound-containing layer on the surface modified layer may be a method in which a solution of the liquid crystal compound is applied to the surface modified layer and dried, or A method of applying a melt of a liquid crystal compound to the surface modification layer is preferred.

  In the present invention, the liquid crystal compound contained in the liquid crystal compound-containing layer may contain a liquid crystal monomer or a liquid crystal prepolymer. Moreover, the liquid crystal compound contained in the liquid crystal compound-containing layer may include a liquid crystal polymer.

  The liquid crystal compound contained in the liquid crystal compound-containing layer may include at least one of a nematic liquid crystal compound and a cholesteric liquid crystal compound.

  In the step (3) of the present invention, the method for regularly aligning the liquid crystal compound contained in the liquid crystal compound-containing layer is to heat the liquid crystal compound-containing layer to its liquid crystal temperature, and in this state the alignment substrate is It is preferable that the liquid crystal compound-containing layer is brought into contact with the alignment substrate and heated to the liquid crystal temperature or higher in this state.

  In the step (3) of the present invention, when the liquid crystal compound-containing layer on the transparent substrate and the alignment substrate are brought into contact, the in-plane alignment axis of the transparent substrate and the in-plane alignment of the alignment substrate The alignment state of the liquid crystal compound in the liquid crystal compound-containing layer is preferably controlled by the angle formed by the axes.

  In the present invention, the liquid crystal compound contained in the liquid crystal compound-containing layer contains at least one of a liquid crystal prepolymer and a liquid crystal monomer, and in the step (4), the alignment state is fixed in the liquid crystal compound-containing layer. The liquid crystal compound is preferably subjected to photopolymerization.

  In the present invention, the liquid crystal compound contained in the liquid crystal compound-containing layer is a liquid crystal polymer, and in the step (4), the fixing of the alignment state cools the liquid crystal compound-containing layer below its liquid crystal temperature. It is preferably carried out by the method.

  The retardation plate of the present invention is a retardation plate obtained by the production method of the present invention.

  The optical element of the present invention is an optical element including the retardation plate of the present invention and a polarizer.

  The image display device of the present invention is an image display device including the retardation plate of the present invention or the optical element of the present invention.

  As described above, the present invention is a retardation plate including an optically anisotropic layer on a transparent substrate, wherein the transparent substrate has a liquid crystal alignment regulating force, and the optically anisotropic layer includes: It is a manufacturing method of a phase difference plate which has a liquid crystal compound which is arranged on the transparent base material through a surface modification layer, and the optically anisotropic layer has an oriented liquid crystal compound.

  The production method of the present invention can be performed, for example, as follows.

  First, the surface modification layer is formed on the surface of the transparent substrate having a liquid crystal alignment regulating force (first step).

  In the transparent substrate, “transparent” means having a light transmittance that can be applied to a retardation plate. The light transmittance is not particularly limited as long as it is in a range suitable for practical use, but the higher the light transmittance, the more advantageous from the viewpoint of the function of the retardation plate, and ideally 100%.

Further, the transparent substrate may be optically isotropic as long as it has a liquid crystal alignment regulating force, but depending on the function required for the liquid crystal display device on which the retardation plate is mounted, the transparent substrate The material may have optical anisotropy. In addition, when the said transparent base material does not have liquid crystal alignment control force, as mentioned later, liquid crystal alignment control force can also be provided by performing a rubbing process etc. previously. The optical anisotropy in this case is not particularly limited. For example, the optical anisotropy showing a positive or negative A-plate phase difference characteristic, the optical anisotropy showing a positive or negative C-plate phase difference characteristic, or a positive Alternatively, optical anisotropy exhibiting negative O-plate retardation characteristics, biaxial optical anisotropy having refractive index anisotropy in different directions (that is, having two optical axes), and the like are possible. The A plate, C plate, and O plate all refer to layers having so-called uniaxial optical anisotropy. The A plate is called a positive A plate when the optical axis is in the in-plane direction and the optical characteristic condition satisfies the following formula (1), and is called a negative A plate when the following formula (2) is satisfied. .
nx> ny = nz (1)
nx <ny = nz (2)

The C plate has an optical axis in the Z-axis direction, that is, in the thickness direction. If the optical characteristic condition satisfies the following formula (3), the C plate is positive. If the optical characteristic condition satisfies the following formula (4), the C plate is negative. Called C plate.
nx = ny <nz (3)
nx = ny> nz (4)

In the above formulas (1) to (4), nx, ny, and nz represent refractive indexes in the X-axis, Y-axis, and Z-axis directions in the layer. However, one of the X axis and the Y axis is an axial direction showing the maximum refractive index in the plane of the layer, and the other is an axial direction in the plane perpendicular to the axis. The Z axis indicates a thickness direction perpendicular to the X axis and the Y axis. In the O plate, the optical axis direction is inclined as viewed from the in-plane direction and the Z-axis direction (thickness direction perpendicular to the in-plane direction). The means for imparting optical anisotropy is not particularly limited, and a known method may be applied as appropriate.For example, the optical anisotropy transparent film is imparted with optical anisotropy by stretching, etc. It can be a transparent substrate.

  Although the material of the said transparent base material is not specifically limited, For example, a polymer film etc. can be used. The polymer that can be used for the polymer film is not particularly limited, but examples thereof include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, and acrylic polymers such as polymethyl methacrylate. , Styrene polymers such as polystyrene, acrylonitrile / styrene copolymer (AS resin), polycarbonate polymers such as bisphenol A / carbonic acid copolymer, linear or branched, such as polyethylene, polypropylene, ethylene / propylene copolymer Polyolefins containing cyclostructures such as polyolefin and polynorbornene, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers Polymers, polyether sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, and epoxy polymers. These may be used alone or in combination of two or more. Among the above polymers, more preferred are cellulose polymers such as triacetyl cellulose, polycarbonate polymers such as bisphenol A / carbonic acid copolymer, polyolefins having a cyclo structure such as polynorbornene, and amides such as aromatic polyamides. Polymers and imide polymers are particularly preferred, and cellulose polymers (cellulose derivatives) are particularly preferred.

  Moreover, as a material of the said transparent base material, the polymer film of Unexamined-Japanese-Patent No. 2001-343529 (WO01 / 37007) is also mentioned. Examples of the polymer material include a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and cyano group in the side chain. Examples thereof include a resin composition having an alternating copolymer composed of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer. The polymer film may be, for example, an extruded product of the resin composition.

  The thickness of the transparent substrate is not particularly limited, but is preferably as thin as possible for reducing the thickness of the retardation plate, for example, 20 to 120 μm, preferably 20 to 80 μm, and more preferably 20 to 40 μm.

  The transparent substrate needs to have a liquid crystal alignment regulating force, but a method for imparting the liquid crystal alignment regulating force is not particularly limited, and a known method can be appropriately used. For example, the transparent base material may be one in which the surface of the polymer film is directly rubbed to impart a liquid crystal alignment regulating force, or an alignment film is provided on the surface of the glass or polymer film, followed by rubbing treatment or irradiation with polarized ultraviolet rays. For example, a liquid crystal alignment regulating force may be applied. The material and manufacturing method of the alignment film are not particularly limited, and known materials and manufacturing methods can be used as appropriate. In addition, the polymer film imparted with optical anisotropy by stretching or the like can be used as a transparent substrate having a liquid crystal alignment regulating force without surface treatment. Among these transparent substrates, those in which the surface of the polymer film is directly rubbed to impart a liquid crystal alignment regulating force are preferable because the treatment is simple and the liquid crystal alignment regulating force is excellent.

  Moreover, it is preferable that the transparent substrate contains a hydrophilic group, such as a hydroxyl group, on the surface because adhesion with the surface modified layer becomes higher. Even if the material of the transparent base material is a material such as triacetyl cellulose that does not contain a hydrophilic group, for example, the surface modified layer is made to express a hydrophilic group by performing a hydrophilic treatment such as a saponification treatment on the surface. Adhesion can be improved. In addition, you may perform the process which makes this hydrophilic group express at any time before or after the said rubbing process.

  The surface modification layer is not particularly limited, but preferably includes, for example, an organosilicon compound, and can be formed using, for example, a surface modification agent such as a silane coupling agent or a silane coupler. A surface modified layer using a surface modifying agent such as a silane coupling agent can enhance the adhesion between the transparent substrate and the liquid crystal compound.

  The said silane coupling agent used for the surface modification layer of this invention is not specifically limited, A well-known thing can be used suitably. The silane coupling agent can include, for example, a compound represented by the following general formula (I).

前記式（Ｉ）において、Ｘは、ハロアルキル基、メルカプト基、アルキルスルファニル基、アミノ基、イソシアナト基、ウレイド基、下記一般式（ａ）で示される基、下記一般式（ｂ）で示される基、エチレン骨格、およびエポキシ基からなる群から選択される基を示し、
Ｒ¹、Ｒ²およびＲ³は、同一または異なって、水酸基の保護基またはアルキル基を示し、
ｎは、１〜１０、好ましくは１〜５の整数を示す。
ただし、Ｒ¹、Ｒ²およびＲ³の少なくとも１つは、水酸基の保護基を示す。

In the formula (I), X represents a haloalkyl group, a mercapto group, an alkylsulfanyl group, an amino group, an isocyanato group, a ureido group, a group represented by the following general formula (a), or a group represented by the following general formula (b). , An ethylene skeleton, and a group selected from the group consisting of epoxy groups,
R ¹ , R ² and R ³ are the same or different and each represents a hydroxyl-protecting group or an alkyl group;
n represents an integer of 1 to 10, preferably 1 to 5.
However, at least one of R ¹ , R ² and R ³ represents a hydroxyl-protecting group.

前記式（ａ）において、Ｙ¹、Ｙ²およびＹ³は、同一または異なって、水素原子、アルキル基およびアリール基からなる群から選択される原子または基を示し、
前記式（ａ）において、Ｚ¹は、結合手、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−および−Ｃ（＝Ｏ）−からなる群から選択される基を示し、
前記式（ｂ）において、Ｙ⁴、Ｙ⁵およびＹ⁶は、同一または異なって、水素原子、アルキル基およびアリール基からなる群から選択される原子または基を示し、
前記式（ｂ）において、Ｚ²は、結合手、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−および−Ｃ（＝Ｏ）−からなる群から選択される基を示す。

In the formula (a), Y ¹ , Y ² and Y ³ are the same or different and represent an atom or group selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group,
In the formula (a), Z ¹ represents a group selected from the group consisting of a bond, —C (═O) —O—, —O—C (═O) — and —C (═O) —. Show
In the formula (b), Y ⁴ , Y ⁵ and Y ⁶ are the same or different and represent an atom or group selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group,
In the formula (b), Z ² represents a group selected from the group consisting of a bond, —C (═O) —O—, —O—C (═O) — and —C (═O) —. Show.

  In the present invention, the “alkyl group” and the “alkyl” part in the haloalkyl group and the alkylsulfanyl group are linear or branched alkyl having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, Examples thereof include butyl, isobutyl, t-butyl, pentyl, hexyl and the like. Among them, those having 1 to 4 carbon atoms are preferable, and methyl is particularly preferable.

  “Halo” in the haloalkyl group includes fluorine, chlorine, bromine and iodine. Examples of haloalkyl groups include chloromethyl, fluoromethyl, methyl iodide, trifluoromethyl, chloroethyl, fluoroethyl, ethyl iodide, chloropropyl, and the like.

  An aryl group means an aromatic hydrocarbon group having 6 to 20 carbon atoms, and examples thereof include phenyl, naphthyl, and anthranyl.

  The hydroxyl protecting group is preferably one that is hydrolyzed and deprotected to a hydroxyl group, and examples thereof include an alkoxy group. Examples of the lower alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, and among them, methoxy and ethoxy are preferable.

Among the compounds represented by the formula (I), In formula (I), compounds in which all of R ^1, R ² and R ³ is a protecting group of a hydroxyl group are preferred, the R ^1, R ² and R ³ More preferred are compounds in which all are alkoxy groups.

  Examples of the compound represented by the formula (I) include γ-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. 3-methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-isocyanatopropyltriethoxysilane. Among them, the compound represented by the formula (I) is preferably γ-acryloxypropyltrimethoxysilane. As the silane coupling agent, one or more of the above may be included.

  A method for forming the surface modification layer on the surface of the transparent substrate having a liquid crystal alignment regulating force is not particularly limited, but the transparent substrate is immersed in a silane coupling agent solution or the transparent substrate. It is preferable to apply a silane coupling agent solution on the surface of the substrate and then dry the silane coupling agent solution. Usable silane coupling agents are not particularly limited as described above.

  The concentration of the silane coupling agent in the silane coupling agent solution is not particularly limited. For example, the silane coupling agent is, for example, 0.1 to 5% by weight, preferably 0.5% with respect to the solvent. -4% by weight, more preferably 1-3% by weight.

The solvent for the silane coupling agent solution is not particularly limited, and may be appropriately determined depending on the type of the forming material, for example, as long as the forming material such as the silane coupling agent can be dissolved. Specific examples include, for example, halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, and orthodichlorobenzene; phenols such as phenol and parachlorophenol; benzene, toluene, Aromatic hydrocarbons such as xylene, methoxybenzene, 1,2-dimethoxybenzene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, N-methyl-2-pyrrolidone; acetic acid Esters such as ethyl and butyl acetate; t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol Alcohols such as coal dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol; Amides such as dimethylformamide and dimethylacetamide; Nitriles such as acetonitrile and butyronitrile; Diethyl ether, Di Examples include ethers such as butyl ether and tetrahydrofuran; acids such as acetic acid, formic acid and hydrochloric acid, carbon disulfide, ethyl cellosolve, and butyl cellosolve. One type of these solvents may be used, or two or more types may be used in combination. Moreover, what does not corrode the said transparent base material is preferable. Among them, as the solvent, acidic water and alcohols are particularly preferable because the solubility of the silane coupling agent is high, and the coating method of the silane coupling agent solution is not particularly limited. Method, roll coating method, flow coating method, die coating method, blade coating method, printing method, dip coating method, casting film forming method, bar coating method, gravure printing method, extrusion method and the like.

  Next, the solution of the silane coupling agent applied to the transparent substrate is solidified to form a surface modified layer on the transparent substrate.

  The solidification method is not particularly limited as long as it is a method for solidifying a forming material such as the silane coupling agent to form the forming material film, and examples thereof include natural drying and drying such as heat drying. . The conditions can also be appropriately determined depending on, for example, the type of the forming material or the type of the solvent in the case of a solution. For example, the temperature is usually 25 ° C. to 150 ° C., preferably 50 It is 70 degreeC-140 degreeC, More preferably, it is 70 degreeC-130 degreeC. Solidification may be performed at a constant temperature or may be performed while increasing or decreasing the temperature stepwise. Although the solidification time is not particularly limited, the solidification time is usually 1 to 10 minutes, preferably 2 to 5 minutes. Since the surface modification layer formed in this way can be a very thin layer of a monomolecular level, the liquid crystal alignment regulating force of the transparent substrate is not disturbed. Therefore, the liquid crystal alignment regulating force of the transparent substrate can be exerted on the liquid crystal compound-containing layer formed as described later via the surface modification layer. The thickness of the surface modification layer is not particularly limited as long as the adhesion between the transparent substrate and the liquid crystal compound is maintained and the liquid crystal alignment regulating force of the liquid crystal substrate is not lost.

  In addition, it is preferable to include the process of making a hydrophilic group express on the surface in which the said surface modification layer of the said transparent base material is formed prior to the said process (1). This is because, as described above, when the transparent substrate contains a hydrophilic group such as a hydroxyl group on the surface, the adhesiveness with the surface modified layer becomes higher. Even if the material of the transparent substrate is a material such as triacetyl cellulose that does not contain a hydrophilic group, for example, the surface is subjected to saponification treatment to develop a hydrophilic group, and adhesion with the surface modified layer Can be increased.

  Then, a liquid crystal compound-containing layer is formed on the surface modified layer (second step).

  The method for forming the liquid crystal compound-containing layer is not particularly limited, but is a method for applying the liquid crystal compound solution to the surface modification layer and drying, or a method for applying the liquid crystal compound melt to the surface modification layer. It is preferable from the viewpoint of ease of production and the like. In the present invention, “melting” of a liquid crystal compound means a liquid crystal state or a liquefied state.

  Here, the liquid crystal compound may be a liquid crystal polymer, but it is more preferable that the liquid crystal compound contains at least one of a liquid crystal prepolymer and a liquid crystal monomer from the viewpoint of low alignment temperature and easy processing. In addition, when at least one of the liquid crystal prepolymer and the liquid crystal monomer is included, it is more preferable to polymerize it later by a method such as photopolymerization to obtain a polymer. Other than that, the type of the liquid crystal compound is not particularly limited.

  Examples of the liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted phenylpyrimidines. , Liquid crystal compounds such as phenyldioxanes, tolanes, alkenylcyclohexylbenzonitriles, and polymers thereof are preferable. In addition, the liquid crystal compound preferably includes at least one of a liquid crystal prepolymer and a liquid crystal monomer because the alignment temperature is low and processing is easy. The liquid crystal compound preferably includes a nematic liquid crystal compound because, for example, a uniform alignment state can be obtained without defects. For example, a negative C-plate compensates the viewing angle in a VA liquid crystal display element or the like. Therefore, it is preferable to include a cholesteric liquid crystal compound from the viewpoint of being effective.

  The range of the temperature at which the liquid crystal compound-containing layer exhibits a liquid crystal state (liquid crystal temperature) is appropriately determined depending on the type of the liquid crystal compound. The temperature range of the liquid crystal is not particularly limited, and may be set as appropriate in consideration of the manufacturing and use convenience of the retardation plate, but is not so much when the deformation due to heat of the transparent substrate in the manufacturing process is considered. It is preferably not too high. The liquid crystal temperature range is, for example, 20 to 150 ° C, preferably 20 to 120 ° C, and particularly preferably 20 to 80 ° C. The heating time is, for example, 1 to 5 minutes, preferably 2 to 4 minutes.

  Further, the solution or melt of the liquid crystal compound may appropriately contain a substance other than the liquid crystal compound, for example, a leveling agent, a viscosity modifier, a chiral agent, and the like within a range that does not hinder the function of the retardation plate.

  When the liquid crystal compound contains a liquid crystal prepolymer or a liquid crystal monomer and is later photopolymerized, it is particularly preferable to add a photopolymerization initiator to the solution or melt of the liquid crystal compound. Although the said photoinitiator is not specifically limited, For example, Irgacure907, Irgacure369, Irgacure184 (all are brand names) by Ciba Specialty Chemicals, or a mixture thereof etc. are preferable. Although the addition amount of the photopolymerization initiator is not particularly limited, it is, for example, 0.1 to 10% by weight, preferably 1 to 5% by weight with respect to the liquid crystal prepolymer and the liquid crystal monomer. In the solution of the liquid crystal compound, the solvent is not particularly limited, but a solvent that can easily dissolve the liquid crystal compound and hardly erode the surface modified layer and the transparent substrate is preferable. As the solvent, for example, ketones such as methyl ethyl ketone, cyclopentanone, and cyclohexanone, esters such as ethyl acetate, and hydrocarbons such as toluene can be used.

  The method for applying the liquid crystal compound solution or melt is not particularly limited. For example, spin coating, roll coating, flow coating, printing, dip coating, casting film forming, bar coating, gravure, and the like. A printing method or the like is preferable.

  Then, an alignment substrate having a liquid crystal alignment regulating force is brought into contact with the liquid crystal compound-containing layer, and the liquid crystal compound in the liquid crystal compound-containing layer is regularly aligned by the transparent substrate and the alignment substrate (third step). .

  In this step, the liquid crystal compound-containing layer is heated to a temperature higher than the liquid crystal temperature, and the alignment substrate is brought into contact with this state, or the liquid crystal compound-containing layer is brought into contact with the alignment substrate, and in this state, the liquid crystal temperature It is preferable to heat above. The liquid crystal temperature range is as described above. The liquid crystal compound-containing layer may be in a solidified state, in a liquid crystal state or in a liquefied state. For example, the alignment substrate is contacted immediately after applying the liquid crystal compound melt, or the alignment substrate is contacted immediately after applying the liquid crystal compound solution and drying at a temperature equal to or higher than the liquid crystal temperature. You may let them.

  Although the time which makes the said alignment substrate contact a liquid crystal compound content layer is not specifically limited, For example, it is 0.1 to 10 minutes, Preferably, it is 0.5 to 5 minutes. The contact direction of the alignment substrate is not particularly limited, and may be set as appropriate according to the purpose.

  The alignment substrate is not particularly limited, for example, a film obtained by stretching a polymer film such as polyethylene terephthalate, a film obtained by directly rubbing a triacetyl cellulose film or the like, or an alignment having a liquid crystal alignment regulating force on a substrate. What provided the film | membrane etc. can use it preferably. For example, the alignment substrate may be provided with a liquid crystal alignment regulating force by rubbing treatment, or may be provided with a liquid crystal alignment regulating force by light irradiation or the like depending on the type of the aligning device.

  The thickness of the alignment substrate is not particularly limited, but is preferably as thin as possible for reducing the thickness of the retardation plate, for example, 20 to 120 μm, preferably 20 to 80 μm, and more preferably 20 to 40 μm.

  The alignment direction of the liquid crystal compound can be controlled by the surface state of the transparent substrate and the alignment substrate and the type of the liquid crystal compound, and this control can be performed according to the same rules as the conventional method. For example, when the liquid crystal compound-containing layer on the transparent substrate and the alignment substrate are brought into contact with each other, the liquid crystal depends on the angle formed by the in-plane alignment axis of the transparent substrate and the in-plane alignment axis of the alignment substrate. It is preferable to control the alignment state of the liquid crystal compound in the compound-containing layer. When the angle formed is 0 °, the liquid crystal compound of the liquid crystal compound-containing layer is aligned, for example, in the same direction as the alignment axis of the transparent substrate and the alignment axis of the alignment substrate. When the angle formed is larger than 0 °, the liquid crystal compound of the liquid crystal compound layer continuously changes, for example, from the same direction as the alignment axis of the transparent substrate to the same direction as the alignment axis of the alignment substrate. Orient.

  And the said orientation state of the liquid crystal compound of the said liquid crystal compound content layer is fixed, and an optically anisotropic layer is formed (4th process).

  When the liquid crystal compound contains at least one of a liquid crystal prepolymer and a liquid crystal monomer, the alignment state is preferably fixed by a method of photopolymerizing the liquid crystal compound. Although the irradiation light in this case is not specifically limited, For example, an ultraviolet-ray is preferable and the wavelength of the said ultraviolet-ray is more preferably 200-400 nm. The light intensity, irradiation time, and integrated light quantity of the irradiation light are not particularly limited as long as the alignment state is sufficiently fixed. Further, the irradiation direction of the irradiation light is not particularly limited as long as the irradiation to the liquid crystal compound-containing layer is not hindered, and the irradiation may be performed from either the transparent substrate side or the alignment substrate side.

  In the case where the liquid crystal compound is a liquid crystal polymer, the alignment state is preferably fixed by a method of cooling the liquid crystal compound-containing layer below its liquid crystal temperature. The cooling method is not particularly limited, and may be simply left under room temperature conditions, or may be rapidly cooled using an appropriate cooler.

  As described above, the optically anisotropic layer has an aligned liquid crystal compound. The liquid crystal compound is not particularly limited, and may be a liquid crystal monomer or a polymer, for example, a rod-like liquid crystal compound, a plate-like liquid crystal compound and a polymer thereof can be used, and two or more kinds can be used alone. May be used in combination. In the case of a polymer, it may be a liquid crystal polymer or a liquid crystal prepolymer, and may be a homopolymer or a heteropolymer (copolymer). Moreover, it is preferable that a nematic liquid crystal compound is included for the reason that orientation is good and alignment defects are few.

  The thickness of the optically anisotropic layer is not particularly limited, but is preferably as thin as possible for reducing the thickness of the retardation plate, for example, 0.5 to 10 μm, preferably 1 to 8 μm, more preferably, 2-6 μm. The alignment direction of the liquid crystal compound in the optically anisotropic layer is not particularly limited, and may be set as appropriate so as to obtain optimal optical compensation. For example, so-called homogeneous tilt alignment, hybrid alignment, chiral nematic alignment, homogeneous horizontal Orientation, homeotropic orientation and the like are preferable.

  And the said alignment substrate is removed and the phase difference plate containing an optically anisotropic layer is obtained on a transparent base material (5th process).

  The production method of the present invention can be carried out as described above, but this is only one embodiment of the present invention, and all modifications can be made without departing from the gist of the present invention. Steps other than (1) to (5) may be included as appropriate.

  The retardation plate manufactured by the manufacturing method of the present invention has no appearance defect and has a high function. The usage method is not particularly limited, and can be widely used for various optical elements, liquid crystal display elements, and the like.

  The optical element of the present invention is an optical element including the retardation plate of the present invention and a polarizer. The optical element further includes a transparent protective film, and the transparent protective film is preferably disposed between the retardation plate and the polarizer. For example, the optical element of the present invention can be obtained by further laminating the retardation plate of the present invention on a polarizing plate in which a transparent protective film is laminated on a polarizer. In addition, the optical element of the present invention may appropriately include arbitrary components other than these polarizers and transparent protective films. Hereinafter, each component of the optical element of the present invention will be described more specifically.

  The polarizer is not particularly limited, but a stretched film is preferable because good optical characteristics can be easily obtained. For example, a film prepared by adsorbing a dichroic substance such as iodine or a dichroic dye on various films by a conventionally known method, dyeing, crosslinking, stretching, and drying can be used. Among these, a film that transmits linearly polarized light when natural light is incident is preferable, and a film that is excellent in light transmittance and degree of polarization is preferable. Examples of the various films that adsorb the dichroic substance include high hydrophilicity such as polyvinyl alcohol (PVA) film, partially formalized PVA film, ethylene / vinyl acetate copolymer partially saponified film, and cellulose film. In addition to these, for example, polyene oriented films such as PVA dehydrated products and polyvinyl chloride dehydrochlorinated products can be used. Among these, a polyvinyl alcohol polarizing film is preferable because good optical characteristics can be easily obtained. Moreover, although the thickness of the said polarizer is the range of 1-80 micrometers, for example, it is not limited to this.

  The transparent protective film is not particularly limited, and a conventionally known transparent film can be used. For example, a film having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. Specific examples of the material for such a transparent protective film include, for example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, polystyrene, and the like. , Styrene polymers such as acrylonitrile / styrene copolymer (AS resin), polycarbonate polymers such as bisphenol A / carbonic acid copolymer, linear or branched polyolefins such as polyethylene, polypropylene, ethylene / propylene copolymer, Polyolefins containing a cyclo structure such as polynorbornene, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyethers Sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, and epoxy polymers, etc. Furthermore, thermosetting resins such as acrylic, urethane, acrylic urethane, epoxy, and silicone, or ultraviolet curable resins are also included. These may be used alone or in combination of two or more. Among these, a TAC film whose surface is saponified with alkali or the like is preferable from the viewpoint of polarization characteristics and durability. In addition, the polymer film described in JP-A-2001-343529 (WO01 / 37007) can be preferably used.

Moreover, it is preferable that the said transparent protective film does not have coloring, for example. Specifically, the retardation value (Rth) in the film thickness direction is preferably in the range of −90 nm to +75 nm, more preferably in the range of −80 nm to +60 nm, and particularly preferably in the range of −70 nm to +45 nm. . When the retardation value is in the range of −90 nm to +75 nm, coloring (optical coloring) caused by the protective film can be sufficiently eliminated. However, Rth in this case shall be represented by the following formula (5). In addition, in a following formula, the definition of nx, ny, and nz is the same as said Formula (1)-(4), and d shows the film thickness of the said transparent protective film.
Rth = [{(nx + ny) / 2} -nz] × d (5)

Although the thickness of the said transparent protective film is not specifically limited, For example, although it can determine suitably according to a phase difference, protective strength, etc., it is 500 micrometers or less normally, Preferably it is 5-300 micrometers, More preferably, it is the range of 5-150 micrometers. It is.

  The said transparent protective film can be suitably formed by conventionally well-known methods, such as the method of apply | coating the said various transparent resin to a polarizer, the method of laminating | stacking the said transparent resin film on the said polarizer, and uses a commercial item, for example. You can also. Moreover, the transparent base material in the phase difference plate of this invention may serve as the said transparent protective film.

  The transparent protective film may be further subjected to, for example, a hard coat treatment, an antireflection treatment, a treatment for preventing sticking or diffusion, antiglare, and the like. The hard coat treatment is for the purpose of preventing scratches on the surface and the like, for example, is a treatment for forming a cured film made of a curable resin and having excellent hardness and slipperiness on the surface of the transparent protective film. . As the curable resin, for example, an ultraviolet curable resin such as silicone, urethane, acryl, and epoxy can be used, and the treatment can be performed by a conventionally known method. The purpose of preventing sticking is to prevent adhesion between adjacent layers. The antireflection treatment is intended to prevent reflection of external light on the surface of the polarizing plate, and can be performed by forming a conventionally known antireflection layer or the like.

  The anti-glare treatment is intended to prevent visual interference of transmitted light due to reflection of external light. For example, a fine uneven structure is formed on the surface of the transparent protective film by a conventionally known method. Can be done. Examples of a method for forming such a concavo-convex structure include a roughening method by sandblasting or embossing, a method of forming the transparent protective film by blending transparent fine particles in the transparent resin as described above, and the like. It is done.

  Examples of the transparent fine particles include silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide, and the like. In addition, conductive inorganic fine particles, crosslinked or uncrosslinked Organic fine particles composed of polymer particles and the like can also be used. Although the average particle diameter of the said transparent fine particle is not specifically limited, For example, it is the range of 0.5-20 micrometers. The blending ratio of the transparent fine particles is not particularly limited, but is generally preferably in the range of 2 to 70 parts by weight, more preferably in the range of 5 to 50 parts by weight per 100 parts by weight of the transparent resin as described above.

  The antiglare layer containing the transparent fine particles can be used as, for example, the transparent protective film itself, or may be formed as a coating layer on the surface of the transparent protective film. Furthermore, the anti-glare layer may also serve as a diffusion layer (visual compensation function or the like) for diffusing transmitted light to expand the viewing angle.

  The antireflection layer, anti-sticking layer, diffusion layer, antiglare layer and the like are laminated on the polarizing plate as an optical layer composed of, for example, a sheet provided with these layers separately from the transparent protective film. May be.

  Further, the polarizing plate may further include other known optical layers used for forming other optical layers, for example, a reflection plate, a transflective plate, a brightness enhancement film, and the like, such as a liquid crystal display device. One kind of these optical layers may be used, two or more kinds may be used in combination, one layer may be used, or two or more layers may be laminated. Hereinafter, such an integrated polarizing plate will be described.

  First, an example of a reflective polarizing plate or a transflective polarizing plate will be described. In the reflective polarizing plate, a reflective plate is further laminated on the polarizer and the transparent protective film, and in the semi-transmissive reflective polarizing plate, a semi-transmissive reflective plate is further laminated on the polarizer and the transparent protective film.

  The reflective polarizing plate can be used, for example, in a liquid crystal display device (reflective liquid crystal display device) that is disposed on the back side of a liquid crystal cell and reflects incident light from the viewing side (display side). Such a reflective polarizing plate, for example, has an advantage that the liquid crystal display device can be thinned because the built-in light source such as a backlight can be omitted.

  The reflective polarizing plate can be produced by a conventionally known method such as a method of forming a reflective plate made of metal or the like on one surface of a polarizing plate exhibiting an elastic modulus. Specifically, for example, one surface (exposed surface) of the transparent protective film in the polarizing plate is mat-treated as necessary, and a metal foil or a vapor deposition film made of a reflective metal such as aluminum is formed on the surface as a reflection plate. And a reflection type polarizing plate formed.

  In addition, as described above, a reflective polarizing plate in which a reflective plate reflecting the fine concavo-convex structure is formed on a transparent protective film containing various fine particles in a transparent resin and having a fine concavo-convex structure on the surface is also included. It is done. A reflector having a fine concavo-convex structure on its surface has an advantage that, for example, incident light can be diffused by irregular reflection to prevent directivity and glaring appearance and to suppress uneven brightness. Such a reflector is, for example, directly on the uneven surface of the transparent protective film by means of a conventionally known method such as a vacuum deposition method, an ion plating method, a sputtering method, or a plating method. It can form as a metal vapor deposition film.

  Moreover, instead of the method of directly forming the reflector on the transparent protective film of the polarizing plate as described above, a reflective sheet having a reflective layer provided on a suitable film such as the transparent protective film is used as the reflector. May be. Since the reflection layer in the reflection plate is usually composed of metal, for example, from the viewpoint of preventing the decrease in reflectivity due to oxidation, and thus the long-term persistence of the initial reflectivity, separately forming a transparent protective film, etc. The usage form is preferably a state in which the reflective surface of the reflective layer is covered with the film, a polarizing plate or the like.

  On the other hand, the transflective polarizing plate has a transflective reflective plate instead of the reflective plate in the reflective polarizing plate. Examples of the transflective reflector include a half mirror that reflects light through a reflective layer and transmits light.

  The transflective polarizing plate is provided, for example, on the back side of a liquid crystal cell, and displays an image by reflecting incident light from the viewing side (display side) when a liquid crystal display device or the like is used in a relatively bright atmosphere. In a relatively dark atmosphere, it can be used for a liquid crystal display device of a type that displays an image using a built-in light source such as a backlight built in the back side of the transflective polarizing plate. That is, the transflective polarizing plate can save the energy of using a light source such as a backlight in a bright atmosphere, and can be used with the built-in light source in a relatively dark atmosphere. It is useful for the formation of etc.

  Next, an example of a polarizing plate in which a brightness enhancement film is further laminated on the polarizer and the transparent protective film will be described.

  The brightness enhancement film is not particularly limited, and for example, a linear multi-layer thin film of dielectric material or a multi-layer laminate of thin film films having different refractive index anisotropy transmits linearly polarized light having a predetermined polarization axis, Other light can be used that reflects light. As such a brightness enhancement film, for example, trade name “D-BEF” manufactured by 3M Co., Ltd. may be mentioned. Also, a cholesteric liquid crystal layer, in particular an oriented film of a cholesteric liquid crystal polymer, or a film in which the oriented liquid crystal layer is supported on a film substrate can be used. These reflect the right and left circularly polarized light and transmit the other light. For example, the product name “PCF350” manufactured by Nitto Denko Corporation, the product name “Transmax” manufactured by Merck, etc. Can be mentioned.

  The method for producing the optical element of the present invention is not particularly limited and can be produced by a conventionally known method. For example, each component (a retardation plate, a polarizer, a transparent protective film, etc.) is bonded to a pressure-sensitive adhesive or an adhesive. It can manufacture by the method of laminating | stacking through layers, such as an agent. For example, first, the retardation plate of the present invention and a polarizer to which a transparent protective film is bonded are prepared, and then an adhesive is applied to one side of the retardation plate or the transparent protective film, Furthermore, the said optical retardation plate can be bonded together on the said transparent protective film, and the target optical element can be manufactured. The type of the pressure-sensitive adhesive or adhesive is not particularly limited, and can be appropriately determined depending on the material of each component, for example, acrylic, vinyl alcohol, silicone, polyester, polyurethane, polyether, etc. Polymer adhesives, rubber adhesives, and the like. In the present invention, there is no clear distinction between “adhesive” and “adhesive”, but among adhesives, adhesives that are relatively easy to peel off and re-adhere to each other are referred to as “adhesives”. Call. The above-mentioned pressure-sensitive adhesives and adhesives are not easily peeled off due to, for example, the influence of humidity and heat, and are excellent in light transmittance and degree of polarization. Specifically, when the polarizer is a PVA-based film, for example, a PVA-based adhesive is preferable from the viewpoint of the stability of the adhesion treatment. These adhesives and pressure-sensitive adhesives may be applied to the surface of a polarizer or a transparent protective film as they are, for example, or a layer such as a tape or sheet composed of the adhesives or pressure-sensitive adhesives is disposed on the surface. May be. For example, when prepared as an aqueous solution, other additives and catalysts such as acids may be blended as necessary. In addition, when apply | coating the said adhesive agent, you may mix | blend another additive and catalysts, such as an acid, with the said adhesive agent aqueous solution, for example. The thickness of such an adhesive layer is not particularly limited, but is, for example, 1 nm to 500 nm, preferably 10 nm to 300 nm, and more preferably 20 nm to 100 nm.

  Each layer such as the polarizer, transparent protective film, optical layer, and pressure-sensitive adhesive layer forming the optical element of the present invention as described above is, for example, a salicylic acid ester compound, a benzophenone compound, a benzotriazole compound, or a cyanoacrylate compound. Further, it may be provided with ultraviolet absorbing ability by appropriately treating with an ultraviolet absorber such as a nickel complex compound.

  The optical element of the present invention can also be manufactured by, for example, a method of sequentially laminating each component on the liquid crystal cell surface or the like in the manufacturing process of a liquid crystal display device or the like. However, it is better to manufacture the liquid crystal display device and the like after laminating the above-mentioned constituent elements in advance and making the optical element of the present invention, for example, the quality stability and the assembly workability are excellent. This is preferable because there is an advantage that the efficiency can be improved.

  The optical element of the present invention has a pressure-sensitive adhesive layer or an adhesive layer as described above on one or both sides of the outer side, for example, since it can be easily laminated on other members such as a liquid crystal cell. Preferably it is. For example, the pressure-sensitive adhesive layer may be a single layer or a laminate. As the laminate, for example, a laminate in which different compositions and different types of single layers are combined can be used. Moreover, when arrange | positioning on both surfaces of the said optical element, the same adhesive layer may respectively be sufficient, for example, a different composition and a different kind of adhesive layer may be sufficient. When the surface of the pressure-sensitive adhesive layer or the like provided on the optical element is exposed as described above, it is preferable to cover the surface with a separator for the purpose of preventing contamination until the pressure-sensitive adhesive layer or the like is put to practical use. . This separator can be formed on a suitable film by, for example, a method of providing a release coat with a release agent such as silicone, long chain alkyl, fluorine, or molybdenum sulfide, if necessary. Although the material of the said film is not specifically limited, For example, the thing similar to the said transparent protective film can be used.

  Although the usage method of the optical element of this invention is not specifically limited, For example, it arrange | positions on the surface of a liquid crystal cell, and is suitable for use for various image display apparatuses.

  Next, the image display apparatus of the present invention will be described. The image display device of the present invention is an image display device including the retardation plate of the present invention or the optical element of the present invention. Other than this, the image display device of the present invention is not particularly limited, and its manufacturing method, structure, usage method, and the like are arbitrary, and conventionally known forms can be applied as appropriate.

  Although the kind of image display apparatus of this invention is not specifically limited, For example, a liquid crystal display device is preferable. For example, the phase difference plate or optical element of the present invention is disposed on one or both sides of a liquid crystal cell to form a liquid crystal panel, which can be used in a liquid crystal display device of a reflective type, a transflective type, a transmissive / reflective type, or the like. The type of the liquid crystal cell forming the liquid crystal display device can be arbitrarily selected, for example, an active matrix drive type represented by a thin film transistor type, a simple matrix drive type represented by a twist nematic type or a super twist nematic type Various types of liquid crystal cells can be used.

  The liquid crystal cell generally has a structure in which liquid crystal is injected into the gap between the opposing liquid crystal cell substrates. The liquid crystal cell substrate is not particularly limited, and for example, a glass substrate or a plastic substrate can be used. In addition, it does not specifically limit as a material of the said plastic substrate, A conventionally well-known material is mentioned.

  Further, the optical element of the present invention may be provided on one side or both sides of the liquid crystal cell, and when the members such as the optical element are provided on both sides of the liquid crystal cell, they may be of the same type or different. May be. Furthermore, when manufacturing a liquid crystal display device, for example, appropriate components such as a prism array sheet, a lens array sheet, a light diffusing plate, and a backlight can be arranged in one or more layers at appropriate positions.

  The structure of the liquid crystal panel in the liquid crystal display device of the present invention is not particularly limited, and includes, for example, a liquid crystal cell, the retardation plate of the present invention, a polarizer and a transparent protective film, and the retardation plate on one surface of the liquid crystal cell. The polarizer and the transparent protective film are preferably laminated in this order. In addition, the arrangement of the retardation plate of the present invention is not particularly limited. For example, the arrangement in which the optically anisotropic layer side faces the liquid crystal cell and the transparent substrate side faces the polarizer. Can be mentioned.

  When the liquid crystal display device of the present invention further includes a light source, the light source is not particularly limited. However, for example, a planar light source that emits polarized light is preferable because the energy of light can be used effectively.

  Further, the image display device of the present invention is not limited to the liquid crystal display device as described above, and for example, an organic electroluminescence (EL) display, a plasma display (PD), an FED (Field Emission Display), etc. The self-luminous display device may be used. When used in a self-luminous flat display, for example, circular polarization can be obtained by setting the in-plane retardation value of the optically anisotropic layer of the retardation plate of the present invention to λ / 4. Can be used as a prevention filter.

  The electroluminescence (EL) display device of the present invention will be described below. The EL display device of the present invention is a display device having the retardation plate or optical element of the present invention, and this EL display device may be either an organic EL display device or an inorganic EL display device.

  In recent years, it has been proposed to use, for example, an optical film such as a polarizer or a polarizing plate together with a λ / 4 plate in an EL display device as an antireflection from an electrode in a black state. The phase difference plate and optical element of the present invention, in particular, when linearly polarized light, circularly polarized light, or elliptically polarized light is emitted from the EL layer, or in an oblique direction even if natural light is emitted in the front direction. This is very useful when the emitted light is partially polarized.

  First, a general organic EL display device will be described. The organic EL display generally includes a light emitter (organic EL light emitter) in which a transparent electrode (anode), an organic light emitting layer, and a metal electrode (cathode) are laminated in this order on a transparent substrate. The organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, or the like. Various combinations such as a laminate of a light-emitting layer and an electron injection layer made of a perylene derivative, or a laminate of the hole injection layer, the light-emitting layer, and the electron injection layer are exemplified.

  The light emission principle of such an organic EL display device is as follows. That is, by applying a voltage to the anode and the cathode, holes and electrons are injected into the organic light emitting layer, and energy is generated by recombination of the holes and electrons. Then, the fluorescent material is excited by the energy, and emits light on the principle that light is emitted when the fluorescent material returns to the ground state. The mechanism of recombination of holes and electrons is the same as that of a general diode, and current and emission intensity show strong nonlinearity with rectification with respect to applied voltage.

  In the organic EL display device, in order to extract light emitted from the organic light emitting layer, at least one of the electrodes needs to be transparent. Therefore, the organic EL display device is usually formed of a transparent conductor such as indium tin oxide (ITO). A transparent electrode is used as the anode. On the other hand, in order to facilitate electron injection and increase luminous efficiency, it is important to use a material having a small work function for the cathode, and usually metal electrodes such as Mg—Ag and Al—Li are used.

  In the organic EL display device having such a configuration, the organic light emitting layer is preferably formed of an extremely thin film having a thickness of about 10 nm, for example. This is because the organic light-emitting layer transmits light almost completely as in the transparent electrode. As a result, at the time of non-light emission, the light incident from the surface of the transparent substrate, transmitted through the transparent electrode and the organic light emitting layer, and reflected by the metal electrode again returns to the surface side of the transparent substrate. For this reason, when viewed from the outside, the display surface of the organic EL display device looks like a mirror surface.

  In the organic EL display device of the present invention, for example, the retardation plate or optical element of the present invention is preferably disposed on the surface of the transparent electrode. By having this configuration, an organic EL display device that exhibits effects such as suppression of external reflection and improvement in visibility can be obtained. For example, the optical element of the present invention including the retardation plate and the polarizing plate has a function of polarizing light incident from the outside and reflected by the metal electrode, and therefore the mirror surface of the metal electrode is made external by the polarization action. There is an effect of not letting it be visually recognized. In particular, if the retardation plate of the present invention is a quarter-wave plate and the angle formed by the polarization direction of the polarizing plate and the retardation plate is adjusted to π / 4, the mirror surface of the metal electrode is completely Can be shielded. That is, only the linearly polarized component of the external light incident on the organic EL display device is transmitted by the polarizing plate. The linearly polarized light becomes generally elliptically polarized light by the retardation plate, but becomes circularly polarized light particularly when the retardation plate is a quarter wavelength plate and the angle is π / 4.

  For example, this circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic thin film, reflected by the metal electrode, again transmitted through the organic thin film, the transparent electrode, and the transparent substrate, and again by the retardation plate. Become. And since this linearly polarized light is orthogonal to the polarization direction of the polarizing plate, it cannot pass through the polarizing plate, and as a result, the mirror surface of the metal electrode can be completely shielded as described above. .

  Next, examples of the present invention will be described.

  A retardation plate was produced as follows. First, a triacetyl cellulose film (thickness: 80 μm) (manufactured by Fuji Photo Film Co., Ltd.) was immersed in a 10% by weight aqueous sodium hydroxide solution at 50 ° C. for 1 minute, washed with water, dried at 120 ° C. for 3 minutes, and then treated. Processed. Thereafter, the film was subjected to 20 reciprocating rubbing treatments with rayon to obtain a transparent substrate having a liquid crystal alignment regulating force.

  Next, γ-acryloxypropyltrimethoxysilane (trade name KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.) (silane coupling agent) is dissolved by stirring in a 2% by weight acetic acid aqueous solution for 30 minutes, and then 2% by weight silane coupling. An agent solution was prepared.

  The silane coupling agent solution was applied onto the transparent substrate by a bar coater (# 3) method. It was heated at 120 ° C. for 5 minutes and dried to form a surface modified layer.

  Another triacetyl cellulose film (thickness: 80 μm) (manufactured by Fuji Photo Film Co., Ltd.) was subjected to 20 reciprocating rubbing treatments with rayon to obtain an alignment substrate having a liquid crystal alignment regulating force.

  Toluene was added to 1 g of an ultraviolet polymerizable nematic liquid crystal compound (liquid crystal monomer) represented by the following chemical formula and 0.05 g of a photopolymerization initiator (Irgacure907 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.) and stirred for 10 minutes to obtain a solid material. Was completely dissolved to prepare a liquid crystal compound solution. At this time, the amount of toluene added was adjusted so that the concentration of the solute was 20% by weight.

前記表面改質層上に、前記液晶化合物の溶液をバーコータ（＃５）法により塗布し、それを１２０℃で２分間加熱乾燥して液晶化合物含有層（厚み１．３μｍ）を形成した。これを室温に冷却し、その温度で、前記液晶化合物含有層表面に前記配向基板のラビング面を密着させた。なお、前記透明基材のラビング処理された方向と、前記配向基板のラビングされた方向が平行になるように、前記透明基材と前記配向基板を配置した。この状態の概略を示す断面図を、図１に示す。図示の通り、透明基材１０、表面改質層１１、液晶化合物含有層１２および配向基板１３がこの順番で積層されている。

On the surface modified layer, the liquid crystal compound solution was applied by a bar coater (# 5) method and dried by heating at 120 ° C. for 2 minutes to form a liquid crystal compound-containing layer (thickness: 1.3 μm). This was cooled to room temperature, and the rubbing surface of the alignment substrate was brought into close contact with the surface of the liquid crystal compound-containing layer at that temperature. The transparent base material and the alignment substrate were arranged so that the direction in which the transparent base material was rubbed and the direction in which the alignment substrate was rubbed were parallel. A cross-sectional view showing the outline of this state is shown in FIG. As shown in the figure, a transparent substrate 10, a surface modification layer 11, a liquid crystal compound-containing layer 12, and an alignment substrate 13 are laminated in this order.

The liquid crystal compound was aligned by being left for 3 minutes at 30 ° C. (liquid crystal temperature range) while maintaining this close contact state. Further, the liquid crystal compound-containing layer was irradiated with ultraviolet rays at an integrated light amount of 600 mJ / cm ² to polymerize the liquid crystal compound to form an optically anisotropic layer (thickness: 1.3 μm). The adhesion time between the alignment substrate and the liquid crystal compound-containing layer was about 4 minutes in total.

  And the said alignment substrate was peeled and removed, and the phase difference plate was manufactured. A cross-sectional view showing the outline of the obtained retardation plate is shown in FIG. As shown in the figure, this retardation plate is formed by laminating a transparent substrate 10, a surface modification layer 11, and an optically anisotropic layer 14 in this order.

  Except for arranging the transparent base material and the alignment substrate so that the rubbing direction of the transparent base material and the direction of rubbing the alignment substrate are 45 °, in the same manner as in Example 1, A retardation plate was obtained.

(Comparative Example 1)
First, a triacetyl cellulose film (thickness: 80 μm) (manufactured by Fuji Photo Film Co., Ltd.) was immersed in a 10% by weight aqueous sodium hydroxide solution at 50 ° C. for 1 minute, washed with water, dried at 120 ° C. for 3 minutes, and then treated. Processed. Thereafter, the film was subjected to 20 reciprocating rubbing treatments with rayon to obtain a transparent substrate having a liquid crystal alignment regulating force.

  Another triacetyl cellulose film (thickness: 80 μm) (manufactured by Fuji Photo Film Co., Ltd.) was subjected to 20 reciprocating rubbing treatments with rayon to obtain an alignment substrate having a liquid crystal alignment regulating force.

On the transparent substrate, the same liquid crystal compound solution as in Example 1 was applied by a bar coater (# 5) method, and dried by heating at 120 ° C. for 2 minutes to obtain a liquid crystal compound-containing layer (thickness 1.3 μm). Formed. This was cooled to room temperature, and the rubbing surface of the alignment substrate was brought into close contact with the surface of the liquid crystal compound-containing layer at that temperature. The transparent base material and the alignment substrate were arranged so that the direction in which the transparent base material was rubbed and the direction in which the alignment substrate was rubbed were parallel. The liquid crystal compound was aligned by heating at 30 ° C. for 3 minutes while maintaining this tight contact state. Furthermore, the liquid crystal compound-containing layer was irradiated with 200 mJ / cm ² of ultraviolet light in an integrated light amount, and the liquid crystal compound was polymerized to form an optically anisotropic layer (thickness: 1.3 μm). The adhesion time between the alignment substrate and the liquid crystal compound-containing layer was about 4 minutes in total. And the said alignment substrate was peeled and removed, and the phase difference plate was manufactured.

(Evaluation of liquid crystal alignment)
About each phase difference plate of Examples 1 and 2 and Comparative Example 1, the alignment state of the liquid crystal compound was evaluated as follows. That is, first, two polarizing plates were prepared, and a retardation plate to be evaluated was sandwiched between them. At this time, the polarization axes of the two polarizing plates were orthogonal to each other. Next, light was irradiated from one polarizing plate side, and it was confirmed whether or not the light was transmitted from the opposite side. Further, the alignment state of the liquid crystal compound was evaluated by rotating only the retardation plate while maintaining the polarization axes in an orthogonal state, and confirming the light transmittance at various angles in the same manner.

  According to the above evaluation, the retardation plates of Example 1 and Comparative Example 1 transmit light when the orientation axis forms an angle of 45 ° with either polarization axis of the two polarizing plates. Was confirmed. Furthermore, it was confirmed that no light was transmitted when the alignment axis was parallel or perpendicular to any of the polarization axes. However, the “alignment axis” means an axis parallel to the direction in which the rubbing axis of the alignment substrate exists in Example 1 before the alignment substrate is peeled and removed from each phase difference plate.

  From this evaluation, it was found that in the retardation plates of Example 1 and Comparative Example 1, the liquid crystal compound was aligned in parallel to the alignment axis.

  On the other hand, it was confirmed that the retardation plate of Example 2 was able to transmit light even when its orientation axis was at any angle with any of the polarization axes of the two polarizing plates. The retardation plate was transparent, and no scattering of transmitted light was confirmed. From this evaluation, it was found that in the retardation plate of Example 2, the liquid crystal compound was twisted.

(Evaluation of adhesion between transparent substrate and optically anisotropic layer)
The respective retardation plates of Examples 1 and 2 and Comparative Example 1 were tested for adhesion between the transparent substrate and the optically anisotropic layer by a cross-cut peel test according to JIS K5400-1990. As a result, in the retardation plates of Examples 1 and 2, the evaluation was 10 points while the optically anisotropic layer having an area ratio of 100% was kept in close contact with the transparent substrate. In the phase difference plate, 100% of the optically anisotropic layer was peeled off.

  As described above, in the retardation plates of Examples 1 and 2, the liquid crystal compounds in the optically anisotropic layer are regularly aligned, and the adhesiveness between the optically anisotropic layer and the transparent substrate is high. I understood. In contrast, in the retardation plate of Comparative Example 1, the liquid crystal compound in the optically anisotropic layer is regularly aligned, but the adhesion between the optically anisotropic layer and the transparent substrate is low. It was.

  As described above, the retardation plate of the present invention is suitable for use as a member of an image display device or the like.

2 is a cross-sectional view illustrating an outline of a precursor in a manufacturing process of a retardation plate of Example 1. FIG. 2 is a cross-sectional view illustrating an outline of a retardation plate obtained in Example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Transparent base material 11 Surface modification layer 12 Liquid crystal compound containing layer 13 Oriented substrate 14 Optically anisotropic layer

Claims (19)

A method for producing a retardation plate in which an optically anisotropic layer is laminated on a transparent substrate,
The manufacturing method characterized by including the process of following (1)-(5).
(1) A step of forming a surface modification layer on the transparent substrate having liquid crystal alignment regulating power.
(2) A step of forming a liquid crystal compound-containing layer on the transparent substrate via the surface modification layer.
(3) A step of bringing an alignment substrate having a liquid crystal alignment regulating force into contact with the liquid crystal compound-containing layer, and regularly aligning the liquid crystal compound of the liquid crystal compound-containing layer with the alignment substrate.
(4) A step of fixing the alignment state of the liquid crystal compound in the liquid crystal compound-containing layer to form an optically anisotropic layer.
(5) A step of removing the alignment substrate.   The manufacturing method according to claim 1, wherein the transparent substrate is a substrate obtained by directly rubbing the polymer film surface.   The production method according to claim 2, wherein the polymer film is formed from a cellulose derivative.   The manufacturing method in any one of Claims 1-3 including the process of making a hydrophilic group express on the surface which forms the said surface modification layer of the said transparent base material prior to the said process (1).   The manufacturing method according to claim 1, wherein the surface modified layer contains an organosilicon compound.   In the step (1), the method of forming the surface modification layer may be performed by immersing the transparent substrate in a silane coupling agent solution or applying a silane coupling agent solution on the surface of the transparent substrate. The method according to any one of claims 1 to 5, which is a method of subsequently drying the silane coupling agent solution. The manufacturing method in any one of Claims 1-5 in which the said silane coupling agent contains the compound represented by the following general formula (I).

In the formula (I), X represents a haloalkyl group, a mercapto group, an alkylsulfanyl group, an amino group, an isocyanate group, a ureido group, a group represented by the following general formula (a), or a group represented by the following general formula (b). , An ethylene skeleton, and a group selected from the group consisting of epoxy groups,
R ¹ , R ² and R ³ are the same or different and each represents a hydroxyl-protecting group or an alkyl group;
n represents an integer of 1 to 10.
However, at least one of R ¹ , R ² and R ³ represents a hydroxyl-protecting group.

In the formula (a), Y ¹ , Y ² and Y ³ are the same or different and represent an atom or group selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group,
In the formula (a), Z ¹ represents a group selected from the group consisting of a bond, —C (═O) —O—, —O—C (═O) — and —C (═O) —. Show
In the formula (b), Y ⁴ , Y ⁵ and Y ⁶ are the same or different and represent an atom or group selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group,
In the formula (b), Z ² represents a group selected from the group consisting of a bond, —C (═O) —O—, —O—C (═O) — and —C (═O) —. Show.   In the step (2), the method of forming the liquid crystal compound-containing layer on the surface modified layer is a method in which a solution of the liquid crystal compound is applied to the surface modified layer and dried, or The manufacturing method according to claim 1, which is a method of applying a melt to the surface modification layer.   The manufacturing method in any one of Claims 1-8 in which the liquid crystal compound contained in the said liquid crystal compound content layer contains a liquid crystal monomer or a liquid crystal prepolymer.   The manufacturing method in any one of Claims 1-8 in which the liquid crystal compound contained in the said liquid crystal compound content layer contains a liquid crystal polymer.   The manufacturing method in any one of Claims 1-10 in which the liquid crystal compound contained in the said liquid crystal compound content layer contains a nematic liquid crystal compound.   The manufacturing method in any one of Claims 1-11 in which the liquid crystal compound contained in the said liquid crystal compound content layer contains a cholesteric liquid crystal compound.   In the step (3), the method of regularly aligning the liquid crystal compound contained in the liquid crystal compound-containing layer is to heat the liquid crystal compound-containing layer to the liquid crystal temperature and contact the alignment substrate in this state. The method according to any one of claims 1 to 12, wherein the liquid crystal compound-containing layer is brought into contact with the alignment substrate and heated to the liquid crystal temperature or higher in this state.   In the step (3), when the liquid crystal compound-containing layer on the transparent substrate is brought into contact with the alignment substrate, an angle formed by an in-plane alignment axis of the transparent substrate and an in-plane alignment axis of the alignment substrate The manufacturing method in any one of Claims 1-13 which controls the orientation state of the liquid crystal compound of the said liquid crystal compound content layer by.   The liquid crystal compound contained in the liquid crystal compound-containing layer contains at least one of a liquid crystal prepolymer and a liquid crystal monomer, and in the step (4), the alignment state is fixed by the liquid crystal compound contained in the liquid crystal compound-containing layer. The manufacturing method in any one of Claims 1-14 implemented by the method to photopolymerize.   The liquid crystal compound contained in the liquid crystal compound-containing layer is a liquid crystal polymer, and in the step (4), the alignment state is fixed by a method of cooling the liquid crystal compound-containing layer below its liquid crystal temperature. The manufacturing method according to claim 1.   The phase difference plate obtained by the manufacturing method in any one of Claims 1-16.   An optical element comprising the retardation plate according to claim 17 and a polarizer.   An image display device comprising the retardation plate according to claim 17 or the optical element according to claim 18.

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