TWI780207B - 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 invention relates to a phase difference plate with optical compensation function for a flexible display.

Flat panel displays such as organic EL image display devices generally have a planar image display surface. The image display surface of the flat panel display maintains a flat state when displaying images or not displaying images.

Retardation plates are often used in such flat panel displays. For example, in an organic EL image display device, in order to prevent light reflection at electrodes constituting the image display device, a circular polarizing plate combining a phase difference plate and a polarizing plate is used.

Among such retardation plates, a retardation plate exhibiting reverse wavelength dispersion is suitably used because it exhibits equal retardation performance in a wide wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersion, there is known a retardation plate comprising a horizontally oriented liquid crystal hardened by polymerizing and hardening a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion in a state of horizontal alignment. membrane.

Moreover, there is also a need for a phase difference plate with an optical compensation function, which has the compensation function "even when viewed from an oblique direction, it can also exhibit the same optical performance as when viewed from a frontal direction". As far as this kind of retardation plate with optical compensation function is concerned, in Patent Document 1 [Japanese Patent Application Laid-Open No. 2015-163935], a polymerizable liquid crystal compound in a vertically oriented state is proposed in addition to a horizontally oriented liquid crystal cured film. A vertically oriented liquid crystal cured film obtained by polymerization and curing. The same document also discloses that the horizontally oriented liquid crystal cured film and the vertically oriented liquid crystal cured film are laminated only through the oriented film or through a protective layer. Furthermore, the same document only discloses that the phase difference plate with an optical compensation function described in the same document can be used for a flat panel display.

(Prior Art Literature) (patent documents)

[Patent Document 1] Japanese Unexamined Patent Publication No. 2015-163935

In addition, a so-called flexible display that is a foldable display has also been developed. In flexible displays, the phase difference plate with optical compensation function is also folded together with the display.

However, if defects such as wrinkles and cracks occur during folding, when the flexible display is unfolded again to display images, the parts with defects such as wrinkles and cracks will become defects and damage the displayed image. Moreover, when folding under the state of displaying images, due to the elevation angle of the folded part (film plane and observation The angle formed by the direction in which the person views the picture) basically becomes extremely small, so the optical performance cannot be fully compensated, and the reflection of external light in the colored state is also a problem.

Therefore, the purpose of the present invention is to develop a flexible phase difference plate with optical compensation function, even if the phase difference plate with optical compensation function is bent, no wrinkles or cracks will occur. It also does not reflect external light in the shaded state.

The inventors of the present invention have completed the present invention as a result of intensive examinations to solve the above-mentioned problems.

That is, the present invention includes those described below.

[1] A manufacturing method of a phase difference plate with optical compensation function, which is to sequentially form a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film through the following steps, through coating, drying, The alignment treatment step forms a horizontal alignment film; forms a horizontal alignment liquid crystal cured film through the steps of coating, drying, and ultraviolet irradiation; further forms a vertical alignment film through the steps of coating and drying; and forms a vertical alignment liquid crystal through the steps of coating, drying, and ultraviolet irradiation hardened film.

[2] The method for manufacturing a phase difference plate with an optical compensation function as described in [1] above, wherein a horizontal alignment film having a film thickness of 1.0 μm or less, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment film are sequentially formed. Oriented liquid crystal hardening film.

[3] The method of manufacturing a phase difference plate with an optical compensation function as described in [1] or [2] above, wherein a horizontal alignment film composed of a light alignment film, a horizontal alignment liquid crystal cured film, Vertical alignment film, vertical alignment liquid crystal cured film.

[4] The method for producing a phase difference plate with an optical compensation function according to any one of the above [1] to [3], wherein a horizontal layer composed of a light alignment film containing a cinnamonyl group is sequentially formed. Alignment film, horizontal alignment liquid crystal cured film, vertical alignment film, vertical alignment liquid crystal cured film.

[5] The method of manufacturing a phase difference plate with an optical compensation function as described in any one of the above [1] to [4], wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a film thickness of 1.0 Vertical alignment film below μm, vertical alignment liquid crystal cured film.

[6] The method for producing a phase difference plate with an optical compensation function as described in any one of [1] to [5] above, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a silicon element-containing film are sequentially formed. Vertical alignment film, vertical alignment liquid crystal cured film.

[7] The method of manufacturing a phase difference plate with an optical compensation function as described in any one of [1] to [6] above, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, and Si/C Vertical alignment film and vertical alignment liquid crystal cured film with an element of 0.03 to 1.00.

[8] The manufacturing method of the phase difference plate with optical compensation function as described in any one of the above [1] to [7], which is to sequentially form a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, A vertically oriented liquid crystal cured film, wherein the horizontally oriented liquid crystal cured film satisfies the following relationship (1), ReA(450)/ReA(550)<1.00...(1)

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

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

[9] The manufacturing method of the phase difference plate with optical compensation function as described in any one of the above [1] to [8], which is to sequentially form a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, a vertical alignment film, and a vertical alignment film. Oriented liquid crystal cured film, wherein the vertically oriented liquid crystal cured film satisfies the following relationship (2), RthC(450)/RthC(550)<1.00...(2)

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

In the formula, nxC(λ) represents the main refractive index of the vertically oriented liquid crystal cured film in the film plane, and is the main refractive index at the wavelength λ (nm); nyC(λ) means that it is at the same The refractive index in the orthogonal direction in the plane 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 it is the refractive index at the wavelength λ (nm) Rate; dC represents the film thickness of the vertical alignment liquid crystal cured film.

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

Furthermore, the present invention also includes the following.

[10] A method of manufacturing a phase difference plate with optical compensation function, which is to sequentially form a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film through the following steps, and then go through the steps of coating and drying Forming a vertical alignment film; forming a vertical alignment liquid crystal cured film through the steps of coating, drying, and ultraviolet irradiation; further forming a horizontal alignment film through the steps of coating, drying, and alignment treatment; and forming a horizontal alignment liquid crystal through the steps of coating, drying, and ultraviolet irradiation hardened film.

[11] The method for manufacturing a phase difference plate with optical compensation function as described in [10] above, wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film with a film thickness of 1.0 μm or less, a horizontal alignment film, and a horizontal alignment film are sequentially formed. Oriented liquid crystal hardening film.

[12] The method of manufacturing a phase difference plate with an optical compensation function as described in [10] or [11] above, wherein a vertical alignment film, a vertical alignment liquid crystal cured film, and a photo-alignment film are sequentially formed. Horizontal alignment film, horizontal alignment liquid crystal cured film.

[13] The method for manufacturing a retardation plate with an optical compensation function as described in any one of [10] to [12] above, wherein the vertical Vertical alignment film, vertical alignment liquid crystal cured film, horizontal alignment film composed of photo-alignment film containing cinnamonyl group, and horizontal alignment liquid crystal cured film.

[14] The method for manufacturing a phase difference plate with an optical compensation function as described in any one of [10] to [13] above, 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, horizontal alignment film, horizontal alignment liquid crystal hardened film.

[15] The method for manufacturing a phase difference plate with an optical compensation function as described in any one of [10] to [14] above, wherein a vertical alignment film containing Si element and a vertical alignment liquid crystal cured film are sequentially formed , Horizontal alignment film, horizontal alignment liquid crystal hardening film.

[16] The method of manufacturing a phase difference plate with an optical compensation function as described in any one of [10] to [15] above, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, and Si/C Vertical alignment film and vertical alignment liquid crystal cured film with an element of 0.03 to 1.00.

[17] The manufacturing method of the phase difference plate with optical compensation function as described in any one of the above [10] to [16] is to sequentially form a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment film. Oriented liquid crystal cured film, wherein the horizontally oriented 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 oriented 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 main refractive index of the horizontally oriented liquid crystal cured film in the film plane, and is the main refractive index at the wavelength λ (nm); nyA(λ) It represents the refractive index in the direction perpendicular to nxA(λ) in the same plane, and is the refractive index at wavelength λ(nm); dA represents the film thickness of the horizontally oriented liquid crystal cured film.

[18] The manufacturing method of the phase difference plate with optical compensation function as described in any one of the above [1] to [17] is to sequentially form a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment film. Oriented liquid crystal cured film, wherein the vertically oriented liquid crystal cured film satisfies the following relationship (4), RthC(450)/RthC(550)<1.00...(4)

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

In the formula, nxC(λ) represents the main refractive index of the vertically oriented liquid crystal cured film in the film plane, and is the main refractive index at the wavelength λ (nm); nyC(λ) means that it is at the same The refractive index in the orthogonal direction in the plane 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 it is the refractive index at the wavelength λ (nm) Rate; dC represents the film thickness of the vertically oriented liquid crystal cured film.

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

According to the manufacturing method of the present invention, a retardation plate with an optical compensation function is obtained, and a polarizing plate is laminated on the retardation plate, whereby an elliptically polarizing plate with an optical compensation function can be manufactured.

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

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

[Horizontal Alignment Liquid Crystal Curing Film]

The horizontally oriented liquid crystal cured film is a film having refractive index anisotropy in the film plane, and is composed of a polymer containing 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 comprising a polymerizable liquid crystal compound in an aligned state by heating and/or light irradiation, It is preferable because thinning of the horizontally oriented liquid crystal cured film can be achieved and wavelength dispersion can be arbitrarily designed.

The 3-dimensional refractive index ellipsoid system formed by the horizontally oriented liquid crystal cured film can have biaxiality, but the one with uniaxiality is better. 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 including a polymerizable liquid crystal compound that is oriented horizontally to the plane of the horizontally oriented liquid crystal cured film, or may be a mixed Orientation (hybrid orientation) liquid crystal cured film or oblique orientation liquid crystal cured film. The refractive index ellipsoid formed by the orientation of the polymeric liquid crystal is at 3 Refractive indices nx, ny and nz in each direction can have the relationship of nx>ny≒nz (called positive A plate) or nx<ny≒nz (called negative A plate). nx represents the main refractive index 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 direction parallel to the plane of the horizontally oriented liquid crystal cured film and perpendicular to the nx direction in the refractive index ellipsoid formed by the horizontally oriented liquid crystal cured film. nz represents the refractive index perpendicular 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.

Any one of rod-like polymerizable liquid crystal and disc-like polymerizable liquid crystal can be used for the horizontal alignment liquid crystal cured film, but rod-like 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 the positive electrode A plate.

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

120nm≦ReA(550)≦170nm...(21)

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

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

When the in-plane retardation value ReA(550) of the horizontally oriented liquid crystal cured film exceeds the range of formula (21), a display using an elliptical polarizer with an optical compensation function and a retardation film with an optical compensation function will produce a positive hue The problem of turning red and turning blue. The better range of in-plane phase difference is 130nm≦ReA(550)≦160nm. When "ReA(450)/ReA(550)" of the horizontally oriented liquid crystal cured film exceeds 1.0, the ellipticity on the short-wavelength side of the elliptically polarizing plate provided with the horizontally oriented liquid crystal cured film deteriorates. The ellipticity of the elliptically polarizing plate on the short-wavelength side deteriorates and becomes smaller than 1.0, and the function of the elliptically polarizing plate tends to be impaired when viewed from the front on the short-wavelength side. The "ReA(450)/ReA(550)" is preferably from 0.75 to 0.92, more preferably from 0.77 to 0.87, and still more preferably from 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 retardation value is determined according to the following formula (24), in order to obtain the desired in-plane retardation value (ReA(λ): the in-plane phase of the horizontally oriented liquid crystal cured film at the wavelength λ(nm) difference), the 3D refractive index and film thickness dA can be adjusted. Furthermore, 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, in the refractive index ellipsoid formed by the horizontally oriented liquid crystal cured film, there is a relationship of nxA(λ)>nyA(λ)≒nzA(λ), and nxA(λ) represents the relationship between light of wavelength λ(nm) The main refractive index in the direction parallel to the plane of the horizontally oriented liquid crystal cured film. nyA(λ) means that in the refractive index ellipsoid formed by the horizontally oriented liquid crystal cured film, the light of wavelength λ (nm) is parallel to the plane of the horizontally oriented liquid crystal cured film and is positive relative to the nxA(λ) direction Refractive index in the intersection direction. dA represents the thickness of the horizontally oriented liquid crystal cured film. ]

The horizontally aligned liquid crystal cured film is preferably a polymer comprising a composition of a polymerizable liquid crystal compound in an aligned state as described above. The polymerizable liquid crystal compound for forming the horizontally oriented liquid crystal cured film is a liquid crystal compound having a polymerizable functional group, especially a liquid crystal compound having a photopolymerizable functional group. The photopolymerizable functional group refers to a group capable of participating in a polymerization reaction by active radicals and acids generated from a photopolymerization initiator. Examples of photopolymerizable functional groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, epoxy Ethyl, oxetanyl, etc. Among them, acryloxy, methacryloxy, vinyloxy, oxiranyl and oxetanyl are preferred, and acryloxy is more preferred. The liquid crystal can be thermotropic liquid crystal or lyotropic liquid crystal. The phase sequence structure can be nematic liquid crystal or smectic liquid crystal.

In the present invention, the polymerizable liquid crystal compound is represented by the following formula ( The compounds shown in I) are preferred.

In formula (I), Ar represents a divalent aromatic group which may have a substituent. Here, the aromatic group refers to a group having a planar ring 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 heteroatoms such as -N= or -S- are included to form a ring structure, it also includes non-covalent bond electron pairs on the heteroatoms and satisfies Hückel's law. The divalent aromatic group preferably contains 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 can be replaced by a halogen atom, an alkyl group having 1 to 4 carbons, a fluoroalkyl group having 1 to 4 carbons, or a fluoroalkyl group having 1 to 4 carbons. 4's alkoxy group, cyano group or nitro group, the carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted by oxygen atom, sulfur atom or 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 atoms contained in the alkanediyl group may be replaced by halogen atoms, and the -CH ₂ - contained in the alkanediyl group may be replaced by - O-, -S-, -Si-substitution. P1 and P2 each independently represent ^a polymerizable group or a ^hydrogen atom, and at least one of them is a polymerizable group.

^G1 and G2 are each independently 1,4 ^- phenylenediyl which may be substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, optionally 1,4-cyclohexanediyl substituted by at least one substituent from the group consisting of a halogen atom and an alkyl group with 1 to 4 carbon atoms is preferred, more preferably 1,4-cyclohexanediyl substituted by methyl Phenylenediyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl, especially unsubstituted 1,4-phenylenediyl, or unsubstituted Substituted 1,4-trans-cyclohexanediyl. Furthermore, it is preferable that at least one of ^G1 and ^G2 present in plural is a divalent alicyclic hydrocarbon group, and at least ^one of ^G1 and ^{G2 bonded} to L1 and L2 is A divalent alicyclic hydrocarbon group is more preferable.

L ¹ and L ² are each independently a single bond, an alkylene group with 1 to 4 carbons, -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- are preferred. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbons, and R ^c and R ^d represent an alkyl group having 1 to 4 carbons or a hydrogen atom. It is more preferable that 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 -} . Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent any of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. L ¹ and L ² are each independently a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ - or OCO-, which is still more preferably.

B ¹ and B ² are each independently a single bond, an alkylene group with 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 carbons. B ¹ and B ² are each independently more 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 independently more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO- or OCOCH ₂ CH ₂ -.

From the point of view of expressing reverse wavelength dispersion, k and l are preferably in the range of 2≦k+l≦6, and k+l=4 is better, and k=2 and l=2 are more preferable. good. When k=2 and l=2, it is more preferable since it has a symmetrical structure.

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

Examples of the polymerizable group represented by P1 or P2 include: epoxy group, vinyl group, vinyloxy group, ^{1 -} chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloxy group, Methacryloxy, oxiranyl, oxetanyl, etc. Among them, acryloxy, methacryloxy, vinyloxy, oxiranyl and oxetanyl are preferred, and acryloxy is more preferred.

環、嘧啶環、三唑環、三

環、吡咯啉環、咪唑環、吡唑環、噻唑環、苯并噻唑環、噻吩并噻唑環、

唑環、苯并

唑環及啡啉環等。該等之中，以具有噻唑環、苯并噻唑環或苯并呋喃環者為佳，以具有苯并噻唑基者更佳。而且，Ar中含有氮原子時，該氮原子以具有π電子者為佳。 Ar preferably has at least one member 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 benzene ring, naphthalene ring, anthracene ring, etc., preferably benzene ring and naphthalene ring. Examples of the aromatic heterocycle include: furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyridine ring,

ring, pyrimidine ring, triazole ring, three

ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring,

Azole ring, benzo

Azole ring and phenanthroline ring, etc. Among them, those having a thiazole ring, a benzothiazole ring or a benzofuran ring are preferable, and those having a benzothiazolyl group are more preferable. Furthermore, when Ar contains a nitrogen atom, it is preferable that the nitrogen atom has π electrons.

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

As for the aromatic group represented by Ar, the following groups are exemplified.

In the formula (Ar-1) to the formula (Ar-22), the mark * represents the linking part, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbons, and a cyano group , nitro, alkylsulfinyl with 1 to 12 carbons, alkylsulfonyl with 1 to 12 carbons, carboxyl, fluoroalkyl with 1 to 12 carbons, alkoxy with 1 to 6 carbons , Alkylthio group with 1 to 12 carbons, N-alkylamino group with 1 to 12 carbons, N,N-dialkylamino group with 2 to 12 carbons, N-alkane with 1 to 12 carbons Aminosulfonyl or N,N-dialkylsulfamoyl with 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 carbons.

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.

The aromatic hydrocarbon groups in Y ¹ , Y ² and Y ³ can be exemplified: phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl and other aromatic hydrocarbon groups with 6 to 20 carbon atoms, with phenyl and naphthyl as the Best, more preferably phenyl. Aromatic heterocyclic groups include, for example, furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl, etc., containing at least one heteroatom such as nitrogen atom, oxygen atom, sulfur atom, etc., with carbon numbers from 4 to 20 The aromatic heterocyclic group is preferably furyl, thienyl, pyridyl, thiazolyl and benzothiazolyl.

Y ¹ and Y ² may each independently be an optionally substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. 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 preferably each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbons, a cyano group, a nitro group, or an alkoxy group with 1 to 12 carbons, and Z ⁰ is A hydrogen atom, an alkyl group with 1 to 12 carbons, 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, or 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 formulas (Ar-1) to (Ar-22), the formulas (Ar-6) and (Ar-7) are preferable from the viewpoint of molecular stability.

環、嘧啶環、吲哚環、喹啉環、異喹啉環、嘌呤環、吡咯啶環等。該芳香族雜環基可具有取代基。而且，Y¹可與其所鍵結之氮原子及Z⁰一起為前述可經取代之多環系芳香族烴基或多環系芳香族雜環基。可列舉例如：苯并呋喃環、苯并噻唑環、苯并

唑環等。而且，前述式(I)所示之化合物係可根據例如日本特開2010-31223號公報所記載之方法製造。 Among the formulas (Ar-16) to (Ar-22), Y ¹ can form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . The aromatic heterocyclic group includes those mentioned above as an aromatic heterocyclic ring that may have Ar, for example: pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrroline ring,

ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring, etc. This aromatic heterocyclic group may have a substituent. Furthermore, Y ¹ may be the aforementioned polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group which may be substituted together with the nitrogen atom to which it is bonded and Z ⁰ . Examples include: benzofuran ring, benzothiazole ring, benzo

Azole ring etc. Furthermore, the compound represented by the aforementioned formula (I) can be produced, for example, according to the method described in JP-A-2010-31223.

A polymeric liquid crystal compound can be used individually or in combination of 2 or more types. When two or more are used in combination, the content of the compound represented by the above formula (I) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and 80 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. The above is even better.

Composition for forming a horizontally oriented liquid crystal cured film (hereinafter also referred to as a polymerizable liquid crystal group) used for forming a horizontally oriented liquid crystal cured film The finished 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 individually or in combination of 2 or more types.

The content of the polymerizable liquid crystal compound is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 90 to 98 parts by mass, relative 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 oriented liquid crystal cured film tends to be high. Here, the solid content refers to the total amount of components after removing the solvent from the composition.

As for the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound is preferred, and a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound is preferred. Examples of solvents include: water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 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; Ethylcyclohexyl Alicyclic hydrocarbon solvents such as alkanes; 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; Amide-based solvents such as acetylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolinone, etc. These solvents can be used individually or in combination of 2 or more types. But, because the compound shown in above-mentioned formula (I) generally has bigger conjugation system, so for solvent The solubility of solvents is low, and among the solvents listed above, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, ether solvents, amide solvents, and aromatic hydrocarbon solvents are preferred, and ester solvents are preferred. , ketone solvents, chlorine-containing solvents, ether-based solvents, and amide-based solvents are more preferable.

With respect to 100 parts by mass of the polymerizable liquid crystal composition, the content of the solvent is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass. Therefore, preferably, the solid fraction accounts for 2 to 50 parts by mass in 100 parts by mass of the composition. When the solid content of the composition is less than 50 parts by mass, since the viscosity of the composition decreases, the thickness of the horizontally aligned cured liquid crystal film becomes substantially uniform, and the cured horizontally aligned liquid crystal film tends to be less likely to be uneven. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the horizontally aligned liquid crystal cured film to be produced.

The polymerization initiator is a compound that generates a reactive species by applying heat or light, and initiates a polymerization reaction of a polymerizable liquid crystal or the like. Examples of the reactive species system include active species such as free radicals, cations or anions. Among them, a photopolymerization initiator that reacts by irradiation with light is preferable from the viewpoint of easy control of the reaction.

化合物等，光陽離子聚合起始劑可列舉如：芳香族重氮鹽、芳香族碘鎓鹽及芳香族鋶鹽等鎓鹽；鐵-芳烴錯合物等。具體上可列舉如：Irgacure(註冊商標)907、Irgacure 184、Irgacure 651、 Irgacure 819、Irgacure 250、Irgacure 369、Irgacure 379、Irgacure 127、Irgacure 2959、Irgacure 754、Irgacure 379EG(以上由BASF日本股份有限公司製造)；Seikuol BZ、Seikuol Z、Seikuol BEE(以上由精工化學股份有限公司製造)；Kayacure BP100(日本化藥股份有限公司製造)；Kayacure-UV1-6992(Dow公司製造)；ADEKA OPTOMER SP-152、ADEKA OPTOMER SP-170、ADEKA OPTOMER N-1717、ADEKA OPTOMER N-1919、ADEKA ARKLES NCI-831、ADEKA ARKLES NCI-930(以上由ADEKA股份有限公司製造)；TAZ-A、TAZ-PP(以上由日本Siber Hegner股份有限公司製造)以及TAZ-104(三和化學公司製造)；KAYARAD(註冊商標)系列(日本化藥股份有限公司製造)；CYRACURE UVI系列(Dow Chemical公司製造)；CPI系列(San Apro股份有限公司製造)、TAZ、BBI及DTS(以上由綠化學股份有限公司製造)；RHODORSIL(註冊商標)(RHODIA股份有限公司製造)等。光聚合起始劑可單獨使用或組合2種以上使用。該等之中，從易於控制反應之觀點來看，以藉由光的照射產生自由基之光自由基聚合起始劑為佳。 As a photopolymerization initiator, a photoradical polymerization initiator, a photocationic polymerization initiator, etc. are mentioned, for example. Examples of photoradical polymerization initiators include benzoin compounds, diphenyl ketone compounds, benzyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, three

Compounds, etc., photocationic polymerization initiators include, for example, onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic permeic acid salts; iron-arene complexes; and the like. Specifically, it can be listed as: Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG Co., Ltd. manufactured); Seikuol BZ, Seikuol Z, Seikuol BEE (the above are manufactured by Seiko Chemical Co., Ltd.); Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.); Kayacure-UV1-6992 (manufactured by Dow Corporation); ADEKA OPTOMER SP-152 , ADEKA OPTOMER SP-170, ADEKA OPTOMER N-1717, ADEKA OPTOMER N-1919, ADEKA ARKLES NCI-831, ADEKA ARKLES NCI-930 (the above are manufactured by ADEKA Co., Ltd.); TAZ-A, TAZ-PP (the above are manufactured by Japan Siber Hegner Co., Ltd.) and TAZ-104 (manufactured by Sanwa Chemical Co.); KAYARAD (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.); CYRACURE UVI series (manufactured by Dow Chemical); CPI series (manufactured by Sanwa Apro Co., Ltd.), TAZ, BBI, and DTS (manufactured by Green Chemical Co., Ltd. above); RHODORSIL (registered trademark) (manufactured by RHODIA Co., Ltd.), etc. A photoinitiator can be used individually or in combination of 2 or more types. Among them, a photoradical polymerization initiator that generates radicals by irradiation with light is preferable from the viewpoint of easiness to control the reaction.

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

As for the α-acetophenone-based polymerization initiator, for example, 2-methyl-2-N-morpholinyl-1-(4-methylsulfanylphenyl)propan-1-one, 2- Dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)- 2-(4-methylphenylmethyl)butan-1-one, etc., with 2-methyl-2-N-morpholinyl-1-(4-methylhydrogenthiophenyl)propane-1 -ketone and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one are more preferred. Commercially available α-acetophenone compounds include, for example, Irgacure 369, 379EG, and 907 (manufactured by BASF Japan Co., Ltd.) and Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.).

化合物及肟酯型咔唑化合物為佳，從靈敏度之觀點來看，以肟酯型咔唑化合物為更佳。肟酯型咔唑化合物可列舉例如：1,2-辛二酮、1-[4-(苯基硫基)-2-(O-苯甲醯基肟)]、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)等。肟酯型咔唑化合物之市售品可列舉如：Irgacure OXE-01、Irgacure OXE-02、Irgacure OXE-03(以上由BASF日本股份有限公司製造)；ADEKA OPTOMER N-1919、ADEKA ARKLES NCI-831(以上由ADEKA股份有限公司製造)等。 Oxime-based photopolymerization initiators generate free radicals when irradiated with light. The polymerization of the polymerizable liquid crystal compound in the deep portion of the horizontally aligned liquid crystal cured film proceeds favorably by the radicals. And it is preferable to use the photoinitiator which can utilize the ultraviolet-ray of wavelength 350nm or more effectively from a viewpoint of advancing the polymerization reaction in the deep part of a horizontal alignment liquid crystal cured film more efficiently. In terms of photopolymerization initiators that can effectively utilize ultraviolet light with a wavelength of 350nm or more, three

Compounds and oxime ester carbazole compounds are preferred, and oxime ester carbazole compounds are more preferred from the viewpoint of sensitivity. Examples of oxime ester carbazole compounds include: 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethyl ketone, 1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. Commercially available products of oxime ester carbazole compounds include: Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (the above are manufactured by BASF Japan Co., Ltd.); ADEKA OPTOMER N-1919, ADEKA ARKLES NCI-831 (the above are manufactured by ADEKA Co., Ltd.), etc.

The amount of the photopolymerization initiator added is generally 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is less likely to be disturbed.

By formulating a polymerization inhibitor, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. Examples of polymerization inhibitors include: hydroquinone and hydroquinones having substituents such as alkyl ethers; catechols having substituents such as alkyl ethers such as butyl catechol; gallol (pyrogallol) Radical scavengers such as 2,2,6,6-tetramethyl-1-piperidinyloxy radicals; thiophenols; β-naphthylamines and β-naphthalene phenols. In order to polymerize the liquid crystal compound without disturbing the alignment 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, preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass is better. A polymerization inhibitor can be used individually or in combination of 2 or more types.

；紅螢烯。光敏劑可單獨使用或組合2種以上使用。相對於聚合性液晶化合物100質量份，光敏劑之含量一般為0.01至10質量份，以0.05至5質量份為佳，以0.1至3質量份為更佳。 Furthermore, by using a photosensitizer, a photopolymerization initiator can be highly sensitive. Photosensitizers include, for example: xanthones such as xanthone and thioxanthone; anthracenes and anthracenes having substituents such as alkyl ethers;

; rubrene. A photosensitizer can be used individually or in combination of 2 or more types. The content of the photosensitizer is generally 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

The leveling agent has the ability to adjust the flow of polymerizable liquid crystal composition Mobility, and additives with the function of making the layer obtained by coating the composition more flat include, for example, polysiloxane-based, polyacrylate-based, and perfluoroalkyl-based leveling agents such as silane coupling agents. Specifically, such as: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (the above are all 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 manufactured by Shin-Etsu Chemical Co., Ltd.); Materials Japan Corporation); Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (the above are all 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, MEGAFAC F-477, MEGAFAC F-479, MEGAFAC F-482, MEGAFAC F-483 (the above are all manufactured by DIC Co., Ltd.); EFTOP (trade name) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (the above are all manufactured by Mitsubishi Materials 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 (the above are all provided by AGC Seimi Chemical Co., Ltd.); trade names E1830, E5800 (the above 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 It is a trade name: BM Chemie company make), etc. A leveling agent can be used individually or in combination of 2 or more types.

The content of the leveling agent is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the obtained horizontally oriented liquid crystal cured film tends to become smoother, which is preferable.

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

The horizontal alignment liquid crystal cured film can be obtained by coating the above-mentioned polymerizable liquid crystal composition on the horizontal alignment film described later, then removing the solvent, heating the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound in the aligned state and/or passing It is obtained by hardening it with active energy rays.

As for the method of coating the polymerizable liquid crystal composition on the horizontal alignment film (hereinafter also referred to as coating method A), examples include: extrusion coating method, direct gravure coating method, reverse Gravure coating method, CAP coating method, slit coating method, micro gravure method, die coating method, inkjet method, etc. Furthermore, coating machines such as a dip coater, a bar coater, and a spin coater can also be used. The method of coating, etc. Among them, when coating continuously in the form of roll-to-roll, micro gravure method, inkjet method, slit coating method and die coating method are preferable.

The method of removing the solvent (hereinafter also referred to as the method of removing the solvent) includes, for example, natural drying, ventilating drying, heating drying, reduced-pressure drying, and a combination thereof. Among them, natural drying or heat drying is preferable. The drying temperature is preferably in the range of 0 to 200°C, more preferably in the range of 20 to 150°C, and more preferably in the range of 50 to 130°C. The drying temperature is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes.

The active energy ray to be irradiated depends on the type of the polymerizable liquid crystal compound (especially the type of photopolymerizable functional group that the polymerizable liquid crystal compound has), and the type of photopolymerization initiator when the photopolymerization initiator is included. The type and the amount thereof are appropriately selected. Specifically, for example, 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 can be mentioned. Among them, in terms of the point that it is easy to control the progress of the polymerization reaction and can be widely used as a photopolymerization device in this technical field, ultraviolet light is preferred, and the method that can carry out photopolymerization by ultraviolet light It is preferable to select the type of polymerizable liquid crystal compound.

The light sources of the above-mentioned active energy rays include, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, and emission wavelengths LED light sources, chemical lamps, black lights, microwave excitation for light in the range 380 to 440nm Mercury lamps, metal halide lamps, etc.

The ultraviolet irradiation intensity is generally 10 to 3,000 mW/cm ² . The preferable ultraviolet irradiation intensity is the intensity|strength of the wavelength region effective to the activation of a photocationic polymerization initiator or a photoradical polymerization initiator. The irradiation time of light is generally 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, more preferably 0.1 second to 1 minute. When one or more irradiations are performed with such an ultraviolet irradiation intensity, the accumulated light intensity is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , more preferably 100 to 1,000 mJ/cm ² . When the accumulated light amount is below the above-mentioned lower limit, hardening of the polymerizable liquid crystal compound may be insufficient, and favorable transferability may not be obtained. Conversely, when the accumulated light quantity is above the above-mentioned upper limit, the phase difference plate with optical compensation function including the horizontal alignment liquid crystal cured film may be colored.

From the viewpoint of thinning the functional film, the film thickness of the horizontally oriented liquid crystal cured film is preferably at most 5 μm, more preferably at most 3 μm, and still more preferably at most 2.5 μm. Furthermore, the lower limit of the film thickness of the horizontally oriented liquid crystal cured film is preferably at least 0.1 μm, more preferably at least 0.5 μm, and still more preferably at least 1.0 μm. The film thickness of the horizontally oriented liquid crystal cured film can be measured using an ellipsometer or a contact film thickness gauge.

[Horizontal Oriented Film]

The orientation film is a film having an orientation binding force to orient the polymerizable liquid crystal compound of the liquid crystal cured film in a predetermined direction. In terms of orientation treatments necessary to exhibit orientation constraints, such as: friction treatments, light orientation Treatment, light exposure treatment, etc. Moreover, various orientations such as vertical orientation, horizontal orientation, hybrid orientation, and oblique orientation can be controlled according to the type of orientation film, rubbing conditions, and light irradiation conditions. Among them, the horizontal alignment film is an alignment film having an alignment binding force for aligning the polymerizable liquid crystal compound of the liquid crystal cured film in the horizontal direction. Therefore, a horizontally aligned liquid crystal film can be formed by using a horizontally aligned film.

As for the alignment film, it is preferable to have solvent resistance that does not dissolve due to coating of the polymerizable liquid crystal composition, and heat resistance to heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound.

As for the horizontal alignment film that exhibits the orientation binding force that aligns the horizontally aligned liquid crystal cured film in the horizontal direction, examples include rubbing alignment films, photo alignment films, and grooves with concavo-convex patterns or multiple grooves on the surface. Oriented film, etc. For example, when applied to a long roll-shaped film, a photo-alignment film is preferable from the viewpoint that the orientation direction can be easily controlled.

The rubbed alignment film generally applies a composition containing an alignment polymer and a solvent (hereinafter also referred to as a composition for forming a rubbed alignment film) on a substrate or the like, removes the solvent to form a coating film, and coats the rubbed alignment film. The membrane is rubbed, thereby imparting directional constraints.

唑、聚伸乙亞胺、聚苯乙烯、聚乙烯基吡咯啶酮、聚丙烯酸及聚丙烯酸酯類。該等定向性聚合物可為單獨使用或組合2種以上使用。 As for the orientation polymer, for example: polyamide or gelatin having an amide bond, polyamic acid of polyimide and its hydrolyzate having an amide bond, polyvinyl alcohol, alkyl Modified polyvinyl alcohol, polyacrylamide, poly

Azole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylates. These alignment polymers may be used alone or in combination of two or more.

The concentration of the alignment polymer in the composition for forming a rubbed alignment film may be such that the alignment polymer is completely dissolved in the solvent. The content of the orientation polymer is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the composition.

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

As the solvent, for example, the solvents exemplified in the paragraph of the horizontally aligned liquid crystal cured film can be used. The method of coating the composition for forming a rubbed alignment film on a substrate or the like includes the aforementioned coating method A, and the method of removing the solvent includes the aforementioned solvent removal method A.

As a method of rubbing treatment, for example, a method of bringing a rotating rubbing roll wrapped with a rubbing cloth into contact with the above-mentioned coating film is mentioned. If masking is performed during the rubbing process, a plurality of regions (patterns) having different orientation directions can be formed on the alignment film.

The photo-alignment film is generally prepared by coating a composition (also called a photo-alignment film-forming composition) containing a polymer or monomer having a photoreactive group and a solvent on a substrate, etc., and removing the solvent It can be obtained by irradiating polarized light (preferably polarized light UV). The light directing film can arbitrarily adjust the direction of the directing force by selecting the polarization direction of the irradiated polarized light.

The photoreactive group refers to a group that produces alignment ability by light irradiation. Specifically, it can be listed as: orientation induction reaction, isomerization reaction, photodimerization reaction, photocrosslinking reaction or photodispersion reaction of molecules produced by light irradiation. The decomposition reaction and the like become the origin of the orientation ability and participate in the photoreaction group. The photoreactive group is preferably a group with an unsaturated bond, especially a group with a double bond, such as a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), At least one group 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 photoreactive groups having C=C bonds include vinyl, polyalkenyl, stilbene, stilbazole, stilbazolium, chalcone and cinnamon Acyl group. Examples of the photoreactive group having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. The photoreactive group with N=N bond can enumerate for example: azophenyl group, azonaphthyl group, aromatic heterocyclic azo group, bis-azo group, formazan group and azoxybenzene (azoxybenzene) group. ) structure of the foundation. Examples of photoreactive groups having a C=O bond include diphenyl ketone groups, coumarin groups, anthraquinone groups, and maleimide groups. These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, halogenated alkyl and the like.

In terms of excellent orientation, a group that participates in a photodimerization reaction or a photocrosslinking reaction is preferable. Among them, the photoreactive group that participates in the photodimerization reaction is preferable; in terms of easily obtaining a photoalignment film that requires less amount of polarized light irradiation required for alignment and is excellent in thermal stability and stability over time, it is based on Cinnamoyl and chalcone groups are preferred. It is particularly preferable that the polymer having a photoreactive group has a cinnamoyl group so that the end of the side chain of the polymer has a cinnamic acid structure or a cinnamate ester structure.

The content of polymers or monomers with photoreactive groups It can be regulated by the type of polymer or monomer or the thickness of the intended photoalignment film. Relative to 100 parts by mass of the composition for forming a photoalignment film, preferably at least 0.2 parts by mass, and 0.3 to 10 parts by mass The range is better.

As the solvent system, for example, the solvents exemplified in the paragraph of the horizontally aligned liquid crystal cured film can be used. The method of applying the composition for forming a photoalignment film on a substrate or the like includes the aforementioned coating method A, and the method of removing the solvent includes the aforementioned solvent removal method A.

In the case of irradiating polarized light, for example, a form in which polarized light is directly irradiated to the solvent-removed composition for forming a light alignment film coated on a substrate or the like. Moreover, it is preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in the wavelength region where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength of 250 to 400 nm is particularly preferred. The light sources for irradiating the polarized light include, for example, xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and the like. Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferred because of their high luminous intensity of ultraviolet rays with a wavelength of 313 nm. By irradiating the light from the above-mentioned light source through an appropriate polarizing element, polarized light UV can be irradiated. Examples of the polarizing element include polarizing filters, Glan-Thompson and Glan-Taylor polarizers, and wire grids. Among them, a wire-grid type polarizing element is preferable from the viewpoint of large area and heat resistance.

In addition, when rubbing or polarized light irradiation is performed, if masking is performed, a plurality of regions (patterns) in which liquid crystal alignment directions are different can also be formed.

The groove (groove) oriented film is a film with a concave-convex pattern or a plurality of grooves on the film surface. 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 oriented along the direction of the grooves.

The method of obtaining the groove alignment film can be exemplified: after exposing the surface of the photosensitive polyimide film through an exposure mask having a pattern-shaped slit, developing and rinsing are performed to form a concave-convex pattern; A method of forming a layer of UV curable resin before hardening on a plate-shaped master having grooves on the surface, and transferring the formed resin layer to a base material or the like to harden; A method in which a master plate is press-bonded to an uncured UV-curable resin film formed on a substrate or the like to form concavities and convexities, and then cured.

The composition for forming a horizontal alignment film such as the above composition for forming a rubbed alignment film and the composition for forming a photo alignment film may contain, in addition to the solvent, the additives exemplified in the paragraph of the horizontal alignment cured film.

From the viewpoint of thinning the retardation plate with optical compensation function, the film thickness of the horizontal alignment film is preferably not more than 1 μm, more preferably not more than 0.5 μm, and still more preferably not more than 0.3 μm. Furthermore, the film thickness of the horizontal alignment film is preferably at least 1 nm, more preferably at least 5 nm, still more preferably at least 10 nm, and particularly preferably at least 30 nm. The film thickness of the horizontally oriented film can be measured using an ellipsometer or a contact film thickness gauge.

[Vertical Alignment Liquid Crystal Curing Film]

The horizontally oriented liquid crystal cured film is a film with refractive index anisotropy in the direction perpendicular to the film plane, and is composed of a polymer containing a polymerizable liquid crystal compound. The method of coating the polymerizable liquid crystal composition on the vertical alignment film and polymerizing the polymerizable liquid crystal composition including the polymerizable liquid crystal compound in the alignment state by heating and/or light irradiation is used to form the vertically aligned liquid crystal cured film. When forming, it is preferable because the thinning of the vertical alignment liquid crystal cured film can be achieved and the wavelength dispersion characteristic can be arbitrarily designed.

The 3-dimensional refractive index ellipsoid formed by vertically oriented liquid crystal cured film can have biaxiality, but the one with uniaxiality is preferable. The vertically aligned liquid crystal cured film may be a vertically aligned liquid crystal cured film, which is composed of a polymer of a polymerizable liquid crystal composition including a polymerizable liquid crystal compound aligned in a direction perpendicular to the plane of the liquid crystal cured film, or may be It is a hybrid oriented liquid crystal cured film or an oblique oriented liquid crystal cured film. The refractive index nx, ny and nz of the three directions of the refractive index ellipsoid formed by the orientation of the polymerizable liquid crystal can have nz>nx≒ny (called positive C plate) or nz<nx≒ny (called negative electrode C board) relationship. nx represents the main refractive index in the direction parallel to the plane of the vertically oriented liquid crystal cured film in the refractive index ellipsoid formed by the vertically oriented liquid crystal cured film. ny represents the refractive index in the direction parallel to the plane of the vertically aligned liquid crystal cured film and perpendicular to the nx direction in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film. Moreover, when nx=ny, nx can be made into arbitrary directions in the plane of the vertical alignment liquid crystal cured film. nz represents the refractive index in the direction perpendicular to the plane of the vertically oriented liquid crystal cured film in the refractive index ellipsoid formed by the vertically oriented liquid crystal cured film.

Rod polymeric liquid can be used for vertical alignment liquid crystal hardening film Either crystal or disc-shaped polymeric liquid crystals, but rod-shaped polymeric liquid crystals are preferred. When the rod-like polymerizable liquid crystal forms a vertically aligned liquid crystal cured film, the vertically aligned liquid crystal cured film becomes a positive electrode C plate.

When the vertically oriented liquid crystal cured film is a positive C plate, the retardation value RthC(λ) of the vertically oriented liquid crystal cured film in the thickness direction to light of wavelength λnm is preferably to satisfy the optical characteristics shown in the following formula (31). Furthermore, it is also preferable to satisfy the optical characteristics represented by the following formula (32) and formula (33). It is more preferable to vertically align the cured liquid crystal film to satisfy the optical characteristics represented by the following formula (31), the following formula (32) and the following formula (33).

-100nm≦RthC(550)≦-50nm...(31)

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

RthC(450)/RthC(550)≦1.0...(32)

1.00≦RthC(650)/RthC(550)...(33)

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

When the retardation value RthC(550) of the vertically oriented liquid crystal cured film in the thickness direction exceeds the range of formula (31), there will be a tendency to apply an elliptical polarizing plate with an optical compensation function to a display that includes a retardation film with an optical compensation function. The problem of the hue turning red or blue. The more preferable range of the retardation value in the thickness direction is -95nm≦RthC(550)≦-55nm, and the more preferable range is -90nm≦RthC(550)≦-60nm. Vertical Alignment Liquid Crystal Curing Film When "RthC(450)/RthC(550)" exceeds 1.0, the ellipticity becomes worse when it observes from the short-wavelength side tendency of the elliptically polarizing plate provided with this vertical alignment liquid crystal cured film. When the ellipticity of the elliptically polarizing plate on the short-wavelength side deteriorates and decreases from 1.0, the function as an elliptically polarizing plate on the short-wavelength side tends to be impaired. "RthC(450)/RthC(550)" is preferably from 0.75 to 0.92, more preferably from 0.77 to 0.87, and still more preferably from 0.79 to 0.85.

The retardation value in the thickness direction of the vertically oriented liquid crystal cured film can be adjusted by the thickness of the vertically oriented 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 retardation value in the thickness direction), the 3D refractive index and film thickness dC can be adjusted. Furthermore, 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, in the refractive index ellipsoid formed by the vertically oriented liquid crystal cured film, there is a relationship of nzC(λ)>nxC(λ)≒nyC(λ). In the formula, nzC(λ) represents the In the formed refractive index ellipsoid, the refractive index of the light of wavelength λ (nm) in the direction perpendicular to the plane of the vertically oriented liquid crystal cured film. nxC(λ) represents the refractive index ellipsoid formed by the vertically oriented liquid crystal cured film , for light of wavelength λ (nm), the maximum refractive index in the direction parallel to the plane of the vertically oriented liquid crystal cured film. nyC(λ) indicates that in the refractive index ellipsoid formed by the vertically oriented liquid crystal cured film, the vertically oriented liquid crystal is hardened The plane of the film is parallel to the nxC direction and is orthogonal to the refractive index of the light of wavelength λ (nm). But when nzC(λ)=nyC(λ), nxC(λ) represents the vertical Orient the refractive index of any direction parallel to the plane of the liquid crystal hardening film. Here, dC represents the thickness of the vertically aligned liquid crystal cured film. )

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

As the polymerizable liquid crystal compound that can be used for the formation of the vertically aligned liquid crystal cured film, it is preferable to use the compound represented by the above formula (I). By using the compound represented by the above-mentioned formula (I), reverse wavelength dispersibility can be expressed, and the relationship between the above-mentioned formulas (31) and (32) can be fully satisfied.

The polymerizable liquid crystal compound which can be used for a vertical alignment liquid crystal cured film can be used individually or in combination of 2 or more types. When two or more are used in combination, the content of the compound represented by the above formula (I) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and 80 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. The above is even better.

The composition for forming a vertically aligned liquid crystal cured film (hereinafter also referred to as a polymerizable liquid crystal composition) used for a vertically aligned liquid crystal cured film may further contain a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, Adhesion promoter. These additives can be used individually or in combination of 2 or more types.

The content of the polymerizable liquid crystal compound is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 90 to 98 parts by mass, relative 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 refers to the total amount of components after removing the solvent from the composition.

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

With respect to 100 parts by mass of the polymerizable liquid crystal composition, the content of the solvent is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass. Therefore, the solid fraction in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is less than 50 parts by mass, since the viscosity of the composition decreases, the thickness of the vertically aligned cured liquid crystal film becomes substantially uniform, and there is a tendency that the vertically aligned cured liquid crystal film becomes less uniform. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the vertically aligned liquid crystal cured film to be produced.

The polymerization initiator system can generate reaction by applying heat or light A compound that responds to active species and initiates polymerization reactions such as polymerizable liquid crystals. Reactive species include, for example, active species such as free radicals, cations or anions. Among them, a photopolymerization initiator that reacts by irradiation with light is preferable from the viewpoint of easy control of the reaction. As the photopolymerization initiator, the same initiator as that used in the composition for forming a horizontally aligned liquid crystal cured film can be used.

The amount of the photopolymerization initiator added is generally 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal composition. Within the above range, the reaction of the polymerizable group can proceed sufficiently, and the orientation of the polymerizable liquid crystal compound is less likely to be disturbed.

By formulating a polymerization inhibitor, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. As the polymerization inhibitor, the same thing as that used in the composition for forming a horizontally aligned liquid crystal cured film can be used. In order to polymerize the liquid crystal compound without disturbing the alignment 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, preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. Quality parts are better. A polymerization inhibitor can be used individually or in combination of 2 or more types.

Furthermore, by using a photosensitizer, the sensitivity of a photopolymerization initiator can be improved. As the photosensitizer, the same thing as that used in 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, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

The leveling agent has the ability to adjust the flow of polymerizable liquid crystal composition As additives for the function of making the layer obtained by coating the composition more flat, the same ones used for the composition for forming a horizontally oriented liquid crystal cured film can be used.

The content of the leveling agent is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the obtained vertically aligned liquid crystal cured film tends to become smoother, which is preferable.

The polymerizable liquid crystal composition used for forming the vertical alignment liquid crystal cured film can be obtained by stirring components other than the polymerizable liquid crystal compound such as the polymerizable liquid crystal compound and additives at a predetermined temperature.

The vertical alignment liquid crystal curing film can be obtained by coating the above-mentioned polymerizable liquid crystal composition on the vertical alignment film described later, then removing the solvent, and heating and/or Hardened by active energy rays.

The method of coating the polymerizable liquid crystal composition on the vertical alignment film can be the same method as that used to form the horizontal alignment liquid crystal cured film.

The method of removing the solvent can use the same method as when forming the horizontally oriented liquid crystal cured film.

The active energy ray to be irradiated depends on the type of the polymerizable liquid crystal compound (especially the type of photopolymerizable functional group that the polymerizable liquid crystal compound has), and the type of photopolymerization initiator when the photopolymerization initiator is included. The type and the amount thereof are appropriately selected. Specifically, it can be cited For example: 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, in terms of the point that it is easy to control the progress of the polymerization reaction and can be widely used as a photopolymerization device in this technical field, ultraviolet light is preferred, so that photopolymerization can be carried out by ultraviolet light It is preferable to select the type of polymerizable liquid crystal compound.

As the light source of the above-mentioned active energy rays, the same ones as those used when forming the horizontally oriented liquid crystal cured film can be used.

The ultraviolet irradiation intensity is generally 10 to 3,000 mW/cm ² . The intensity of ultraviolet irradiation is preferably the intensity of the wavelength region effective for activation of the photocationic polymerization initiator or the photoradical polymerization initiator. The irradiation time of light is generally 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, more preferably 0.1 second to 1 minute. When one or more irradiations are performed with such an ultraviolet irradiation intensity, the accumulated light intensity is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , more preferably 100 to 1,000 mJ/cm ² . When the accumulated light amount is below the above-mentioned lower limit, hardening of the polymerizable liquid crystal compound becomes insufficient, and favorable transferability may not be obtained. Conversely, when the accumulated light quantity is above the above-mentioned upper limit, the phase difference plate with optical compensation function including the vertical alignment liquid crystal cured film may be colored.

From the viewpoint of thinning the functional film, the film thickness of the vertically aligned liquid crystal cured film is preferably 3 μm or less, more preferably 2 μm or less, and more preferably 1.5 μm or less. Moreover, the lower limit of the film thickness of the vertically aligned liquid crystal cured film is preferably at least 0.1 μm, more preferably at least 0.3 μm, and 0.5 μm or more is still more preferable. The film thickness of the vertically oriented liquid crystal cured film can be measured with an ellipsometer or a contact film thickness gauge.

[Vertical Orientation Film]

The orientation film is a film having an orientation binding force to orient the polymerizable liquid crystal compound of the liquid crystal cured film in a predetermined direction. Furthermore, various orientations such as vertical orientation, horizontal orientation, hybrid orientation, and oblique orientation can be controlled by the type of orientation film, rubbing conditions, and light irradiation conditions. Among them, the vertical alignment film is an alignment film having an alignment binding force for aligning the polymerizable liquid crystal compound of the liquid crystal cured film in the vertical direction. Therefore, by using a vertical alignment film, a vertical alignment liquid crystal film can be formed.

It is preferable to use a material that lowers the surface tension of the substrate or the like for the vertical alignment film. Such materials can include the above-mentioned directional polymers, such as: polyimide, polyamide, polyamic acid of its hydrolyzate, perfluoroalkyl and other fluorine-based polymers and silane compounds, and these through condensation reaction The obtained polysiloxane compound. The vertical alignment film system can be obtained by applying a composition (hereinafter also referred to as a composition for forming a vertical alignment film) containing such a material and a solvent (for example, the solvent exemplified in the paragraph of the vertical alignment liquid crystal film) on a substrate or the like. On, after removing the solvent, it is obtained by applying heat or the like to the coating film.

When a silane compound is used for the vertical alignment film, the vertical alignment film is made of a compound containing Si and C as constituent elements from the viewpoint of easily reducing the surface tension and improving the adhesion with the layer adjacent to the vertical alignment film. The formed film is preferable, and a silane compound can be suitably used. In the present invention, the liquid crystal film is arranged between the horizontal alignment liquid crystal film and the vertical alignment liquid crystal film When the vertical alignment film is used, in the phase difference plate with 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 gap between the layers. Interface stripping.

The silane compound can be suitably applied to polysiloxanes such as the above-mentioned silane coupling agent, for example: vinyltrimethoxysilane, vinyltriethoxysilane, vinylparaffin (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-Methacryloxypropyltrimethoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropyltriethoxysilane, 3-Glycidoxypropyldimethoxymethylsilane, 3-Glycidoxypropylethoxydimethylsilane, etc.

The silane compound can be polysiloxane monomer type or polysiloxane oligomer (polymer) type. When polysiloxane oligomers are expressed in the form of (monomer)-(monomer) copolymers, such as: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercapto Propyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane Copolymers containing mercaptopropyl groups; such as mercaptomethyltrimethoxysilane alkane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer and mercaptomethyltriethoxysilane Copolymers containing mercaptomethyl groups of silane-tetraethoxysilane copolymers; such as 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacrylyl Oxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane Propyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryl Oxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3- Copolymers of methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymers containing methacryloxypropyl groups; such as 3-acryloxypropyltrimethyl Oxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane Methoxysilane Copolymer, 3-Acryloxypropyltriethoxysilane-Tetraethoxysilane Copolymer, 3-Acryloxypropylmethyldimethoxysilane-Tetramethoxysilane silane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane silane copolymer and 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer containing acryloxypropyl copolymer; such as vinyltrimethoxysilane- Tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, ethylene Triethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, ethylene Methyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer and vinylmethyldiethoxysilane-tetraethoxysilane Copolymers containing vinyl copolymers; such as 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, -Aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxy silane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane silane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer containing amine groups, etc. A silane compound can be used individually or in combination of 2 or more types. In addition, it is also used as a leveling agent, and can also be used as a silane coupling agent.

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

From the point of view of easy to further improve the adhesion and the coating properties of the composition for forming a cured vertically aligned liquid crystal film, and the point of view that the layer disposed in the lower layer is not easily soluble in the production method of the retardation plate with optical compensation function described later From the point of view, the vertical alignment film is preferably a film composed of a compound whose constituent elements include Si element, C element, and O element. Furthermore, C including C bonded to the Si atom of the silane compound forming the vertical alignment film The number of carbon atoms of the preferred alkyl or alkoxy substituent is preferably from 1 to 30, more preferably from 2 to 25, and still more preferably from 3 to 20. That is, the ratio of Si element to 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 not less than the above-mentioned lower limit, the coatability of the composition for forming a vertically aligned liquid crystal cured film can be improved, and when the Si/C ratio is not more than the above-mentioned upper limit, the adhesion to the adjacent layer can be improved.

As the solvent system, for example, the solvents exemplified in the paragraph of the horizontally aligned liquid crystal cured film can be used. The coating method of the vertical alignment film-forming composition includes the above coating method A, and the solvent removal method includes the solvent removal method A above.

The composition for vertical alignment film formation may contain the additive etc. which were illustrated in the paragraph of the horizontal alignment liquid crystal cured film other than a solvent.

From the point of view of thinning the retardation plate with optical compensation function and the presentation of the directional constraint force, 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. Furthermore, the film thickness of the vertical alignment film is preferably at least 1 nm, more preferably at least 5 nm, still more preferably at least 10 nm, and particularly preferably at least 30 nm. The film thickness of the vertically oriented film can be measured by using an ellipsometer or a contact film thickness gauge.

[Substrate]

The substrate is in the form of a composition for forming an alignment film or a liquid crystal cured film. When the composition is used, it can be designed to transfer the film coated on the substrate by peeling off the substrate, or it can be designed to be non-transferable due to the adhesion to the substrate. However, from the point of view of thin film, it is better to transfer to the transfer object and the design of the peelable substrate. Examples of the above-mentioned substrates include glass substrates and film substrates. From the viewpoint of processability, film substrates are preferred. In terms of continuous production, long roll-shaped films are used. for better. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norcamphene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate ; Polyacrylate; Cellulose esters such as cellulose triacetate, cellulose diacetate and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Plastics such as phenylene sulfide and polyphenylene ether. The surface of the substrate may be subjected to release treatment such as silicone treatment. Examples of commercially available cellulose ester substrates include: "FUJITAC FILM" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (all manufactured by Konica Minolta Optical (manufactured by Konica Minolta Opto Co., Ltd.) and the like. Such a resin can be used as a base material by forming a film by a conventional method such as a solvent casting method and a melt extrusion method.

Commercially available cyclic olefin-based resins include, for example, "Topas" (registered trademark) (manufactured by Ticona (Germany)), "ARTON" (registered trademark) (manufactured by JSR Co., Ltd.), "ZEONOR" (registered trademark) , "ZEONEX" (registered trademark) (manufactured by ZEON Co., Ltd., Japan), and "APEL" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.). Commercially available cyclic olefin-based resin substrates can also be used. commercially available cyclic alkenes Examples of hydrocarbon-based resin substrates include "ESUSHINA" (registered trademark), "SCA40" (registered trademark) (manufactured by Sekisui Chemical Industry Co., Ltd.), "ZEONOR FILM" (registered trademark) (manufactured by OPTES Co., Ltd. ) and "ARTON FILM" (registered trademark) (manufactured by JSR Co., Ltd.).

The substrate is preferably one with a thickness that is easy to laminate horizontally oriented liquid crystal cured film, horizontal oriented film, vertically oriented liquid crystal cured film, and vertical oriented film, and is easy to peel off. The thickness of such a substrate is generally 5 to 300 μm, preferably 20 to 200 μm.

[Retardation plate with optical compensation function]

The phase difference plate with optical compensation function of the present invention preferably contains a horizontally oriented liquid crystal cured film, a horizontally oriented film or a vertically oriented film, and a vertically oriented liquid crystal cured film in sequence, and satisfies the following (1) to (4) essentials.

The layer-to-layer distance between the horizontally oriented liquid crystal cured film and the vertically oriented liquid crystal cured film is 5 μm or less. ...(1)

A horizontal alignment film or a vertical alignment film is included between the layers of the horizontal alignment cured liquid crystal film and the vertical alignment liquid crystal cured film. ...(2)

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

Wherein, ReA(λ) represents the in-plane retardation value of the horizontally oriented liquid crystal cured film at a wavelength of λnm.

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

But nxA represents the main position of the horizontally oriented liquid crystal cured film in the film plane Refractive index, nyA represents the refractive index in the direction perpendicular to nxA in the same plane, and dA represents the film thickness of the horizontally oriented liquid crystal cured film.

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

Wherein, RthC(λ) represents the retardation value in the thickness direction of the vertically oriented liquid crystal cured film in the wavelength λnm. The phase difference value 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 the direction perpendicular to nxC in the same plane, nzC represents the refractive index in the thickness direction of the vertically oriented liquid crystal cured film, and dC represents The film thickness of vertical alignment liquid crystal cured film.

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

Moreover, the interlayer distance between the horizontally oriented liquid crystal cured film and the vertically oriented liquid crystal cured film is shown in formula (1), 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 excellent. Furthermore, the film thickness of the horizontal alignment film is preferably at least 1 nm, more preferably at least 5 nm, still more preferably at least 10 nm, and particularly preferably at least 30 nm.

The retardation plate with optical compensation function is preferably to satisfy the following relationship (5). In terms of the value of |R0(550)-R40(550)|, when an ellipsoidal polarizing plate 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 inclined wavelength near 550nm The amount of light leakage becomes less and the smaller one is appropriate. The value of |R0(550)-R40(550)| is preferably below 10nm, more preferably below 5nm, and below 4nm. Even better, especially preferably below 3nm.

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

Among them, R0(λ) represents the in-plane retardation value of the phase difference plate with optical compensation function including the horizontally oriented liquid crystal cured film and the vertically oriented liquid crystal cured film. In addition, R40 represents the direction perpendicular to the main refractive index direction in the plane of the film (fast axis direction) in the phase difference plate with optical compensation function including the horizontally oriented liquid crystal cured film and the vertically oriented liquid crystal cured film. ) is rotated 40 degrees around. The apparent phase difference when .

The retardation plate with optical compensation function is preferably one that satisfies the following relational expression (6). As far as the value of |R0(450)-R40(450)| is concerned, when an ellipsoidal polarizing plate 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 inclined wavelength near 450nm The amount of light leakage is reduced and the smaller one is appropriate. The value of |R0(450)-R40(450)| is preferably below 10nm, more preferably below 5nm, even more preferably below 4nm, especially preferably below 3nm

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

However, R0(λ) represents the in-plane retardation value of the phase difference plate with optical compensation function including the horizontally oriented liquid crystal cured film and the vertically oriented liquid crystal cured film. In addition, R40 indicates that in a phase difference plate with an optical compensation function including a horizontally oriented liquid crystal cured film and a vertically oriented liquid crystal cured film, it is perpendicular to the main refractive index direction in the film plane (fast axis direction) in the same plane Apparent phase difference values when the orientation periphery is rotated by 40°.

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

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

When the relationship (7) is satisfied, when the ellipsoidal polarizing plate with optical compensation function is applied to the display, in order to make the front and oblique reflection hue close to black, the value of (7) It is preferably less than 3 nm, more preferably less than 2 nm, and more preferably less than 1 nm.

And when the average refractive index difference of each layer, that is, the difference between the average refractive index of each layer constituting the phase difference plate with optical compensation function of the present invention and the average refractive index of other layers adjacent to the layer is large, it will Light leakage may occur due to the influence of interface reflection between layers. The average refractive index difference of each layer at a wavelength of 550 nm is preferably at most 0.20, more preferably at most 0.15, still more preferably at most 0.10, and most preferably at most 0.05. Within this range, the generation of light leakage due to interface reflection can be suppressed.

The average refractive index difference of each layer can specifically include the following: (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 difference between the horizontally oriented liquid crystal cured film and the When the horizontal alignment film is included between the vertical alignment liquid crystal hardening films, (2-a) the difference between the average refractive index of the horizontal alignment liquid crystal hardening film and the average refractive index of the horizontal alignment film, (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 the 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 optical compensation function of the present invention may include layers other than horizontally oriented liquid crystal cured film, horizontally oriented liquid crystal cured film, vertically oriented liquid crystal cured film, and vertical oriented film. Other orientation films, protective layers, etc. Other oriented liquid crystal cured films include, for example, the above-mentioned vertically oriented liquid crystal cured films, horizontally oriented liquid crystal cured films, etc. Other oriented films include, for example, the above-mentioned oriented films.

The protective layer is generally preferably formed of a composition for forming a protective layer, and 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.

The solvent contained in the composition for forming a protective layer may be the same as the solvents exemplified above, and among them, water, alcohol solvent and At least one solvent selected from the group consisting of ether solvents. Alcohol solvent can be enumerated such as: methanol, ethanol, butanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, Ethylene glycol butyl ether and propylene glycol monomethyl ether. Examples of ether solvents 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, preferably 0.1 μm to 3 μm.

[Manufacturing method of retardation plate with optical compensation function]

The manufacturing method of the phase difference plate with optical compensation function of the present invention is not particularly limited if it is a method that can laminate horizontally oriented liquid crystal cured film, horizontally oriented film or vertically oriented film, and vertically oriented liquid crystal cured film in the order described. Preferably: a method of laminating a horizontal alignment film on a substrate, followed by lamination of a horizontal alignment liquid crystal cured film, and further lamination of a vertical alignment film, and then lamination of a vertical alignment liquid crystal cured film (hereinafter referred to as manufacturing method A); or on a substrate A method of laminating a vertical alignment film, followed by lamination of a vertical alignment cured film, further lamination of a horizontal alignment film, and then lamination of a horizontal alignment cured film (hereinafter referred to as manufacturing method B). The lamination method of the horizontal alignment liquid crystal cured film, horizontal alignment film, vertical alignment liquid crystal cured film, and vertical alignment film can use the above-mentioned formation methods of each layer.

When the retardation plate with optical compensation function is manufactured by manufacturing method A or manufacturing method B, poor alignment or alignment defects may occur due to the alignment of the liquid crystal cured film disposed on the lower layer. That is, in the case of manufacturing method A, the vertical alignment cured film is laminated after the horizontal alignment cured film is laminated on the lower layer. Therefore, when the vertical alignment cured film is formed, it may be affected by the horizontal alignment cured film of the lower layer. influences In the case of poor orientation or orientation defects, in the case of manufacturing method B, the horizontal orientation liquid crystal cured film is also laminated after the vertically aligned liquid crystal cured film of the lower layer, so when forming the horizontally aligned liquid crystal cured film, it will Poor alignment or alignment defects may occur due to the influence of the vertically aligned liquid crystal cured film on the lower layer. Therefore, depending on the composition of each layer used to form the laminate (horizontal alignment film-forming composition, horizontal alignment liquid crystal cured film-forming composition, vertical alignment film-forming composition, vertical alignment liquid crystal cured film-forming composition) Depending on the type of solvent, the lower layer may be dissolved to cause changes in optical properties, poor alignment, and alignment defects. Therefore, it is necessary to appropriately select materials/solvents/solid content concentrations/coating methods/film thicknesses, etc. contained in compositions used to form the respective layers of the laminate.

[Elliptic polarizer with optical compensation function]

The phase difference plate with optical compensation function of the present invention can be transferred by peeling off the base material after being bonded with the transfer object, or laminated with an adhesive or the like in the state where the base material is attached, and can be equipped with an optical compensation function. The function of the phase difference plate, that is, to impart its optical properties to the object to be transferred, and to manufacture an optical laminate that has the optical properties of a phase difference 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 produced. In the 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 be laminated so as to form substantially 45°. By laminating so that the slow axis (optical axis) of the optical film of the present invention and the absorption axis of the polarizing plate become substantially 45°, the function as a circular polarizing plate can be obtained. In addition, basically 45° is generally in the range of 45±5°.

[to be transferred]

The material to be transferred can include: single-layer optical film, such as polarizing plate, phase difference plate, brightness enhancement film, anti-glare film, anti-reflection film, diffusion film, light-concentrating film, etc.; multi-layer optical film, such as phase Among them, a retardation plate, a retardation plate, a polarizing plate, and an elliptically polarizing plate can be suitably used. 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, electron emission display devices ( Field emission display devices (FED, etc.), surface conduction electron emission display devices (SED, surface-conduction electron-emitter display)), electronic paper (display devices using electronic ink, electrophoretic components), plasma display devices, projection Type display devices (grating light valve (GLV, grating light valve) display devices, display devices with digital micromirror devices (DMD), etc.), piezoelectric ceramic display devices, etc., especially suitable for organic EL display devices and touch panels display device, etc.

[polarizer]

The polarizer is composed of a polarizing element with a polarizing function. Examples of the polarizing element include: a stretched film adsorbed with an anisotropic absorption dye, or a film coated with an anisotropic absorption dye. Examples of dyes having absorption anisotropy include dichroic dyes.

The stretched film that absorbs the pigment with absorption anisotropy is generally produced through the following steps: the polyvinyl alcohol-based resin film is uniaxially Extending step; dyeing the polyvinyl alcohol-based resin film with a dichroic dye to absorb the dichroic dye; treating the polyvinyl alcohol-based resin film adsorbed with the dichroic dye with a boric acid aqueous solution and a step of washing with water after being treated with an aqueous solution of boric acid. The polarizing element thus obtained is bonded to a transparent protective film to obtain a polarizing plate. Examples of dichroic dyes include iodine and dichroic organic dyes. Dichroic organic dyes include, for example, dichroic direct dyes containing disazo compounds such as C.I. Direct Red 39, and dichroic direct dyes containing compounds such as para-azo and tetra-azo. As mentioned above, the thickness of the polarizing element obtained by uniaxially stretching the polyvinyl alcohol resin film, dyeing with a dichroic dye, treating with boric acid, washing with water and drying is preferably 5 μm to 40 μm.

[adhesive]

Adhesives include, for example, pressure-sensitive adhesives, dry-curable adhesives, and chemically reactive adhesives. As a chemical reaction type adhesive agent, an active energy ray hardening type adhesive agent is mentioned, for example.

Pressure-sensitive adhesives usually contain polymers and may also contain solvents. Examples of polymers include acrylic polymers, polysiloxane polymers, polyesters, polyurethanes, polyethers, and the like. Among them, acrylic adhesives containing acrylic polymers have excellent optical transparency, appropriate wettability and cohesion, excellent adhesion, and high weather resistance and heat resistance. Floating and peeling etc. are preferred.

Acrylic polymers use the alkyl group of the ester part as a methyl group, (meth)acrylic esters of alkyl groups with 1 to 20 carbons such as ethyl or butyl, and (meth)acrylic monomers with 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 if the adhesive is removed after being attached to the transferred object, there will be no adhesive residue on the transferred object, and it will be easier to remove , so it is better. The glass transition temperature of the acrylic polymer is preferably below 25°C, more preferably below 0°C. The mass average molecular weight of such an acrylic polymer is preferably 100,000 or more.

As a solvent, the solvent etc. which were mentioned above-mentioned solvent are mentioned, for example. The pressure sensitive adhesive may contain a light diffusing agent. The light-diffusing agent is an additive for imparting light-diffusing properties to the adhesive, and may be fine particles having a refractive index different from that of a polymer included in the adhesive. As a light-diffusion agent, the fine particle containing an inorganic compound, and the fine particle containing an organic compound (polymer), are mentioned, for example. Most polymers containing an acrylic polymer and an adhesive as an active ingredient have a refractive index of about 1.4 to 1.6, so it is better to select a light diffusing agent with a refractive index of 1.2 to 1.8. The difference in refractive index between the polymer containing the adhesive as an active ingredient and the light diffusing agent is generally more than 0.01, preferably 0.01 to 0.2 from the viewpoint of brightness and displayability of the display device. The microparticles used as the light diffusing agent are preferably spherical microparticles and close to monodisperse microparticles, more preferably microparticles with an average particle diameter of 2 to 6 μm. The refractive index is measured by a general minimum deviation method or an Abbe refractometer.

Microparticles containing inorganic compounds can be listed such as: oxidation Aluminum (refractive index 1.76) and silicon oxide (refractive index 1.45), etc. Microparticles containing organic compounds (polymers) can be exemplified as: melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), 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 Polysiloxane 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 adhesive force, etc., and is generally 1 μm to 40 μm, although not particularly limited. From the standpoint of processability and durability, the thickness is preferably 3 μm to 25 μm, 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 viewing the display device from the front or obliquely, and the displayed image is less prone to bleeding or blurring.

The dry-curable adhesive may contain a solvent. Dry-curable adhesives include, for example, polymers of monomers having protic functional groups such as hydroxyl, carboxyl, or amine groups and ethylenically unsaturated groups, or polymers containing urethane polymers as the main component and further containing polysaccharides. Aldehydes, epoxy compounds, epoxy resins, melamine compounds, zirconia compounds, zinc compounds and other crosslinking agents or compositions of hardening compounds. Polymers having protic functional groups such as hydroxyl, carboxyl or amine groups and monomers with ethylenically unsaturated groups include: ethylene-maleic acid copolymers, itaconic acid copolymers, acrylic acid copolymers, and acrylamide copolymers Saponified products of polyvinyl acetate and polyvinyl alcohol-based resins.

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

Examples of the urethane resin include polyester-based ionomer type urethane resins and the like. Here, the polyester-based ionomer type urethane resin 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. The ionomer-type urethane resin does not use an emulsifier, and is emulsified in water to form an emulsion, so it can be made into a water-based adhesive. When using a polyester-based ionomer-type urethane resin, it is effective to mix a water-soluble epoxy compound as a crosslinking agent.

Examples of epoxy resins include polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine or triethylenetetramine with dicarboxylic acids such as adipic acid, and combining the polyamide polyamines with Polyamide epoxy resin obtained by reaction of epichlorohydrin, etc. Commercially available polyamide epoxy resins include, for example, "Sumirez Resin (registered trademark) 650" and "Sumirez Resin (registered trademark) 675" (the above are manufactured by Sumika Chemtex Co., Ltd.), "WS-525" (manufactured by Japan PMC Co., Ltd.), etc. When preparing epoxy resin, the amount of epoxy resin added is generally 1 to 100 parts by mass, preferably 1 to 50 parts by mass, relative to 100 parts by mass of polyvinyl alcohol-based resin.

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

The active energy ray-curable adhesive may contain a solvent. The active energy ray-curable adhesive is an adhesive that is cured by irradiation with active energy rays. Examples of active energy ray-curable adhesives include cationic polymerizable adhesives containing epoxy compounds and cationic polymerization initiators; radical polymerizable adhesives containing acrylic hardening components and radical polymerization initiators; Adhesives that contain both cationically polymerizable hardening components such as epoxy compounds and radically polymerizable hardening components such as acrylic compounds, and further contain cationic polymerization initiators and radical polymerization initiators; and do not contain These polymerization initiators are adhesives or the like that are cured by electron beam irradiation.

Among them, radically polymerizable active energy ray-curable adhesives containing acrylic hardening components and photoradical polymerization initiators, and cationically polymerizable active energy ray adhesives containing epoxy compounds and photocationic polymerization initiators Hardening adhesives are 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 agent containing an epoxy compound may further contain compounds other than an epoxy compound. Examples of compounds other than epoxy compounds include oxetane compounds, acrylic compounds, and the like.

Photoradical polymerization initiators and photocationic polymerization initiators can be listed such as: the above-mentioned photoradical polymerization initiators and photocationic polymerization initiators starter. The content of the radical polymerization initiator and cationic polymerization initiator is generally 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, relative to 100 parts by mass of the active energy ray-curable adhesive.

The active energy ray-curable adhesive may further contain ion scavengers, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, defoamers, and the like.

In this specification, an active energy ray is defined as an energy ray that decomposes a compound capable of generating an active species to generate an active species. Such active energy rays include, for example, visible light, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, gamma rays, and electron rays, among which ultraviolet rays and electron rays are preferable. Preferable ultraviolet irradiation conditions are the same as those for the polymerization of the above-mentioned polymerizable liquid crystal compound.

[Example]

Hereinafter, the present invention will be described more specifically by way of examples. In addition, "%" and "parts" in the examples refer to mass % and mass parts unless otherwise specified. In addition, in the following examples, the film thickness was measured using Ellipsometer M-220 manufactured by JASCO Corporation or a contact film thickness meter (MH-15M, Counter TC101, MS-5C manufactured by Nikon Corporation). In addition, the retardation value Rth(λ) in the thickness direction, the in-plane retardation value Re(λ), and the apparent retardation value R40(λ) when measured from the 40° direction are from Oji Scientific Instruments Co., Ltd. KOBRA-WPR , or Ellipsometer M-220 manufactured by JASCO Co., Ltd. to measure and calculate. Furthermore, the ratio of Si/C can be calculated from elemental analysis of the vertically oriented film, measurement of surface constituent elements using X-ray photoelectron spectroscopy, or in a fully understood In the case of the structural formula of the compound used for forming the vertical alignment film, it can be calculated from the structural formula. In addition, as a corona treatment device, AGF-B10 manufactured by Kasuga Electric Co., Ltd. was used. When applying the composition to a substrate, corona treatment may be appropriately performed. Using the above-mentioned corona treatment device, it was performed once under the conditions of an output of 0.3kW and a treatment speed of 3m/min.

[Example 1] [Preparation of composition for horizontal alignment film formation]

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

[Preparation of composition for vertical alignment film formation]

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

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

With respect to the mixture of polymerizable liquid crystal compound A and polymerizable liquid crystal compound B shown below at a mass ratio of 90:10, 1.0 parts of a leveling agent (F-556; manufactured by DIC Corporation) was added and belonged to the polymerization initiation 2-Dimethylamino-2-benzyl-1-(4-morpholinophenyl)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 it stirred at 80 degreeC for 1 hour, thereby obtaining the composition for forming a cured film for horizontal alignment liquid crystal and the composition for vertical alignment. A composition for forming an oriented liquid crystal cured film.

The polymerizable liquid crystal compound A was produced by the method described in JP-A-2010-31223. Furthermore, the polymerizable liquid crystal compound B was produced according to the method described in JP-A-2009-173893. Each molecular structure is shown below.

[Polymerizable Liquid Crystal Compound A]

[Polymerizable Liquid Crystal Compound B]

[Manufacture of polarizing plate]

Immerse a polyvinyl alcohol film with an average degree of polymerization of about 2,400, a saponification degree of more than 99.9 mol%, and a thickness of 75 μm in pure water at 30°C, and then soak it in iodine/potassium iodide/water at a mass ratio of 0.02/2/ 100 aqueous solution, iodine staining (iodine staining step). The polyvinyl alcohol film after the iodine dyeing step was immersed in an aqueous solution with a mass ratio of potassium iodide/boric acid/water of 12/5/100 at 56.5° C. for boric acid treatment (boric acid treatment step). The polyvinyl alcohol film treated with boric acid was washed with pure water at 8° C., and then dried at 65° C. to obtain a polarizing element (thickness after stretching: 27 μm) with oriented iodine adsorbed on the polyvinyl alcohol film. In this case, the elongation is performed in the iodine staining step and the boric acid treatment step. The total extension ratio of this extension was 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. The obtained bonded product was dried at 60° C. for 2 minutes while maintaining a tension of 430 N/m to obtain a polarizing plate having a cellulose triacetate film as a protective film on one side. In addition, the above-mentioned water-based adhesive agent added 3 parts of carboxyl-modified polyvinyl alcohol ("Kuraray Poval KL 318" manufactured by Kuraray) and water-soluble polyamide epoxy resin ("Sumirez Resin 650" manufactured by Sumika Chemtex) to 100 parts of water. ", prepared by 1.5 parts of an aqueous solution with a solid content concentration of 30%.

Optical characteristics of the obtained polarizing plate were measured. The measurement was implemented with a spectrophotometer ("V7100", manufactured by JASCO Corporation) using the polarizer surface of the polarizing plate obtained above as the incident surface. The absorption axis of the polarizing plate is consistent with the extension direction of polyvinyl alcohol. The photometrically corrected monomer transmittance of the obtained polarizing plate is 42.1%, the photometrically corrected polarization degree is 99.996%, the monomer hue a is -1.1, and the monomer hue b is 3.7.

[Manufacture of a laminate composed of a base material, a horizontal alignment film, and a horizontal alignment liquid crystal cured film]

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

Next, the composition for forming a horizontally oriented liquid crystal cured film was coated on the horizontally oriented film with a bar coater, and dried at 120° C. for 1 minute, and then, by using a high-pressure mercury lamp (“UNICURE VB-15201BY-A”, Ushio Electric Manufactured by Co., Ltd.) to irradiate ultraviolet light (accumulated light intensity at wavelength 365nm: 500mJ/cm ² under nitrogen atmosphere) to form a horizontally oriented liquid crystal cured film, and obtain a laminate composed of a substrate, a horizontally oriented film, and a horizontally oriented liquid crystal cured film body. The film thickness of the horizontally oriented liquid crystal cured film was measured with an ellipsometer, and it was 2.3 μm.

[Re measurement of horizontally oriented liquid crystal cured film]

The in-plane retardation value ReA(λ) of the horizontally oriented liquid crystal cured film manufactured by the above method is measured by a measuring machine ("KOBRA-WPR ", Oji Scientific Instruments Co., Ltd.) measurement. The measurement results of the phase difference ReA(λ) at each wavelength are ReA(450)=121nm, ReA(550)=142nm, ReA(650)=146nm, ReA(450)/ReA(550)=0.85.

[Manufacture of a laminate composed of substrate, horizontal alignment film, horizontal alignment cured liquid crystal film, vertical alignment film, and vertical alignment liquid crystal cured film]

After performing corona treatment on the laminate composed of the base material, horizontal alignment film, and horizontal alignment liquid crystal cured film manufactured by the above method, apply the composition for vertical alignment film formation with a bar coater, and dry at 80°C For 1 minute, a vertically oriented film was obtained. The film thickness of the obtained vertical alignment film was measured with an ellipsometer, and it was 50 nm.

Furthermore, the vertical alignment film was coated with a composition for forming a vertical alignment liquid crystal cured film with a bar coater, dried at 120° C. for 1 minute, and then dried by using a high-pressure mercury lamp ("UNICURE VB-15201BY-A", Ushio Electric Co., Ltd.) to irradiate ultraviolet rays (under a nitrogen environment, the cumulative light intensity at a wavelength of 365nm is 500mJ/cm ² ), to form a vertically oriented liquid crystal cured film, and to obtain a base material, a horizontally oriented film, a horizontally oriented liquid crystal cured film, and a vertically oriented film. , A laminate composed of a vertically oriented liquid crystal cured film. The film thickness of the vertically oriented liquid crystal cured film was measured with an ellipsometer, and it was 1.2 μm. Furthermore, the interlayer distance between the horizontally oriented liquid crystal cured film and the vertically oriented liquid crystal cured film was 50 nm. Furthermore, the constituent element ratio of the vertical alignment film was Si/C=0.33.

[Rth measurement of vertical alignment liquid crystal cured film]

In order to measure the Rth of the vertical alignment liquid crystal cured film, the vertical alignment film and the vertical alignment liquid crystal cured film were manufactured on the COP film (ZF-14-50) manufactured by Zeon Co., Ltd. in Japan in the same order as above, and passed through the adhesive ( The pressure-sensitive adhesive (15 μm) manufactured by Lintec Co., Ltd. is used to bond the vertically oriented liquid crystal hardened film to the glass. After confirming that there is no phase difference in the COP, the phase of changing the incident angle of the light on the sample is measured by an ellipsometer. difference. In addition, the average refractive index at the wavelength λ of 450 nm and 550 nm was measured using the refractometer (manufactured by Atago Co., Ltd., "multi-wavelength Abbe refractometer DR-M4"). The ReC obtained from the obtained film thickness, average refractive index and the measurement results of the ellipsometer are RthC(450)=-63nm, RthC(550)=-73nm, RthC(450)/RthC(550)=0.85 .

[Measurement of R0 and R40 of a laminate composed of a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film (retardation plate with optical compensation function)]

The laminate composed of the base material, horizontal alignment film, horizontal alignment liquid crystal cured film, vertical alignment film, and vertical alignment liquid crystal cured film produced by the above method was passed through an adhesive (pressure-sensitive adhesive manufactured by Lintec, 15 μm) and After laminating the glass and peeling off the COP to make a sample for measurement, after 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 retardation plate with optical compensation function The retardation value R0(λ) of the orientation and the retardation value R40(λ) when the fast axis of the horizontally oriented liquid crystal cured film is inclined 40°. From the obtained values of R0(λ) and R40(λ), calculate |R0(550)-R40(550)|, |R0(450)-R40(450)| and |{R0(450)-R40(450) }-{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 according to the above method, and the average refractive index of each layer was calculated with a refractometer (manufactured by Atago Co., Ltd., "Multi-Wavelength Abbe Refractometer DR-M4") or an ellipsometer, and it was confirmed that each layer The in-plane average refractive index difference is 0.2 or less.

[Bendability test]

A glass plate with a thickness of 0.7 mm is placed on the coating film side of the laminate composed of the base material, horizontal alignment film, horizontal alignment liquid crystal cured film, vertical alignment film, and vertical alignment liquid crystal cured film produced by the above method, and the laminate After the body is bent 180° by 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 whether there are wrinkles or cracks. The results are shown in Table 1.

[Confirmation of the reflection hue of the curved part]

Corona treatment is carried out on the coating film side of the laminated body composed of the base material, 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, so that the polarizing plate absorb The angle between the axis and the slow axis of the horizontal alignment film is 45°, and the polarizing plate produced by the above method is bonded through the adhesive, and the substrate is peeled off to produce an elliptical polarizing plate with optical compensation function. Then, it was bonded to aluminum foil through an adhesive, and bent 180° so that the radius on the polarizing plate side became 1 cm, and the reflection hue of the bent portion was observed with the naked eye. The results are shown in Table 1.

(Example 2 and 3)

Except that the film thickness of the vertical alignment film was changed as described in Table 1, a phase difference plate with an optical compensation function was produced in the same manner as in Example 1, and phase difference measurement, bendability test, and reflection hue of the bent part were carried out. confirm. The results are shown in Table 1.

(Example 4)

0.5% by weight of polyimide (“Sun Ever SE-610”, manufactured by Nissan Chemical Industry Co., Ltd.), 72.3% by weight of N-methyl-2-pyrrolidone, 18.1% by weight of 2-butoxy Propylene glycol, 9.1% by weight of ethylcyclohexane, and 0.01% by weight of DPHA (manufactured by Shin-Nakamura Chemical Co., Ltd.) were mixed to prepare composition B for forming a vertical alignment film, except that the composition B for forming a vertical alignment film was used , the same operation as in Example 1 was used to manufacture a phase difference plate with optical compensation function, and to perform phase difference measurement, bendability test and reflection hue confirmation of the curved part. The results are shown in Table 1. In addition, the film thickness of the vertical alignment film was measured with an ellipsometer and found to be 0.2 μm. It can be known that the interlayer distance between the horizontally oriented liquid crystal cured film and the vertically oriented liquid crystal cured film is 0.2 μm. Moreover, it was confirmed that the vertically aligned liquid crystal hard in the coated When the film-forming composition is deposited, the vertical alignment film is corroded by a solvent, and alignment defects and poor alignment may be partially generated.

(Example 5)

In addition to changing the base material to a polyethylene terephthalate film (manufactured by Lintec Co., Ltd.; SP-PLR382050, hereinafter referred to as "separator") that has undergone mold release treatment, and changing the lamination order to a vertically oriented film, Except for the order of vertically oriented liquid crystal cured film, horizontally oriented film, and horizontally oriented liquid crystal cured film, a phase difference plate with optical compensation function was produced in the same manner as in Example 1, and phase difference measurement, bendability test and bending part were carried out. The reflection hue confirmation. The results are shown in Table 1. In addition, the film thickness of the horizontal alignment film was measured with an ellipsometer and found to be 0.2 μm. It can be known that the interlayer distance between the horizontally oriented liquid crystal cured film and the vertically oriented liquid crystal cured film is 0.2 μm.

(Example 6 and 7)

Except that the values of RthC(450) and RthC(550) are changed to those recorded in Table 1 by changing the film thickness of the vertically oriented liquid crystal cured film, the same operation as in Example 1 is carried out to produce an optical compensation function Phase difference plate, and carry out phase difference measurement, bending test and reflection hue confirmation of the bending part. The results are shown in Table 1.

(Embodiment 8)

In addition to changing the composition for forming a vertical alignment liquid crystal cured film to the following The composition (B) for forming a vertically aligned liquid crystal cured film described below, and the drying temperature after coating the above-mentioned composition (B) for forming a vertically aligned liquid crystal cured film was changed from 120°C to 80°C. The same operation as in Example 1 was used to manufacture a phase difference plate with optical compensation function, and to perform phase difference measurement, bendability test and reflection hue confirmation of the curved part. The results are shown in Table 1.

(Adjustment of composition (B) for vertical alignment liquid crystal cured film formation)

With respect to the liquid crystal compound LC242 described below: Paliocolor LC242 (registered trademark of BASF Corporation), 0.1 part of leveling agent F-556 and 3 parts of polymerization initiator Irg 369 were added, and the solid content concentration became 13%. Cyclopentanone was added to obtain a composition (B) for forming a vertically aligned liquid crystal cured film. Let the name of the obtained liquid crystal composition be "composition V". Liquid crystal composition LC242: Paliocolor LC242 (registered trademark of BASF Corporation)

(comparative example 1)

After the laminate of the horizontal alignment film and the horizontal alignment liquid crystal cured film was manufactured by the method described in Example 1, the vertical alignment film and the laminate of the vertical alignment liquid crystal cured film were prepared on the COP in the same way as in the embodiment (Lintec Corporation manufacture). The obtained laminates were bonded together with an adhesive (15 μm pressure-sensitive adhesive manufactured by Lintec Co., Ltd.), and phase difference measurement, flexibility test, and reflection hue confirmation of the bent portion were implemented. The results are shown in Table 1.

Curved portion reflection hue: ◯ when black, and × when coloring is clearly confirmed.

Bendability test: ◯ when no flaw occurs, and × when flaws such as wrinkles and cracks occur.

By applying the manufacturing method of the present invention, it is possible to obtain a phase difference plate with an optical compensation function that can suppress defects such as wrinkles and cracks that occur during bending

Claims (14)

A method for manufacturing a phase difference plate with optical compensation function, which is to sequentially form a horizontal alignment film composed of a photo-alignment film containing cinnamonyl groups, and a horizontal alignment film composed of methacryloxy or acryl groups by the following steps: Horizontal alignment liquid crystal cured film, vertical alignment film, and vertical alignment liquid crystal cured film composed of oxygen-based liquid crystal compounds form a horizontal alignment film through the steps of coating, drying, and alignment treatment; form a horizontal alignment film through the steps of coating, drying, and ultraviolet irradiation A cured liquid crystal film; further forming a vertical alignment film through coating and drying steps; and forming a vertical alignment liquid crystal cured film through the steps of coating, drying, and ultraviolet irradiation. The manufacturing method of the phase difference plate with optical compensation function as described in item 1 of the scope of the patent application, wherein the horizontal alignment film with a film thickness of 1.0 μm or less, the horizontal alignment liquid crystal cured film, the vertical alignment film, and the vertical alignment film are sequentially formed. Liquid crystal hardening film. The manufacturing method of the phase difference plate with optical compensation function as described in item 1 or 2 of the scope of the patent application, wherein the horizontal alignment film, the horizontal alignment liquid crystal cured film, the vertical alignment film with a film thickness of 1.0 μm or less are formed sequentially, Vertically oriented liquid crystal cured film. The manufacturing method of the phase difference plate with optical compensation function as described in item 1 or 2 of the scope of the patent application, wherein the horizontal alignment film, the horizontal alignment liquid crystal cured film, the vertical alignment film containing Si element, the vertical alignment film, and the vertical alignment film are sequentially formed. Directly oriented liquid crystal hardening film. The manufacturing method of the phase difference plate with optical compensation function as described in item 1 or 2 of the scope of the patent application, wherein the horizontal alignment film, the horizontal alignment liquid crystal cured film, and the vertical alignment film with Si/C elements of 0.03 to 1.00 are sequentially formed. Alignment film, vertical alignment liquid crystal cured film. The manufacturing method of the phase difference plate with optical compensation function as described in item 1 or 2 of the scope of the patent application is to sequentially form a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film, wherein, The horizontally oriented liquid crystal hardening film system satisfies the following relationship (1), ReA(450)/ReA(550)<1.00...(1) In the formula, ReA(λ) represents the surface of the horizontally oriented liquid crystal hardening film at the wavelength λnm The internal retardation value, 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) means horizontally oriented liquid crystal The main refractive index of the hardened film in the film plane is the main refractive index at the wavelength λ (nm); nyA(λ) is the refractive index in the direction perpendicular to nxA(λ) in the same plane, and is Refractive index at λ (nm); dA represents the film thickness of the horizontally oriented liquid crystal cured film. The manufacturing method of the phase difference plate with optical compensation function as described in item 1 or 2 of the scope of the patent application is to sequentially form a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured 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 retardation value of the vertically oriented liquid crystal cured film in the thickness direction of the wavelength λnm, and the definition of the retardation value RthC(λ) is as follows, RthC(λ)=((nxC(λ)+ nyC(λ))/2-nzC(λ))×dC In the formula, nxC(λ) represents the main refractive index of the vertically oriented liquid crystal cured film in the film plane, and is the main refraction at the wavelength λ (nm) nyC(λ) means the refractive index in the direction perpendicular to nxC(λ) in the same plane, and is the refractive index at the wavelength λ(nm); nzC(λ) means the thickness of the vertically oriented liquid crystal cured film The refractive index in the direction is the refractive index at the wavelength λ (nm); dC represents the film thickness of the vertically oriented liquid crystal cured film. A method for manufacturing a phase difference plate with an optical compensation function, which is to sequentially form a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film composed of a photo-alignment film containing a cinnamonyl group, and a A horizontally oriented liquid crystal cured film composed of acryloxy or acryloxy liquid crystal compounds forms a vertically oriented film through coating and drying steps; a vertically oriented liquid crystal cured film is formed through the steps of coating, drying, and ultraviolet irradiation ; further forming a horizontal alignment film through the steps of coating, drying, and alignment treatment; and forming a horizontal alignment liquid crystal cured film through the steps of coating, drying, and ultraviolet irradiation. Phase with optical compensation function as described in item 8 of the scope of patent application A method of manufacturing a difference plate, wherein a vertical alignment film, a vertical alignment cured liquid crystal film, a horizontal alignment film having a film thickness of 1.0 μm or less, and a horizontal alignment liquid crystal cured film are sequentially formed. The manufacturing method of a phase difference plate with optical compensation function as described in claim 8 or 9 of the scope of the patent application, wherein a vertical alignment film with a film thickness of less than 1.0 μm, a vertical alignment liquid crystal cured film, a horizontal alignment film, Horizontally oriented liquid crystal cured film. The manufacturing method of the phase difference plate with optical compensation function as described in item 8 or 9 of the scope of the patent application, wherein the vertical alignment film containing Si element, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment film are sequentially formed. Liquid crystal hardening film. The manufacturing method of the phase difference plate with optical compensation function as described in item 8 or 9 of the scope of the patent application, wherein the horizontal alignment film, the horizontal alignment liquid crystal cured film, and the vertical alignment film with Si/C elements of 0.03 to 1.00 are sequentially formed. Alignment film, vertical alignment liquid crystal cured film. The manufacturing method of the phase difference plate with optical compensation function as described in item 8 or 9 of the scope of the patent application is to sequentially form a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film, wherein, The horizontally oriented 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 of the horizontally oriented liquid crystal cured film at the wavelength λnm The phase difference value, 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 main refractive index of the horizontally oriented liquid crystal cured film in the film plane, and is the main refractive index at the wavelength λ (nm); nyA(λ) represents the same The refractive index in the orthogonal direction in the plane is the refractive index at λ (nm); dA represents the film thickness of the horizontally oriented liquid crystal cured film. The manufacturing method of the phase difference plate with optical compensation function as described in item 8 or 9 of the scope of the patent application is to sequentially form a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film, wherein, The vertically oriented liquid crystal cured film satisfies the following relationship (4): RthC(450)/RthC(550)<1.00...(4) In the formula, RthC(λ) represents the thickness direction of the vertically oriented liquid crystal cured film at the wavelength λnm The phase difference value, the definition of the phase difference value RthC(λ) is as follows, RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC where nxC( λ) represents the main refractive index of the vertically oriented liquid crystal hardening film in the film plane, and is the main refractive index at the wavelength λ (nm); The refractive index in the direction, and is the refractive index at 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 indicates the vertical orientation The film thickness of the liquid crystal cured film.