JP2021092685A - Optical laminate, manufacturing method therefore, liquid crystal panel, and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated optical film capable of suppressing a change in color while contributing to a thinning of a liquid crystal panel and a liquid crystal display device and simplifying a manufacturing process. An optical laminate (10) used in a liquid crystal display device and arranged on a visible side of a liquid crystal cell, comprising a polarizing element (11) and a retardation layer (12) arranged on one side of the polarizing element. The in-plane retardation value Re (590) at a wavelength of 590 nm of the retardation layer is 90 nm or more and 190 nm or less, and the angle θ formed by the absorption axis of the polarizer and the slow axis of the retardation layer is 5 ° or more and 85 ° or less. , The optical laminate 10 in which the retardation layer 12 contains a polymer of a compound having a group represented by a specific formula and a polymerizable group. [Selection diagram] Fig. 1

Description

The present invention relates to an optical laminate, specifically, an optical laminate that can contribute to thinning of a liquid crystal panel and a liquid crystal display device.

In recent years, with the start of one-segment broadcasting and the like, mobile devices such as mobile phones have also been used as image / moving images. For this reason, display methods for mobile devices are diversifying. For example, a portable device whose display screen can be rotated in a plane can be mentioned. When such a display screen is viewed through a polarized lens such as polarized sunglasses, the image may not be visible.

Therefore, a liquid crystal display device has been proposed in which a transparent cover (λ / 4 plate), which is a lens-shaped resin molded product, is provided on the visual side of the display screen (Patent Document 1). Further, it is disclosed that a liquid crystal film is applied as a λ / 4 plate (Patent Document 2).

Japanese Unexamined Patent Publication No. 2005-148119 JP-A-2009-103900

However, if a new member such as the transparent cover is provided, the thickness of the liquid crystal display device increases. On the other hand, the liquid crystal display device is required to be thinner. Further, as the number of members increases, the number of manufacturing processes of the liquid crystal display device increases, and there is a high possibility that foreign matter is mixed between the layers and a problem occurs due to the mixed foreign matter.

Further, the conventional liquid crystal film has a problem that when viewed through a polarizing lens such as polarized sunglasses, the color of the screen changes greatly and the visibility is not sufficient.

The present invention has been made to solve the above problems, and an object of the present invention is to contribute to thinning of a liquid crystal panel and a liquid crystal display device, and to simplify a manufacturing process while suppressing a change in color. To provide the body.

The present invention provides the following optical laminate, a method for manufacturing the optical laminate, a liquid crystal panel, and a liquid crystal display device.
[1] An optical laminate used in a liquid crystal display device and arranged on the visual side of a liquid crystal cell.
A polarizer and a retardation layer arranged on one side of the polarizer are provided.
The in-plane retardation value Re (590) at a wavelength of 590 nm of the retardation layer is 90 nm or more and 190 nm or less.
The angle θ formed by the absorption axis of the polarizer and the slow axis of the retardation layer is 5 ° or more and 85 ° or less.
An optical laminate in which the retardation layer contains a polymer of a compound having a group represented by the formula (A) and a polymerizable group.
−G ^a −D ^a −Ar ^a −D ^b −G ^b − (A)
[In the formula (A), the Ar ^a group represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and is included in the aromatic ring in the ^{Ar a group.} The number of π electrons to be generated Nπ _a is 12 or more.
D ^a and D ^b are single-bonded independently of each other, * ^1- C (= O) -O-, * ¹ -OC (= O)-, * ^1- C (= S) -O-, ^{* 1 -O-C (= S} ) -, * 1 -CR 1 R 2 -, * 1 -CR 1 R 2 -CR 3 R 4 -, * 1 -O-CR 1 R 2 -, * 1 -CR ^{1 R 2 -O -, * 1} -CR 1 R 2 -O-CR 3 R 4 -, * 1 -CR 1 R 2 -O-C (= O) -, * 1 -O-C (= O) ^{-CR 1 R 2 -, * 1} -CR 1 R 2 -O-C (= O) -CR 3 R 4 -, * 1 -CR 1 R 2 -C (= O) -O-CR 3 R 4 - , * ^1- NR ^1- CR ² R ^3- , * ^1- CR ¹ R ^2- NR ^3- , * ^1- C (= O) -NR ^1- , or * ^1- NR ^1- C (= O) Represents − (* ¹ represents the position of binding to Ar ^a).
R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ^a and G ^b independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. ]
[2] The optical laminate according to [1], wherein the compound having a group represented by the formula (A) and a polymerizable group is a compound having a group represented by the formula (B) and a polymerizable group. ..
−E ¹ −G ^a −D ^a −Ar ^a −D ^b −G ^b −E ^2- (B)
Wherein ^{(B), Ar a, D} a, D b, G a and ^{G b} have the definitions in the formula (A).
E ¹ and E ² are independent of each other, * ^2- CR ⁵ R ^6- , * ^2- CH _2- CH _2- , * ² -O-, * ^2- S-, * ^2- C (= O). -O-, * ^2- OC (= O)-, * ^2- OC (= O) -O-, * ^2- C (= S) -O-, * ^2- OC (=) S)-, * ^2- OC (= S) -O-, * ^2- C (= O) -NR ^5- , * ^2- NR ^5- C (= O)-, * ^2- O-CH _{^{2 -, * 2 -CH 2 -O}} -, * 2 -S-CH 2 -, * 2 -CH 2 -S- or a single bond ^{(* 2} represents a position bonded to ^{G a} or ^{G b} ).
R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. ]
[3] The optical laminate according to [2], wherein the compound having a group represented by the formula (B) and a polymerizable group is a compound having a group represented by the formula (C) and a polymerizable group. ..
-(B ^1- A ¹ ) _k- E ^1- G ^a- D ^a- Ar ^a- D ^b- G ^b- E ^2- (A ^2- B ² ) _l- (C)
Wherein ^{(C), Ar a, D} a, D b, G a, G b, E 1 and ^{E 2} have the definitions in the formula (B).
B ¹ and B ² are independent of each other, * ^3- CR ⁵ R ^6- , * ^3- CH _2- CH _2- , * ³ -O-, * ^3- S-, * ^3- C (= O). -O-, * ^3- OC (= O)-, * ^3- OC (= O) -O-, * ^3- C (= S) -O-, * ^3- OC (=) S)-, * ^3- OC (= S) -O-, * ^3- C (= O) -NR ^5- , * ^3- NR ^5- C (= O)-, * ^3- O-CH _{^{2 -, * 3 -CH 2 -O}} -, * 3 -S-CH 2 -, * 3 represents a _-CH 2 -S- or a single bond ^{(* 3} represents a position bonded to the ^{a 1} or ^{a 2} ).
R ⁵ and R ⁶ have the same meanings as above.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. Alternatively, it may be substituted with a nitro group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom. k and l represent integers 0 to 3 independently of each other. ]
[4] The optical laminate according to any one of [1] to [3], _{wherein the number Nπ a of} π electrons contained in the aromatic ring in the ^{Ar a group is 13 or more and 22 or less.}
[5] The Ar ^a group, a benzene ring, a naphthalene ring, an anthracene ring, phenanthroline ring, a furan ring, pyrrole ring, thiophene ring, pyridine ring, at least one selected from the group consisting of a thiazole ring and a benzothiazole ring The optical laminate according to [1] to [4], which is a divalent group having an aromatic ring.
[6] The ^{G a} and ^{G b} is a 1,4-cyclohexylene group, [1] to the optical laminate according to any one of [5].
[7] The optical laminate according to [1], wherein the compound having the group represented by the formula (A) and the polymerizable group is the compound represented by the formula (1).
P ^1- F ^1- (B ^1- A ¹ ) _k- E ^1- G ^1- D ^1- Ar-D ^2- G ^2- E ^2- (A ^2- B ² ) _l- F ^2- P ² ( 1)
[In formula (1), Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and π electrons contained in the aromatic ring in the Ar group. The number Nπ of is 12 or more and 22 or less.
D ¹ and ^{D 2,} independently of one ^{another, * 4 -C (= O)} -O -, * 4 -O-C (= O) -, * 4 -C (= S) -O -, * 4 - ^{O-C (= S) -} , * 4 -CR 1 R 2 -, * 4 -CR 1 R 2 -CR 3 R 4 -, * 4 -O-CR 1 R 2 -, * 4 -CR 1 R 2 ^{-O -, * 4 -CR 1 R} 2 -O-CR 3 R 4 -, * 4 -CR 1 R 2 -O-C (= O) -, * 4 -O-C (= O) -CR 1 ^{R 2 -, * 4 -CR 1} R 2 -O-C (= O) -R 3 R 4 -, * 4 -CR 1 R 2 -C (= O) -O-CR 3 R 4 -, * 4 Represents −NR ¹ −CR ² R ³ −, * ⁴ −CR ² R ³ −NR ¹ −, * ⁴ −C (= O) −NR ¹ −, or * ⁴ −NR ¹ −C (= O) − (* ⁴ represents the position where it binds to Ar).
R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² represent divalent alicyclic hydrocarbon groups independently of each other. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or −NH−.
E ¹ , E ² , B ¹ and B ² are independent of each other, * ^5- CR ⁵ R ^6- , * ^5- CH _2- CH _2- , * ^5- O-, * ^5- S-, * ⁵ -C (= O) -O-, * ^5- OC (= O)-, * ^5- OC (= O) -O-, * ^5- C (= S) -O-, * ⁵ -OC (= S)-, * ^5- OC (= S) -O-, * ^5- C (= O) -NR ^5- , * ^5- NR ^5- C (= O)-, _{^{* 5 -O-CH 2 -,}} * 5 -CH 2 -O -, * 5 -S-CH 2 -, * 5 -CH 2 -S- or represents a single bond ^{(* 5, G 1,} G ² , Represents a position that binds to ^{A 1} or A ^2).
R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or the like. It may be substituted with a nitro group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l represent integers 0 to 3 independently of each other.
F ¹ and F ² represent an alkylene group having 1 to 12 carbon atoms independently of each other. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and the methylene group contained in the alkylene group is −O. It may be replaced with − or −C (= O) −.
P ¹ and P ² represent a hydrogen atom or a polymerizable group independently of each other. However, ^{at least one of P 1} and P ² represents a polymerizable group. ]
[8] The optical laminate according to any one of [1] to [7], wherein the retardation layer has optical characteristics represented by the formulas (α) and (β).
Re (450) / Re (550) ≤ 1.00 (α)
1.00 ≤ Re (650) / Re (550) (β)
[In the formulas (α) and (β), Re (450) represents the in-plane retardation value at a wavelength of 450 nm, Re (550) represents the in-plane retardation value at a wavelength of 550 nm, and Re (650) represents the wavelength. Represents an in-plane retardation value at 650 nm. ]
[9] The optical laminate according to any one of [1] to [8], wherein the optical laminate is arranged in the liquid crystal cell so that the retardation layer is on the visual side of the polarizer.
[10] The optical laminate according to any one of [1] to [9], further comprising a hard coat layer arranged on the opposite side of the retardation layer to the polarizer.
[11] The optical laminate according to any one of [1] to [10], further comprising a first protective film arranged between the polarizer and the retardation layer.
[12] The optical laminate according to any one of [1] to [10], further comprising a first protective film arranged on the opposite side of the retardation layer from the polarizer.
[13] The optical laminate according to any one of [1] to [12], wherein the angle θ is 40 ° or more and 50 ° or less.
[14] The optical laminate according to any one of [1] to [13], wherein the retardation layer is a cured layer of a liquid crystal material.
[15] The optical laminate according to any one of [1] to [14], wherein the retardation layer contains an ultraviolet blocking agent.
[16] The method for manufacturing an optical laminate according to [1].
A manufacturing method including a step of laminating the polarizer and the retardation layer by a roll-to-roll method.
[17] A liquid crystal panel comprising the optical laminate according to any one of [1] to [15].
[18] A liquid crystal display device including the liquid crystal panel according to [17].

According to the present invention, it is possible to provide an optical laminate capable of suppressing a change in color while contributing to a thinning of a liquid crystal panel and a liquid crystal display device and simplifying a manufacturing process.

It is the schematic sectional drawing which shows an example of the layer structure of an optical laminate. It is the schematic sectional drawing which shows an example of the layer structure of an optical laminate. It is the schematic sectional drawing which shows an example of the manufacturing method of an optical laminate. It is the schematic sectional drawing which shows an example of the layer structure of a liquid crystal panel. It is the schematic sectional drawing which shows an example of the layer structure of a liquid crystal cell. It is a side view and the exploded perspective view which shows the measurement system of a color change schematicly.

Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments. In all the drawings below, the scale is appropriately adjusted to make it easier to understand each component, and the scale of each component shown in the drawings does not necessarily match the scale of the actual component.

Definitions of terms and symbols in the present specification are as follows.
(1) Refractive index (nx, ny, nz)
“Nx” is the refractive index in the direction in which the in-plane refractive index is maximized (that is, the slow-phase axis direction), “ny” is the direction orthogonal to the slow-phase axis in the in-plane, and “nz” is the thickness direction. Refractive index.
(2) In-plane retardation value The in-plane retardation value [Re (λ)] refers to the in-plane retardation value of the retardation layer at a wavelength of λ (nm) at 23 ° C. Re (λ) is obtained by Re (λ) = (nx−ny) × d, where d (nm) is the thickness of the retardation layer.

<Optical laminate>
FIG. 1 is a schematic cross-sectional view of an optical laminate according to a preferred embodiment of the present invention. The optical laminate 10 includes a polarizer 11 and a retardation layer 12 arranged on one side of the polarizer 11. The optical laminate 10 includes a hard coat layer 13 arranged on the side opposite to the polarizing element 11 of the retardation layer 12, and a first protective film 14 arranged between the polarizing element 11 and the retardation layer 12. A second protective film 15 arranged on the side opposite to the retardation layer 12 of the polarizer 11 is further provided. FIG. 2 is a schematic cross-sectional view of an optical laminate according to another preferred embodiment of the present invention. The optical laminate 10'includes a polarizer 11 and a retardation layer 12 arranged on one side of the polarizer 11. The optical laminate 10'is arranged on the side opposite to the retarder 11 of the retarder 11 with the hard coat layer 13 and the first protective film 14 arranged on the opposite side of the retarder 11. A second protective film 15 is further provided. In the present embodiment, the first protective film 14 is arranged between the retardation layer 12 and the hard coat layer 13.

The optical laminates 10, 10'can further include any other suitable retardation layer. Any suitable adhesive layer or adhesive layer may be provided between the members constituting the optical laminate of the present invention. Each layer (film) will be described later.

The optical laminates 10, 10'are suitable for liquid crystal display devices. At that time, the optical laminates 10, 10'are arranged on the visual side of the liquid crystal cell. Further, the optical laminates 10 and 10'can be arranged in the liquid crystal cell so that the retardation layer 12 is on the visual side of the polarizer 11. Specifically, the polarizer 11 is arranged so as to be on the liquid crystal cell side (the retardation layer 12 is on the viewing side). By arranging in this way, the polarized light emitted from the polarizer 11 can be appropriately converted into elliptically polarized light. As a result, it is possible to provide a liquid crystal display device having excellent visibility even when the display screen is visually recognized through a polarized lens such as polarized sunglasses.

The angle θ formed by the absorption axis of the polarizer 11 and the slow axis of the retardation layer 12 is 5 ° or more and 85 ° or less, preferably 30 ° or more and 60 ° or less, and more preferably 40 ° or more and 50 ° or less. .. By setting in such a range, the polarized light emitted from the polarizer 11 can be more appropriately converted into elliptically polarized light.

(Polarizer)
As used herein, the term "polarizer" refers to an element capable of converting natural light or polarized light into arbitrary polarized light. Preferably, natural light or polarized light is converted into linearly polarized light. Such a polarizer has a function of separating incident light into two orthogonal polarizing components, transmitting one polarizing component, and absorbing, reflecting and / or scattering the other polarizing component.

The polarizer 11 is usually subjected to a step of uniaxially stretching a polyvinyl alcohol-based resin film, a step of adsorbing a dichroic dye by dyeing the polyvinyl alcohol-based resin film with a dichroic dye, and adsorbing the dichroic dye. It is produced through a step of treating a polyvinyl alcohol-based resin film with an aqueous boric acid solution and cross-linking the film, and a step of washing with water after the cross-linking treatment with the aqueous boric acid solution.

The polyvinyl alcohol-based resin can be produced by saponifying the polyvinyl acetate-based resin. The polyvinyl acetate-based resin can be a copolymer of vinyl acetate and another monomer copolymerizable therewith, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The saponification degree of the polyvinyl alcohol-based resin is usually 85 mol% or more and 100 mol% or less, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 or more and 10,000 or less, preferably 1,500 or more and 5,000 or less.

A film formed of such a polyvinyl alcohol-based resin is used as a raw film for a polarizer. The method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based resin raw film is, for example, 10 μm or more and 100 μm or less, preferably 10 μm or more and 50 μm or less.

The longitudinal uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, at the same time as dyeing, or after dyeing. When the longitudinal uniaxial stretching is performed after dyeing, the longitudinal uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. Of course, longitudinal uniaxial stretching can also be performed at the plurality of stages shown here. For the longitudinal uniaxial stretching, a method of uniaxially stretching between rolls having different peripheral speeds, a method of uniaxially stretching using a thermal roll, and the like can be adopted. Further, the longitudinal uniaxial stretching may be carried out by dry stretching in which stretching is performed in the atmosphere, or by wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent such as water. The draw ratio is usually about 3 to 8 times.

The polyvinyl alcohol-based resin film can be dyed with a dichroic dye, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye. Specifically, iodine or a dichroic organic dye is used as the dichroic dye. The polyvinyl alcohol-based resin film is preferably subjected to a treatment of swelling by immersing it in water before the dyeing treatment.

When iodine is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide for dyeing is usually adopted. The content of iodine in this aqueous solution is usually 0.01 parts by mass or more and 1 part by mass or less per 100 parts by mass of water, and the content of potassium iodide is usually 0.5 parts by mass or more per 100 parts by mass of water. It is 20 parts by mass or less. The temperature of the aqueous solution used for dyeing is usually 20 ° C. or higher and 40 ° C. or lower. The immersion time (staining time) in this aqueous solution is usually 20 seconds or more and 1,800 seconds or less.

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic organic dye and dyeing is usually adopted. The content of the dichroic organic dye in this aqueous solution is usually 1 × 10 ^-4 parts by mass or more and 10 parts by mass or less, preferably 1 × 10 ^-3 parts by mass or more and 1 part by mass or less per 100 parts by mass of water. is there. This aqueous dye solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dichroic organic dye aqueous solution used for dyeing is usually 20 ° C. or higher and 80 ° C. or lower. The immersion time (staining time) in this aqueous solution is usually 10 seconds or more and 1,800 seconds or less.

The boric acid treatment after dyeing with a dichroic dye can be performed by immersing the dyed polyvinyl alcohol-based resin film in a boric acid-containing aqueous solution. The content of boric acid in the boric acid-containing aqueous solution is usually 2 parts by mass or more and 15 parts by mass or less, preferably 5 parts by mass or more and 12 parts by mass or less, per 100 parts by mass of water. When iodine is used as the dichroic pigment, the boric acid-containing aqueous solution preferably contains potassium iodide. The content of potassium iodide in the boric acid-containing aqueous solution is usually 0.1 parts by mass or more and 15 parts by mass or less, preferably 5 parts by mass or more and 12 parts by mass or less, per 100 parts by mass of water. The immersion time in the boric acid-containing aqueous solution is usually 60 seconds or more and 1,200 seconds or less, preferably 150 seconds or more and 600 seconds or less, and more preferably 200 seconds or more and 400 seconds or less. The temperature of the boric acid-containing aqueous solution is usually 50 ° C. or higher, preferably 50 ° C. or higher and 85 ° C. or lower, and more preferably 60 ° C. or higher and 80 ° C. or lower.

The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of water in the washing treatment is usually 5 ° C. or higher and 40 ° C. or lower. The immersion time is usually 1 second or more and 120 seconds or less.

After washing with water, a drying treatment is performed to obtain a polarizer. The drying process can be performed using a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually 30 ° C. or higher and 100 ° C. or lower, preferably 50 ° C. or higher and 80 ° C. or lower. The drying treatment time is usually 60 seconds or more and 600 seconds or less, preferably 120 seconds or more and 600 seconds or less. By the drying treatment, the moisture content in the polarizer is reduced to a practical level. The water content is usually 5% by mass or more and 20% by mass or less, preferably 8% by mass or more and 15% by mass or less. If the moisture content is less than 5% by mass, the polarizer loses its flexibility and may be damaged or broken after drying. Further, when the water content exceeds 20% by mass, the thermal stability tends to be insufficient.

As described above, a polarizer in which the dichroic dye is adsorbed and oriented on the polyvinyl alcohol-based resin film can be produced. The thickness of the obtained polarizer can be, for example, 3 μm or more and 40 μm or less.

In order to keep the contractile force of the polarizer low, it is preferable that the thickness of the polarizer is 12 μm or less. The thickness of the polarizer is usually 3 μm or more in that good optical characteristics can be imparted.

(Phase difference layer)
The retardation layer 12 is arranged on one side of the polarizer 11. The retardation layer 12 can function as a so-called λ / 4 plate. The in-plane retardation value Re (590) at a wavelength of 590 nm of the retardation layer is 90 nm or more and 190 nm or less, preferably 110 nm or more and 170 nm or less, and more preferably 120 nm or more and 160 nm or less. By setting in such a range, the polarized light emitted from the polarizer 11 can be more appropriately converted into elliptically polarized light.

The retardation layer 12 contains a polymer of a compound having a group represented by the formula (A) and a polymerizable group (hereinafter, also referred to as compound (A)).
−G ^a −D ^a −Ar ^a −D ^b −G ^b − (A)
[In the formula (A), Ar ^a represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and is included in the aromatic ring in the ^{Ar a group.} The number of π electrons Nπ _a is 12 or more.
D ^a and D ^b are single-bonded independently of each other, * ^1- C (= O) -O-, * ¹ -OC (= O)-, * ^1- C (= S) -O-, ^{* 1 -O-C (= S} ) -, * 1 -CR 1 R 2 -, * 1 -CR 1 R 2 -CR 3 R 4 -, * 1 -O-CR 1 R 2 -, * 1 -CR ^{1 R 2 -O -, * 1} -CR 1 R 2 -O-CR 3 R 4 -, * 1 -CR 1 R 2 -O-C (= O) -, * 1 -O-C (= O) ^{-CR 1 R 2 -, * 1} -CR 1 R 2 -O-C (= O) -CR 3 R 4 -, * 1 -CR 1 R 2 -C (= O) -O-CR 3 R 4 - , * ^1- NR ^1- CR ² R ^3- , * ^1- CR ¹ R ^2- NR ^3- , * ^1- C (= O) -NR ^1- , or * ^1- NR ^1- C (= O) Represents − (* ¹ represents the position of binding to Ar ^a).
R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ^a and G ^b independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. ]

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrolin ring, and examples of the aromatic heterocycle include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole. Rings and the like can be mentioned. Of these, a benzene ring, a thiazole ring, and a benzothiazole ring are preferable.

Ar ^a is a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and the π electron of the aromatic ring contained in the divalent group. The total number Nπ is 12 or more, preferably 12 or more and 22 or less, and more preferably 13 or more and 22 or less.

Ar ^a is preferably a divalent group having at least two aromatic rings selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles.

In the formula (A), ^{it is preferable that Ar a} is any divalent group represented by the formulas (Ar-1) to (Ar-13).

[In formulas (Ar-1) to (Ar-13), Z ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, and a carbon number of carbon atoms. Alkylsulfonyl groups 1 to 6, carboxyl groups, fluoroalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkylthio groups having 1 to 6 carbon atoms, N-alkylamino groups having 1 to 6 carbon atoms. , N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms or N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
Q ¹ and ^{Q 3} are, each ^{independently, -CR 7 R 8 -, -} S -, - NR 7 -, - CO- or an -O-.
R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.
W ¹ and W ² independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, respectively.
m represents an integer from 0 to 6.
n represents an integer of 0 to 2. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom, a chlorine atom and a bromine atom are preferable.

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like. Alkyl groups having a number of 1 to 4 are preferable, alkyl groups having 1 to 2 carbon atoms are more preferable, and methyl groups are particularly preferable.

The alkylsulfinyl groups having 1 to 6 carbon atoms include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, and pentylsulfinyl. Examples thereof include a group and a hexyl group sulfinyl, and an alkylsulfinyl group having 1 to 4 carbon atoms is preferable, an alkylsulfinyl group having 1 to 2 carbon atoms is more preferable, and a methylsulfinyl group is particularly preferable.

The alkylsulfonyl groups having 1 to 6 carbon atoms include methylsulfonyl groups, ethylsulfonyl groups, propylsulfonyl groups, isopropylsulfonyl groups, butylsulfonyl groups, isobutylsulfonyl groups, sec-butylsulfonyl groups, tert-butylsulfonyl groups, and pentylsulfonyl groups. Examples thereof include a group and a hexylsulfonyl group, and an alkylsulfonyl group having 1 to 4 carbon atoms is preferable, an alkylsulfonyl group having 1 to 2 carbon atoms is more preferable, and a methylsulfonyl group is particularly preferable.

Examples of the fluoroalkyl group having 1 to 6 carbon atoms include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group and the like, and have 1 to 4 carbon atoms. A fluoroalkyl group is preferable, a fluoroalkyl group having 1 to 2 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable.

Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and a hexyloxy group. The alkoxy group having 1 to 4 carbon atoms is preferable, the alkoxy group having 1 to 2 carbon atoms is more preferable, and the methoxy group is particularly preferable.

Examples of the alkylthio group having 1 to 6 carbon atoms include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group and a hexylthio group. , An alkylthio group having 1 to 4 carbon atoms is preferable, an alkylthio group having 1 to 2 carbon atoms is more preferable, and a methylthio group is particularly preferable.

Examples of the N-alkylamino group having 1 to 6 carbon atoms include N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group and N-isobutylamino group. Examples thereof include N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group, N-hexylamino group, and N-alkylamino group having 1 to 4 carbon atoms is preferable, and N-alkylamino group having 1 to 4 carbon atoms is preferable. The N-alkylamino group of 2 is more preferable, and the N-methylamino group is particularly preferable.

Examples of the N, N-dialkylamino group having 2 to 12 carbon atoms include an N, N-dimethylamino group, an N-methyl-N-ethylamino group, an N, N-diethylamino group, and an N, N-dipropylamino group. N, N-diisopropylamino group, N, N-dibutylamino group, N, N-diisobutylamino group, N, N-dipentylamino group, N, N-dihexylamino group and the like, which have 2 to 8 carbon atoms. The N, N-dialkylamino group is preferable, the N, N-dialkylamino group having 2 to 4 carbon atoms is more preferable, and the N, N-dimethylamino group is particularly preferable.

Examples of the N-alkylsulfamoyl group having 1 to 6 carbon atoms include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group and N-. Butyl sulfamoyl group, N-isobutyl sulfamoyl group, N-sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N-hexyl sulfamoyl group, etc. The N-alkylsulfamoyl group having 1 to 4 carbon atoms is preferable, the N-alkylsulfamoyl group having 1 to 2 carbon atoms is more preferable, and the N-methylsulfamoyl group is particularly preferable.

Examples of the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms include an N, N-dimethylsulfamoyl group, an N-methyl-N-ethylsulfamoyl group, and an N, N-diethylsulfamoyl group. N, N-dipropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diisobutylsulfamoyl group, N, N-dipentylsulfamoyl group, Examples thereof include an N, N-dihexyl sulfamoyl group, preferably an N, N-dialkyl sulfamoyl group having 2 to 8 carbon atoms, and more preferably an N, N-dialkyl sulfamoyl group having 2 to 4 carbon atoms. , N, N-dimethylsulfamoyl groups are particularly preferred.

Z ¹ is a halogen atom, a methyl group, a cyano group, a nitro group, a carboxyl group, a methylsulfonyl group, a trifluoromethyl group, a methoxy group, a methylthio group, an N-methylamino group, an N, N-dimethylamino group, an N- It is preferably a methyl sulfamoyl group or an N, N-dimethylsulfamoyl group.

Examples of the alkyl group having 1 to 4 carbon atoms in R ⁷ and R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group and the like, and have 1 to 2 carbon atoms. Alkyl groups are preferred, and methyl groups are more preferred.
Q ¹ is, -S -, - CO -, - NH -, - N (CH 3) - are preferred, ^{Q 3} it is in, -S -, - is preferably a CO-.

Examples of the aromatic hydrocarbon group in Y ¹ , Y ² and Y ³ include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group. , A naphthyl group is preferable, and a phenyl group is more preferable. The aromatic heterocyclic group contains at least one nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group, and a hetero atom such as an oxygen atom and a sulfur atom, and has 4 to 20 carbon atoms. The aromatic heterocyclic group of the above is mentioned, and a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group and a thiazolyl group are preferable.

The aromatic hydrocarbon group and the aromatic heterocyclic group may have at least one substituent, and the substituents include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, and a nitro group. Alkyl sulfinyl group with 1 to 6 carbon atoms, alkylsulfonyl group with 1 to 6 carbon atoms, carboxyl group, fluoroalkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkylthio group with 1 to 6 carbon atoms , N-alkylamino group with 1 to 6 carbon atoms, N, N-dialkylamino group with 2 to 12 carbon atoms, N-alkylsulfamoyl group with 1 to 6 carbon atoms, N, N with 2 to 12 carbon atoms -Dialkylsulfamoyl groups and the like include halogen atoms, alkyl groups having 1 to 2 carbon atoms, cyano groups, nitro groups, alkylsulfonyl groups having 1 to 2 carbon atoms, fluoroalkyl groups having 1 to 2 carbon atoms, and carbon atoms. An alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, an N-alkylamino group having 1 to 2 carbon atoms, an N, N-dialkylamino group having 2 to 4 carbon atoms, and an alkyl having 1 to 2 carbon atoms. Sulfamoyl groups are preferred.

Halogen atom, alkyl group with 1 to 6 carbon atoms, cyano group, nitro group, alkylsulfinyl group with 1 to 6 carbon atoms, alkylsulfonyl group with 1 to 6 carbon atoms, carboxyl group, fluoroalkyl group with 1 to 6 carbon atoms , An alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, 1 to 6 carbon atoms. Examples of the N-alkylsulfamoyl group and the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms are the same as those described above.

It is preferable that Y ¹ , Y ² and Y ³ are independently one of the groups represented by the formulas (Y-1) to (Y-6).

[In formulas (Y-1) to (Y-6), Z ² is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, and a carbon number of carbon atoms. Alkylsulfonyl groups 1 to 6, carboxyl groups, fluoroalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, thioalkyl groups having 1 to 6 carbon atoms, N-alkylamino groups having 1 to 6 carbon atoms. , N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms or N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
a ₁ is an integer from 0 to 5, a ₂ is an integer from 0 to 4, b ₁ is an integer from 0 to 3, b ₂ is an integer from 0 to 2, and R is a hydrogen atom or a methyl group. .. ]

As Z ² , a halogen atom, a methyl group, a cyano group, a nitro group, a sulfone group, a carboxyl group, a trifluoromethyl group, a methoxy group, a thiomethyl group, an N, N-dimethylamino group or an N-methylamino group is preferable.

Furthermore, the fact that Y ¹ , Y ² and Y ³ are independently represented by the formula (Y-1) or the formula (Y-3) in terms of the manufacturing process and cost of the compound (A). Especially preferable.

It is preferable that W ¹ and W ² are independently hydrogen atoms, cyano groups or methyl groups, respectively, and it is particularly preferable that they are hydrogen atoms.
m is preferably 0 or 1. n is preferably 0.

In the formula (A), Ar ^a is a divalent compound represented by the formula (Ar-6a), the formula (Ar-6b), the formula (Ar-6c), the formula (Ar-10a) or the formula (Ar-10b). More preferably it is a group.

[In the formulas (Ar-6a) to (Ar-6c), formulas (Ar-10a) and formulas (Ar-10b), Z ¹ , n, Q ¹ , Z ² , a ₁ and b ₁ are as described above. Represents the same meaning. ]

Examples of Ar ^a are shown in equations (ar-1) to (ar-189).

Specific examples of the groups represented by the formulas (Ar-1) to (Ar-4) include the groups represented by the formulas (ar-1) to (ar-29).

Specific examples of the groups represented by the formula (Ar-5) include the groups represented by the formulas (ar-30) to (ar-39).

Specific examples of the groups represented by the formula (Ar-6) or the formula (Ar-7) include the groups represented by the formulas (ar-40) to (ar-119).

Specific examples of the groups represented by the formula (Ar-8) or the formula (Ar-9) include the groups represented by the formulas (ar-120) to (ar-129).

Specific examples of the groups represented by the formula (Ar-10) include the groups represented by the formulas (ar-130) to (ar-149).

Specific examples of the groups represented by the formula (Ar-11) include the groups represented by the formulas (ar-150) to (ar-159).

Specific examples of the groups represented by the formula (Ar-12) include the groups represented by the formulas (ar-160) to (ar-179).

Specific examples of the groups represented by the formula (Ar-13) include the groups represented by the formulas (ar-180) to (ar-189).

D ¹ and D ² are independent of each other, preferably * ^1- O-CO-, * ^1- OC (= S)-, * ^1- O-CR ¹ R ^2- , * ^1- NR ^1-. CR ² R ^3- or * ^1- NR ^1- CO-, more preferably * ^1- O-CO-, * ^1- OC (= S) ^{-or * 1-} NR ^1- CO-. .. R ¹ , R ² , R ³ and R ⁴ are independent of each other, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.

Examples of the divalent alicyclic hydrocarbon group in G ¹ and G ² include an alicyclic hydrocarbon group which may contain a heteroatom represented by the formulas (g-1) to (g-10). It is preferably a 5- or 6-membered alicyclic hydrocarbon group.

The groups represented by the formulas (g-1) to (g-10) are alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group and a tert-butyl group; carbons such as a methoxy group and an ethoxy group. Alkoxy group of number 1 to 4; fluoroalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; fluoroalkoxy group having 1 to 4 carbon atoms such as trifluoromethoxy group; cyano group; nitro group; fluorine atom, It may be substituted with a halogen atom such as a chlorine atom or a bromine atom.

The G ¹ and G ² are preferably an alicyclic hydrocarbon group composed of a 6-membered ring represented by the formula (g-1), more preferably a 1,4-cyclohexylene group, and trans. It is more preferably a -1,4-cyclohexylene group.

The compound (A) is preferably a compound having a group represented by the formula (B) and a polymerizable group (hereinafter, also referred to as compound (B)).
−E ¹ −G ^a −D ^a −Ar ^a −D ^b −G ^b −E ^2- (B)
Wherein ^{(B), Ar a, D} a, D b, G a and ^{G b} have the definitions in the formula (A).
E ¹ and E ² are independent of each other, * ^2- CR ⁵ R ^6- , * ^2- CH _2- CH _2- , * ² -O-, * ^2- S-, * ^2- C (= O). -O-, * ^2- OC (= O)-, * ^2- OC (= O) -O-, * ^2- C (= S) -O-, * ^2- OC (=) S)-, * ^2- OC (= S) -O-, * ^2- C (= O) -NR ^5- , * ^2- NR ^5- C (= O)-, * ^2- O-CH _{^{2 -, * 2 -CH 2 -O}} -, * 2 -S-CH 2 -, * 2 -CH 2 -S- or a single bond ^{(* 2} represents a position bonded to ^{G a} or ^{G b} ).
R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. ]

^{Ar a, D a, D b} , examples and preferable range of ^{G a} and ^{G b} are examples and preferable range of the compound (A) is applied.

Examples of the alkyl group having 1 to 4 carbon atoms in R ⁵ and R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group and the like, and have 1 to 2 carbon atoms. Alkyl groups are preferred, and methyl groups are more preferred.

As R ⁵ and R ⁶ , hydrogen atoms and fluorine atoms are preferable independently of each other.

E ¹ and E ² are preferably * ^2- CH _2- CH _2- , * ^2- C (= O) -O-, * ^2- OC (= O)-, * ^2- CO-NH- ^{, * 2 -NH-C (=} O) -, * 2 -O-CH 2 -, a * 2 _-CH 2 -O- or a single bond, more preferably ^* 2 -C (= O) -O- , * ^2- OC (= O)-or single bond.

The compound having a group represented by the formula (B) and a polymerizable group is more preferably a compound having a group represented by the formula (C) and a polymerizable group (hereinafter, also referred to as a compound (C)).
-(B ^1- A ¹ ) _k- E ^1- G ^a- D ^a- Ar ^a- D ^b- G ^b- E ^2- (A ^2- B ² ) _l- (C)
Wherein ^{(C), Ar a, D} a, D b, G a, G b, E 1 and ^{E 2} have the definitions in the formula (B).
B ¹ and B ² are independent of each other, * ^3- CR ⁵ R ^6- , * ^3- CH _2- CH _2- , * ³ -O-, * ^3- S-, * ^3- C (= O). -O-, * ^3- OC (= O)-, * ^3- OC (= O) -O-, * ^3- C (= S) -O-, * ^3- OC (=) S)-, * ^3- OC (= S) -O-, * ^3- C (= O) -NR ^5- , * ^3- NR ^5- C (= O)-, * ^3- O-CH _{^{2 -, * 3 -CH 2 -O}} -, * 3 -S-CH 2 -, * 3 represents a _-CH 2 -S- or a single bond ^{(* 3} represents a position bonded to the ^{a 1} or ^{a 2} ).
R ⁵ and R ⁶ have the same meanings as above.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro. It may be substituted with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom. k and l represent integers 0 to 3 independently of each other. ]

^{Ar a, D a, D b} , G a, G b, examples and preferable range of ^{E 1} and ^{E 2,} examples and preferable range of the compound (A) and (B) is applied.

Examples of the divalent alicyclic hydrocarbon group or aromatic hydrocarbon group in A ¹ and A ² include a 5-membered ring or a 6-membered ring represented by the above formulas (g-1) to (g-10). Examples thereof include an alicyclic hydrocarbon group composed of the above, and a divalent aromatic hydrocarbon group having about 6 to 20 carbon atoms represented by the formulas (a-1) to (a-8).

As A ¹ and A ² , some of the hydrogen atoms of the above-exemplified groups are alkyl groups having about 1 to 4 carbon atoms such as methyl group, ethyl group, i-propyl group or t-butyl group; methoxy. Alkoxy group having about 1 to 4 carbon atoms such as group or ethoxy group; trifluoromethyl group; trifluoromethyloxy group; cyano group; nitro group; substituted with halogen atom such as fluorine atom, chlorine atom or bromine atom. May be good.

As A ¹ and A ^2, it is particularly preferable that both of them are groups of the same type because the compound (C) can be easily produced. Further, A ¹ and A ² are preferably a monocyclic 1,4-phenylene group or a 1,4-cyclohexylene group, and in particular, a 1,4-phenylene group because the compound (C) can be easily produced. Is preferable.

It is preferable that B ¹ and B ² are divalent groups of the same type because the compound (C) can be easily produced. Since even more easier preparation of the compound (C), ^{B 1} and of ^{B 2, B 1} and ^{B 2} are attached only ^{A 1} and ^{A 2} are each _{independently,} -CH 2 -CH ₂ -, -CO-O-, -O-C (= O)-, -C (= O) -NH-, -NH-C (= O)-, _{-O-CH 2-} , -CH _2-O -Or a single bond is preferable, and -C (= O) -O- or -OC (= O)-is preferable because it exhibits particularly high liquid crystallinity. Of B ¹ and ^{B 2,} the ^{B 1} and ^{B 2} is bound to ^{E 1} or ^{E 2,} each independently, -O -, - C (= O) -O -, - O-C (= O )-, -OC (= O) -O-, -C (= O) -NH-, -NH-C (= O)-or more preferably a single bond.

From the viewpoint of liquid crystallinity, k and l preferably independently represent an integer of 0 to 3, and more preferably k and l are 0 to 2. The total of k and l is preferably 5 or less, and more preferably 4 or less.

The compound having a group represented by the formula (A) and a polymerizable group is more preferably a compound represented by the formula (1) (hereinafter, also referred to as a compound (1)).
P ^1- F ^1- (B ^1- A ¹ ) _k- E ^1- G ^1- D ^1- Ar-D ^2- G ^2- E ^2- (A ^2- B ² ) _l- F ^2- P ² ( 1)
[In formula (1), Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and π electrons contained in the aromatic ring in the Ar group. The number Nπ of is 12 or more and 22 or less.
D ¹ and ^{D 2,} independently of one ^{another, * 1 -C (= O)} -O -, * 4 -O-C (= O) -, * 4 -C (= S) -O -, * 4 - ^{O-C (= S) -} , * 4 -CR 1 R 2 -, * 4 -CR 1 R 2 -CR 3 R 4 -, * 4 -O-CR 1 R 2 -, * 4 -CR 1 R 2 ^{-O -, * 4 -CR 1 R} 2 -O-CR 3 R 4 -, * 4 -CR 1 R 2 -O-C (= O) -, * 4 -O-C (= O) -CR 1 ^{R 2 -, * 4 -CR 1} R 2 -O-C (= O) -R 3 R 4 -, * 4 -CR 1 R 2 -C (= O) -O-CR 3 R 4 -, * 4 Represents −NR ¹ −CR ² R ³ −, * ⁴ −CR ² R ³ −NR ¹ −, * ⁴ −C (= O) −NR ¹ −, or * ⁴ −NR ¹ −C (= O) − (* ⁴ represents the position where it binds to Ar).
R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² represent divalent alicyclic hydrocarbon groups independently of each other. The hydrogen atom contained in the alicyclic hydrocarbon group may be a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. It may be substituted, and the methylene group contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-.
E ¹ , E ² , B ¹ and B ² are independent of each other, * ^5- CR ⁵ R ^6- , * ^5- CH _2- CH _2- , * ^5- O-, * ^5- S-, * ⁵ -C (= O) -O-, * ^5- OC (= O)-, * ^5- OC (= O) -O-, * ^5- C (= S) -O-, * ⁵ -OC (= S)-, * ^5- OC (= S) -O-, * ^5- C (= O) -NR ^5- , * ^5- NR ^5- C (= O)-, _{^{* 5 -O-CH 2 -,}} * 5 -CH 2 -O -, * 5 -S-CH 2 -, * 5 -CH 2 -S- or represents a single bond ^{(* 5, G 1,} G ² , Represents a position that binds to ^{A 1} or A ^2).
R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro. It may be substituted with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l represent integers 0 to 3 independently of each other.
F ¹ and F ² represent an alkylene group having 1 to 12 carbon atoms independently of each other. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and the methylene group contained in the alkylene group is −O. It may be replaced with − or −C (= O) −.
P ¹ and P ² represent a hydrogen atom or a polymerizable group independently of each other. However, ^{at least one of P 1} and P ² represents a polymerizable group. ]

The compound (1) preferably satisfies the requirements represented by the formulas (2) and (3).
(Nπ-4) / 3 <k + l + 4 (2)
12 ≦ Nπ ≦ 22 (3)
[In equations (2) and (3), Nπ, k and l have the same meanings as described above. ]

^{Ar, D 1, D 2,} G 1 and examples and preferable range of ^{G 2,} respectively, ^Ar a in the compound ^(A), examples and preferable range of the D ^1, D ^{2, G a} and ^{G b} are applied.

Each Examples and preferable range of E ¹ and ^{E 2,} examples and preferable range of ^{E 1} and ^{E 2} in the compound (B) is applied.

^{A 1, A 2, B 1} , B 2, respectively examples and preferable range of k and l, application examples and preferred ranges of ^{A 1, A 2, B 1} , B 2, k and l in the compound (C) Will be done.

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that ^{at least one of P 1} and P ² represents a polymerizable group). It is preferable that both P ¹ and P ² are polymerizable groups because the film hardness of the obtained retardation layer tends to be excellent.
The polymerizable group is a substituent capable of polymerizing the compound (1), and specifically, a vinyl group, a p-stylben group, an acryloyl group, a metachloroyl group, an acryloyloxy group, a metachloroyloxy group, and a carboxyl group. Examples thereof include a group, a methylcarbonyl group, a hydroxyl group, an amide group, an alkylamino group having 1 to 4 carbon atoms, an amino group, an epoxy group, an oxetanyl group, an aldehyde group, an isocyanate group or a thioisocyanate group. Further, the polymerizable group may contain a group represented as ^{B 1} and B ² in order to bond ^{E 1} and E ^{2 to the above-exemplified group.} For example, a radically polymerizable or cationically polymerizable group suitable for photopolymerization is preferable, and an acryloyl group or a metachloroyl group is preferable, and an acryloyl group is more preferable because it is easy to handle and easy to produce. It is more preferable that both P ¹ and P ² are polymerizable groups because the film hardness of the obtained retardation layer tends to be excellent.

−D ¹ −G ¹ −E ¹ − (A ¹ −B ¹ ) _k −F ¹ −P ¹ , −D ² −G ² −E ² − (A ² −B ² ) _l −F ² −P ² Specific examples include groups represented by the formulas (R-1) to (R-134). * Indicates the connection position with Ar. Further, n in the formulas (R-1) to (R-134) represents an integer of 2 to 12.

Further, examples of the compound (1) include compounds (i) to (xxxiv). In the table, R1 is −D ¹ −G ¹ −E ¹ − (A ¹ −B ¹ ) _k −F ¹ −P ¹ , and R2 is −D ² −G ² −E ² − (A ² −B. ² ) Represents _l −F ² −P ^2.

In the compound (xxx) and the compound (xxxi), either one of R1 and R2 is any of (R-57) to (R-120).
In Table 1 above, the compound (xvii) is a compound in which the group represented by Ar is a group represented by the formula (ar-78) and a compound in which the group represented by Ar is a group represented by the formula (ar-79). Alternatively, it means that the group represented by Ar is either a mixture of a compound which is a group represented by the formula (ar-78) and a compound which is a group represented by the formula (ar-79).
In Table 2 above, the compound (xxx) is a compound in which the group represented by Ar is a group represented by the formula (ar-120) and a compound in which the group represented by Ar is a group represented by the formula (ar-121). Alternatively, it means that the group represented by Ar is either a mixture of a compound which is a group represented by the formula (ar-120) and a compound which is a group represented by the formula (ar-121), and the compound (xxxxi). ) Is a compound in which the group represented by Ar is a group represented by the formula (ar-122), a compound in which the group represented by Ar is a group represented by the formula (ar-123), or a group represented by Ar is a formula. It means that it is one of a mixture of the compound which is the group represented by (ar-122) and the compound which is the group represented by the formula (ar-123).

Further, the compound (i), the compound (ii), the compound (iv), the compound (v), the compound (vi), the compound (ix), the compound (x), the compound (xi), the compound (xvi), and the compound in Table 1 are shown. (Xviii), compound (xix), compound (xx), compound (xxi), compound (xxiii), compound (xxx), compound (xxv), compound (xxvi), compound (xxvii), compound (xxviii), compound Typical structural formulas of (xxx), compound (xxxiii) and compound (xxxiv) are represented by formula (i-1), formula (ii-1), formula (iv-1), formula (v-1), respectively. Formula (v-2), formula (v-3), formula (v-4), formula (v-5), formula (v-6), formula (v'-1), formula (vi-1), Formula (ix-1), formula (x-1), formula (xi-1), formula (xvi-1), formula (xviii-1), formula (xx-1), formula (xx-1), formula (Xxi-1), formula (xxiii-1), formula (xxiv-1), formula (xxv-1), formula (xxvi-1), formula (xxvii-1), formula (xxviii-1), formula (xxvi-1), formula (xxvi-1) It is illustrated in the formula (xxx-1), the formula (xxxiii-1), and the formula (xxxiv-1). A plurality of different types of compounds (1) may be used in the retardation layer.

Further, as the compound (1), for example, the following are exemplified. However, n1 and n2 in the equation independently represent integers of 2 to 12.

The retardation layer is formed by using a liquid crystal material. By using the liquid crystal material, the difference between nx and ny of the obtained retardation layer can be remarkably increased as compared with the non-liquid crystal material. As a result, the thickness of the retardation layer for obtaining a desired in-plane retardation value can be remarkably reduced, which can contribute to the thinning of the obtained optical laminate, liquid crystal panel, and liquid crystal display device. .. Further, in the production of the optical laminate, the lamination by the roll-to-roll method becomes possible, and the production process can be remarkably shortened. Details will be described later.

The liquid crystal material preferably has a nematic phase (nematic liquid crystal). The liquid crystal expression mechanism of the liquid crystal material may be lyotropic or thermotropic. The orientation state of the liquid crystal material is preferably a homogeneous orientation. As the liquid crystal material, for example, a liquid crystal polymer or a liquid crystal monomer can be used. The liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.

The retardation layer is preferably a cured layer of a liquid crystal material. The liquid crystal material is preferably a polymerizable liquid crystal compound and / or a crosslinkable liquid crystal compound. This is because the orientation state of the liquid crystal material can be fixed by polymerizing or cross-linking the liquid crystal material. After the liquid crystal materials are oriented, for example, if the liquid crystal materials are polymerized or crosslinked with each other, the oriented state can be fixed. Here, a polymer is formed by polymerization, and a three-dimensional network structure is formed by cross-linking, but these are non-liquid crystal. Therefore, the formed retardation layer does not undergo a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change peculiar to a liquid crystal compound, for example. As a result, the retardation layer can be an extremely stable layer that is not affected by temperature changes.

In order for the layer formed by polymerizing the polymerizable liquid crystal compound to exhibit an in-plane retardation, the polymerizable liquid crystal compound may be oriented in a suitable direction.
When the polymerizable liquid crystal compound is rod-shaped, an in-plane phase difference is exhibited by orienting the optical axis of the polymerizable liquid crystal compound horizontally with respect to the plane of the substrate. In this case, the optical axis direction and the slow phase axis direction coincide with each other.
When the polymerizable liquid crystal compound has a disk shape, an in-plane phase difference is exhibited by orienting the optical axis of the polymerizable liquid crystal compound horizontally with respect to the plane of the substrate. In this case, the optical axis and the slow phase axis are orthogonal to each other. The orientation state of the polymerizable liquid crystal compound can be adjusted by the combination of the alignment film and the polymerizable liquid crystal compound.

The retardation layer preferably has optical characteristics represented by the formulas (α) and (β).
Re (450) / Re (550) ≤ 1.00 (α)
1.00 ≤ Re (650) / Re (550) (β)
[In the formulas (α) and (β), Re (450) represents the in-plane retardation value at a wavelength of 450 nm, Re (550) represents the in-plane retardation value at a wavelength of 550 nm, and Re (650) represents the wavelength. Represents an in-plane retardation value at 650 nm. ]
By using the cured layer of the polymerizable liquid crystal compound described below, a retardation layer having optical characteristics represented by the formulas (α) and (β) can be obtained. In order to exhibit such optical characteristics, it is also useful to use two or more retardation layers.

The polymerizable liquid crystal compound is a compound having a polymerizable group and having liquid crystallinity. The polymerizable group means a group involved in the polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in the polymerization reaction by an active radical, an acid, or the like generated from a photopolymerization initiator described later. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxylanyl group, an oxetanyl group and the like. Of these, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystal property of the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a riotropic liquid crystal, and when the thermotropic liquid crystal is classified by order, it may be a nematic liquid crystal or a smectic liquid crystal.

Compound (A) may be a polymerizable liquid crystal compound. When the compound (A) is a polymerizable liquid crystal compound, it is preferably the compound (1) from the viewpoint of optical properties.

The method for producing the compound (A) will be described below by taking the compound (1) as an example.
Compound (1) is a known organic synthesis reaction (for example, condensation reaction, esterification reaction, Williamson reaction, etc.) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. Ulmann reaction, Wittich reaction, Schiff base formation reaction, benzylation reaction, Soto reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Heartwig reaction, Friedelcraft reaction, Heck reaction, Aldor reaction, etc. ) Can be produced by appropriately combining them according to their structure.

For example, in ^{the case of the compound (1) in which D 1} and D ² are * ^4- OC (= O)-, the formula (1-1):

（式中、Ａｒは上記と同一の意味を表わす。）
で示される化合物と式（１−２）：

(In the formula, Ar has the same meaning as above.)
Compound represented by and formula (1-2):

（式中、Ｒ^１、Ｒ^２、Ｇ^１、Ｅ^１、Ａ^１、Ｂ^１、Ｆ^１、Ｐ^１及びｋは上記と同一の意味を表わす。）
で示される化合物とを反応させることにより、式（１−３）：

(In the formula, R ¹ , R ² , G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k have the same meanings as above.)
By reacting with the compound represented by, the formula (1-3):

（式中、Ａｒ、Ｒ^１、Ｒ^２、Ｇ^１、Ｅ^１、Ａ^１、Ｂ^１、Ｆ^１、Ｐ^１及びｋは上記と同一の意味を表わす。）
で示される化合物を得、得られた式（１−３）で示される化合物と式（１−４）：

(In the formula, Ar, R ¹ , R ² , G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k have the same meanings as above.)
The compound represented by the above was obtained, and the obtained compound represented by the formula (1-3) and the formula (1-4):

（式中、Ｒ^１、Ｒ^２、Ｇ^２、Ｅ^２、Ａ^２、Ｂ^２、Ｆ^２、Ｐ^２及びｌは上記と同一の意味を表わす。）
で示される化合物とを反応させることにより製造することができる。

(In the formula, R ¹ , R ² , G ² , E ² , A ² , B ² , F ² , P ² and l have the same meanings as above.)
It can be produced by reacting with the compound represented by.

The reaction between the compound represented by the formula (1-1) and the compound represented by the formula (1-2) and the reaction between the compound represented by the formula (1-3) and the compound represented by the formula (1-4) are , It is preferable to carry out in the presence of an ester agent.

Examples of the esterifying agent (condensing agent) include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimidemeth-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-. Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (partially water-soluble carbodiimide: commercially available as WSC), bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropylcarbodiimide, Carbodiimides such as 2-methyl-6-nitrobenzoic acid anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1 (4-nitrobenzenesulfonyl) -1H-1, 2,4-triazole, 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazole-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N , N', N'-tetramethyl-O- (N-succinimidyl) uronium tetrafluoroborate, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbodibenzoxis succinimide, O -(6-Chlorobenzotriazole-1-yl) -N, N, N', N'-tetramethyluronium tetrafluoroborate, O- (6-chlorobenzotriazole-1-yl) -N, N, N ', N'-Tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazoli Examples thereof include nium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium paraltoluenesulfonate, 2-fluoro-1-methylpyridinium paraltoluenesulfonate, and trichloroacetic acid pentachlorophenyl ester. In terms of reactivity, cost, and usable solvent, the condensing agents include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. , Bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropylcarbodiimide, 2,2'-carbonylbis-1H-imidazole are more preferred.

The retardation layer can be formed from a composition containing compound (A) (hereinafter, also referred to as composition (A)). The content of the compound (A) in the composition (A) may be, for example, 10% by mass or more and less than 100% by mass, preferably 40% by mass or more and 99, based on the total solid content of the composition (A). It is mass% or less, more preferably 60% by mass or more and 98% by mass or less, and further preferably 80% by mass or more and 97% by mass or less. The total amount of solids in the composition (A) refers to the total amount of components excluding all solvent components.

The composition (A) can further contain a liquid crystal compound (however, different from the compound (A)).

Specific examples of liquid crystal compounds include Chapter 3 of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published on October 30, 2000 by Maruzen Co., Ltd.), 3.2 non-chiral rod-shaped liquid crystal molecules with molecular structure and liquid crystal properties, 3 .3 Among the compounds described in the chiral rod-shaped liquid crystal molecule, a compound having a polymerizable group can be mentioned.
As the liquid crystal compound, a plurality of different compounds may be used in combination.

Examples of the liquid crystal compound include a compound represented by the formula (4) (hereinafter, may be referred to as “compound (4)”) and the like.

^{P 11 -E 11 - (B 11} -A 11) t -B 12 -G (4)
Wherein (4), A ¹¹ is an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, include aromatic hydrocarbon group, alicyclic hydrocarbon group and the heterocyclic group The hydrogen atom may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a nitro group, a nitrile group or a mercapto group. ..
B ¹¹ and ^{B 12} are each ^{independently, -CR 14 R 15 -, -} C≡C -, - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O)-, -C (= O) -O-, -O-C (= O)-, -OC (= O) -O-, -C (= S)-, -C (= S) -O -, - O-C ( = S) -, - CH = N -, - N = CH -, - N = N -, - C (= O) -NR 14 -, - NR 14 -C (= ^{_{O) -, - OCH 2 -}} , - OCF 2 -, - NR 14 -, - CH 2 O -, - CF 2 O -, - CH = CH-C (= O) -O -, - O-C ( = O) -CH = CH- or single bond. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and even ^{if R 14 and R 15} are linked to form an alkylene group having 4 to 7 carbon atoms. Good.
E ¹¹ represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
P ¹¹ represents a polymerizable group.
G is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an alkylamino group having 1 to 13 carbon atoms, a nitrile group, and the like. It represents a nitro group or a polymerizable group bonded via an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkylene group is an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. It may be substituted with an alkoxy group or a halogen atom.
t represents an integer of 1-5. ]

In particular, the polymerizable group in the P ¹¹ and G, may be any group which can be polymerized with the compound (A), a vinyl group, vinyloxy group, p- stilbene group, an acryloyl group, an acryloyloxy group, a methacryloyl group, Metachloroyloxy group, carboxyl group, acetyl group, hydroxyl group, carbamoyl group, amino group, alkylamino group having 1 to 4 carbon atoms, epoxy group, oxetanyl group, formyl group, -N = C = O or N = C = S And so on. Among them, a radical-polymerizable group or a cationically polymerizable group is preferable in that it is suitable for photopolymerization, and an acryloyloxy group, a metachloroyloxy group or a vinyloxy group is easy in that it is easy to handle and a liquid crystal compound can be produced. Radicals are preferred.

It aromatic hydrocarbon group A ^11, the number of carbon atoms in the alicyclic hydrocarbon group and the heterocyclic group, respectively, for example, 3 to 18, preferably from 5 to 12, 5 or 6 Is particularly preferable.

Examples of the compound (4) include compounds represented by the formulas (4-1) and (4-2).

^{P 11 -E 11 - (B 11} -A 11) t1 -B 12 -E 12 -P 12 (4-1)
^{P 11 -E 11 - (B 11} -A 11) t2 -B 12 -F 11 (4-2)
[In formulas (4-1) and (4-2), P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , and B ¹² have the same meanings as above.
F ¹¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an alkylamino group having 1 to 13 carbon atoms, and a nitrile group. , Represents a nitro group.
E ¹² is synonymous with ^{E 11.}
P ¹² is synonymous with ^{P 11.}
t ¹ and t ² are synonymous with t. ]

Further, as the compounds represented by these formulas (4-1) and (4-2), they are represented by formulas (I), formulas (II), formulas (III), formulas (IV) or formulas (V). Contains compounds.

P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -A ¹⁴ -B ¹⁵ -A ¹⁵ -B ¹⁶ -E ¹² -P ¹² (I)
P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -A ¹⁴ -B ¹⁵ -E ¹² -P ¹² (II)
P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -E ¹² -P ¹² (III)
P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -F ¹¹ (IV)
P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -F ¹¹ (V)
Wherein (I) ~ formula ^{(V), A} 12 ^{~A 15 has} the same meaning as ^{A 11, B} 13 ^{~B 16 is B 11} as synonymous.

Incidentally, the formula (4-1), (4-2) a compound of formula (I), Formula (II), formula (III), in the compounds represented by formula (IV) and formula ^{(V), P 11} and by appropriately selecting the combination of E ^11, by further appropriately selecting the combination of P ¹² and E ^12, it is preferable that they are bonded through an ether bond or an ester bond.

Specific examples of the compound (4) include the following formulas (I-1) to (I-5), formulas (II-1) to (II-6), and formulas (III-1) to formulas (III-1) to (1). III-19), compounds represented by formulas (IV-1) to (IV-14), formulas (V-1) to formulas (V-5), and the like can be mentioned. However, k in the formula represents an integer of 1 to 11. These liquid crystal compounds are preferable because they are easy to synthesize and are easily available, such as on the market.

The content of the liquid crystal compound in the composition (A) can be 90 parts by mass or less with respect to 100 parts by mass in total of the liquid crystal compound and the compound (A), for example.

The composition (A) preferably further contains a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator.

Examples of the photopolymerization initiator include benzoins, benzophenones, benzyl ketals, α-hydroxyketones, α-aminoketones, iodonium salts, sulfonium salts and the like, and more specifically, Irgacure 907. , Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all manufactured by Ciba Japan Co., Ltd.), Sakeol BZ, Sakeol Z, Sakeol BEE (all manufactured by Seiko Kagaku Co., Ltd.), kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Co., Ltd.), ADEKA PTOMER SP-152 or ADEKA PTOMER SP-170 (all manufactured by ADEKA Corporation) and the like can be mentioned.

The content of the polymerization initiator in the composition (A) is, for example, 0.1 part by mass or more and 30 parts by mass or less, preferably 0, based on 100 parts by mass of the total of the liquid crystal compound and the compound (A). .5 parts by mass or more and 10 parts by mass or less. Within the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

The liquid crystal material contained in the retardation layer 12 is obtained by polymerizing the compound (A). The composition (A) can contain a solvent. The retardation layer 12 can be formed by applying the composition (A) containing a solvent as a coating liquid onto a base material and curing the composition (A) to form a cured film.

The wavelength dispersion characteristic of the retardation layer 12 can be arbitrarily determined by the content of the structural unit derived from the compound (A). Increasing the content of the structural unit derived from the compound (A) among the structural units in the retardation layer results in a flatter wavelength dispersion characteristic, and further, an inverse wavelength dispersion characteristic that satisfies the formulas (α) and (β). Is shown.

Specifically, with respect to the composition containing the liquid crystal compound and the compound (A), about 2 to 5 kinds of compositions having different contents of structural units derived from the compound (A) are prepared, and each composition will be described later. As described above, the retardation value of the retardation layer obtained by producing the retardation layer having the same film thickness is obtained, and from the result, the content of the structural unit derived from the compound (A) and the retardation value of the optical film are obtained. The content of the structural unit derived from the compound (A) required to give a desired retardation value to the retardation layer at the above film thickness may be determined from the obtained correlation.

The retardation layer 12 preferably contains an ultraviolet blocking agent. The retardation layer 12 can be arranged so as to be on the visual side of the polarizer. Therefore, the retardation layer 12 tends to be easily affected by ultraviolet rays. Since the retardation layer 12 contains an ultraviolet blocking agent, the influence of ultraviolet rays tends to be easily suppressed. Specifically, the deterioration of the retardation layer 12 can be suppressed, and the optical characteristics of the retardation layer 12 can be kept good. Further, it is possible to suppress the influence of ultraviolet rays on each member (for example, the polarizer 11) arranged inside the retardation layer 12 (on the liquid crystal cell side).

Examples of the ultraviolet blocking agent include an organic ultraviolet absorber and an inorganic ultraviolet scattering agent. Examples of the organic ultraviolet absorber include benzotriazole-based, benzophenone-based, and triazine-based. Examples of the inorganic ultraviolet scattering agent include titanium oxide, zinc oxide, cerium oxide and the like. These can be used alone or in combination of two or more. Preferably, it is an organic UV absorber. By using an organic ultraviolet absorber, the thickness of the retardation layer 12 can be achieved, and the transparency of the retardation layer 12 can be excellent.

The thickness of the retardation layer 12 can be set to best function as a λ / 4 plate. In other words, the thickness can be set to obtain the desired optical properties. The thickness of the retardation layer 12 is preferably 0.5 μm or more and 10 μm or less, more preferably 0.5 μm or more and 8 μm or less, and particularly preferably 0.5 μm or more and 5 μm or less.

(Hard coat layer)
The hard coat layer 13 is preferably a cured layer of any suitable UV curable resin. Examples of the ultraviolet curable resin include acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, epoxy resin and the like. The hard coat layer may optionally contain any suitable additive. Typical examples of the additive include inorganic fine particles and / or organic fine particles. By including fine particles, for example, an appropriate refractive index can be provided.

The thickness of the hard coat layer can be set to any suitable value. It is preferably 50 μm or less, more preferably 1 μm or more and 50 μm or less, still more preferably 1 μm or more and 40 μm or less, and particularly preferably 1 μm or more and 30 μm or less. The pencil hardness of the hard coat layer is preferably 2H or more, more preferably 3H or more and 8H or less.

The hard coat layer is typically provided to an optical laminate in a state in which a substrate is previously subjected to a hard coat treatment to form a laminate. The base material may be any suitable resin film. Typical examples of the resin film include polyester-based resin, cellulose-based resin, polycarbonate-based resin, (meth) acrylic-based resin, and the like. The base material may function as the first protective film. In addition, in this specification, "(meth) acrylic type" means an acrylic type and / or a methacryl type.

(Protective film)
As the first protective film 14 and the second protective film 15, any suitable film capable of functioning as a protective layer for the polarizer may be adopted. Specific examples of the material that is the main component of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based. , Polystyrene-based, polycarbonate-based, polyolefin-based, (meth) acrylic-based, acetate-based transparent resins and the like. Further, thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, and silicone, or ultraviolet curable resins can also be mentioned. In addition to this, for example, glassy polymers such as siloxane-based polymers can also be mentioned. Further, the polymer film described in JP-A-2001-343529 (WO01 / 37007) can also be used. As the material of this film, for example, 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 a nitrile group in the side chain. Can be used, and examples thereof include a resin composition having an alternating copolymer composed of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer. The polymer film can be, for example, an extruded product of the above resin composition.

The cellulosic resin may be an organic acid ester or mixed organic acid ester of cellulosic, in which some or all of the hydrogen atoms at the hydroxyl group of cellulose are substituted with an acetyl group, a propionyl group and / or a butyryl group. For example, those composed of acetic acid ester of cellulose, propionic acid ester, butyric acid ester, mixed ester thereof and the like can be mentioned. Of these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferable.

Cyclic polyolefin-based resins are obtained by polymerizing cyclic olefin monomers such as norbornene and other cyclopentadiene derivatives in the presence of a catalyst. It is preferable to use such a cyclic polyolefin resin because it is easy to obtain a protective film having a predetermined retardation value described later.

As the cyclic polyolefin resin, for example, ring-opening metathesis polymerization is carried out from cyclopentadiene and olefins or (meth) acrylic acid or esters thereof using norbornene or a derivative thereof obtained by a deal alder reaction as a monomer, followed by ring-opening metathesis polymerization. Resin obtained by hydrogenation; ring-opening metathesis polymerization is carried out using tetracyclododecene or a derivative thereof obtained by a deal alder reaction from dicyclopentadiene and olefins or (meth) acrylic acid or esters thereof as a monomer. Resin obtained by subsequent hydrogenation; at least two monomers selected from norbornene, tetracyclododecene, derivatives thereof, and other cyclic olefin monomers are similarly ring-opened metathesis copolymerized and subsequently obtained by hydrogenation. Resins: Resins obtained by addition-copolymerizing a cyclic olefin such as norbornene, tetracyclododecene, or a derivative thereof with an aromatic compound having a chain olefin and / or a vinyl group.

The acrylic resin is typically a polymer containing 50% by mass or more of methyl methacrylate units. The content of the methyl methacrylate unit is preferably 70% by mass or more, and may be 100% by mass.

As the (meth) acrylic resin, Tg (glass transition temperature) is preferably 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. This is because it can be excellent in durability. The upper limit of Tg of the (meth) acrylic resin is not particularly limited, but is preferably 170 ° C. or lower from the viewpoint of moldability and the like.

As the (meth) acrylic resin, any suitable (meth) acrylic resin can be adopted as long as the effects of the present invention are not impaired. For example, poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymers, methyl methacrylate- (meth) acrylic acid ester copolymers, methyl methacrylate-acrylic acid esters. -(Meta) acrylate copolymer, (meth) methyl acrylate-styrene copolymer (MS resin, etc.), polymer having alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer) , Methyl methacrylate- (meth) norbornyl acrylate copolymer, etc.). Preferred are C1-6 alkyl poly (meth) acrylates such as methyl poly (meth) acrylate. More preferably, a methyl methacrylate-based resin containing methyl methacrylate as a main component (50% by mass or more and 100% by mass or less, preferably 70% by mass or more and 100% by mass or less) can be mentioned.

It is preferable that the first protective film and the second protective film are transparent and have no coloring. The retardation value Rth [590] in the thickness direction of the first protective film and the second protective film is preferably −90 nm to +90 nm, more preferably −80 nm to +80 nm, and further preferably −70 nm to +70 nm.

The side of the first protective film 14 opposite to the polarizer 11 may be subjected to a hard coat treatment, an antireflection treatment, a sticking prevention treatment, an antiglare treatment, or the like, if necessary.

As the thickness of the first protective film and the second protective film, any appropriate thickness can be adopted. It is preferably 200 μm or less, more preferably 1 μm or more and 200 μm or less, still more preferably 3 μm or more and 150 μm or less, and particularly preferably 5 μm or more and 100 μm or less.

The first protective film and the second protective film may contain additives, if necessary. Examples of the additive include a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a lightproofing agent, an impact resistance improving agent, an antistatic agent and the like. The amount added is preferably kept within a range that does not adversely affect the optical physical characteristics.

<Manufacturing method of optical laminate>
The polarizer 11 and the retardation layer 12 are typically laminated via an adhesive. Specific examples of the adhesive include polyvinyl alcohol-based adhesives. As shown in FIG. 1, when the first protective film 14 is provided between the polarizer 11 and the retardation layer 12, it is preferable that the polarizer 11 and the first protective film 14 are laminated in advance and polarized light. A plate is produced, and the retardation layer 12 is laminated on the first protective film 14. The first protective film 14 and the retardation layer 12 are typically laminated with an adhesive. Specific examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives. The polarizer 11 and the first protective film 14 are typically laminated via an adhesive. Examples of the adhesive include polyvinyl alcohol-based adhesives.

In one embodiment, the retardation layer 12 is formed on the substrate in advance to form a laminated body, and the retardation layer 12 is formed by the polarizer 11, the first protective film 14, or another layer (for example, hard). It is laminated on the coat layer 13). In this case, the retardation layer 12 formed on the substrate is transferred from the substrate to the polarizer 11, the first protective film 14, or other layers.

Any suitable method can be adopted as the method for forming the retardation layer. For example, a method in which the surface of the substrate is oriented and a coating liquid containing the liquid crystal material is applied to the surface to form a retardation layer can be mentioned. When the above-mentioned composition (A) preferably contains a solvent, the composition (A) can be used as the coating liquid. As the orientation treatment, any appropriate orientation treatment can be adopted. Specific examples thereof include mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment. Specific examples of the mechanical orientation treatment include a rubbing treatment and a stretching treatment. Specific examples of the physical orientation treatment include magnetic field orientation treatment and electric field orientation treatment. Specific examples of the chemical alignment treatment include an orthorhombic deposition method and a photoalignment treatment. A rubbing process is preferable. The alignment treatment may be applied directly to the surface of the substrate, or an arbitrary suitable alignment film (typically, a silane coupling agent layer, a polyvinyl alcohol layer or a polyimide layer) is formed on the substrate and applied to the alignment film. You may. When the rubbing treatment is applied, it is preferably applied directly to the surface of the substrate.

The orientation direction of the orientation treatment can be set according to the desired angle θ. By performing the orientation treatment, the liquid crystal material can be oriented according to the orientation direction of the substrate, so that the slow axis of the formed retardation layer is substantially the same as the orientation direction of the substrate. Therefore, for example, when the polarizer 11 (long shape) has an absorption axis in the longitudinal direction thereof, the orientation process is performed in the direction of an angle θ with respect to the longitudinal direction of the substrate (long shape). The details will be described later, but by forming the retardation layer 12 in this way, the polarizer 11 (polarizing plate) and the retardation layer 12 can be continuously laminated by a roll-to-roll method. As a result, the manufacturing process can be significantly shortened as compared with the method for manufacturing an optical laminate including a retardation layer made of a stretched film. According to the manufacturing method of the present invention in which the polarizer 11 (polarizing plate) and the retardation layer 12 can be continuously laminated by a roll-to-roll method, the retardation layer as in the manufacturing method using a stretched film as the retardation layer. The polarizer and the retardation layer can be laminated without performing the film stretching step or the film cutting step in the forming step. Further, it is possible to manufacture an optical laminate having a thickness smaller than that of an optical laminate including a retardation layer made of a stretched film.

The coating liquid containing the liquid crystal material can be typically obtained by dissolving or dispersing the liquid crystal material in a solvent. As the solvent, any suitable solvent can be adopted depending on the type of liquid crystal material and the like. Specific examples include halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, methylene chloride, trichloroethylene, tetrachloroethylene, chlorobenzene and orthodichlorobenzene; phenol, p-chlorophenol, o-chlorophenol, m. -Phenols such as cresol, o-cresol, p-cresol; aromatic hydrocarbons such as benzene, toluene, xylene, mecitylene, methoxybenzene, 1,2-dimethoxybenzene; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone , Cyclohexanone, cyclopentanone, 2-pyrrolidone, N-methyl-2-pyrrolidone and other ketone solvents; ethyl acetate, butyl acetate, propyl acetate and other ester solvents; t-butyl alcohol, glycerin, ethylene glycol, triethylene Alcohol-based solvents such as glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol; amide-based solvents such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile and butyronitrile System solvent; Ether solvent such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane; or carbon disulfide, ethyl cellosolve, butyl cellosolve, ethyl celloacetate acetate and the like can be mentioned. Preferred are toluene, xylene, mesitylene, MEK, methyl isobutyl ketone, cyclohexanone, ethyl cellosolve, butyl cellosolve, ethyl acetate, butyl acetate, propyl acetate and ethyl celloacetate acetate. These solvents may be used alone or in combination of two or more.

The content of the liquid crystal material in the coating liquid can be appropriately set according to the type of the liquid crystal material, the thickness of the target layer, and the like. The content of the liquid crystal material in the coating liquid is preferably 5% by mass or more and 50% by mass or less, more preferably 7% by mass or more and 40% by mass or less, and most preferably 9% by mass or more and 30% by mass or less.

The coating liquid may further contain any suitable additive, if desired. Specific examples of the additive include a polymerization initiator and a cross-linking agent. These are particularly preferably used when a liquid crystal monomer is used as the liquid crystal material. Specific examples of the polymerization initiator include benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), and the like, in addition to the above-mentioned photopolymerization initiator. Specific examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate cross-linking agents. These can be used alone or in combination of two or more.

Specific examples of the additive include an antiaging agent, a denaturing agent, a surfactant, a photosensitizer, a polymerization inhibitor, a dye, a pigment, a discoloration inhibitor, a leveling agent, an ultraviolet blocking agent and the like. These can be used alone or in combination of two or more. Examples of the antiaging agent include phenolic compounds, amine compounds, organic sulfur compounds, and phosphine compounds. Examples of the denaturing agent include glycols, silicones and alcohols. The surfactant is used, for example, to smooth the surface of the retardation layer, and specific examples thereof include silicone-based, acrylic-based, and fluorine-based surfactants. The photosensitizer is used to increase the sensitivity of the polymerization of the liquid crystal compound and the compound (A), and specific examples thereof include xanthones such as xanthones and thioxanthones, and anthracenes having substituents such as anthracene and alkyl ethers. , Photosensitizers such as phenothiazine or rubrene. The polymerization inhibitor is used to improve the stability of the obtained retardation layer by controlling the polymerization of the liquid crystal compound or the compound (A), and specifically, a substituent such as hydroquinone or an alkyl ether is used. Hydroquinones, catechols having substituents such as alkyl ethers such as butyl catechol, pyrogallols, radical supplements such as 2,2,6,6-tetramethyl-1-piperidinyloxy radicals, thiophenols, Examples thereof include polymerization inhibitors such as β-naphthylamines and β-naphthols. The leveling agent is used to smooth the surface of the retardation layer, and in the process of manufacturing the retardation layer, it controls the fluidity of the mixed solution containing the compound (A), and the liquid crystal compound or the compound (A). ) Can be polymerized to adjust the crosslink density of the retardation layer. Specifically, additives for radiation-curable paints (manufactured by Big Chemie Japan: BYK-352, BYK-353, BYK-361N), paint additives (manufactured by Toray Dow Corning Co., Ltd .: SH28PA, DC11PA, ST80PA), paints Additives (manufactured by Shin-Etsu Chemical Co., Ltd .: KP321, KP323, X22-161A, KF6001) or fluorine-based additives (manufactured by Dainippon Ink and Chemicals Co., Ltd .: F-445, F-470, F-479) The belling agent can be raised. The UV blocking agent is as described above.

The content of the UV blocking agent can be set as appropriate. Preferably, it is 0.01 part by mass or more and 0.1 part by mass or less, and more preferably 0.03 part by mass or more and 0.07 part by mass or less with respect to 100 parts by mass of the liquid crystal material.

As the coating method of the coating liquid, any appropriate method can be adopted. Specific examples include a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, an extrusion method, a curtain coating method, and a spray coating method. The coating amount of the coating liquid can be appropriately set according to the concentration of the coating liquid, the thickness of the target layer, and the like. For example, when the liquid crystal material concentration of the coating liquid is 20% by mass, the coating amount is preferably 0.03 ml or more and 0.17 ml or less, more preferably 0.05 ml, per ^{area (100 cm 2) of the transparent protective film.} It is 0.15 ml or more, most preferably 0.08 ml or more and 0.12 ml or less.

Next, the liquid crystal material is oriented according to the orientation direction of the substrate surface. The orientation of the liquid crystal material is performed by treating the liquid crystal material to be used at a temperature at which the liquid crystal material exhibits a liquid crystal phase. By performing such temperature treatment, the liquid crystal material takes a liquid crystal state, and the liquid crystal material is oriented according to the orientation direction of the substrate surface. As a result, birefringence is generated in the layer (coating layer) formed by coating, and a retardation layer is formed.

The temperature of the above temperature treatment can be appropriately determined depending on the type of the liquid crystal material. It is preferably 40 to 120 ° C, more preferably 50 to 100 ° C, and most preferably 60 to 90 ° C. The treatment time of the temperature treatment is preferably 30 seconds or longer, more preferably 1 minute or longer, particularly preferably 2 minutes or longer, and most preferably 4 minutes or longer. If the processing time is less than 30 seconds, the liquid crystal material may not sufficiently take a liquid crystal state. On the other hand, the treatment time is preferably 10 minutes or less, more preferably 8 minutes or less, and most preferably 7 minutes or less. If the treatment time exceeds 10 minutes, the additive may sublimate.

When a liquid crystal monomer is used as the liquid crystal material, it is preferable that the coating layer is further subjected to a polymerization treatment or a cross-linking treatment. By performing the polymerization treatment, the liquid crystal monomer is polymerized, and the liquid crystal monomer is fixed as a repeating unit of the polymer molecule. By performing the cross-linking treatment, the liquid crystal monomer forms a three-dimensional network structure, and the liquid crystal monomer is fixed as a part of the cross-linked structure. As a result, the orientation of the liquid crystal material is fixed. The polymer or three-dimensional network structure formed by polymerizing or cross-linking the liquid crystal monomer is "non-liquid crystal". Therefore, the formed retardation layer does not undergo a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change peculiar to a liquid crystal molecule, for example. The specific procedure of the polymerization treatment or the cross-linking treatment can be appropriately selected depending on the type of the polymerization initiator and the cross-linking agent used. For example, when a photopolymerization initiator or a photocrosslinking agent is used, light irradiation may be performed, and when an ultraviolet polymerization initiator or an ultraviolet crosslinking agent is used, ultraviolet irradiation may be performed. The irradiation time, irradiation intensity, total irradiation amount, etc. of light or ultraviolet rays can be appropriately set according to the type of liquid crystal material, the type of substrate, the type of orientation treatment, the desired characteristics of the retardation layer, and the like.

The method for producing an optical laminate of the present invention can include a step of laminating a polarizer and a retardation layer by a roll-to-roll method. FIG. 3 shows one step in an example of the method for manufacturing an optical laminate of the present invention. As shown in FIG. 3A, a laminate of the polarizing plate 110 [the first protective film 14 (not shown), the polarizer 11 (not shown), and the second protective film 15 (not shown). ] And the laminated body 120 formed by coating the retardation layer 12 on the substrate 12a are sent out in the direction of the arrow and bonded together with the above adhesive (not shown) in a state where the longitudinal directions of the laminates are aligned. In this way, by continuously laminating the retardation layer and the polarizer (polarizing plate) while transporting them (roll-to-roll), the manufacturing process can be significantly shortened. Further, it is possible to prevent foreign matter from being mixed between the retardation layer and the polarizing element (polarizing plate), and it is possible to provide an optical laminate having excellent visibility. Finally, the substrate 12a is peeled off from the laminated body 130 as shown in FIG. 3B. In FIG. 3A, reference numerals 111 and 112 indicate rolls for winding the films forming the respective layers, and reference numeral 113 indicates guide rolls for bonding the films to each other.

<LCD panel>
The liquid crystal panel of the present invention includes the above optical laminate. FIG. 4 is a schematic cross-sectional view of a liquid crystal panel according to a preferred embodiment of the present invention. The liquid crystal panel 100 includes a liquid crystal cell 20, an optical laminate 10 arranged on the visual side of the liquid crystal cell 20, and a polarizer 11'arranged on the backlight side of the liquid crystal cell 20. The optical laminate 10 is arranged so that the retardation layer 12 is on the visual side of the polarizer 11. Although not shown, the liquid crystal panel 100 may include any other suitable retardation layer located between the liquid crystal cell 20 and the optical laminate 10 and / or between the liquid crystal cell and the polarizer 11'. .. Further, the liquid crystal panel 100 has a third protective film 14'arranged on the backlight side of the polarizer 11'and / or a fourth protective film 15 arranged between the liquid crystal cell 20 and the polarizer 11'. 'Can be equipped. As the third protective film 14', the same film as the first protective film 14 can be adopted. As the fourth protective film 15', a film similar to the above-mentioned second protective film can be adopted.

Any suitable adhesive layer or adhesive layer may be provided between the members constituting the liquid crystal panel of the present invention.

(Liquid crystal cell)
As shown in FIG. 5, the liquid crystal cell 20 can have a pair of substrates 21, 21'and a liquid crystal layer 22 as a display medium sandwiched between the substrates 21, 21'. One substrate (color filter substrate) is provided with a color filter and a black matrix (neither of which is shown). On the other substrate (active matrix substrate), a switching element (typically a TFT) (not shown) that controls the electro-optical characteristics of the liquid crystal and a scanning line (not shown) that gives a gate signal to the switching element are used. A signal line (not shown) for giving a source signal and a pixel electrode (not shown) are provided. The color filter may be provided on the active matrix substrate side. The distance (cell gap) between the substrates 21 and 21'is controlled by a spacer (not shown). An alignment film (not shown) made of polyimide, for example, is provided on the side of the substrates 21 and 21'in contact with the liquid crystal layer 22.

As the drive mode of the liquid crystal cell 20, any appropriate drive mode can be adopted. Specific examples of the drive mode include STN (Super Twisted Nematic) mode, TN (Twisted Nematic) mode, IPS (In-Plane Switching) mode, VA (Vertical Aligned) mode, OCB (Optical Birefringence), and OCB (Optical Birefringence). Examples include the Aligned Nematic mode, the ASM (Axially Symmetrically Aligned Microcell) mode, and the ECB (Electrically Controlled Birefringence) mode.

<Liquid crystal display device>
The liquid crystal display device of the present invention includes the above liquid crystal panel. The liquid crystal panel is arranged so that the optical laminate is on the visual side.

Hereinafter, the present invention will be described in more detail with reference to Examples. Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.

(1) Measurement of thickness The thickness was measured using a digital micrometer "MH-15M" manufactured by Nikon Corporation.

(2) Measurement of in-plane retardation and thickness direction retardation Using a phase difference meter "KOBRA (registered trademark) -WPR" manufactured by Oji Measuring Instruments Co., Ltd. based on the parallel Nicol rotation method, at a temperature of 23 ° C. In-plane retardation and thickness direction retardation at each wavelength were measured.

(Making a polarizer)
A polyvinyl alcohol film having a thickness of 30 μm (average degree of polymerization of about 2400, saponification degree of 99.9 mol% or more) was uniaxially stretched about 4 times by dry stretching, and further uniaxially stretched to pure water at 40 ° C. while maintaining a tense state. After soaking for 40 seconds, it was immersed in an aqueous solution having a mass ratio of iodine / potassium iodide / water of 0.052 / 5.7 / 100 at 28 ° C. for 30 seconds for dyeing. Then, it was immersed in an aqueous solution having a mass ratio of potassium iodide / boric acid / water of 11.0 / 6.2 / 100 at 70 ° C. for 120 seconds. Subsequently, after washing with pure water at 8 ° C. for 15 seconds, while holding at a tension of 300 N, the iodine was adsorbed and oriented on the polyvinyl alcohol film by drying at 60 ° C. for 50 seconds and then at 75 ° C. for 20 seconds. An absorption type polarizer having a thickness of 12 μm was obtained.

(Preparation of coating liquid A)
Compound (v-1) is 30% by mass, Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. is 3% by mass as a photopolymerizable initiator, BYK361N manufactured by Big Chemy Japan is 1% by mass as a leveling agent, and benzotriazole. A coating solution (mixed solution) having a composition of 3% by mass of the ultraviolet absorber and 63% by mass of chloroform as a solvent was used as the coating solution A. The mass% of each component means the mass% when the coating liquid is 100% by mass. The same applies thereafter.

(Preparation of coating liquid B)
Compound (iv-1) was 9% by mass, Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. was 0.3% by mass as a photopolymerizable initiator, and BYK361N manufactured by Big Chemie Japan was used as a leveling agent. A coating solution (mixed solution) having a composition of 1% by mass, 0.3% by mass of the benzotriazole-based ultraviolet absorber and 90.3% by mass of chloroform as a solvent was used as the coating solution B.

(Preparation of coating liquid C)
Compound (v'-1) was 9% by mass, Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. was 0.3% by mass as a photopolymerizable initiator, and BYK361N manufactured by Big Chemie Japan was 0 as a leveling agent. A coating solution (mixed solution) having a composition of 1% by mass, 0.3% by mass of the benzotriazole-based ultraviolet absorber and 90.3% by mass of chloroform as a solvent was used as the coating solution C.

(Preparation of coating liquid D)
Compound (v-1) was 10% by mass, Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. was 0.3% by mass as a photopolymerizable initiator, and BYK361N manufactured by Big Chemie Japan was used as a leveling agent. A coating solution (mixed solution) having a composition of 1% by mass, 0.3% by mass of the benzotriazole-based ultraviolet absorber and 89.3% by mass of chloroform as a solvent was used as the coating solution D.

(Preparation of coating liquid E)
Compound (x-1) was 15% by mass, Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. was 0.45% by mass as a photopolymerizable initiator, and BYK361N manufactured by Big Chemie Japan was used as a leveling agent. A coating solution (mixed solution) having a composition of 02% by mass, 0.45% by mass of the benzotriazole-based ultraviolet absorber, and 84.08% by mass of cyclopentanone as the solvent was used as the coating solution E.

(Preparation of coating liquid F)
20% by mass of compound (v'-1), 0.6% by mass of Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. as a photopolymerizable initiator, and 0% of BYK361N manufactured by Big Chemie Japan as a leveling agent. A coating solution (mixed solution) having a composition of .2% by mass, 0.6% by mass of the benzotriazole-based ultraviolet absorber, and 78.6% by mass of chloroform as a solvent was used as the coating solution F.

(Preparation of coating liquid G)
Compound (xx-1) was 15% by mass, Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. was 0.45% by mass as a photopolymerizable initiator, and BYK361N manufactured by Big Chemie Japan was used as a leveling agent. A coating solution (mixed solution) having a composition of 02% by mass, 0.45% by mass of a benzotriazole-based ultraviolet absorber, and 84.08% by mass of cyclopentanone as a solvent was used as the coating solution G.

(Preparation of coating liquid H)
Compound (v-5) was 15% by mass, Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. was 0.3% by mass as a photopolymerizable initiator, and BYK361N manufactured by Big Chemie Japan was used as a leveling agent. A coating solution (mixed solution) having a composition of 1% by mass, 0.3% by mass of the benzotriazole-based ultraviolet absorber and 84.3% by mass of chloroform as a solvent was used as the coating solution H.

(Preparation of coating liquid I)
19.8% by mass of a polymerizable liquid crystal compound having the following structure (BASF, trade name Palocolor LC242) and a photopolymerization initiator (Ciba Speciality Chemicals, trade name Irgacure 907, benzotriazole) for the polymerizable liquid crystal compound. A coating solution I was prepared by dissolving 0.99% by mass (containing 1% of the ultraviolet absorber) in 79.21% by mass of toluene. This polymerizable liquid crystal compound showed a nematic liquid crystal phase.

<Example 1>
(Preparation of retardation layer A)
After forming a polyvinyl alcohol film (thickness 0.1 μm) on the surface of the substrate (TAC film, thickness 40 μm), the surface of the polyvinyl alcohol film is rubbed in a direction of 45 ° with respect to the longitudinal direction of the substrate using a rubbing cloth. To prepare an oriented substrate.

Next, the coating liquid A was applied to the surface of the oriented substrate obtained above with a bar coater, dried at 80 ° C. for 1 minute, and then further dried at 210 ° C. for 1 minute. The obtained unpolymerized film was cooled to 190 ° C. and irradiated with ultraviolet rays of ^{1200 mJ / cm 2 while keeping the temperature at the same temperature to obtain a retardation layer A.} When the film thickness of the obtained retardation layer A was measured with a laser microscope, the film thickness was 2.43 μm. When the retardation value was measured, Re (590) = 124.7 nm, and the orientation angle was 45 ° with respect to the longitudinal direction of the substrate. Moreover, when the phase difference values of the wavelength 450 nm and the wavelength 650 nm were measured, it was Re (450) / Re (550) = 0.848 and Re (650) / Re (550) = 1.033.

(Formation of hard coat layer)
By adding 0.5% by mass of a leveling agent to an acrylic resin raw material (manufactured by Dainippon Ink Co., Ltd., trade name: GRANDIC PC1071) and further diluting with ethyl acetate so that the solid content concentration becomes 50% by mass. A coating solution for forming a hard coat layer was prepared. The leveling agent is a copolymer obtained by copolymerizing with a molar ratio of dimethylsiloxane: hydroxypropylsiloxane: 6-isocyanatehexyl isocyanuric acid: aliphatic polyester = 6.3: 1.0: 2.2: 1.0. Is.
Next, the obtained coating solution was applied to the surface of a TAC film (manufactured by Konica Minolta, trade name: KC4UY-TAC, thickness 40 μm) with a bar coater, and then heated at 100 ° C. for 1 minute to form a coating film. It was dried. Then, the coating film was cured by irradiating with an ultraviolet ray having an integrated light intensity of 300 mJ / cm ^{2 with a metal halide lamp to form a hard coat layer (thickness 3 μm).}

(Preparation of optical laminate)
The retardation layer A obtained above was laminated on the TAC film side of the TAC film on which the hard coat layer was formed via an acrylic adhesive (thickness 5 μm), and the substrate was peeled off.

Then, the polarizer obtained above was laminated on the surface of the retardation layer via a polyvinyl alcohol-based adhesive (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Z200, thickness 200 nm). At this time, the layers were laminated so that the angle θ formed by the absorption axis of the polarizer and the slow axis of the retardation layer was 45 °. After that, a TAC film (manufactured by Konica Minolta, trade name: KC4UY-TAC, thickness 40 μm) was laminated on the surface of the polarizer via a polyvinyl alcohol-based adhesive (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Z200, thickness 200 nm). Further, an acrylic pressure-sensitive adhesive (thickness 20 μm) was laminated.
The thickness of the optical laminate thus obtained was 122 μm.

<Example 2>
(Preparation of retardation layer B)
After forming a polyvinyl alcohol film (thickness 0.1 μm) on the surface of the substrate (TAC film, thickness 40 μm), the surface of the polyvinyl alcohol film is rubbed in a direction of 45 ° with respect to the longitudinal direction of the substrate using a rubbing cloth. To prepare an oriented substrate.

Next, the coating liquid B was applied to the surface of the oriented substrate obtained above with a bar coater, dried at 80 ° C. for 1 minute, and then further heated to 160 ° C. and dried. ^{The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ / cm 2} while being kept warm at the same temperature to obtain a retardation layer B. When the film thickness of the obtained retardation layer B was measured with a laser microscope, the film thickness was 2.27 μm. When the retardation value was measured, Re (590) = 151.9 nm, and the orientation angle was 45 ° with respect to the longitudinal direction of the substrate. Moreover, when the phase difference values of the wavelength 450 nm and the wavelength 650 nm were measured, it was Re (450) / Re (550) = 0.988 and Re (650) / Re (550) = 1.031.

An optical laminate was produced in the same manner as in Example 1 except that the retardation layer B was used. The thickness of the optical laminate thus obtained was 122 μm.

<Example 3>
(Preparation of retardation layer C)
After forming a polyvinyl alcohol film (thickness 0.1 μm) on the surface of the substrate (TAC film, thickness 40 μm), the surface of the polyvinyl alcohol film is rubbed in a direction of 45 ° with respect to the longitudinal direction of the substrate using a rubbing cloth. To prepare an oriented substrate.

Next, the coating liquid C was applied to the surface of the oriented substrate obtained above with a bar coater, dried at 80 ° C. for 1 minute, and then further heated to 160 ° C. and dried. ^{The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ / cm 2} while being kept warm at the same temperature to obtain a retardation layer C. When the film thickness of the obtained retardation layer C was measured with a laser microscope, the film thickness was 2.10 μm. When the retardation value was measured, Re (590) = 141.3 nm, and the orientation angle was 45 ° with respect to the longitudinal direction of the substrate. Moreover, when the phase difference values of the wavelength 450 nm and the wavelength 650 nm were measured, it was Re (450) / Re (550) = 0.953 and Re (650) / Re (550) = 1.006.

An optical laminate was produced in the same manner as in Example 1 except that the retardation layer C was used. The thickness of the optical laminate thus obtained was 122 μm.

<Example 4>
(Preparation of retardation layer D)
After forming a polyvinyl alcohol film (thickness 0.1 μm) on the surface of the substrate (TAC film, thickness 40 μm), the surface of the polyvinyl alcohol film is rubbed in a direction of 45 ° with respect to the longitudinal direction of the substrate using a rubbing cloth. To prepare an oriented substrate.

Next, the coating liquid D was applied to the surface of the oriented substrate obtained above with a bar coater, dried at 80 ° C. for 1 minute, and then further dried at 210 ° C. for 1 minute. The obtained unpolymerized film was cooled to 190 ° C. and irradiated with ultraviolet rays of ^{1200 mJ / cm 2 while keeping the temperature at the same temperature to obtain a retardation layer D.} When the film thickness of the obtained retardation layer D was measured with a laser microscope, the film thickness was 2.41 μm. When the retardation value was measured, Re (590) = 124.7 nm, and the orientation angle was 45 ° with respect to the longitudinal direction of the substrate. Moreover, when the phase difference values of the wavelength 450 nm and the wavelength 650 nm were measured, it was Re (450) / Re (550) = 0.848 and Re (650) / Re (550) = 1.033.

An optical laminate was produced in the same manner as in Example 1 except that the retardation layer D was used. The thickness of the optical laminate thus obtained was 122 μm.

<Example 5>
(Preparation of retardation layer E)
After forming a polyvinyl alcohol film (thickness 0.1 μm) on the surface of the substrate (TAC film, thickness 40 μm), the surface of the polyvinyl alcohol film is rubbed in a direction of 45 ° with respect to the longitudinal direction of the substrate using a rubbing cloth. To prepare an oriented substrate.

Next, the coating liquid E was applied to the surface of the oriented substrate obtained above with a bar coater, dried at 80 ° C. for 1 minute, and then further heated to 160 ° C. and dried. The obtained unpolymerized film was irradiated with ultraviolet rays of ^{1200 mJ / cm 2} while being kept warm at the same temperature to obtain a retardation layer E. When the film thickness of the obtained retardation layer E was measured with a laser microscope, the film thickness was 1.48 μm. When the retardation value was measured, Re (590) = 118.1 nm, and the orientation angle was 45 ° with respect to the longitudinal direction of the substrate. Moreover, when the phase difference values of the wavelength 450 nm and the wavelength 650 nm were measured, it was Re (450) / Re (550) = 0.979 and Re (650) / Re (550) = 1.003.

An optical laminate was produced in the same manner as in Example 1 except that the retardation layer E was used. The thickness of the optical laminate thus obtained was 121 μm.

<Example 6>
(Preparation of retardation layer F)
After forming a polyvinyl alcohol film (thickness 0.1 μm) on the surface of the substrate (TAC film, thickness 40 μm), the surface of the polyvinyl alcohol film is rubbed in a direction of 45 ° with respect to the longitudinal direction of the substrate using a rubbing cloth. To prepare an oriented substrate.

Next, the coating liquid F was applied to the surface of the oriented substrate obtained above with a bar coater, dried at 80 ° C. for 1 minute, and then further heated to 160 ° C. and dried. ^{The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ / cm 2} while being kept warm at the same temperature to obtain a retardation layer F. When the film thickness of the obtained retardation layer F was measured with a laser microscope, the film thickness was 2.05 μm. When the retardation value was measured, Re (590) = 141.3 nm, and the orientation angle was 45 ° with respect to the longitudinal direction of the substrate. Moreover, when the phase difference values of the wavelength 450 nm and the wavelength 650 nm were measured, it was Re (450) / Re (550) = 0.953 and Re (650) / Re (550) = 1.006.

An optical laminate was produced in the same manner as in Example 1 except that the retardation layer F was used. The thickness of the optical laminate thus obtained was 122 μm.

<Example 7>
(Preparation of retardation layer G)
After forming a polyvinyl alcohol film (thickness 0.1 μm) on the surface of the substrate (TAC film, thickness 40 μm), the surface of the polyvinyl alcohol film is rubbed in a direction of 45 ° with respect to the longitudinal direction of the substrate using a rubbing cloth. To prepare an oriented substrate.

Next, the coating liquid G was applied to the surface of the oriented substrate obtained above with a bar coater, dried at 80 ° C. for 1 minute, and then further heated to 160 ° C. and dried. The obtained unpolymerized film was irradiated with ultraviolet rays of ^{1200 mJ / cm 2} while being kept warm at the same temperature to obtain a retardation layer G. When the film thickness of the obtained retardation layer G was measured with a laser microscope, the film thickness was 1.50 μm. When the retardation value was measured, Re (590) = 117.8 nm, and the orientation angle was 45 ° with respect to the longitudinal direction of the substrate. Moreover, when the phase difference values of the wavelength 450 nm and the wavelength 650 nm were measured, it was Re (450) / Re (550) = 0.973 and Re (650) / Re (550) = 1.004.

An optical laminate was produced in the same manner as in Example 1 except that the retardation layer G was used. The thickness of the optical laminate thus obtained was 121 μm.

<Example 8>
(Preparation of retardation layer H)
After forming a polyvinyl alcohol film (thickness 0.1 μm) on the surface of the substrate (TAC film, thickness 40 μm), the surface of the polyvinyl alcohol film is rubbed in a direction of 45 ° with respect to the longitudinal direction of the substrate using a rubbing cloth. To prepare an oriented substrate.

Next, the coating liquid H was applied to the surface of the oriented substrate obtained above with a bar coater, dried at 80 ° C. for 1 minute, and then further dried at 210 ° C. for 1 minute. The obtained unpolymerized film was cooled to 190 ° C. and irradiated with ultraviolet rays of ^{1200 mJ / cm 2 while keeping the temperature at the same temperature to obtain a retardation layer H.} When the film thickness of the obtained retardation layer H was measured with a laser microscope, the film thickness was 1.45 μm. When the retardation value was measured, Re (590) = 117.2 nm, and the orientation angle was 45 ° with respect to the longitudinal direction of the substrate. Moreover, when the phase difference values of the wavelength 450 nm and the wavelength 650 nm were measured, it was Re (450) / Re (550) = 0.934 and Re (650) / Re (550) = 1.013.

An optical laminate was produced in the same manner as in Example 1 except that the retardation layer H was used. The thickness of the optical laminate thus obtained was 121 μm.

<Comparative example 1>
(Preparation of retardation layer I)
After forming a polyvinyl alcohol film (thickness 0.1 μm) on the surface of the substrate (TAC film, thickness 40 μm), the surface of the polyvinyl alcohol film is rubbed in a direction of 45 ° with respect to the longitudinal direction of the substrate using a rubbing cloth. To prepare an oriented substrate.

Next, the surface of the alignment substrate obtained above is coated with the coating liquid I by a bar coater in the same manner as in Example 1, dried at 100 ° C. for 1 minute, and then subjected to ultraviolet rays using a high-pressure mercury lamp. (Integrated light intensity at a wavelength of 365 nm under a nitrogen atmosphere: 1200 mJ / cm ² ) to obtain a retardation layer I. When the film thickness of the obtained retardation layer I was measured with a laser microscope, the film thickness was 972 nm. When the retardation value was measured, Re (590) = 135 nm, and the orientation angle was 45 ° with respect to the longitudinal direction of the substrate. Moreover, when the phase difference values of the wavelength 450 nm and the wavelength 650 nm were measured, it was Re (450) / Re (550) = 1.07 and Re (650) / Re (550) = 0.98.

An optical laminate was produced in the same manner as in Example 1 except that the retardation layer I was used. The thickness of the optical laminate thus obtained was 121 μm.

<Comparative example 2>
(Preparation of optical laminate)
An optical laminate was obtained in the same manner as in Comparative Example 1 except that the following retardation film was used instead of the retardation layer I.
The thickness of the optical laminate thus obtained was 153 μm.
(Phase difference film)
By uniaxially stretching a long norbornene-based resin film (manufactured by Zeon Corporation, trade name Zeonor, thickness 40 μm, photoelastic coefficient 3.10 × ^10-12 m ² / N) at 140 ° C. by 1.52 times. A long film was made. The obtained film was cut into a predetermined size. The thickness of this film was 33 μm, and the in-plane retardation value Re (590) was 140 nm. Further, Re (450) / Re (550) = 1.00 and Re (650) / Re (550) = 1.00.

<Evaluation of color change>
With reference to FIGS. 6 (a) and 6 (b), which schematically show a color change measurement system, first, the optical laminate and the glass plate obtained in Examples and Comparative Examples are combined with an adhesive layer. A sample for evaluation was obtained by laminating through the above. Next, this evaluation sample was set in a viewing angle characteristic measurement evaluation device [trade name "EZContrast" manufactured by ELDIM). At this time, the evaluation samples were arranged in the order of the light source (cold cathode ray), the glass plate, the polarizer, the retardation layer, and the light receiving unit (camera). Further, a polarizing film assuming polarized sunglasses is formed between the optical film of the optical laminate and the light receiving portion, and the absorption axis of the polarizer of the optical laminate and the absorption axis of the polarizing film assuming polarized sunglasses form a cross Nicol. Arranged to do. As a polarizing film assuming polarized sunglasses, a polyvinyl alcohol-based adhesive (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Z200, thickness 200 nm) is used as a polarizing element prepared on one side of a thickness of 40 μm (Konica Minolta Co., Ltd .: KC4UY). The one pasted together was used.

With the above viewing angle characteristic measurement and evaluation device, azimuth angles of 0, 45, 90, 135, 180, 225, 270, 315 ° at polar angles 0, 10, 20, 30, 40, 50, 60, 70, 80 ° The chromaticity (total 9 × 8 = 72 points) was measured as the (x, y) value of the CIE-XYZ color system. Then, the difference Δx between the maximum value and the minimum value of x and the difference Δy between the maximum value and the minimum value of y for these 72 points are obtained, and from the total value Δx + Δy of them, through the polarized sunglasses according to the following evaluation criteria. The change in color when the screen was viewed from various directions (azimuth and polar angle) was evaluated.
A: Δx + Δy is less than 0.065 B: Δx + Δy is 0.065 or more and less than 0.100 C: Δx + Δy is 0.100 or more.

The color change of the optical laminate produced in Example 1 was evaluated. The maximum value of x was 0.3325, the minimum value of x was 0.3004, and Δx = 0.0321. The maximum value of y was 0.3689, the minimum value of y was 0.3402, and Δy = 0.0287. The total value Δx + Δy was 0.0608.

The color change of the optical laminate produced in Example 2 was evaluated. The maximum value of x was 0.3281, the minimum value of x was 0.2951, and Δx = 0.0330. The maximum value of y was 0.3570, the minimum value of y was 0.3255, and Δy = 0.0315. The total value Δx + Δy was 0.0645.

The color change of the optical laminate produced in Example 3 was evaluated. The maximum value of x was 0.3219, the minimum value of x was 0.2882, and Δx = 0.0337. The maximum value of y was 0.3596, the minimum value of y was 0.3264, and Δy = 0.0332. The total value Δx + Δy was 0.0669.

The color change of the optical laminate produced in Example 4 was evaluated. The maximum value of x was 0.3335, the minimum value of x was 0.3014, and Δx = 0.0321. The maximum value of y was 0.3649, the minimum value of y was 0.3364, and Δy = 0.0285. The total value Δx + Δy was 0.0606.

The color change of the optical laminate produced in Example 5 was evaluated. The maximum value of x was 0.3332, the minimum value of x was 0.2975, and Δx = 0.0357. The maximum value of y was 0.3654, the minimum value of y was 0.3278, and Δy = 0.0376. The total value Δx + Δy was 0.0697.

The color change of the optical laminate produced in Example 6 was evaluated. The maximum value of x was 0.3242, the minimum value of x was 0.2910, and Δx = 0.0332. The maximum value of y was 0.3586, the minimum value of y was 0.3238, and Δy = 0.0348. The total value Δx + Δy was 0.0680.

The color change of the optical laminate produced in Example 7 was evaluated. The maximum value of x was 0.3362, the minimum value of x was 0.3014, and Δx = 0.0348. The maximum value of y was 0.3631, the minimum value of y was 0.3274, and Δy = 0.0357. The total value Δx + Δy was 0.0705.

The color change of the optical laminate produced in Example 8 was evaluated. The maximum value of x was 0.3242, the minimum value of x was 0.2926, and Δx = 0.0316. The maximum value of y was 0.3570, the minimum value of y was 0.3255, and Δy = 0.0315. The total value Δx + Δy was 0.0631.

The color change of the optical laminate produced in Comparative Example 1 was evaluated. The maximum value of x was 0.3299, the minimum value of x was 0.2748, and Δx = 0.0551. The maximum value of y was 0.3722, the minimum value of y was 0.3064, and Δy = 0.0658. The total value Δx + Δy was 0.1209.

The color change of the optical laminate produced in Comparative Example 2 was evaluated. The maximum value of x was 0.3219, the minimum value of x was 0.2882, and Δx = 0.0337. The maximum value of y was 0.3596, the minimum value of y was 0.3264, and Δy = 0.0332. The total value Δx + Δy was 0.0669.

Table 2 summarizes the evaluation results of the color change in the above Examples and Comparative Examples together with the phase difference values.

The optical laminates of Examples 1 to 8 of the present invention had a smaller change in color than the optical laminate of Comparative Example 1, and were significantly thinner than the optical laminate of Comparative Example 2. Moreover, a film stretching step is not required for producing the retardation layer. It is understood that the optical laminate of the present invention contributes to the thinning of the liquid crystal panel and the liquid crystal display device, and can suppress the color change while simplifying the manufacturing process.

10,10'optical laminate, 11,11' polarizer, 12 retardation layer, 12a substrate, 13 hard coat layer, 14 first protective film, 14'third protective film, 15 second protective film, 15'fourth protective film, 20 liquid crystal cells, 21 and 21' substrates, 22 liquid crystal layers, 100 liquid crystal panels, 110 polarizing plates, 111,112 rolls, 113 guide rolls, 120,130 laminates.

Claims (18)

An optical laminate used in a liquid crystal display device and arranged on the visual side of a liquid crystal cell.
A polarizer and a retardation layer arranged on one side of the polarizer are provided.
The in-plane retardation value Re (590) at a wavelength of 590 nm of the retardation layer is 90 nm or more and 190 nm or less.
The angle θ formed by the absorption axis of the polarizer and the slow axis of the retardation layer is 5 ° or more and 85 ° or less.
An optical laminate in which the retardation layer contains a polymer of a compound having a group represented by the formula (A) and a polymerizable group.
−G ^a −D ^a −Ar ^a −D ^b −G ^b − (A)
[In the formula (A), the Ar ^a group represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and is included in the aromatic ring in the ^{Ar a group.} The number of π electrons to be generated Nπ _a is 12 or more.
D ^a and D ^b are single-bonded independently of each other, * ^1- C (= O) -O-, * ¹ -OC (= O)-, * ^1- C (= S) -O-, ^{* 1 -O-C (= S} ) -, * 1 -CR 1 R 2 -, * 1 -CR 1 R 2 -CR 3 R 4 -, * 1 -O-CR 1 R 2 -, * 1 -CR ^{1 R 2 -O -, * 1} -CR 1 R 2 -O-CR 3 R 4 -, * 1 -CR 1 R 2 -O-C (= O) -, * 1 -O-C (= O) ^{-CR 1 R 2 -, * 1} -CR 1 R 2 -O-C (= O) -CR 3 R 4 -, * 1 -CR 1 R 2 -C (= O) -O-CR 3 R 4 - , * ^1- NR ^1- CR ² R ^3- , * ^1- CR ¹ R ^2- NR ^3- , * ^1- C (= O) -NR ^1- , or * ^1- NR ^1- C (= O) Represents − (* ¹ represents the position of binding to Ar ^a).
R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ^a and G ^b independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. ] The optical laminate according to claim 1, wherein the compound having a group represented by the formula (A) and a polymerizable group is a compound having a group represented by the formula (B) and a polymerizable group.
−E ¹ −G ^a −D ^a −Ar ^a −D ^b −G ^b −E ^2- (B)
Wherein ^{(B), Ar a, D} a, D b, G a and ^{G b} have the definitions in the formula (A).
E ¹ and E ² are independent of each other, * ^2- CR ⁵ R ^6- , * ^2- CH _2- CH _2- , * ² -O-, * ^2- S-, * ^2- C (= O). -O-, * ^2- OC (= O)-, * ^2- OC (= O) -O-, * ^2- C (= S) -O-, * ^2- OC (=) S)-, * ^2- OC (= S) -O-, * ^2- C (= O) -NR ^5- , * ^2- NR ^5- C (= O)-, * ^2- O-CH _{^{2 -, * 2 -CH 2 -O}} -, * 2 -S-CH 2 -, * 2 -CH 2 -S- or a single bond ^{(* 2} represents a position bonded to ^{G a} or ^{G b} ).
R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. ] The optical laminate according to claim 2, wherein the compound having a group represented by the formula (B) and a polymerizable group is a compound having a group represented by the formula (C) and a polymerizable group.
-(B ^1- A ¹ ) _k- E ^1- G ^a- D ^a- Ar ^a- D ^b- G ^b- E ^2- (A ^2- B ² ) _l- (C)
Wherein ^{(C), Ar a, D} a, D b, G a, G b, E 1 and ^{E 2} have the definitions in the formula (B).
B ¹ and B ² are independent of each other, * ^3- CR ⁵ R ^6- , * ^3- CH _2- CH _2- , * ³ -O-, * ^3- S-, * ^3- C (= O). -O-, * ^3- OC (= O)-, * ^3- OC (= O) -O-, * ^3- C (= S) -O-, * ^3- OC (=) S)-, * ^3- OC (= S) -O-, * ^3- C (= O) -NR ^5- , * ^3- NR ^5- C (= O)-, * ^3- O-CH _{^{2 -, * 3 -CH 2 -O}} -, * 3 -S-CH 2 -, * 3 represents a _-CH 2 -S- or a single bond ^{(* 3} represents a position bonded to the ^{a 1} or ^{a 2} ).
R ⁵ and R ⁶ have the same meanings as above.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. Alternatively, it may be substituted with a nitro group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom. k and l represent integers 0 to 3 independently of each other. ] The optical laminate according to any one of claims 1 to 3, wherein _{the number Nπ a of} π electrons contained in the aromatic ring in the ^{Ar a group is 13 or more and 22 or less.} The Ar ^a group comprises at least one aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthroline ring, a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring and a benzothiazole ring. The optical laminate according to any one of claims 1 to 4, which is a divalent group having. Wherein ^{G a} and ^{G b} are 1,4-a cyclohexylene group, the optical laminate according to any one of claims 1 to 5. The optical laminate according to claim 1, wherein the compound having the group represented by the formula (A) and the polymerizable group is the compound represented by the formula (1).
P ^1- F ^1- (B ^1- A ¹ ) _k- E ^1- G ^1- D ^1- Ar-D ^2- G ^2- E ^2- (A ^2- B ² ) _l- F ^2- P ² ( 1)
[In formula (1), Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and π electrons contained in the aromatic ring in the Ar group. The number Nπ of is 12 or more and 22 or less.
D ¹ and ^{D 2,} independently of one ^{another, * 4 -C (= O)} -O -, * 4 -O-C (= O) -, * 4 -C (= S) -O -, * 4 - ^{O-C (= S) -} , * 4 -CR 1 R 2 -, * 4 -CR 1 R 2 -CR 3 R 4 -, * 4 -O-CR 1 R 2 -, * 4 -CR 1 R 2 ^{-O -, * 4 -CR 1 R} 2 -O-CR 3 R 4 -, * 4 -CR 1 R 2 -O-C (= O) -, * 4 -O-C (= O) -CR 1 ^{R 2 -, * 4 -CR 1} R 2 -O-C (= O) -R 3 R 4 -, * 4 -CR 1 R 2 -C (= O) -O-CR 3 R 4 -, * 4 Represents −NR ¹ −CR ² R ³ −, * ⁴ −CR ² R ³ −NR ¹ −, * ⁴ −C (= O) −NR ¹ −, or * ⁴ −NR ¹ −C (= O) − (* ⁴ represents the position where it binds to Ar).
R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² represent divalent alicyclic hydrocarbon groups independently of each other. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or −NH−.
E ¹ , E ² , B ¹ and B ² are independent of each other, * ^5- CR ⁵ R ^6- , * ^5- CH _2- CH _2- , * ^5- O-, * ^5- S-, * ⁵ -C (= O) -O-, * ^5- OC (= O)-, * ^5- OC (= O) -O-, * ^5- C (= S) -O-, * ⁵ -OC (= S)-, * ^5- OC (= S) -O-, * ^5- C (= O) -NR ^5- , * ^5- NR ^5- C (= O)-, _{^{* 5 -O-CH 2 -,}} * 5 -CH 2 -O -, * 5 -S-CH 2 -, * 5 -CH 2 -S- or represents a single bond ^{(* 5, G 1,} G ² , Represents a position that binds to ^{A 1} or A ^2).
R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or the like. It may be substituted with a nitro group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l represent integers 0 to 3 independently of each other.
F ¹ and F ² represent an alkylene group having 1 to 12 carbon atoms independently of each other. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and the methylene group contained in the alkylene group is −O. It may be replaced with − or −C (= O) −.
P ¹ and P ² represent a hydrogen atom or a polymerizable group independently of each other. However, ^{at least one of P 1} and P ² represents a polymerizable group. ] The optical laminate according to any one of claims 1 to 7, wherein the retardation layer has optical characteristics represented by the formulas (α) and (β).
Re (450) / Re (550) ≤ 1.00 (α)
1.00 ≤ Re (650) / Re (550) (β)
[In the formulas (α) and (β), Re (450) represents the in-plane retardation value at a wavelength of 450 nm, Re (550) represents the in-plane retardation value at a wavelength of 550 nm, and Re (650) represents the wavelength. Represents an in-plane retardation value at 650 nm. ] The optical laminate according to any one of claims 1 to 8, wherein the optical laminate is arranged in the liquid crystal cell so that the retardation layer is on the visual side of the polarizer. The optical laminate according to any one of claims 1 to 9, further comprising a hard coat layer arranged on the opposite side of the retardation layer to the polarizer. The optical laminate according to any one of claims 1 to 10, further comprising a first protective film arranged between the polarizer and the retardation layer. The optical laminate according to any one of claims 1 to 10, further comprising a first protective film arranged on the opposite side of the retardation layer to the polarizer. The optical laminate according to any one of claims 1 to 12, wherein the angle θ is 40 ° or more and 50 ° or less. The optical laminate according to any one of claims 1 to 13, wherein the retardation layer is a cured layer of a liquid crystal material. The optical laminate according to any one of claims 1 to 14, wherein the retardation layer contains an ultraviolet blocking agent. The method for manufacturing an optical laminate according to claim 1.
A manufacturing method including a step of laminating the polarizer and the retardation layer by a roll-to-roll method. A liquid crystal panel comprising the optical laminate according to any one of claims 1 to 15. A liquid crystal display device including the liquid crystal panel according to claim 17.

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