TW201921000A - Retardation plate with optical compensation function for flexible display - Google Patents

Abstract

The present invention provides a manufacturing method for retardation plate with optical compensation function for flexible use which does not cause problems such as wrinkles and cracks even when being bended, and does not reflect outside light in a colored state even when being folded. The manufacturing method of the present invention forms a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film in this order to manufacture a retardation plate with optical compensation function for flexible display; wherein, the horizontal alignment film is formed via coating, drying, and alignment treatment steps; the horizontal alignment liquid crystal cured film is formed via coating, drying and ultraviolet irradiation steps, after forming the horizontal alignment film; further, the vertical alignment film is formed via a coating, drying step; and the vertical alignment liquid crystal cured film is formed via a coating, drying, and ultraviolet irradiation steps.

Description

Phase difference plate with optical compensation function for flexible display

The present invention relates to a retardation plate with an optical compensation function for a flexible display.

Flat panel displays such as organic EL video display devices generally have a flat video display surface. When the image display surface of a flat panel display displays or does not display an image, it remains flat.

Such a flat panel display often uses a retardation plate. For example, in an organic EL image display device, in order to prevent light reflection at the electrodes constituting the image display device, a circular polarizing plate in which a retardation plate and a polarizing plate are combined is used.

Among such retardation plates, retardation plates exhibiting reverse wavelength dispersion are suitable for use because they exhibit equal retardation performance over a wide wavelength range of visible light. As a retardation plate showing reverse wavelength dispersion, a retardation plate is known which includes a horizontally oriented liquid crystal hardened by polymerizing and curing a polymerizable liquid crystal compound showing reverse wavelength dispersion in a horizontally oriented state. membrane.

In addition, there is also a need for a retardation plate with an optical compensation function, which has a compensation function that "even when viewed from an oblique direction, it can exhibit the same optical performance as when viewed from the front direction". With regard to such a retardation plate with an optical compensation function, Patent Document 1 [Japanese Patent Application Laid-Open No. 2015-163935] proposes a polymerizable liquid crystal compound having a horizontal alignment liquid crystal cured film and a vertical alignment state. A vertical alignment liquid crystal cured film obtained by polymerization and hardening. It is also disclosed in the same document that the emphasis of the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film are laminated only through an alignment film or a protective layer. Furthermore, the same document only discloses the use of a retardation plate with an optical compensation function described in the same document for a flat panel display.

(Prior technical literature) (Patent Literature)

[Patent Document 1] Japanese Patent Laid-Open No. 2015-163935

In addition, a so-called flexible display which is a foldable display has also been developed. In flexible displays, retardation plates with optical compensation are also folded with the display.

However, if defects such as wrinkles and cracks occur during folding, when the flexible display is unfolded again to display an image, the defective portions such as wrinkles and cracks become defects and damage the displayed image. In addition, when the image is folded while the image is being displayed, The angle formed by the direction in which the user views the screen) becomes basically extremely small, so that the optical performance cannot be fully compensated, and reflection of external light in a colored state also becomes a problem.

Therefore, the object of the present invention is to develop a flexible retardation plate with an optical compensation function. Even if the retardation plate with an optical compensation function is bent, no defects such as wrinkles or cracks are generated. Also, no external light is reflected in the colored state.

In order to solve the above-mentioned problems, the present inventors devoted themselves to the results of the review and thus completed the present invention.

That is, the present invention includes the following.

[1] A method for manufacturing a retardation plate with an optical compensation function is to sequentially form a horizontal alignment film, a horizontal alignment liquid crystal hardened film, a vertical alignment film, and a vertical alignment liquid crystal cured film by the following steps. The alignment processing step forms a horizontal alignment film; the coating, drying, and ultraviolet irradiation steps form a horizontal alignment liquid crystal hardened film; further, the coating and drying steps form a vertical alignment film; and the coating, drying, and ultraviolet irradiation steps form a vertical alignment liquid crystal. Hardened film.

[2] The method for manufacturing a retardation plate with an optical compensation function according to the above [1], wherein a horizontal alignment film having a film thickness of 1.0 μm or less, a horizontal alignment liquid crystal hardened film, a vertical alignment film, and a vertical Oriented liquid crystal hardened film.

[3] The method for manufacturing a retardation plate with an optical compensation function according to the above [1] or [2], wherein a horizontal alignment film composed of a light alignment film, a horizontal alignment liquid crystal hardened film, Vertical alignment film, vertical alignment liquid crystal hardened film.

[4] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [1] to [3], wherein a level composed of a light-orientation film including a cinnamon base is sequentially formed Alignment film, horizontal alignment liquid crystal hardened film, vertical alignment film, vertical alignment liquid crystal cured film.

[5] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [1] to [4], wherein a horizontal alignment film, a horizontal alignment liquid crystal hardened film, and a film thickness of 1.0 are sequentially formed Vertical alignment film and vertical liquid crystal hardened film below μm.

[6] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [1] to [5], wherein a horizontal alignment film, a horizontal alignment liquid crystal hardened film, and a Si element are sequentially formed Vertical alignment film, vertical alignment liquid crystal hardened film.

[7] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [1] to [6], wherein a horizontal alignment film, a horizontal alignment liquid crystal hardened film, and Si / C are sequentially formed Vertically oriented film, vertically oriented liquid crystal hardened film with elements of 0.03 to 1.00.

[8] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [1] to [7], which sequentially forms a horizontal fixed film, a horizontally oriented liquid crystal hardened film, a vertically oriented film, A vertical alignment liquid crystal cured film, wherein the horizontal alignment liquid crystal cured film satisfies the following relationship (1), ReA (450) / ReA (550) <1.00 ... (1)

In the formula, ReA (λ) represents an in-plane retardation value of the horizontally aligned liquid crystal cured film at a wavelength λnm. The definition of the in-plane phase difference value ReA (λ) is as follows, ReA (λ) = (nxA (λ) -nyA (λ)) × dA

In the formula, nxA (λ) represents the principal refractive index of the horizontally oriented liquid crystal hardened film in the film plane, and is the principal refractive index at the wavelength λ (nm); nyA (λ) represents the same as nxA (λ) The refractive index in a direction orthogonal to the plane is a refractive index at a wavelength λ (nm); dA represents the film thickness of the horizontally-oriented liquid crystal cured film.

[9] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [1] to [8], which sequentially forms a horizontal alignment film, a horizontal alignment liquid crystal hardened film, a vertical alignment film, and a vertical Oriented liquid crystal cured film, wherein the vertically aligned liquid crystal cured film satisfies the following relationship (2), RthC (450) / RthC (550) <1.00 ... (2)

In the formula, RthC (λ) represents a retardation value of the vertical alignment liquid crystal cured film in the thickness direction of the wavelength λnm. The definition of the phase difference value RthC (λ) is as follows, RthC (λ) = ((nxC (λ) + nyC (λ)) / 2-nzC (λ)) × dC

In the formula, nxC (λ) represents the principal refractive index of the vertically-oriented liquid crystal hardened film in the film plane, and is the principal refractive index at the wavelength λ (nm); nyC (λ) represents the same as nxC (λ) The refractive index in the direction orthogonal to the plane is the refractive index at the wavelength λ (nm); nzC (λ) is the refractive index of the thickness direction of the vertically oriented liquid crystal cured film and is the refractive index at the wavelength λ (nm) rate; dC represents the film thickness of the vertically aligned liquid crystal cured film.

When nxC (λ) = nyC (λ), nxC (λ) may have a refractive index in any direction within the film plane.

The present invention also includes the following.

[10] A method for manufacturing a retardation plate with an optical compensation function, which sequentially forms a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film by the following steps, through the coating and drying steps Forming a vertical alignment film; forming a vertical alignment liquid crystal hardened film through the steps of coating, drying, and ultraviolet irradiation; further forming a horizontal alignment film through the steps of coating, drying, and ultraviolet irradiation; and forming a horizontal alignment liquid crystal through the steps of coating, drying, and ultraviolet irradiation Hardened film.

[11] The method for manufacturing a retardation plate with an optical compensation function according to the above [10], wherein a vertical alignment film, a vertical alignment liquid crystal hardened film, a horizontal alignment film having a thickness of 1.0 μm or less are sequentially formed, and a horizontal Oriented liquid crystal hardened film.

[12] The method for manufacturing a retardation plate with an optical compensation function according to the above [10] or [11], wherein a vertical alignment film, a vertical alignment liquid crystal hardened film, and a light alignment film are sequentially formed Horizontal alignment film, horizontal alignment liquid crystal hardened film.

[13] The method for manufacturing a phase difference plate with an optical compensation function according to any one of the above [10] to [12], wherein the vertical plates are sequentially formed A straight alignment film, a vertical alignment liquid crystal hardened film, a horizontal alignment film composed of a light alignment film containing a cinnamon bark group, and a horizontal alignment liquid crystal hardened film.

[14] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [10] to [13], wherein a vertical alignment film having a film thickness of 1.0 μm or less and a vertical alignment liquid crystal are sequentially formed Hardened film, horizontally oriented film, horizontally oriented liquid crystal hardened film.

[15] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [10] to [14], wherein a vertical alignment film containing a Si element and a vertical alignment liquid crystal hardened film are sequentially formed , Horizontal alignment film, horizontal alignment liquid crystal hardened film.

[16] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [10] to [15], wherein a horizontal alignment film, a horizontal alignment liquid crystal hardened film, and Si / C are sequentially formed Vertically oriented film, vertically oriented liquid crystal hardened film with elements of 0.03 to 1.00.

[17] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [10] to [16], which sequentially forms a vertical alignment film, a vertical alignment liquid crystal hardened film, a horizontal alignment film, and a horizontal Oriented liquid crystal cured film, wherein the horizontally aligned liquid crystal cured film satisfies the following relationship (3), ReA (450) / ReA (550) <1.00 ... (3)

In the formula, ReA (λ) represents the in-plane retardation value of the horizontally aligned liquid crystal cured film at the wavelength λnm; the definition of the in-plane retardation value ReA (λ) is as follows, ReA (λ) = (nxA (λ)- nyA (λ)) × dA

In the formula, nxA (λ) represents the principal refractive index of the horizontally-oriented liquid crystal cured film in the film plane, and is the principal refractive index at the wavelength λ (nm); nyA (λ) Is the refractive index in the direction orthogonal to nxA (λ) in the same plane, and is the refractive index at the wavelength λ (nm); dA represents the film thickness of the horizontally aligned liquid crystal hardened film.

[18] The method for manufacturing a retardation plate with an optical compensation function according to any one of the above [1] to [17], which sequentially forms a vertical alignment film, a vertical alignment liquid crystal hardened film, a horizontal alignment film, and a horizontal Oriented liquid crystal cured film, wherein the vertically aligned liquid crystal cured film satisfies the following relationship (4), RthC (450) / RthC (550) <1.00 ... (4)

In the formula, RthC (λ) represents the phase difference value of the thickness direction of the wavelength λnm of the vertically-oriented liquid crystal cured film; the definition of the phase difference value RthC (λ) is as follows, RthC (λ) = ((nxC (λ) + nyC (λ)) / 2-nzC (λ)) × dC

In the formula, nxC (λ) represents the principal refractive index of the vertically-oriented liquid crystal hardened film in the film plane, and is the principal refractive index at the wavelength λ (nm); nyC (λ) represents the same as nxC (λ) The refractive index in the direction orthogonal to the plane is the refractive index at the wavelength λ (nm); nzC (λ) is the refractive index of the thickness direction of the vertically oriented liquid crystal cured film and is the refractive index at the wavelength λ (nm) DC means the film thickness of the vertically-aligned liquid crystal cured film.

When nxC (λ) = nyC (λ), nxC (λ) may have a refractive index in any direction within the film plane.

A phase difference plate with an optical compensation function is obtained according to the manufacturing method of the present invention, and a polarizing plate is laminated on the phase difference plate, whereby an elliptical polarizing plate with an optical compensation function can be manufactured.

The elliptically polarizing plate with an optical compensation function is preferably used by incorporating an organic EL display device, for example.

The retardation plate with an optical compensation function of the present invention can suppress defects such as wrinkles or cracks generated during bending.

[Horizontal alignment liquid crystal hardened film]

The horizontally oriented liquid crystal cured film is a film having a refractive index anisotropy in a film plane, and is composed of a polymer including a polymerizable liquid crystal compound. When forming a horizontally-oriented liquid crystal cured film by coating a polymerizable liquid crystal composition on a horizontally-oriented film and polymerizing a composition containing a polymerizable liquid-crystalline compound in an aligned state by heating and / or light irradiation, It is preferable because a thin film of a horizontally-oriented liquid crystal cured film can be achieved and a wavelength dispersibility can be arbitrarily designed.

The 3-dimensional refractive index elliptical system formed by the horizontally oriented liquid crystal hardened film may have biaxiality, but it is preferable to have a uniaxiality. The horizontally-oriented liquid crystal cured film may be a horizontally-oriented liquid crystal cured film composed of a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a state of being oriented horizontally with respect to the plane of the horizontally-oriented liquid crystal cured film, or it may be a mixture A liquid crystal cured film with a hybrid orientation or an obliquely aligned liquid crystal cured film. The refractive index ellipsoid formed by the orientation of the polymerizable liquid crystal is The refractive indices nx, ny, and nz in each direction may have a relationship of nx> ny ≒ nz (referred to as a positive A plate) or nx <ny ≒ nz (referred to as a negative A plate). nx represents a principal refractive index that is parallel to the plane of the horizontally-oriented liquid crystal cured film in the refractive index ellipsoid formed by the horizontally-oriented liquid crystal cured film. ny represents the refractive index in the refractive index ellipsoid formed by the horizontally-oriented liquid crystal cured film, which is parallel to the plane of the horizontally-oriented liquid crystal cured film and orthogonal to the nx direction. nz represents the refractive index in the refractive index ellipsoid formed by the horizontally oriented liquid crystal cured film, which is perpendicular to the plane of the horizontally oriented liquid crystal cured film.

The horizontal alignment liquid crystal cured film may use either a rod-shaped polymerizable liquid crystal or a disc-shaped polymerizable liquid crystal, but a rod-shaped polymerizable liquid crystal is preferred. When the rod-shaped polymerizable liquid crystal forms a horizontally-oriented liquid crystal cured film, the horizontally-oriented liquid crystal cured film becomes a positive electrode A plate.

When the horizontally-oriented liquid crystal cured film has optical anisotropy in the film plane, it is preferable that Rel (550) of the in-plane retardation value for light having a wavelength of 550 nm satisfies the optical characteristics shown in the following formula (21). Moreover, the horizontally oriented liquid crystal cured film has Rel (450) for in-plane retardation value for light with a wavelength of 450 nm, Rel (550) for in-plane retardation value for light with a wavelength of 550 nm, and in-plane phase for light with a wavelength of 650 nm. The Rel (650) of the difference also satisfies the optical characteristics shown in the following formulae (22) and (23). It is more preferable that the horizontally-oriented liquid crystal cured film satisfies the optical characteristics represented by the following formula (21), (22), and (23).

120nm ≦ ReA (550) ≦ 170nm ... (21)

[In the formula, ReA (550) represents an in-plane retardation value (in-plane retardation) of a horizontally-oriented liquid crystal cured film with respect to light having a wavelength of 550 nm]

ReA (450) / ReA (550) ≦ 1.0 ... (22)

1.00 ≦ ReA (650) / ReA (550) ... (23)

[In the formula, ReA (450) represents the in-plane retardation value of the horizontally-oriented liquid crystal cured film for light with a wavelength of 450 nm, and ReA (550) represents the in-plane retardation of the horizontally-oriented liquid crystal cured film for light with a wavelength of 550 nm. 650) represents the in-plane retardation value of the horizontally-oriented liquid crystal cured film with respect to light having a wavelength of 650 nm].

When the in-plane retardation value ReA (550) of the horizontally oriented liquid crystal hardened film exceeds the range of the formula (21), a display using an elliptical polarizer with an optical compensation function including a retardation plate with an optical compensation function will produce a hue on the front side. The problem of turning red and blue. A more preferable range of the in-plane retardation value is 130 nm ≦ ReA (550) ≦ 160 nm. When the "ReA (450) / ReA (550)" of the horizontal alignment liquid crystal cured film exceeds 1.0, the ellipticity of the short-wavelength side of the elliptical polarizing plate provided with the horizontal alignment liquid crystal cured film is deteriorated. The ellipticity of the elliptically polarizing plate on the short-wavelength side deteriorates and becomes smaller from 1.0. When viewed from the front on the short-wavelength side, the function of the elliptically polarizing plate tends to be impaired. The "ReA (450) / ReA (550)" is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, and even more preferably 0.79 to 0.85.

The in-plane retardation value of the horizontally-oriented liquid crystal cured film can be adjusted by the thickness of the horizontally-oriented liquid crystal cured film. Since the in-plane phase difference value is determined according to the following formula (24), in order to obtain a desired in-plane phase difference value (ReA (λ): the in-plane phase of the horizontally-oriented liquid crystal cured film at a wavelength λ (nm) Difference), 3D refractive index and film thickness dA can be adjusted. The three-dimensional refractive index depends on the molecular structure and alignment state of the polymerizable liquid crystal compound described later.

ReA (λ) = (nxA (λ) -nyA (λ)) × dA ... (24)

[In the formula, the refractive index ellipsoid formed by the horizontally-oriented liquid crystal hardened film has a relationship of nxA (λ)> nyA (λ) ≒ nzA (λ), and nxA (λ) represents the wavelength of light with a wavelength of λ (nm) The main refractive index of the horizontally oriented liquid crystal hardened film plane is parallel. nyA (λ) means that in the refractive index ellipsoid formed by the horizontally oriented liquid crystal hardened film, the light with a wavelength of λ (nm) is parallel to the plane of the horizontally oriented liquid crystal hardened film and is positive with respect to the direction of the nxA (λ) Refractive index of intersection. dA represents the thickness of the horizontally aligned liquid crystal cured film. ]

The horizontally oriented liquid crystal cured film is preferably a polymer of a composition containing a polymerizable liquid crystal compound in an aligned state as described above. The polymerizable liquid crystal compound forming a horizontally oriented liquid crystal cured film is a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group. The photopolymerizable functional group refers to a group capable of participating in a polymerization reaction through living radicals and acids generated from a photopolymerization initiator. Examples of the photopolymerizable functional group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acrylfluorenyloxy group, a methacrylfluorenyloxy group, and an epoxy group. Ethyl, oxetanyl and the like. Among them, acrylfluorenyloxy, methacrylfluorenyloxy, vinyloxy, ethylene oxide, and oxetanyl are preferred, and acrylfluorenyloxy is more preferred. The liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal. The phase sequence structure may be a nematic liquid crystal or a smectic liquid crystal.

In the present invention, the polymerizable liquid crystal compound is represented by the following formula (from the viewpoint of exhibiting reverse wavelength dispersibility and satisfying the relationship of the above-mentioned formulae (21) and (22) or the following (31) and (32)) The compounds shown in I) are preferred.

In the formula (I), Ar represents a divalent aromatic group which may have a substituent. The so-called aromatic group refers to a base having a planar cyclic structure, and the number of π electrons in the ring structure is [4n + 2] according to Hückel's rule. Here, n represents an integer. When a ring structure is formed by including a hetero atom such as -N = or -S-, it also includes a case where non-covalent bond electron pairs included in these hetero atoms satisfy the Hückel rule. The divalent aromatic group is preferably one containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom.

G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent 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, or 1 to 4 carbon atoms. The carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom.

L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.

k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ≦ k + l. Here, when 2 ≦ k + 1, B ¹ and B ² , G ¹ and G ² may be the same or different from each other.

E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms. Here, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH ₂ -in the alkanediyl group may be- O-, -S-, -Si- substituted. P ¹ and P ² each independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

G ¹ and G ² are each independently a 1,4-phenylenediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, and may be optionally selected. 1,4-cyclohexanediyl substituted with at least one substituent in the group consisting of a halogen atom and an alkyl group having 1 to 4 carbons is more preferable, and 1,4-substituted with methyl is more preferable. Diphenylene, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl, particularly preferably unsubstituted 1,4-phenylenediyl, or unsubstituted Substituted 1,4-trans-cyclohexanediyl. Further, it is preferable that at least one of G ¹ and G ² existing in plural is a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ and L ² is Divalent alicyclic hydrocarbon groups are more preferred.

L ¹ and L ² are each independently a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2- , -R ^a3 COOR ^a4- , -R ^a5 OCOR ^a6- , -R ^a7 OC = OOR ^a8- , -N = N-, CR ^c = CR ^d- , or C≡C- is preferred. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d represent an alkyl group or hydrogen atom having 1 to 4 carbon atoms. L ¹ and L ² each independently represent a single bond, -OR ^a2-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a4-1} -or OCOR ^a6-1 -more preferably. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent a single bond, -CH _2- , or -CH ₂ CH _2- . L ¹ and L ² are each preferably a single bond, -O-, -CH ₂ CH _2- , -COO-, -COOCH ₂ CH _2- , or OCO-.

B ¹ and B ² are each independently a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10- , -R ^a11 COOR ^a12- , -R ^a13 OCOR ^a14- Or R ^a15 OC = OOR ^a16 -is better. Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are each preferably a single bond, -OR ^a10-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a12-1} -or OCOR ^a14-1- . Here, R ^a10-1- , R ^a12-1- , and R ^a14-1 -each independently represent any of a single bond, -CH _2- , and -CH ₂ CH _2- . B ¹ and B ² are each preferably a single bond, -O-, -CH ₂ CH _2- , -COO-, -COOCH ₂ CH _2- , -OCO-, or OCOCH ₂ CH _2- .

From the standpoint of showing reverse wavelength dispersion, k and l are preferably in the range of 2 ≦ k + l ≦ 6, and k + l = 4 is more preferred, and k = 2 and l = 2 are more preferred. good. When k = 2 and l = 2, a symmetrical structure is more preferable.

E ¹ and E ² are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.

Examples of the polymerizable group represented by P ¹ or P ² include epoxy groups, vinyl groups, vinyloxy groups, 1-chlorovinyl groups, isopropenyl groups, 4-vinylphenyl groups, allyloxy groups, Methacrylfluorenyloxy, ethylene oxide and oxetanyl. Among them, acrylfluorenyloxy, methacrylfluorenyloxy, vinyloxy, ethylene oxide, and oxetanyl are preferred, and acrylfluorenyloxy is more preferred.

Ar is preferably at least one selected from the group consisting of an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferred. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, and a pyridine. Ring, pyrimidine ring, triazole ring, triazole Ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring, Azole ring, benzo Azole ring and morpholine ring. Among them, those having a thiazole ring, a benzothiazole ring, or a benzofuran ring are more preferable, and those having a benzothiazolyl group are more preferable. When Ar contains a nitrogen atom, the nitrogen atom is preferably one having a π electron.

In the formula (I), the total number of π electrons N _π contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, 14 or more and more preferably, and 16 The above is particularly good. Furthermore, it is preferably 30 or less, more preferably 26 or less, and even more preferably 24 or less.

The aromatic group represented by Ar includes the following groups.

In the formulae (Ar-1) to (Ar-22), the * symbol represents a connecting portion, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group. , Nitro, alkylsulfinyl having 1 to 12 carbons, alkylsulfinyl having 1 to 12 carbons, carboxyl, fluoroalkyl having 1 to 12 carbons, alkoxy having 1 to 6 carbons , Alkylthio groups of 1 to 12 carbon atoms, N-alkylamino groups of 1 to 12 carbon atoms, N, N-dialkylamino groups of 2 to 12 carbon atoms, N-alkanes of 1 to 12 carbon atoms Aminosulfonyl or N, N-dialkylaminesulfonyl having 2 to 12 carbons.

Q ¹ and Q ² each independently represent ^{-CR 2 'R 3' -,} - S -, - NH-, NR 2 '-, - CO- , or O-. R ^{2 ′} and R ^{3 ′} each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

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 each independently represent a hydrogen atom, a cyano group, a methyl group, or a halogen atom, and m represents an integer of 0 to 6.

Examples of the aromatic hydrocarbon group in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthracenyl, phenanthryl, and biphenyl. Phenyl and naphthyl are used as examples. Preferably, phenyl is more preferred. Examples of the aromatic heterocyclic group include: furanyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl and the like, which contain at least one hetero atom such as a nitrogen atom, oxygen atom, sulfur atom, etc., and the carbon number is 4 to 20 As the aromatic heterocyclic group, furyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl are preferred.

Y ¹ and Y ² may each independently be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from aromatic ring assemblies. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring aggregate.

Z ⁰ , Z ¹ and Z ² are each preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms, and Z ⁰ is preferably A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group are more preferable, and Z ¹ and Z ² are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group.

Q ¹ and Q ² are preferably -NH-, -S-, -NR ^{2 '} -, -O-, and R ^2' is preferably a hydrogen atom. Among them, -S-, -O-, and -NH- are particularly preferred.

Among the formulae (Ar-1) to (Ar-22), from the viewpoint of molecular stability, the formulae (Ar-6) and (Ar-7) are preferred.

In the formulae (Ar-16) to (Ar-22), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom and Z ⁰ to which it is bonded. Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring which may have Ar. Examples thereof include a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, and a pyridine. Ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring and the like. The aromatic heterocyclic group may have a substituent. In addition, Y ¹ may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted together with the nitrogen atom and Z ⁰ to which it is bonded. Examples include: benzofuran ring, benzothiazole ring, benzo Azole ring and so on. The compound represented by the formula (I) can be produced by a method described in, for example, Japanese Patent Application Laid-Open No. 2010-31223.

The polymerizable liquid crystal compound can be used alone or in combination of two or more kinds. When two or more types are used in combination, the content of the compound represented by the formula (I) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and 80 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound. The above is even better.

A composition for forming a horizontal alignment liquid crystal cured film (hereinafter also referred to as a polymerizable liquid crystal group) used for forming a horizontal alignment liquid crystal cured film The product) may further include a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and an adhesion promoter. These additives can be used alone or in combination of two or more.

The content of the polymerizable liquid crystal compound is, for example, 70 to 99.5 parts by mass, more preferably 80 to 99 parts by mass, and even more preferably 90 to 98 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. When the content is within the above range, the orientation of the horizontally aligned liquid crystal cured film tends to be high. Here, the solid content means the total amount of the components after the solvent is removed from the composition.

The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound, and more preferably a solvent which is inert to the polymerization reaction of the polymerizable liquid crystal compound. Examples of the solvent include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, and 2-butoxy Alcohol solvents such as ethyl alcohol and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate ; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; ethyl cyclohexanone Alicyclic hydrocarbon solvents such as alkane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, anisole and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; Amidamine-based solvents such as acetofluoramine, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolinone, and the like. These solvents can be used alone or in combination of two or more. However, since the compound represented by the formula (I) generally has a large conjugated system, The solubility of the solvent is low. Among the solvents exemplified above, it is preferable to use an alcohol solvent, an ester solvent, a ketone solvent, a chlorine-containing solvent, an ether solvent, an amidine solvent, and an aromatic hydrocarbon solvent. The ester solvent is preferably used. , Ketone solvent, chlorine-containing solvent, ether-based solvent, amidine-based solvent are more preferred.

The solvent content is preferably 50 to 98 parts by mass, and more preferably 70 to 95 parts by mass based on 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content of 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is 50 parts by mass or less, the viscosity of the composition is reduced, so that the thickness of the horizontally-oriented liquid crystal cured film becomes approximately uniform, and the horizontally-oriented liquid crystal cured film tends to be less prone to unevenness. The solid content may be appropriately determined in consideration of the thickness of the horizontally oriented liquid crystal cured film to be manufactured.

The polymerization initiator is a compound capable of generating a reactive species by initiating heat or light and initiating a polymerization reaction such as a polymerizable liquid crystal. Reactive species include active species such as free radicals, cations, or anions. Among these, a photopolymerization initiator which performs a reaction by irradiation of light is preferable from the viewpoint of easily controlling the reaction.

Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. Examples of the photo-radical polymerization initiator include benzoin compounds, diphenyl ketone compounds, benzyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and Examples of the compound include a photocationic polymerization initiator such as an onium salt such as an aromatic diazonium salt, an aromatic iodonium salt, and an aromatic sulfonium salt; an iron-aromatic hydrocarbon complex; and the like. Specific examples include: Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above by BASF Japan Co., Ltd. (Manufactured); Seikuol BZ, Seikuol Z, Seikuol BEE (above manufactured by Seiko Chemical Co., Ltd.); Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.); Kayacure-UV1-6992 (manufactured by Dow); ADEKA OPTOMER SP-152 ADEKA OPTOMER SP-170, ADEKA OPTOMER N-1717, ADEKA OPTOMER N-1919, ADEKA ARKLES NCI-831, ADEKA ARKLES NCI-930 (above manufactured by ADEKA Co., Ltd.); TAZ-A, TAZ-PP (above by (Made by Japan Siber Hegner Co., Ltd.) and TAZ-104 (made by Sanwa Chemical Co., Ltd.); KAYARAD (registered trademark) series (made by Nippon Kayaku Co., Ltd.); CYRACURE UVI series (made by Dow Chemical Co.); (Produced by Apro Co., Ltd.), TAZ, BBI, and DTS (above manufactured by Green Chemical Co., Ltd.); RHODORSIL (registered trademark) (produced by RHODIA Co., Ltd.), etc. The photopolymerization initiator can be used alone or in combination of two or more. Among these, a photoradical polymerization initiator that generates radicals by irradiation of light is preferred from the viewpoint of easily controlling the reaction.

From the viewpoint of making full use of the energy emitted by the light source and having excellent productivity, it is preferable that the maximum absorption wavelength of the photopolymerization initiator is in the range of 300 nm to 400 nm, and more preferably in the range of 300 nm to 380 nm good. From the same viewpoint, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred.

As the α-acetophenone-based polymerization initiator, for example, 2-methyl-2-N-morpholinyl-1- (4-methylhydrothiophenyl) propane-1-one, 2- Dimethylamino-1- (4-morpholinylphenyl) -2-benzylbutane-1-one and 2-dimethylamino-1- (4-morpholinylphenyl)- 2- (4-methylphenylmethyl) butane-1-one, etc., with 2-methyl-2-N-morpholinyl-1- (4-methylhydrothiophenyl) propane-1 -Ketones and 2-dimethylamino-1- (4-morpholinylphenyl) -2-benzylbutane-1-one are more preferred. Examples of commercially available products of the α-acetophenone compound include Irgacure 369, 379EG, and 907 (above manufactured by BASF Japan Co., Ltd.) and Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.).

The oxime-based photopolymerization initiator generates radicals upon irradiation with light. By this radical, the polymerization of the polymerizable liquid crystal compound in the deep portion of the horizontally-oriented liquid crystal cured film can proceed favorably. Furthermore, from the viewpoint of more efficiently performing the polymerization reaction in the deep portion of the horizontally-oriented liquid crystal cured film, it is preferable to use a photopolymerization initiator that can efficiently use ultraviolet rays having a wavelength of 350 nm or more. As for a photopolymerization initiator which can effectively use ultraviolet rays having a wavelength of 350 nm or more, Compounds and oxime ester carbazole compounds are preferred, and from the viewpoint of sensitivity, oxime ester carbazole compounds are more preferred. Examples of the oxime ester type carbazole compound include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzylideneoxime)], ethyl ketone, 1- [9 -Ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-acetamidooxime) and the like. Examples of commercially available oxime ester carbazole compounds include: Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above manufactured by BASF Japan Co., Ltd.); ADEKA OPTOMER N-1919, ADEKA ARKLES NCI-831 (The above is manufactured by ADEKA Co., Ltd.) and so on.

The addition amount of the photopolymerization initiator is generally 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. If it is in the said range, reaction of a polymerizable group will fully advance and orientation of a polymerizable liquid crystal compound will not be disturbed easily.

The polymerization reaction of the polymerizable liquid crystal compound can be controlled by blending a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinones and hydroquinones having a substituent such as an alkyl ether; catechols such as butyl catechol having a substituent such as an alkyl ether; and gallophenol Classes; 2,2,6,6-tetramethyl-1-piperidinyloxy radicals and other radical scavengers; thiophenols; β-naphthylamines and β-naphthalene Phenols. In order to polymerize the liquid crystal compound without disturbing the orientation of the polymerizable liquid crystal compound, the content of the polymerization inhibitor is generally 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and 0.1 to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass is more preferred. A polymerization inhibitor can be used individually or in combination of 2 or more types.

Furthermore, by using a photosensitizer, the photopolymerization initiator can be made more sensitive. Examples of the photosensitizer include xanthone and xanthone; xanthone and xanthone; anthracenes and anthracenes having substituents such as alkyl ether; phenanthrene ; Rubrene. The photosensitizer can be used alone or in combination of two or more. The content of the photosensitizer is generally 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass.

Leveling agent has the ability to adjust the polymerizable liquid crystal composition Additives that have a function of making the layer obtained by coating the composition more flat include polysiloxane-based, polyacrylate-based, and perfluoroalkyl-based leveling agents such as silane coupling agents. Specific examples include: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (the above are manufactured by Toray. Dow Corning Co., Ltd.); KP321, KP323, KP324, KP326, KP340 , KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE -502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-802, KBM-802 , KBM-803, KBE-846, KBE-9007 (the above are all manufactured by Shin-Etsu Chemical Industry Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of which are by Momentive Performance Materials Japan Company); Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (all of which are manufactured by Sumitomo 3M Co., Ltd.); MEGAFAC (registered trademark) R-08, MEGAFAC R-30, MEGAFAC R-90, MEGAFAC F-410, MEGAFAC F-411, MEGAFAC F-443, MEGAFAC F-445, MEGAFAC F-470, MEGAFA C F-477, MEGAFAC F-479, MEGAFAC F-482, MEGAFAC F-483 (all of which are manufactured by DIC Corporation); EFTOP (trade name) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (all of which are manufactured by Mitsubishi Materials Electronics Corporation (Manufactured); SURFLON (registered trademark) S-381, SURFLON S-382, SURFLON S-383, SURFLON S-393, SURFLON SC-101, SURFLON SC-105, KH-40, SA-100 (all above by AGC Seimi Chemical Co., Ltd.); trade names E1830, E5800 (both are manufactured by Daikin Fine Chemical Research Institute Co., Ltd.); BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all of the above are Trade name: BM Chemie). Leveling agents can be used alone or in combination of two or more.

The content of the leveling agent with respect to 100 parts by mass of the polymerizable liquid crystal compound is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass. When the content of the leveling agent is within the above range, the resulting horizontally-oriented liquid crystal cured film tends to become smoother, so it is preferable.

The polymerizable liquid crystal composition can be obtained by stirring, for example, a polymerizable liquid crystal compound and a component other than the polymerizable liquid crystal compound such as an additive at a predetermined temperature.

The horizontal alignment liquid crystal hardened film system can be coated with the above-mentioned polymerizable liquid crystal composition on a horizontal alignment film described later, and then the solvent is removed to heat and / or pass the polymerizable liquid crystal composition including the polymerizable liquid crystal compound in an aligned state. It is obtained by hardening active energy rays.

Examples of a method for applying a polymerizable liquid crystal composition to a horizontal alignment film (hereinafter, also referred to as a coating method A) include an extrusion coating method, a direct gravure coating method, and a reverse direction. Gravure coating method, CAP coating method, slit coating method, micro gravure method, die coating method, inkjet method, and the like. In addition, it is also possible to use a coating machine such as a dip coater, a bar coater, or a spin coater. Coating method. Among them, in the case of continuous coating in a roll-to-roll format, a coating method using a microgravure method, an inkjet method, a slit coating method, or a die coating method is preferred.

Examples of the method for removing the solvent (hereinafter also referred to as a method for removing the solvent) include, for example, natural drying, ventilation drying, heating drying, drying under reduced pressure, and combinations thereof. Among them, natural drying or heat drying is preferred. The drying temperature is preferably in the range of 0 to 200 ° C, more preferably in the range of 20 to 150 ° C, and even more preferably in the range of 50 to 130 ° C. The drying temperature is preferably 10 seconds to 20 minutes, and more preferably 30 seconds to 10 minutes.

The active energy rays irradiated are based on the type of the polymerizable liquid crystal compound (especially the type of the photopolymerizable functional group possessed by the polymerizable liquid crystal compound) and the photopolymerization initiator when the photopolymerization initiator is included. The type and the amount of these are appropriately selected. Specific examples include one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays. Among them, the point that it is easy to control the progress of the polymerization reaction and that it can be widely used as a photopolymerization device in this technical field is that ultraviolet light is preferred, and photopolymerization can be performed by ultraviolet light. The type of the polymerizable liquid crystal compound is preferably selected.

Examples of the light source of the above active energy rays include: low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, halogen lamp, carbon arc lamp, tungsten lamp, gallium lamp, excimer laser, emission wavelength LED light source, chemical light, black light, microwave excitation in the range of 380 to 440 nm Mercury lamps, metal halide lamps, etc.

The ultraviolet irradiation intensity is generally 10 to 3,000 mW / cm ² . A preferred ultraviolet irradiation intensity is an intensity in a wavelength region where activation of a photocationic polymerization initiator or a photoradical polymerization initiator is effective. The light irradiation time is generally from 0.1 seconds to 10 minutes, preferably from 0.1 seconds to 5 minutes, more preferably from 0.1 seconds to 3 minutes, and even more preferably from 0.1 seconds to 1 minute. When the ultraviolet irradiation intensity in such a once or a plurality of irradiation, the integrated light amount of 10 to 3,000mJ / cm ^2, from 50 to 2,000mJ / cm ² preferably, 100 to 1,000mJ / cm ² is more preferred. When the accumulated light amount is below the above-mentioned lower limit, the polymerizable liquid crystal compound may not be sufficiently hardened and may not be able to obtain good transferability. Conversely, when the accumulated light amount is above the upper limit described above, the retardation plate including an optical compensation function with a horizontal alignment liquid crystal cured film may be colored.

From the viewpoint of thinning the functional film, the film thickness of the horizontal alignment liquid crystal cured film is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2.5 μm or less. The lower limit of the film thickness of the horizontal alignment liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1.0 μm or more. The film thickness of the horizontally oriented liquid crystal cured film can be measured using an ellipsometer or a contact film thickness meter.

[Horizontal orientation film]

The alignment film is a film having an alignment restraining force that orients a polymerizable liquid crystal compound of a liquid crystal cured film in a predetermined direction. As for the directional processing necessary to present the directional binding force, examples include friction processing, light directional processing Treatment, light irradiation treatment, etc. In addition, various orientations such as vertical orientation, horizontal orientation, mixed orientation, and oblique orientation can be controlled depending on the type of orientation film, friction conditions, and light irradiation conditions. Among them, the horizontal alignment film is an alignment film having an alignment constraint force that allows the polymerizable liquid crystal compound of the liquid crystal cured film to be aligned in the horizontal direction. Therefore, a horizontal alignment liquid crystal film can be formed by using a horizontal alignment film.

As for the alignment film, it is preferred that it has solvent resistance that does not dissolve due to application of the polymerizable liquid crystal composition, etc., and that it has heat resistance in the heat treatment for removing the solvent and orienting the polymerizable liquid crystal compound.

Examples of the horizontal alignment film exhibiting a binding force for aligning the horizontal alignment liquid crystal cured film in the horizontal direction include friction alignment films, light alignment films, and grooves with a concave-convex pattern on the surface or grooves. Orientation film, etc. For example, when applied to a long roll-shaped film, a light-oriented film is preferred from the viewpoint that the orientation direction can be easily controlled.

The rubbing alignment film is generally a composition including a directional polymer and a solvent (hereinafter also referred to as a composition for forming a rubbing alignment film) is coated on a substrate or the like, the solvent is removed to form a coating film, and the coating is applied. The film is rubbed, whereby orientation restraint can be imparted.

Examples of the directional polymer include polyamines or gelatins having a fluorene bond, and polyamic acids, polyvinyl alcohols, and alkyl groups having a fluorene imine bond and a hydrolyzate thereof. Modified Polyvinyl Alcohol, Polyacrylamide, Poly Azole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylates. These directional polymers may be used alone or in combination of two or more.

The concentration of the directional polymer in the composition for rubbing the aligning film may be such that the directional polymer is completely dissolved in the solvent. The content of the directional polymer is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the composition.

The composition for forming a friction-oriented film is commercially available. Examples of commercially available products include Sun Ever (registered trademark; manufactured by Nissan Chemical Industry Co., Ltd.), Optomer (registered trademark; manufactured by JSR Corporation), and the like.

As the solvent, for example, the solvent exemplified in the paragraph of the horizontally aligned liquid crystal cured film can be used. The method of applying the composition for forming a frictionally oriented film to a substrate or the like includes the above-mentioned coating method A, and the method of removing the solvent includes the above-mentioned solvent removal method A.

Examples of the method for the rubbing treatment include a method in which a rotating rubbing roller wound with a rubbing cloth is brought into contact with the coating film. If masking is performed during the rubbing treatment, a plurality of regions (patterns) with different orientation directions may be formed on the alignment film.

The photo-alignment film is generally formed by applying a composition (also referred to as a composition for forming a photo-alignment film) containing a polymer or monomer having a photoreactive group and a solvent, and removing the solvent. It can be obtained by irradiating polarized light (preferably polarized UV). The light aligning film can arbitrarily adjust the direction of the directional restraint by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that generates alignment ability by light irradiation. Specific examples include: orientation-induced reactions of molecules generated by light irradiation, isomerization reactions, photodimerization reactions, photocrosslinking reactions, or light analysis The reaction and so on become the basis of the photoreaction that is the origin of the directional ability. The photoreactive group is preferably a group having an unsaturated bond, especially a group having a double bond, in order to have a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), At least one radical selected from the group consisting of a nitrogen-nitrogen double bond (N = N bond) and a carbon-oxygen double bond (C = O bond) is particularly preferred.

Examples of the photoreactive group having a C = C bond include vinyl, polyalkenyl, stilbene, stilbazole, stilbazolium, chalcone, and cinnamon醯 基. Examples of the photoreactive group having a C = N bond include an aromatic Schiff base and a group having a structure such as an aromatic fluorene. Examples of the photoreactive group having an N = N bond include azophenyl, azonaphthyl, aromatic heterocyclic azo, diazo, formazan, and azoxybenzene. ) The basis of structure. Examples of the photoreactive group having a C = O bond include a diphenyl ketone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and halogenated alkyl.

From the viewpoint of excellent orientation, it is preferably a base that participates in a photodimerization reaction or a photocrosslinking reaction. Among them, a photoreactive group participating in a photodimerization reaction is preferred; in order to easily obtain a light alignment film having a small amount of polarized light irradiation required for orientation and excellent thermal stability and stability over time, it is based on Cinnamyl and chalcone are preferred. The polymer having a photoreactive group is particularly preferably one having a cinnamyl group so that the terminal portion of the side chain of the polymer has a cinnamic acid structure or a cinnamic acid ester structure.

Content of polymer or monomer with photoreactive group It can be controlled by the type of the polymer or monomer or the thickness of the photo-alignment film. It is preferably at least 0.2 parts by mass, and 0.3 to 10 parts by mass, relative to 100 parts by mass of the photo-alignment film-forming composition. The range is better.

As the solvent, for example, the solvent exemplified in the paragraph of the horizontally aligned liquid crystal cured film can be used. A method for applying the composition for forming a light alignment film on a substrate or the like includes the above-mentioned coating method A, and a method for removing the solvent includes the above-mentioned solvent removal method A.

When the polarized light is irradiated, for example, the polarized light may be directly irradiated to a person who removes the solvent from the composition for forming a light alignment film applied on a substrate or the like. The polarized light is preferably substantially parallel light. The wavelength of the polarized light to be irradiated is preferably a wavelength region where the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, UV (ultraviolet) having a wavelength in a range of 250 to 400 nm is particularly preferable. Examples of the light source irradiating the polarized light include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, KrF, and ArF ultraviolet lasers. Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferred because of their relatively high luminous intensity of ultraviolet light at a wavelength of 313 nm. By irradiating the light from the light source with an appropriate polarizing element, polarized UV can be irradiated. Examples of the polarizing element include polarizing filters, polarizing chirps such as Glan-Thompson and Glan-Taylor, and wire grids. Among them, a wire grid type polarizing element is preferred from the viewpoint of large area and heat resistance.

In addition, when rubbing or polarizing light irradiation, if masking is performed, a plurality of regions (patterns) with different directions of liquid crystal alignment may be formed.

The groove-oriented film is a film having a concave-convex pattern or a plurality of grooves on the surface of the film. When a polymerizable liquid crystal compound is coated on a film having a plurality of linear grooves arranged at equal intervals, the liquid crystal molecules are aligned along the direction of the grooves.

The method for obtaining the groove alignment film can be exemplified as: a method for forming a concave-convex pattern after exposing on the surface of the photosensitive polyimide film through an exposure mask with a slit having a pattern shape, and developing and rinsing treatment; A method for forming a layer of a UV-curable resin before curing on a plate-shaped master having grooves on its surface, and moving the formed resin layer to a substrate, etc., and curing; and, forming a roller-like shape having a plurality of grooves A method in which a master is pressure-bonded to a film of a UV-curable resin formed on a substrate or the like before curing to form unevenness, and then cured.

The composition for forming a horizontal alignment film, such as the composition for forming a rubbing alignment film and the composition for forming a photoalignment film, may contain, in addition to a solvent, the additives and the like exemplified in the paragraph of the horizontal alignment liquid crystal cured film.

From the viewpoint of thinning the retardation plate with an optical compensation function, the film thickness of the horizontal alignment film is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. The thickness of the horizontal alignment film is preferably 1 nm or more, more preferably 5 nm or more, even more preferably 10 nm or more, and particularly preferably 30 nm or more. The film thickness of the horizontal alignment film can be measured using an ellipsometry or a contact film thickness meter.

[Vertical alignment liquid crystal hardened film]

The horizontally oriented liquid crystal cured film is a film having refractive index anisotropy in a direction perpendicular to the film plane, and is composed of a polymer containing a polymerizable liquid crystal compound. The vertically-aligned liquid crystal cured film is formed by coating a polymerizable liquid crystal composition on a vertical alignment film and polymerizing a polymerizable liquid crystal composition including a polymerizable liquid crystal compound in an aligned state by heating and / or light irradiation. At the time of formation, it is preferable because the thickness of the vertically-aligned liquid crystal cured film can be achieved and the wavelength dispersion characteristics can be arbitrarily designed.

The three-dimensional refractive index ellipsoid formed by the vertically oriented liquid crystal hardened film may have biaxiality, but it is preferably one having uniaxiality. The vertically-oriented liquid crystal cured film may be a vertically-oriented liquid crystal cured film, which is composed of a polymer of a polymerizable liquid crystal composition including a polymerizable liquid crystal compound in a state in which the liquid crystal cured film is oriented in a direction perpendicular to the plane of the liquid crystal cured film. It is a mixed alignment liquid crystal cured film or an oblique alignment liquid crystal cured film. The refractive index nx, ny, and nz in three directions of the refractive index ellipsoid formed by the orientation of the polymerizable liquid crystal may have nz> nx ≒ ny (referred to as a positive C plate) or nz <nx ≒ ny (referred to as a negative electrode) C board). nx represents the principal refractive index in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film, which is parallel to the plane of the vertically aligned liquid crystal cured film. ny represents the refractive index in the refractive index ellipsoid formed by the vertically-oriented liquid crystal cured film, which is parallel to the plane of the vertically-oriented liquid crystal cured film and orthogonal to the nx direction. Moreover, when nx = ny, nx can be set to an arbitrary direction in a plane in which the liquid crystal cured film is vertically aligned. nz indicates the refractive index in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film, which is perpendicular to the plane of the vertically aligned liquid crystal cured film.

Vertically oriented liquid crystal cured film can use rod-shaped polymerizable liquid Either crystalline or disc-shaped polymerizable liquid crystal is preferred, but rod-shaped polymerizable liquid crystal is preferred. When the rod-shaped polymerizable liquid crystal forms a vertical alignment liquid crystal cured film, the vertical alignment liquid crystal cured film becomes a positive electrode C plate.

When the vertical alignment liquid crystal cured film is a positive electrode C plate, the retardation value RthC (λ) of the vertical alignment liquid crystal cured film with respect to light having a wavelength of λ nm in the thickness direction is preferably to satisfy the optical characteristics shown in the following formula (31). In addition, it is preferable to satisfy the optical characteristics shown in the following formulae (32) and (33). It is more preferable that the vertically aligned liquid crystal cured film satisfies the optical characteristics represented by the following formula (31), (32), and (33).

-100nm ≦ RthC (550) ≦ -50nm ... (31)

(In the formula, RthC (550) represents a retardation value in the thickness direction for light having a wavelength of 550 nm.)

RthC (450) / RthC (550) ≦ 1.0 ... (32)

1.00 ≦ RthC (650) / RthC (550) ... (33)

(In the formula, RthC (450) represents the retardation value in the thickness direction for light with a wavelength of 450nm, RthC (550) represents the retardation value in the thickness direction for light with a wavelength of 550nm, and RthC (650) represents the light with a wavelength of 650nm Phase difference value in the thickness direction.)

When the retardation value RthC (550) in the thickness direction of the vertically-oriented liquid crystal cured film exceeds the range of the formula (31), a display having an elliptical polarizer with an optical compensation function including a retardation plate with an optical compensation function tends to have a tendency. The hue becomes red or blue. A more preferable range of the phase difference value in the thickness direction is −95 nm ≦ RthC (550) ≦ −55 nm, and a more preferable range is −90 nm ≦ RthC (550) ≦ −60 nm. Vertically oriented liquid crystal hardened film When "RthC (450) / RthC (550)" exceeds 1.0, the observability of the elliptically polarized plate including the vertically-oriented liquid crystal cured film on the short-wavelength side of the ellipsoidal system is deteriorated. When the ellipticity of the elliptically polarizing plate on the short-wavelength side deteriorates and decreases from 1.0, the function of the elliptically-polarizing plate on the short-wavelength side tends to be impaired. "RthC (450) / RthC (550)" is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, and even more preferably 0.79 to 0.85.

The retardation value in the thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness of the vertically aligned liquid crystal cured film. Since the retardation value in the thickness direction is determined according to the following formula (34), in order to obtain the desired retardation value in the thickness direction (RthC (λ): the vertical alignment of the liquid crystal cured film at the wavelength λ (nm) Retardation value in the thickness direction), and the 3-dimensional refractive index and the film thickness dC can be adjusted. The three-dimensional refractive index depends on the molecular structure and orientation of the polymerizable liquid crystal compound described later.

RthC (λ) = [(nxC (λ) + nyC (λ)) / 2-nzC (λ)] × dC ... (34)

(In the formula, the refractive index ellipsoid formed by the vertically aligned liquid crystal hardened film has a relationship of nzC (λ)> nxC (λ) ≒ nyC (λ), where nzC (λ) represents the vertically aligned liquid crystal cured film In the formed refractive index ellipsoid, the refractive index of light with a wavelength of λ (nm) is perpendicular to the plane of the liquid crystal cured film of vertical orientation. NxC (λ) represents the refractive index ellipsoid formed of the vertically oriented liquid crystal cured film. The maximum refractive index of light with a wavelength of λ (nm) that is parallel to the plane of the vertically-oriented liquid crystal hardened film. NyC (λ) represents the refractive index ellipsoid formed by the vertically-oriented liquid crystal hardened film, which hardens the vertically-oriented liquid crystal. The plane of the film is parallel and orthogonal to the nxC direction with respect to the refractive index of light of wavelength λ (nm). However, when nzC (λ) = nyC (λ), nxC (λ) means vertical The plane of the directional liquid crystal hardened film has a refractive index in any direction parallel to the plane. Here, dC represents the thickness of the vertically aligned liquid crystal cured film. )

The vertical alignment liquid crystal cured film is preferably a polymer of a polymerizable liquid crystal composition including a polymerizable liquid crystal compound in a vertical alignment state as described above. The polymerizable liquid crystal compound forming the vertically-aligned liquid crystal cured film is a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group. The photopolymerizable functional group refers to a group that can participate in a polymerization reaction by a living radical or an acid generated from a photopolymerization initiator. Examples of the photopolymerizable functional group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acrylfluorenyloxy group, a methacrylfluorenyloxy group, and an epoxy group. Ethyl, oxetanyl and the like. Among them, acrylfluorenyloxy, methacrylfluorenyloxy, vinyloxy, ethylene oxide, and oxetanyl are preferred, and acrylfluorenyloxy is more preferred. The liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase sequence structure may be a nematic liquid crystal or a smectic liquid crystal.

The polymerizable liquid crystal compound that can be used for the formation of the vertically-aligned liquid crystal cured film is preferably a compound represented by the above formula (I). By using the compound represented by the formula (I), the reverse wavelength dispersibility can be exhibited, and the relationship of the formulas (31) and (32) can be sufficiently satisfied.

The polymerizable liquid crystal compound that can be used for the vertical alignment liquid crystal cured film can be used alone or in combination of two or more kinds. When two or more kinds are used in combination, the content of the compound represented by the formula (I) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and 80 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound. The above is even better.

The composition for forming a vertical alignment liquid crystal cured film (hereinafter also referred to as a polymerizable liquid crystal composition) used for the vertical alignment liquid crystal cured film may further include a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, Adhesion promoter. These additives can be used alone or in combination of two or more.

The content of the polymerizable liquid crystal compound is, for example, 70 to 99.5 parts by mass, more preferably 80 to 99 parts by mass, and even more preferably 90 to 98 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. When the content is within the above range, the orientation of the vertically-aligned liquid crystal cured film tends to be high. Here, the solid content means the total amount of the components after the solvent is removed from the composition.

The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound, and more preferably a solvent which is inert to the polymerization reaction of the polymerizable liquid crystal compound. As the solvent, the same solvent as that used by the user of the composition for forming a horizontally-oriented liquid crystal cured film can be used.

The solvent content is preferably 50 to 98 parts by mass, and more preferably 70 to 95 parts by mass based on 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is 50 parts by mass or less, the viscosity of the composition is reduced, so the thickness of the vertically-aligned liquid crystal cured film becomes substantially uniform, and the vertical-oriented liquid crystal cured film tends to be less likely to be uneven. The solid content may be appropriately determined in consideration of the thickness of the vertical alignment liquid crystal cured film to be manufactured.

Polymerization initiators can react with heat or light. A compound that reacts with an active species and initiates a polymerization reaction such as a polymerizable liquid crystal. Examples of reactive species include reactive species such as free radicals, cations, or anions. Among these, a photopolymerization initiator which performs a reaction by irradiation of light is preferable from the viewpoint of easily controlling the reaction. As the photopolymerization initiator system, the same initiators as those used for the composition for forming a horizontally oriented liquid crystal cured film can be used.

The addition amount of the photopolymerization initiator is generally 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal composition. If it is in the said range, reaction of a polymerizable group can fully advance, and orientation of a polymerizable liquid crystal compound is not easily disturbed.

The polymerization reaction of the polymerizable liquid crystal compound can be controlled by blending a polymerization inhibitor. As the polymerization inhibitor, the same thing as a user of a composition for forming a horizontally oriented liquid crystal cured film can be used. In order to polymerize the liquid crystal compound without disturbing the orientation of the polymerizable liquid crystal compound, the content of the polymerization inhibitor is generally 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and 0.1 to 3 parts with respect to 100 parts by mass of the polymerizable liquid crystal compound. Better quality. A polymerization inhibitor can be used individually or in combination of 2 or more types.

Moreover, by using a photosensitizer, the sensitivity of a photopolymerization initiator can be improved. As a photosensitizer, the same thing as a user of the composition for forming a horizontally-aligned liquid crystal cured film can be used. The content of the photosensitizer is generally 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass.

Leveling agent has the ability to adjust the polymerizable liquid crystal composition As the additive having the function of making the layer obtained by applying the composition more flat, the same thing as the user of the composition for forming a horizontally oriented liquid crystal cured film can be used.

The content of the leveling agent with respect to 100 parts by mass of the polymerizable liquid crystal compound is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass. When the content of the leveling agent is within the above range, the obtained vertical alignment liquid crystal cured film tends to become smoother, so it is preferable.

The polymerizable liquid crystal composition used for the formation of the vertical alignment liquid crystal cured film can be obtained by stirring, for example, a polymerizable liquid crystal compound and a component other than the polymerizable liquid crystal compound such as an additive at a predetermined temperature.

The vertically-aligned liquid crystal cured film system can be coated with the above-mentioned polymerizable liquid crystal composition on a later-described vertical alignment film, followed by removing the solvent, and heating and / or heating the polymerizable liquid crystal composition including the polymerizable liquid crystal compound in an aligned state. Hardened by active energy rays.

The method of applying the polymerizable liquid crystal composition to the vertical alignment film can be the same as that used when forming a horizontal alignment liquid crystal cured film.

The method of removing the solvent can be the same as that used when forming a horizontally-oriented liquid crystal cured film.

The active energy rays irradiated are based on the type of the polymerizable liquid crystal compound (especially the type of the photopolymerizable functional group possessed by the polymerizable liquid crystal compound) and the photopolymerization initiator when the photopolymerization initiator is included. The type and the amount of these are appropriately selected. Specific examples include For example: one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays. Among them, the point that it is easy to control the progress of the polymerization reaction and that it can be widely used as a photopolymerization device in this technical field is that ultraviolet light is preferred, so that photopolymerization can be performed by ultraviolet light. The type of the polymerizable liquid crystal compound is preferably selected.

As the light source of the above-mentioned active energy ray, the same thing as that used by a user when forming a horizontally-oriented liquid crystal cured film can be used.

The ultraviolet irradiation intensity is generally 10 to 3,000 mW / cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activation of a photocationic polymerization initiator or a photoradical polymerization initiator. The light irradiation time is generally from 0.1 seconds to 10 minutes, preferably from 0.1 seconds to 5 minutes, more preferably from 0.1 seconds to 3 minutes, and even more preferably from 0.1 seconds to 1 minute. When the ultraviolet irradiation intensity in such a once or a plurality of irradiation, the integrated light amount of 10 to 3,000mJ / cm ^2, from 50 to 2,000mJ / cm ² preferably, 100 to 1,000mJ / cm ² is more preferred. When the accumulated light amount is below the above-mentioned lower limit, curing of the polymerizable liquid crystal compound becomes insufficient, and good transferability may not be obtained. Conversely, when the accumulated light amount is above the upper limit described above, the retardation plate including an optical compensation function with a vertical alignment liquid crystal cured film may be colored.

From the viewpoint of thinning the functional film, the film thickness of the vertical alignment liquid crystal cured film is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1.5 μm or less. In addition, the lower limit of the film thickness of the vertically aligned liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.3 μm or more, and 0.5 μm or more is more preferable. The film thickness of the vertically oriented liquid crystal cured film can be measured using an elliptical polarimeter or a contact film thickness meter.

[Vertical orientation film]

The alignment film is a film having an alignment restraining force that orients a polymerizable liquid crystal compound of a liquid crystal cured film in a predetermined direction. Moreover, various orientations such as vertical orientation, horizontal orientation, mixed orientation, and oblique orientation can be controlled by the type of orientation film, friction conditions, and light irradiation conditions. Among them, the vertical alignment film is an alignment film having an alignment constraint force that allows the polymerizable liquid crystal compound of the liquid crystal cured film to be aligned in the vertical direction. Therefore, by using a vertical alignment film, a vertical alignment liquid crystal film can be formed.

The vertical alignment film is preferably a material that reduces the surface tension of the surface of a substrate or the like. Examples of such materials include the above-mentioned directional polymers, for example, polyimide, polyamidine, polyamic acid of its hydrolyzate, fluorine-based polymers such as perfluoroalkyl, silane compounds, and the like through condensation reactions. The resulting polysiloxane compound. The vertical alignment film is formed by applying a composition (hereinafter also referred to as a composition for forming a vertical alignment film) containing such a material and a solvent (such as the solvent exemplified in the paragraph of the vertical alignment liquid crystal film) to a substrate or the like. After the solvent is removed, the coating film is obtained by heating or the like.

When a silane compound is used in a vertical alignment film, from the viewpoints that it is easy to reduce the surface tension and to improve the adhesion with the layer adjacent to the vertical alignment film, the vertical alignment film is a compound containing a Si element and a C element as constituent elements. The formed film is preferably a silane compound. In the present invention, it is arranged between a horizontally-oriented liquid crystal film and a vertically-oriented liquid crystal film In the case of a vertical alignment film, in a retardation plate with an optical compensation function that exhibits high adhesion between the vertical alignment film and the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film, it can effectively suppress or prevent the Interface peeling.

The silane compound can be suitably used for polysiloxanes such as the silane coupling agent, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-amine Propyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylmethyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsilane, and the like.

The silane compound may be a polysiloxane monomer type or a polysiloxane oligomer (polymer) type. When the polysiloxane oligomer is expressed in the form of a (monomer)-(monomer) copolymer, examples include: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercapto Propyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane Copolymers containing mercaptopropyl; such as mercaptomethyltrimethoxysilane Alkane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, and mercaptomethyltriethoxy Silane-tetraethoxysilane copolymer containing mercaptomethyl copolymers; such as 3-methacrylfluorenyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacrylfluorene Oxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacrylfluorenyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacrylfluorenyloxy Propyltriethoxysilane-tetraethoxysilane copolymer, 3-methacrylmethylpropylpropyldimethoxysilane-tetramethoxysilane copolymer, 3-methacrylfluorene Methoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacrylmethyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3- Methacrylfluorenyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymers containing methacrylfluorenyloxypropyl; such as 3-acrylfluorenyl Propyltrimethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropyltriethoxy Silane-tetramethoxysilane copolymer, 3-propenyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropylmethyldimethoxysilane -Tetramethoxysilane copolymer, 3-propenyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropylmethyldiethoxysilane -Tetramethoxysilane copolymer and 3-propenyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer containing acryloxypropyl group; such as vinyl trimethyl Ethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, ethylene Triethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, ethylene Methylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, and vinylmethyldiethoxysilane-tetraethoxysilane Copolymers containing vinyl copolymers; such as 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3 -Aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxy Silane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxyoxide Aminosilane-based copolymers and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymers containing amine groups and the like. Silane compounds can be used alone or in combination of two or more. In addition, it may be used as a leveling agent, and it may also be used as a silane coupling agent.

Among these, a silane compound having an alkyl group at the molecular terminal is preferred, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferred.

From the viewpoint of further improving the adhesion, the viewpoint of the coating property of the composition for forming a vertically-aligned liquid crystal cured film, and the viewpoint of being difficult to dissolve the layer arranged on the lower layer in the method for manufacturing a retardation plate with an optical compensation function described later In view of this, the vertical alignment film is preferably a film composed of a compound including Si, C, and O as constituent elements. In addition, C containing Si atoms bonded to a silane compound forming a vertical alignment film The atomic substituent is, in terms of the number of carbon atoms of the preferred alkyl or alkoxy group, preferably from 1 to 30, more preferably from 2 to 25, and even more preferably from 3 to 20. That is, the ratio of the Si element to the C element (Si / C: Molar ratio) is preferably 0.03 to 1.00, more preferably 0.04 to 0.50, and still more preferably 0.05 to 0.33. When the Si / C ratio is greater than or equal to the above lower limit, the coating properties of the composition for forming a vertical alignment liquid crystal cured film can be improved. When the Si / C ratio is less than or equal to the above upper limit, the adhesion to adjacent layers can be improved.

As the solvent, for example, the solvent exemplified in the paragraph of the horizontally aligned liquid crystal cured film can be used. Examples of the coating method of the composition for forming a vertical alignment film include the above-mentioned coating method A, and examples of the method of removing the solvent include the method of removing the solvent A described above.

The composition for forming a vertical alignment film may contain, in addition to a solvent, additives such as those exemplified in the paragraph of the horizontal alignment liquid crystal cured film.

From the viewpoint of thinning of the retardation plate with optical compensation function and the presentation of orientation restraint, the film thickness of the vertical alignment film is preferably 1 μm or less, more preferably 0.3 μm or less, and 0.1 μm or less. Better. The thickness of the vertical alignment film is preferably 1 nm or more, more preferably 5 nm or more, even more preferably 10 nm or more, and particularly preferably 30 nm or more. The film thickness of the vertical alignment film can be measured using an ellipsometer or a contact film thickness meter.

[Substrate]

The substrate is coated with a composition for forming an alignment film or a liquid crystal cured film. When the composition is used, the user may design the substrate to be peeled off and transfer the film coated on the substrate, or it may be designed to be unable to transfer due to the adhesion to the substrate. However, from the viewpoint of thin film formation, it is preferable to design the peelable base material by transferring it to an object to be transferred. Examples of the substrates mentioned above include glass substrates and film substrates. From the viewpoint of processability, film substrates are preferred, and from the viewpoint of continuous production, a long roll film is used. For the better. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate Polyacrylates; cellulose esters such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polyfluorene; polyetherfluorene; polyetherketone; Plastics such as phenylene sulfide and polyphenylene ether. It may be a mold release treatment such as silicone treatment on the surface of the substrate. Examples of commercially available cellulose ester substrates include: "FUJITAC FILM" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY", and "KC4UY" (all of which are by Konica Minolta Optical (Konica Minolta Opto Co., Ltd.) and so on. Such a resin can be formed into a film by a conventional method such as a solvent casting method and a melt extrusion method as a substrate.

Examples of commercially available cyclic olefin resins include "Topas" (registered trademark) (made by Ticona (Germany)), "ARTON" (registered trademark) (made by JSR Corporation), and "ZEONOR" (registered trademark) , "ZEONEX" (registered trademark) (above manufactured by Japan Zeon Corporation) and "APEL" (registered trademark) (Mitsui Chemical Co., Ltd.). A commercially available cyclic olefin-based resin substrate may be used. Commercially available cyclic olefins Examples of the hydrocarbon resin substrate include: "ESUSHINA" (registered trademark), "SCA40" (registered trademark) (the above are manufactured by Sekisui Chemical Industry Co., Ltd.), "ZEONOR FILM" (registered trademark) (manufactured by OPTES Co., Ltd.) ) And "ARTON FILM" (registered trademark) (made by JSR Corporation).

The base material is preferably one having a layer of a horizontally-oriented liquid crystal cured film, a horizontally-oriented film, a vertically-oriented liquid crystal-hardened film, and a vertically-oriented film, and having a thickness that is easy to peel off. The thickness of such a substrate is generally 5 to 300 μm, and preferably 20 to 200 μm.

[Phase difference plate with optical compensation function]

The retardation plate with an optical compensation function of the present invention preferably contains a horizontally-oriented liquid crystal cured film, a horizontally-oriented film or a vertical-oriented film, and a vertically-oriented liquid-crystal cured film in order, and satisfies the following (1) to (4) Requirements.

The interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film is 5 μm or less. ...(1)

A layer between the horizontally-oriented liquid crystal cured film and the vertically-oriented liquid crystal cured film includes a horizontally-oriented film or a vertically-oriented film. ...(2)

Meet the following relationship: ReA (450) / ReA (550) <1.00 ... (3)

Among them, ReA (λ) represents an in-plane retardation value of the horizontally aligned liquid crystal cured film at a wavelength of λnm.

The definition of the phase difference is as follows: ReA (λ) = (nxA-nyA) × dA

However, nxA represents the principal of the horizontally oriented liquid crystal hardened film in the film plane. The refractive index and nyA represent the refractive index in a direction orthogonal to nxA in the same plane, and dA represents the film thickness of the horizontally aligned liquid crystal cured film.

Meet the following relationship: RthC (450) / RthC (550) <1.00 ... (4)

Here, RthC (λ) represents a retardation value of the thickness direction of the vertically aligned liquid crystal cured film at a wavelength λnm. The phase difference is defined as follows: RthC (λ) = ((nxC + nyC) / 2-nzC) × dC

However, nxC represents the main refractive index of the vertically-oriented liquid crystal cured film in the film plane, nyC represents the refractive index in a direction orthogonal to nxC in the same plane, nzC represents the refractive index of the thickness direction of the vertically-oriented liquid crystal cured film, and dC represents The film thickness of the vertically aligned liquid crystal hardened film.

In addition, when nxC = nyC, nxC may be a refractive index in any direction within the film plane.

In addition, the distance between the horizontally-oriented liquid crystal cured film and the vertically-oriented liquid crystal cured film is as shown in formula (1), which is preferably 5 μm or less, more preferably 1 μm or less, more preferably 0.5 μm or less, and 0.3 μm. The following are particularly good. The thickness of the horizontal alignment film is preferably 1 nm or more, more preferably 5 nm or more, even more preferably 10 nm or more, and particularly preferably 30 nm or more.

It is preferable that the retardation plate with an optical compensation function satisfies the following expression (5). In terms of the values of | R0 (550) -R40 (550) |, when an elliptical polarizer with an optical compensation function using a phase difference plate with an optical compensation function is applied to a display, in order to make the tilted wavelength near 550nm The smaller the amount of light leakage, the smaller it is. The value of | R0 (550) -R40 (550) | is preferably less than 10nm, more preferably 5nm or less, and 4nm or less More preferably, 3 nm or less is particularly preferred.

| R0 (550) -R40 (550) | <10nm ... (5)

Among them, R0 (λ) represents an in-plane retardation value of a retardation plate with an optical compensation function including a horizontal alignment liquid crystal cured film and a vertical alignment liquid crystal cured film. Furthermore, R40 represents a direction (fast axis direction) orthogonal to the main refractive index direction in the plane of the film in the retardation plate with optical compensation function including the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film. ) Rotate around 40. Apparent phase difference at time.

It is preferable that the retardation plate with optical compensation function satisfies the following relational expression (6). In terms of the values of | R0 (450) -R40 (450) |, when an elliptical polarizer with an optical compensation function using a phase difference plate with an optical compensation function is applied to a display, in order to make the tilted wavelength near 450nm The amount of light leakage is reduced and the smaller one is preferable. The value of | R0 (450) -R40 (450) | is preferably less than 10nm, more preferably less than 5nm, more preferably less than 4nm, and particularly preferably less than 3nm

| R0 (450) -R40 (450) | <10nm ... (6)

However, R0 (λ) represents the in-plane retardation value of the retardation plate with optical compensation function including the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film. In addition, R40 indicates that in a retardation plate with optical compensation function including a horizontally-oriented liquid crystal cured film and a vertically-oriented liquid crystal cured film, the main refractive index direction in the film plane is orthogonal (fast axis direction) in the same plane. Apparent phase difference value when the direction is rotated around 40 °.

Furthermore, it is preferable that the difference between the values shown in the relational expressions (5) and (6) satisfies the following relational expression (7).

| {R0 (450) -R40 (450)}-{R0 (550) -R40 (550)} | <3nm ... (7)

When satisfying the relational expression (7), when an elliptical polarizer with an optical compensation function using a phase difference plate with an optical compensation function is applied to a display, in order to make the front and inclined reflection hue close to black, the value of (7) It is preferably 3 nm or less, more preferably 2 nm or less, and even more preferably 1 nm or less.

Furthermore, when the average refractive index difference of each layer, that is, the difference between the average refractive index of each layer constituting the retardation plate with an optical compensation function of the present invention and the average refractive index of other layers adjacent to the layer is large, Light leakage may occur due to the influence of interface reflections between layers. The difference in the average refractive index of each layer at a wavelength of 550 nm is preferably 0.20 or less, more preferably 0.15 or less, even more preferably 0.10 or less, and particularly preferably 0.05 or less. If it is within this range, the occurrence of light leakage due to interface reflection can be suppressed.

The average refractive index difference of each layer can be specifically listed as follows: (1) the difference between the average refractive index of the horizontally oriented liquid crystal cured film and the average refractive index of the vertically oriented liquid crystal cured film; (2) the horizontally oriented liquid crystal cured film and When a horizontal alignment film is included between the vertical alignment liquid crystal cured films, (2-a) the difference between the average refractive index of the horizontal alignment liquid crystal cured film and the average refractive index of the horizontal alignment film, and (2-b) the average refractive index of the horizontal alignment film. The difference from the average refractive index of the vertical alignment liquid crystal cured film; (3) When a vertical alignment film is included between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film, (3-a) the difference between the average refractive index of the horizontally oriented liquid crystal cured film and the average refractive index of the vertically oriented film, (3-b) the difference between the average refractive index of the vertically oriented film and the average refractive index of the vertically oriented liquid crystal cured film; Wait.

The phase difference plate with an optical compensation function of the present invention may include layers other than a horizontal alignment liquid crystal cured film, a horizontal alignment film, a vertical alignment liquid crystal cured film, and a vertical alignment film. Specific examples thereof include other alignment liquid crystal cured films, Other orientation films, protective layers, etc. Examples of other directional liquid crystal cured films include the vertical alignment liquid crystal cured film and horizontal directional liquid crystal cured films illustrated above, and other alignment films include the above-exemplified alignment films and the like.

The protective layer is generally preferably formed of a composition for forming a protective layer. The composition for forming a protective layer contains: polyfunctional acrylate (methacrylate), urethane acrylate, polyester acrylate Acrylic oligomers or polymers composed of epoxy acrylate, etc .; polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose , Sodium alginate and other water-soluble polymers, and solvents.

Examples of the solvent system contained in the composition for forming a protective layer are the same as those exemplified above. Among them, water, an alcohol solvent, and At least one solvent selected from the group consisting of ether solvents. Examples of the alcohol solvent include: methanol, ethanol, butanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, Ethylene glycol butyl ether and propylene glycol monomethyl ether. Examples of the ether solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. Among them, ethanol, isopropanol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferred.

The film thickness of the protective layer is 0.1 μm to 10 μm, and preferably 0.1 μm to 3 μm.

[Manufacturing method of retardation plate with optical compensation function]

The method for manufacturing a retardation plate with an optical compensation function of the present invention is not particularly limited if it can be a method of laminating a horizontally-oriented liquid crystal cured film, a horizontally-oriented film or a vertically-oriented film, and a vertically-oriented liquid crystal-hardened film in the stated order. Preferably, a method of laminating a horizontally-oriented film on a substrate, then laminating a horizontally-oriented liquid crystal cured film, and further laminating a vertical-oriented film, and then laminating a vertically-oriented liquid-crystalline cured film (hereinafter referred to as manufacturing method A); or A method of laminating a vertical alignment film on top, then laminating a liquid crystal hardening film on a vertical alignment layer, and further laminating a horizontal alignment film, and then laminating a horizontal alignment liquid crystal curing film (hereinafter referred to as a manufacturing method B). The lamination method of the horizontal alignment liquid crystal cured film, the horizontal alignment film, the vertical alignment liquid crystal cured film, and the vertical alignment film can use the above-mentioned formation method of each layer.

When the phase difference plate with optical compensation function is manufactured by the manufacturing method A or the manufacturing method B, the alignment of the liquid crystal hardened film disposed on the lower layer may cause poor alignment or alignment defects. That is, in the case of the manufacturing method A, the vertical alignment liquid crystal cured film is laminated after the horizontal alignment liquid crystal cured film of the lower layer is laminated. Therefore, when the vertical alignment liquid crystal cured film is formed, the horizontal alignment liquid crystal cured film of the lower layer may be affected. influences In the case of poor alignment or alignment defects, in the case of the manufacturing method B, the horizontal alignment liquid crystal cured film is also laminated after the vertical alignment liquid crystal cured film is laminated in the lower layer. Therefore, when the horizontal alignment liquid crystal cured film is formed, Under the influence of the vertically oriented liquid crystal hardened film of the lower layer, poor alignment or alignment defects may occur. Therefore, according to the composition of each layer used to form the laminate (the composition for forming a horizontal alignment film, the composition for forming a horizontal alignment liquid crystal cured film, the composition for forming a vertical alignment film, and the composition for forming a vertical alignment liquid crystal curing film) Depending on the type of solvent, the lower layer may be dissolved to cause changes in optical characteristics, poor alignment, or alignment defects. Therefore, it is necessary to appropriately select materials / solvent / solid content concentration / coating method / film thickness and the like contained in the composition used for each layer forming the laminate.

[Elliptical polarizer with optical compensation function]

The retardation plate with an optical compensation function of the present invention can be transferred by peeling off the substrate after being bonded to the object to be transferred, or by laminating an adhesive or the like in a state with the substrate, so that the optical compensation function can be added. The retardation plate has a function, that is, imparts its optical characteristics to a material to be transferred, and it is possible to manufacture an optical laminated body provided with the optical characteristics of the retardation plate with an optical compensation function. Among them, when laminated with a polarizing plate, an elliptical polarizing plate with an optical compensation function can be manufactured. In an embodiment of the present invention, it is preferable that the slow axis (optical axis) of the horizontally-oriented liquid crystal cured film and the absorption axis of the polarizing plate are laminated so that they are substantially 45 °. By laminating the slow axis (optical axis) of the optical film of the present invention and the absorption axis of the polarizing plate at substantially 45 °, a function as a circular polarizing plate can be obtained. In addition, 45 ° is generally in the range of 45 ± 5 °.

[Transferred]

Examples of the material to be transferred include: single-layer optical films, such as polarizers, retardation plates, brightness enhancement films, anti-glare films, anti-reflection films, diffusion films, and light-condensing films; multilayer optical films, such as phase A retardation plate, an elliptically polarizing plate, etc., among these, a retardation plate, a retardation plate, a polarizing plate, and an elliptically polarizing plate can be used suitably. The optical multilayer system of the present invention can be used in image display devices, such as: liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, and electron emission display devices ( Electric field emission display devices (FED, etc.)), surface-conduction electron-emitter display (SED)), electronic paper (display devices using electronic printing ink, electrophoretic elements), plasma display devices, projection Type display devices (grating light valve (GLV) display devices, display devices with digital micromirror devices (DMD), etc.) and piezoelectric ceramic display devices, especially suitable for organic EL display devices and touch panels Display device, etc.

[Polarizer]

The polarizing plate is composed of a polarizing element having a polarizing function. Examples of the polarizing element include an stretched film having an anisotropic absorption pigment adsorbed thereto, or a film having an anisotropic absorption pigment adsorbed upon application and orientation. Examples of pigments having absorption anisotropy include dichroic pigments.

An stretched film having an anisotropic pigment that has been adsorbed is generally produced by the following steps: a uniaxially oriented polyvinyl alcohol resin film Step of extending; step of adsorbing the dichroic pigment by dyeing the polyvinyl alcohol-based resin film with a dichroic pigment; treating the polyvinyl alcohol-based resin film having the dichroic pigment adsorbed with an aqueous boric acid solution A step; and a step of washing with an aqueous solution of boric acid, followed by washing. A polarizing plate can be obtained by bonding the polarizing element obtained in this way to a transparent protective film. Examples of the dichroic pigment include iodine and dichroic organic dyes. Examples of the dichroic organic dye include: dichroic direct dyes containing a diazo compound, such as C.I. Direct Red 39, and dichroic direct dyes containing a compound such as quinazo and azo. As described above, the thickness of the polarizing element obtained by uniaxially stretching the polyvinyl alcohol resin film, dyeing a dichroic dye, boric acid treatment, washing with water, and drying is preferably 5 μm to 40 μm.

[Adhesive]

Examples of the adhesive include pressure-sensitive adhesives, dry-curing adhesives, and chemically reactive adhesives. Examples of the chemically reactive adhesive include an active energy ray-curable adhesive.

The pressure-sensitive adhesive usually contains a polymer and may also contain a solvent. Examples of the polymer include acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers. Among them, acrylic adhesives containing acrylic polymers are excellent in optical transparency, have appropriate wetting and cohesiveness, and have excellent adhesion. They also have high weather resistance and heat resistance, and are not easily produced under heating and humidifying conditions. Floating and peeling are preferred.

Acrylic polymers have an alkyl group in the ester portion as the methyl group, (Meth) acrylic esters having 1 to 20 alkyl groups such as ethyl or butyl, and (meth) acrylic monomers having functional groups such as (meth) acrylic acid or hydroxyethyl (meth) acrylate Copolymers are preferred.

The pressure-sensitive adhesive containing such a copolymer is excellent in adhesiveness, and even when the adhesive is removed after being adhered to a material to be transferred, residues and the like are not generated on the material to be transferred, and are relatively easy to remove. , So it is better. The glass transition temperature of the acrylic polymer is preferably 25 ° C or lower, and more preferably 0 ° C or lower. The mass average molecular weight of such an acrylic polymer is preferably 100,000 or more.

Examples of the solvent include the solvents listed above. The pressure-sensitive adhesive may contain a light diffusing agent. The light diffusing agent is an additive that imparts light diffusivity to the adhesive, and may be fine particles having a refractive index different from that of the polymer contained in the adhesive. Examples of the light diffusing agent include fine particles containing an inorganic compound and fine particles containing an organic compound (polymer). Since a polymer containing an acrylic polymer and containing an adhesive as an active ingredient often has a refractive index of about 1.4 to 1.6, a light diffusing agent having a refractive index of 1.2 to 1.8 is appropriately selected. The refractive index difference between a polymer containing an adhesive as an active ingredient and a light diffusing agent is generally 0.01 or more. From the standpoint of brightness and display properties of a display device, 0.01 to 0.2 is preferred. The fine particles used as the light diffusing agent are preferably spherical fine particles and close to monodisperse fine particles, and more preferably fine particles having an average particle diameter of 2 to 6 μm. The refractive index is measured by a general minimum deviation method or an Abbe refractometer.

Examples of fine particles containing inorganic compounds include: oxidation Aluminum (refractive index 1.76) and silicon oxide (refractive index 1.45). Examples of the fine particles containing an organic compound (polymer) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), and methyl methacrylate / styrene copolymer resin beads ( (Refractive index 1.50 to 1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46), and Silicone resin beads (refractive index 1.46), etc. The content of the light diffusing agent is generally 3 to 30 parts by mass relative to 100 parts by mass of the polymer.

The thickness of the pressure-sensitive adhesive depends on its adhesion, etc. Although it is not particularly limited, it is generally 1 μm to 40 μm. From the viewpoints of processability and durability, the thickness is preferably 3 μm to 25 μm, and more preferably 5 μm to 20 μm. By setting the thickness of the adhesive layer formed by the adhesive to 5 μm to 20 μm, the brightness can be maintained when viewed from the front or when the display device is viewed from an oblique direction, and the display image is less prone to bleeding or blurring.

The dry-curable adhesive may contain a solvent. Examples of the dry-curing type adhesive include a polymer having a protonic functional group such as a hydroxyl group, a carboxyl group, or an amine group and an ethylenically unsaturated group, or a polymer containing a urethane polymer as a main component and further containing A composition of a cross-linking agent such as a valent aldehyde, an epoxy compound, an epoxy resin, a melamine compound, a zirconia compound, a zinc compound, or a hardening compound, and the like. Examples of the polymer having a protonic functional group such as a hydroxyl group, a carboxyl group, or an amine group and an ethylenically unsaturated group include ethylene-maleic acid copolymer, itaconic acid copolymer, acrylic acid copolymer, and acrylamide copolymer Materials, saponification of polyvinyl acetate, and polyvinyl alcohol resins.

Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl modified polyvinyl alcohol, acetoacetyl modified polyvinyl alcohol, and methylol modified polyethylene. Alcohol and amine modified polyvinyl alcohol. The content of the polyvinyl alcohol-based resin in the water-based adhesive is generally 1 to 10 parts by mass, and preferably 1 to 5 parts by mass with respect to 100 parts by mass of water.

Examples of the urethane resin include a polyester-based ionic polymer-type urethane resin and the like. The polyester-based ionic polymer-type urethane resin here is a urethane resin having a polyester skeleton, and is a resin into which a small amount of an ionic component (hydrophilic component) is introduced. This ionic polymer type urethane resin does not use an emulsifier and is emulsified in water to become an emulsion, so it can be used as an aqueous adhesive. When a polyester-based ionic polymer-type urethane resin is used, it is effective to prepare a water-soluble epoxy compound as a crosslinking agent.

Examples of the epoxy resin include polyamine polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine or triethylenetetramine with dicarboxylic acids such as adipic acid. Polyamine epoxy resin and the like obtained by epichlorohydrin reaction. Examples of commercially available products of the polyamine epoxy resin include: "Sumirez Resin (registered trademark) 650" and "Sumirez Resin (registered trademark) 675" (above manufactured by Sumika Chemtex Co., Ltd.), and "WS-525" (Manufactured by Japan PMC Co., Ltd.). When blending an epoxy resin, the amount of the epoxy resin is generally 1 to 100 parts by mass, preferably 1 to 50 parts by mass, relative to 100 parts by mass of the polyvinyl alcohol resin.

Adhesive layer formed from dry-curing adhesive The thickness is generally 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5 μm. When the adhesive layer formed from the dry-curing type adhesive is too thick, the appearance is liable to deteriorate.

The active energy ray-curable adhesive may contain a solvent. The active energy ray-curable adhesive is an adhesive that is hardened by irradiation with active energy rays. Examples of the active energy ray-curable adhesive include: a cationic polymerizable adhesive containing an epoxy compound and a cationic polymerization initiator; a radical polymerizable adhesive containing an acrylic curing component and a radical polymerization initiator; Contains both a cationically polymerizable hardening component such as an epoxy compound and a radically polymerizable hardening component such as an acrylic compound, and further contains a cationic polymerization initiator and a radical polymerization initiator adhesive; and does not contain These polymerization initiators are adhesives and the like which are hardened by irradiation with an electron beam.

Among them, radically polymerizable active energy ray hardening type adhesives containing an acrylic hardening component and a photoradical polymerization initiator, and cationically polymerizable active energy rays containing an epoxy compound and a photocationic polymerization initiator are particularly preferred. A hardening type adhesive is preferred. Examples of the acrylic curing component include (meth) acrylates such as methyl (meth) acrylate and hydroxyethyl (meth) acrylate, and (meth) acrylic acid. The active energy ray-curable adhesive containing an epoxy compound may further contain a compound other than the epoxy compound. Examples of the compound other than the epoxy compound include an oxetane compound and an acrylic compound.

Examples of the photo-radical polymerization initiator and photo-cationic polymerization initiator include the above-mentioned photo-radical polymerization initiator and photo-cationic polymerization. Starting agent. The content of the radical polymerization initiator and the cationic polymerization initiator is generally 0.5 to 20 parts by mass, and preferably 1 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable adhesive.

The active energy ray-curable adhesive may further contain an ion trapping agent, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow regulator, a plasticizer, and an antifoaming agent.

In the present specification, an active energy ray is defined as an energy ray that can decompose a compound capable of generating an active species so that the active species generates. Examples of such active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, gamma rays, and electron rays, and ultraviolet rays and electron rays are preferred. The preferable ultraviolet irradiation conditions are the same as those of the polymerizable liquid crystal compound.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, "%" and "part" in the examples refer to mass% and mass parts unless otherwise specified. In the following examples, the film thickness was measured using an Ellipsometer M-220 or a contact-type film thickness meter (MH-15M, Counter TC101, MS-5C, manufactured by Nikon Corporation). In addition, the phase difference value Rth (λ) and the in-plane phase difference value Re (λ) in the thickness direction and the apparent phase difference value R40 (λ) when measured from the 40 ° direction are based on the use of Oji Measurement Equipment Co., Ltd. KOBRA-WPR Or calculated by Ellipsometer M-220 manufactured by JASCO Corporation. Moreover, the Si / C ratio can be calculated by elemental analysis of a vertical alignment film, measurement of surface constituent elements using X-ray photoelectron spectroscopy, or a complete understanding When the structural formula of the compound used for forming the vertical alignment film is calculated from the structural formula. The corona treatment device was AGF-B10 manufactured by Kasuga Electric Corporation. When applying a composition to a base material, corona treatment can be performed suitably. Using the above-mentioned corona treatment device, it was performed once under the conditions of an output of 0.3 kW and a processing speed of 3 m / min.

[Example 1] [Modulation of composition for forming horizontal alignment film]

5 parts (weight-average molecular weight: 30,000) of a photo-alignment material having the following structure and 95 parts of cyclopentanone (solvent) were mixed as components, and the resulting mixture was stirred at 80 ° C for 1 hour to obtain a horizontal alignment film Formation composition.

[Modulation of composition for forming vertical alignment film]

The silane coupling agent "KBE-9103" manufactured by Shin-Etsu Chemical Industry Co., Ltd. was dissolved in a mixed solvent in which ethanol and water were mixed at a ratio of 9: 1 (mass ratio) to obtain a composition for vertical alignment film formation with a solid content of 0.5%. Thing.

[Composition for forming a horizontally-oriented liquid crystal cured film and curing the vertically-oriented liquid crystal Preparation of film-forming composition]

1.0 part of a leveling agent (F-556; manufactured by DIC Corporation) is added to the mixture in which the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B shown below are mixed at a mass ratio of 90:10 and belongs to the start of polymerization 6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinylphenyl) butane-1-one ("Irgacure369 (Irg369)", manufactured by BASF Japan Co., Ltd.) .

Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%, and the mixture was stirred at 80 ° C for 1 hour, thereby obtaining a composition for forming a horizontally-oriented liquid crystal cured film and vertical Composition for forming alignment liquid crystal cured film.

The polymerizable liquid crystal compound A is produced by a method described in Japanese Patent Application Laid-Open No. 2010-31223. The polymerizable liquid crystal compound B is produced by a method described in Japanese Patent Application Laid-Open No. 2009-173893. Each molecular structure is shown below.

[Polymerizable liquid crystal compound A]

[Polymerizable liquid crystal compound B]

[Manufacture of polarizing plate]

A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of more than 99.9 mol%, and a thickness of 75 μm was immersed in pure water at 30 ° C, and then immersed in 30% of iodine / potassium iodide / water at a mass ratio of 0.02 / 2 / In an aqueous solution of 100, iodine staining was performed (iodine staining step). The polyvinyl alcohol film subjected to the iodine dyeing step was immersed in an aqueous solution having a mass ratio of potassium iodide / boric acid / water of 12/5/100 at 56.5 ° C. to perform boric acid treatment (boric acid treatment step). Then, the polyvinyl alcohol film subjected to the boric acid treatment step was washed with pure water at 8 ° C., and then dried at 65 ° C. to obtain a polarizing element (the thickness after extension was 27 μm) that adsorbed the oriented iodine on the polyvinyl alcohol film. At this time, the stretching is performed in the iodine staining step and the boric acid treatment step. The total extension ratio of this extension is 5.3 times. The obtained polarizing element and a saponified cellulose triacetate film (manufactured by Konica Minolta; KC4UYTAC 40 μm) were bonded together with a nip roll via a water-based adhesive. While maintaining the tension of the obtained paste at 430 N / m, drying was performed at 60 ° C. for 2 minutes to obtain a polarizing plate having a cellulose triacetate film as a protective film on one side. In addition, the above water-based adhesive was added to 100 parts of water with 3 parts of carboxyl modified polyvinyl alcohol ("Kuraray Poval KL 318" manufactured by Kuraray) and water-soluble polyamine epoxy resin ("Sumirez Resin 650 manufactured by Sumika Chemtex"). ", 30% aqueous solution of solid content concentration) 1.5 parts.

The obtained polarizing plate was measured for optical characteristics. The measurement was performed using a polarizing element surface of the polarizing plate obtained as described above as an incident surface and using a spectrophotometer ("V7100", manufactured by JASCO Corporation). The absorption axis of the polarizing plate is the same as the extending direction of the polyvinyl alcohol. The obtained polarized plate has a photometric corrected cell transmittance of 42.1%, a photometric corrected polarized degree of 99.996%, a monomer hue a of -1.1, and a monomer hue b Is 3.7.

[Manufacturing of a laminated body composed of a substrate, a horizontal alignment film, and a horizontal alignment liquid crystal hardened film]

After performing a corona treatment on a COP film (ZF-14-50) manufactured by Japan Zeon Co., Ltd., a composition for forming a horizontally oriented film was coated with a bar coater, dried at 80 ° C for 1 minute, and irradiated with polarized UV light. The device ("SPOT CURE SP-9", manufactured by Ushio Electric Co., Ltd.) performs polarized UV exposure at a cumulative light amount of 100 mJ / cm ² at a wavelength of 313 nm and an axial angle of 45 °. The film thickness of the obtained horizontal alignment film was measured with an ellipsometer, and was 100 nm.

Next, the horizontal alignment film was coated with a composition for forming a horizontal alignment liquid crystal cured film by a bar coater and dried at 120 ° C for 1 minute. Then, a high pressure mercury lamp ("UNICURE VB-15201BY-A", Ushio Electric Co., Ltd.) was irradiated with ultraviolet rays (accumulated light quantity at a wavelength of 365 nm in a nitrogen environment: 500 mJ / cm ² ) to form a horizontally-oriented liquid crystal cured film, and a laminated layer composed of a substrate, a horizontally oriented film and a horizontally oriented liquid crystal cured film was obtained body. The film thickness of the horizontally-oriented liquid crystal cured film was measured by an ellipsometry, and was 2.3 μm.

[Re determination of horizontally oriented liquid crystal hardened film]

The in-plane retardation value ReA (λ) of the horizontally-oriented liquid crystal cured film produced by the above method is obtained after the COP belonging to the substrate is peeled off after being bonded to the glass via an adhesive, and then measured by a measuring machine ("KOBRA-WPR ", Manufactured by Oji Measurement Equipment Co., Ltd.). The measurement results of the phase difference values ReA (λ) at each wavelength were ReA (450) = 121nm, ReA (550) = 142nm, ReA (650) = 146nm, ReA (450) / ReA (550) = 0.85.

[Manufacturing of a laminated body composed of a substrate, a horizontal alignment film, a horizontal alignment liquid crystal hardened film, a vertical alignment film, and a vertical alignment liquid crystal cured film]

After performing a corona treatment on a laminate composed of the substrate, the horizontal alignment film, and the horizontal alignment liquid crystal cured film produced by the above method, the composition for forming a vertical alignment film was coated with a bar coater and dried at 80 ° C 1 minute, a vertical alignment film was obtained. The film thickness of the obtained vertical alignment film was measured with an ellipsometer, and was 50 nm.

Furthermore, the vertical alignment film was coated with a composition for forming a vertical alignment liquid crystal cured film by a bar coater, and dried at 120 ° C for 1 minute, and then a high-pressure mercury lamp ("UNICURE VB-15201BY-A", Ushio Electric Co., Ltd.) was irradiated with ultraviolet rays (with a cumulative light amount of 500 mJ / cm ^{2 in a} wavelength of 365 nm under a nitrogen environment) to form a vertically-oriented liquid crystal cured film, and obtained a substrate, a horizontally oriented film, a horizontally oriented liquid crystal cured film, and a vertically oriented film A laminated body composed of a vertically aligned liquid crystal cured film. The film thickness of the vertically aligned liquid crystal cured film was measured by an ellipsometry, and was 1.2 μm. Moreover, the interlayer distance between the horizontally-oriented liquid crystal cured film and the vertically-oriented liquid crystal cured film is 50 nm. The constituent element ratio of the vertical alignment film was Si / C = 0.33.

[Rth measurement of vertical alignment liquid crystal hardened film]

In order to determine the Rth of the vertical alignment liquid crystal cured film, a vertical alignment film and a vertical alignment liquid crystal cured film were manufactured on a COP film (ZF-14-50) made by Zeon Co., Ltd. in Japan in the same order as above, and passed through an adhesive ( Lintec's pressure-sensitive adhesive 15 μm) Laminates a vertically-aligned liquid crystal hardened film with glass. Before confirming that there is no phase difference in the COP, the phase of the incident angle of the light to the sample is measured by an ellipsometry. Difference. The average refractive index at a wavelength λ of 450 nm and 550 nm is measured using a refractive index meter (manufactured by Atago Co., Ltd., "multi-wavelength Abbe refractometer DR-M4"). The ReCs obtained from the obtained film thickness, average refractive index, and measurement results of an ellipsometry are RthC (450) =-63nm, RthC (550) =-73nm, RthC (450) / RthC (550) = 0.85 .

[Measurement of R0 and R40 of a multilayer body (phase difference plate with optical compensation function) composed of a horizontally oriented liquid crystal cured film, a vertically oriented film, and a vertically oriented liquid crystal cured film]

A laminated body composed of a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film manufactured by the above method was passed through an adhesive (a pressure-sensitive adhesive made by Lintec Corporation 15 μm) and After bonding the glass and peeling the COP to produce a measurement sample, before confirming that there is no phase difference between the horizontal alignment film and the vertical alignment film, use KOBRA-WPR to measure the front side of the phase difference plate with optical compensation function. The phase difference value R0 (λ) in the vertical direction and the phase difference value R40 (λ) when the horizontal axis of the liquid crystal cured film is centered on the fast axis and is inclined by 40 °. Calculate R0 (550) -R40 (550) |, R0 (450) -R40 (450) |, and | {R0 (450) -R40 (450) from the obtained values of R0 (λ) and R40 (λ) }-{R0 (550) -R40 (550)} |, and the results are shown in Table 1.

[Difference in In-Plane Average Refractive Index of Each Layer]

Each layer was coated on glass in accordance with the method described above, and the average refractive index of each layer was calculated using a refractive index meter (manufactured by Atago Co., Ltd., "Multiwavelength Abbe Refractometer DR-M4") or an ellipsometry, and each layer was confirmed The difference in the in-plane average refractive index is 0.2 or less.

[Flexibility test]

A glass plate having a thickness of 0.7 mm was placed on the coating film surface side of a multilayer body composed of a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film produced by the above method, so that the stack was laminated. After bending the body 180 ° while lying on the glass plate, use a 10x magnifying glass to transmit the light of the fluorescent lamp, and observe the bent part to confirm the existence of wrinkles and cracks. The results are shown in Table 1.

[Confirmation of reflection hue of curved part]

After applying the corona treatment to the coating film surface side of the multilayer body composed of the substrate, the horizontal alignment film, the horizontal alignment liquid crystal cured film, the vertical alignment film, and the vertical alignment liquid crystal cured film produced by the above method, the polarizing plate absorb The angle between the axis and the slow axis of the horizontal alignment film is 45 °. The adhesive is bonded to the polarizing plate produced in the above method, and the substrate is peeled off to form an elliptical polarizing plate with an optical compensation function. Then, it was bonded to the aluminum foil via an adhesive, and bent 180 ° so that the radius of the polarizer side became 1 cm, and the reflected hue of the bent portion was observed with the naked eye. The results are shown in Table 1.

(Examples 2 and 3)

Except that the thickness of the vertical alignment film was changed as described in Table 1, a retardation plate with an optical compensation function was produced by the same operation as in Example 1, and the retardation value measurement, bendability test, and reflection hue of the bent portion were performed. confirm. The results are shown in Table 1.

(Example 4)

0.5% by weight of polyimide ("Sun Ever SE-610", manufactured by Nissan Chemical Industries, Ltd.), 72.3% by weight of N-methyl-2-pyrrolidone, and 18.1% by weight of 2-butoxy Ethyl alcohol, 9.1% by weight of ethylcyclohexane, and 0.01% by weight of DPHA (manufactured by Shin Nakamura Chemical Co., Ltd.) were mixed to prepare a composition B for forming a vertical alignment film, except for using the composition B for forming a vertical alignment film. In the same manner as in Example 1, a phase difference plate with an optical compensation function was produced, and a phase difference measurement, a bendability test, and a reflection hue of the bent portion were performed. The results are shown in Table 1. The thickness of the vertical alignment film was measured with an ellipsometer, and was 0.2 μm. From this, it can be seen that the interlayer distance between the horizontally-oriented liquid crystal cured film and the vertically-oriented liquid crystal cured film is 0.2 μm. Furthermore, it was confirmed that the vertical alignment liquid crystal was hard during coating. When the composition for forming a film is formed, the vertical alignment film is eroded by a solvent, and alignment defects and poor alignment sometimes occur.

(Example 5)

In addition to changing the substrate to a polyethylene terephthalate film (manufactured by Lintec Co., Ltd .; SP-PLR382050, hereinafter referred to as "separator") subjected to release treatment, and changing the lamination order to a vertically oriented film, Except for the order of the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film, a retardation plate with an optical compensation function was produced by the same operation as in Example 1, and the retardation measurement, bendability test, and bent portion were performed. The reflection hue is confirmed. The results are shown in Table 1. The film thickness of the horizontal alignment film was measured with an ellipsometer, and was 0.2 μm. From this, it can be seen that the interlayer distance between the horizontally-oriented liquid crystal cured film and the vertically-oriented liquid crystal cured film is 0.2 μm.

(Examples 6 and 7)

Except changing the film thickness of the vertically-oriented liquid crystal cured film to change the values of RthC (450) and RthC (550) to those described in Table 1, the same operation as in Example 1 was performed to produce an optical compensation function. Phase difference plate, and perform phase difference measurement, bendability test, and reflection hue confirmation of the bend. The results are shown in Table 1.

(Example 8)

In addition to changing the composition for forming a vertical alignment liquid crystal cured film to The composition (B) for forming a vertical alignment liquid crystal cured film described below, and the drying temperature after applying the composition (B) for forming a vertical alignment liquid crystal cured film described above were changed from 120 ° C to 80 ° C or more. The same operation as in Example 1 was performed to produce a retardation plate with an optical compensation function, and a retardation measurement, a bendability test, and a reflection hue confirmation of the bent portion were performed. The results are shown in Table 1.

(Adjustment of the composition (B) for forming a vertical alignment liquid crystal cured film)

With respect to the liquid crystal compound LC242: Paliocolor LC242 (registered trademark of BASF), 0.1 parts of leveling agent F-556 and 3 parts of polymerization initiator Irg 369 are added, and the solid content concentration becomes 13%. Cyclopentanone was added to obtain a composition (B) for forming a vertical alignment liquid crystal cured film. The name of the obtained liquid crystal composition is referred to as "composition V". Liquid crystal composition LC242: Paliocolor LC242 (registered trademark of BASF Corporation)

(Comparative example 1)

After the laminated body of the horizontal alignment film and the horizontal alignment liquid crystal cured film was produced by the method described in Example 1, the laminated body of the vertical alignment film and the vertical alignment liquid crystal cured film was prepared on the COP by the same method as in the example (Lintec Corporation). Manufacturing). The obtained laminated bodies were bonded to each other with an adhesive (pressure-sensitive adhesive 15 μm manufactured by Lintec), and a phase difference measurement, a bendability test, and a reflection hue of the bent portion were performed. The results are shown in Table 1.

Hue reflection hue: ○ in the case of black, and X in the case where coloring is clearly confirmed.

Bendability test: ○ when no defect occurs, and × when there are defects such as wrinkles or cracks.

By applying the manufacturing method of the present invention, it is possible to obtain a retardation plate with an optical compensation function capable of suppressing defects such as wrinkles and cracks generated during bending.

Claims (18)

A method for manufacturing a retardation plate with an optical compensation function is to sequentially form a horizontal alignment film, a horizontal alignment liquid crystal hardened film, a vertical alignment film, and a vertical alignment liquid crystal cured film by the following steps, and through the steps of coating, drying, and orientation treatment Forming a horizontal alignment film; forming a horizontal alignment liquid crystal hardened film through the steps of coating, drying, and ultraviolet irradiation; further forming a vertical alignment film through the coating, drying, and ultraviolet steps; and forming a vertical alignment liquid crystal hardened film through the steps of coating, drying, and ultraviolet radiation. The method for manufacturing a retardation plate with an optical compensation function as described in item 1 of the scope of patent application, wherein a horizontal alignment film having a film thickness of 1.0 μm or less, a horizontal alignment liquid crystal hardened film, a vertical alignment film, and a vertical alignment are sequentially formed. Liquid crystal hardened film. The method for manufacturing a retardation plate with an optical compensation function according to any one of claims 1 to 2, wherein a horizontal alignment film composed of a light alignment film and a horizontal alignment liquid crystal hardened film are sequentially formed. , Vertical alignment film, vertical alignment liquid crystal hardened film. The method for manufacturing a retardation plate with an optical compensation function according to any one of claims 1 to 3, wherein a horizontal alignment film composed of a light alignment film including a cinnamon base, is sequentially formed, Horizontal alignment liquid crystal hardened film, vertical alignment film, vertical alignment liquid crystal cured film. The method for manufacturing a phase difference plate with an optical compensation function as described in any one of the scope of application for patents 1 to 4, wherein Orientation film, horizontally oriented liquid crystal cured film, vertical oriented film with a thickness of 1.0 μm or less, and vertically oriented liquid crystal cured film. The method for manufacturing a retardation plate with an optical compensation function according to any one of claims 1 to 5, wherein a horizontal alignment film, a horizontal alignment liquid crystal hardened film, and a vertical alignment including Si element are sequentially formed. Film, vertical alignment liquid crystal hardened film. The method for manufacturing a retardation plate with an optical compensation function according to any one of claims 1 to 6, wherein the horizontal alignment film, the horizontal alignment liquid crystal hardened film, and the Si / C element are 0.03 in this order. Vertical alignment film to 1.00, vertical alignment liquid crystal hardened film. According to the method for manufacturing a retardation plate with an optical compensation function according to any one of the scope of application for patents, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal are sequentially formed. Film, wherein the horizontally oriented liquid crystal hardened film system satisfies the following relationship (1), ReA (450) / ReA (550) <1.00 ... (1) In the formula, ReA (λ) represents the The in-plane phase difference value of the wavelength λnm, and the definition of the in-plane phase difference value ReA (λ) are as follows. ReA (λ) = (nxA (λ) -nyA (λ)) × dA In the formula, nxA (λ) is Represents the principal refractive index in the film plane of the horizontally oriented liquid crystal hardened film, and is the principal refractive index at the wavelength λ (nm); nyA (λ) means the refraction in a direction orthogonal to nxA (λ) in the same plane And a refractive index at λ (nm); dA represents the film thickness of the horizontally aligned liquid crystal cured film. According to the method for manufacturing a retardation plate with an optical compensation function according to any one of the scope of application patents, the horizontal alignment film, the horizontal alignment liquid crystal hardened film, the vertical alignment film, and the vertical alignment liquid crystal are sequentially formed. Film, wherein the vertical alignment liquid crystal cured film satisfies the following relationship (2), RthC (450) / RthC (550) <1.00 ... (2) In the formula, RthC (λ) represents the vertical alignment liquid crystal cured film to the wavelength The phase difference value in the thickness direction of λnm, the definition of the phase difference value RthC (λ) is as follows, RthC (λ) = ((nxC (λ) + nyC (λ)) / 2-rzC (λ)) × dC Here, nxC (λ) represents the principal refractive index of the vertically-oriented liquid crystal hardened film in the film plane and is the principal refractive index at the wavelength λ (nm); nyC (λ) represents the same plane as nxC (λ) The refractive index in the internal orthogonal direction is the refractive index at the wavelength λ (nm); nzC (λ) is the refractive index in the thickness direction of the vertically oriented liquid crystal cured film and is the refractive index at the wavelength λ (nm) ; DC represents the film thickness of the vertically aligned liquid crystal cured film. A method for manufacturing a retardation plate with an optical compensation function is to sequentially form a vertical alignment film, a vertical alignment liquid crystal hardened film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film by the following steps, and form a vertical alignment through coating and drying steps. A film; forming a vertically aligned liquid crystal hardened film through the steps of coating, drying, and ultraviolet irradiation; further forming a horizontally oriented film through the steps of coating, drying, and directional treatment; and A horizontally-oriented liquid crystal cured film is formed through the steps of coating, drying, and ultraviolet irradiation. The method for manufacturing a retardation plate with an optical compensation function as described in item 10 of the scope of patent application, wherein a vertical alignment film, a vertical alignment liquid crystal hardened film, a horizontal alignment film with a thickness of 1.0 μm or less, and a horizontal alignment are sequentially formed. Liquid crystal hardened film. The method for manufacturing a retardation plate with an optical compensation function according to item 10 or 11 of the scope of the patent application, wherein a vertical alignment film, a vertical alignment liquid crystal hardened film, and a horizontal alignment film composed of a light alignment film are sequentially formed. 2. Horizontally oriented liquid crystal hardened film. The method for manufacturing a retardation plate with an optical compensation function according to any one of claims 10 to 12, wherein a vertical alignment film, a vertical alignment liquid crystal hardened film, and Horizontal alignment film and horizontal alignment liquid crystal hardened film composed of light alignment film. The method for manufacturing a retardation plate with an optical compensation function according to any one of claims 10 to 13, wherein a vertical alignment film having a film thickness of 1.0 μm or less, a vertically aligned liquid crystal cured film, Horizontal alignment film, horizontal alignment liquid crystal hardened film. The method for manufacturing a retardation plate with an optical compensation function according to any one of claims 10 to 14, wherein a vertical alignment film containing a Si element, a vertically aligned liquid crystal hardened film, and a horizontal alignment are sequentially formed. Film, horizontally oriented liquid crystal hardened film. The method for manufacturing a retardation plate with an optical compensation function according to any one of claims 10 to 15 in the scope of application for a patent, wherein the phase difference plates are formed sequentially Alignment film, horizontal alignment liquid crystal hardened film, vertical alignment film with Si / C element 0.03 to 1.00, vertical alignment liquid crystal hardened film. According to the method for manufacturing a retardation plate with an optical compensation function according to any one of the claims 10 to 16, a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal are sequentially formed. Film, wherein the horizontal alignment liquid crystal cured film satisfies the following relationship (3), ReA (450) / ReA (550) <1.00 ... (3) In the formula, ReA (λ) represents the horizontal alignment liquid crystal cured film as a function of wavelength The in-plane phase difference value of λnm, the definition of the in-plane phase difference value ReA (λ) is as follows, ReA (λ) = (nxA (λ) -nyA (λ)) × dA In the formula, nxA (λ) is expressed as The principal refractive index in the film plane of the horizontally oriented liquid crystal hardened film is the principal refractive index at the wavelength λ (nm); nyA (λ) means the refractive index in a direction orthogonal to nxA (λ) in the same plane And is a refractive index at λ (nm); dA represents the film thickness of the horizontally aligned liquid crystal cured film. According to the method for manufacturing a retardation plate with an optical compensation function according to any one of claims 10 to 17, a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal are sequentially formed. Film, wherein the vertical alignment liquid crystal cured film satisfies the following relationship (4): RthC (450) / RthC (550) <1.00 ... (4) In the formula, RthC (λ) represents the vertical alignment liquid crystal cured film as a function of wavelength The phase difference value in the thickness direction of λnm, and the definition of the phase difference value RthC (λ) are as follows, RthC (λ) = ((nxC (λ) + nyC (λ)) / 2-nzC (λ)) × dC In the formula, nxC (λ) represents the principal refractive index of the vertically oriented liquid crystal hardened film in the film plane. And is the principal refractive index at the wavelength λ (nm); nyC (λ) means the refractive index in a direction orthogonal to nxC (λ) in the same plane, and is the refractive index at λ (nm); nzC ( λ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and is a refractive index at a wavelength λ (nm); dC represents the film thickness of the vertically aligned liquid crystal cured film.