JP2020181152A - Liquid crystal cured film-forming composition and use thereof - Google Patents

Abstract

To provide a liquid crystal cured film-forming composition for producing a liquid crystal cured film with less thickness unevenness.SOLUTION: A liquid crystal cured film-forming composition is provided, containing at least one type of silicon-based or fluorine-based leveling agent, at least one type of acrylic leveling agent, and at least one type of polymerizable liquid crystal compound, where the total leveling agent content is 3.0 wt.% or less with respect to a total amount of the polymerizable liquid crystal compound.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal cured film forming composition, a liquid crystal cured film, an elliptical polarizing plate, and an organic EL display device.

An elliptical polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated. For example, in a device that displays an image in a planar state (for example, an organic EL display device), light reflection is performed by electrodes constituting the device. It is used to prevent it. In this elliptical polarizing plate, a so-called λ / 4 plate is used as the retardation plate.

As the retardation plate used for such an elliptical polarizing plate, a retardation plate exhibiting inverse wavelength dispersibility is preferable in that it exhibits equivalent retardation performance in a wide wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersibility, a retardation plate made of a horizontally oriented liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility in a horizontally oriented state is known. ..

Further, by forming a vertically oriented liquid crystal cured film and combining the vertically oriented liquid crystal cured film with the elliptical polarizing plate, it is possible to suppress an oblique hue change at the time of black display when combined with an organic EL display device. It has been known.

JP 2015-163935

However, liquid crystal cured films such as horizontally oriented cured films and vertically oriented liquid crystal cured films are generally liquid crystal cured by producing a composition containing a polymerizable liquid crystal compound, applying the composition to a substrate, an alignment film, or the like and curing the composition. A film is formed, but the liquid crystal cured film formed is generally a thin film of 5 μm or less, and there has been a problem that the appearance of the product is significantly deteriorated due to uneven film thickness. Further, when an additive is added to a composition containing a polymerizable liquid crystal compound, there is a problem that the orientation of the polymerizable liquid crystal compound is deteriorated depending on the additive.

The present invention has been carried out in view of the above circumstances, and is to provide a composition for producing a liquid crystal cured film having less uneven film thickness.

As a result of diligent studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention provides the following preferred embodiments.

[1] Containing at least one silicon-based or fluorine-based leveling agent, at least one acrylic leveling agent, and at least one polymerizable liquid crystal compound.
A composition for forming a liquid crystal cured film in which the total amount of the leveling agent is 3.0% by mass or less with respect to the total amount of the polymerizable liquid crystal compound.
[2] The composition for forming a liquid crystal cured film according to [1], which contains at least one silicon-based leveling agent, at least one acrylic leveling agent, and one or more polymerizable liquid crystal compounds.
[3] The composition for forming a liquid crystal cured film according to any one of [1] and [2], which further contains a dichroic dye.
[4] The composition for forming a liquid crystal cured film according to any one of [1] to [3], wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound exhibiting a smectic phase.
[5] The composition for forming a liquid crystal cured film according to any one of [1] to [4], wherein the polymerizable liquid crystal compound is a liquid crystal compound having a T-shaped structure.
[6] A liquid crystal cured film cured in a state in which the polymerizable liquid crystal compound contained in the composition for forming a liquid crystal cured film according to any one of [1] to [5] is oriented.
[7] The liquid crystal cured film according to [6], wherein the liquid crystal cured film has a film thickness of 0.3 μm or more and 5.0 μm or less.
[8] The liquid crystal cured film according to any one of [6] and [7], which is a horizontally oriented liquid crystal cured film cured in a state in which the polymerizable liquid crystal compound is oriented in a direction parallel to the in-plane.
[9] The liquid crystal cured film according to any one of [6] to [8], which further satisfies the following formula (S1).
100 nm ≤ ReA (550) ≤ 180 nm ... (S1)
(In the equation, ReA (550) represents the in-plane retardation value at a wavelength of 550 nm.)
[10] The liquid crystal cured film according to any one of [6] to [9], which further satisfies the following formula (S2).
ReA (450) / ReA (550) <1.0 ... (S2)
(In the equation, ReA (450) represents the in-plane retardation value at a wavelength of 450 nm.)
[11] The horizontally oriented liquid crystal cured film according to any one of [6] to [10], wherein the liquid crystal cured film is a horizontally oriented liquid crystal cured film and shows a Bragg peak in X-ray diffraction measurement.
[12] The liquid crystal cured film according to any one of [6] and [7], which is a vertically oriented liquid crystal cured film in which the polymerizable liquid crystal compound is cured in a state of being oriented in a direction perpendicular to the in-plane.
[13] The liquid crystal cured film according to [12], which further satisfies the following relational expression (S3).
-150 ≤ RthC (550) ≤ -30 ... (S3)
[In the relational expression (S3), RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm].
[14] The liquid crystal cured film according to any one of [12] and [13], which further satisfies the following relational expression (S4).
RthC (450) / RthC (550) ≤ 1.0 ... (S4)
[In the relational expression (S4), RthC (450) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 450 nm, and RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm].
[15] An elliptical polarizing plate including a horizontally oriented retardation film and a polarizing film.
An elliptical polarizing plate in which at least one of the horizontally oriented film or the polarizing film is the liquid crystal cured film according to any one of [6] to [11].
[16] An elliptical polarizing plate including a horizontally oriented retardation film, a vertically oriented liquid crystal cured film, and a polarizing film.
An elliptical polarizing plate in which at least one of a horizontally oriented film, a vertically oriented liquid crystal cured film, and a polarizing film is the liquid crystal cured film according to any one of [6] to [14].
[17] The elliptical polarizing plate according to any one of [15] and [16], wherein the angle formed by the slow axis of the horizontally oriented retardation film and the absorption axis of the polarizing plate is 45 ± 5 °.
[18]
An organic EL display device including the elliptical polarizing plate according to any one of [15] to [17].

According to the present invention, the total amount of the two types of leveling agents (that is, silicon-based or fluorine-based leveling agent and acrylic-based leveling agent) is 3.0% by mass or less with respect to the total amount of the polymerizable liquid crystal compound. It is blended in the polymerizable liquid crystal composition in a blending amount. These two types of leveling agents work differently in the liquid crystal composition. Since silicon-based or fluorine-based leveling agents have low surface free energy, they tend to segregate on the surface layer of the liquid crystal composition, and by reducing the surface tension of the composition, they are effective in flattening the surface layer of the coating film. The acrylic leveling agent has the effect of equalizing the local unevenness of the liquid physical properties in the film of the liquid crystal composition, and by including the combination of both in a specific blending amount, a liquid crystal cured film having less uneven film thickness can be obtained. Can be provided.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without impairing the gist of the present invention.

<Leveling agent>
In the present invention, as described above, at least one silicon-based or fluorine-based leveling agent and at least one acrylic-based leveling agent are used, and the total amount of the leveling agent is the total amount of the polymerizable liquid crystal compound. It is characterized in that it is blended in a polymerizable liquid crystal composition in an amount of 0% by mass or less.

Examples of the silicon-based leveling agent include leveling agents having a polyorganosiloxane skeleton. Examples of the group bonded to the silicon atom (silicon atom forming the siloxane bond) in the polyorganosiloxane include a hydrocarbon group and the like. Among them, an alkyl group and an aryl group having 1 to 10 carbon atoms are preferable, a methyl group and a phenyl group are more preferable, and a methyl group is more preferable. The group bonded to the silicon atom may be only one type or two or more types. The number of repetitions (degree of polymerization) of the siloxane unit is not particularly limited, but is preferably 2 to 10000, more preferably 3 to 5000, and further preferably 5 to 1000.

Commercially available products can be used as the silicon-based leveling agent, for example, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-. 322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510 (above, manufactured by Big Chemie Japan Co., Ltd.), KF-945, KF-6015, KF-6020 (above, Shin-Etsu Chemical Co., Ltd.) ), TEGORad2300, TEGORad2200N, TEGORad2011 (manufactured by Degussa), BYK-UV3500, BYK-UV3505, BYK-3510 as having a radically polymerizable group such as a (meth) acryloyl group added to the polyether chain. , BYK-UV3530, BYK-UV3570, BYK-UV3575, BYK-UV3576 (all manufactured by Big Chemie Japan Co., Ltd.), KP-422, KP-416, KP-418, KP-410, KP-411, KP- Examples thereof include 412, KP-413, KP-423, KP-414, KP-415, KP-420, and KP-983 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

The content of the silicon-based leveling agent in the polymerizable liquid crystal composition is preferably 0.001 part by mass to 2 parts by mass, and more preferably 0.01 part by mass to 100 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is 1.5 parts by mass, more preferably 0.1 parts by mass to 1.5 parts by mass.

The fluorine-based leveling agent is not particularly limited, and examples thereof include leveling agents having a fluoroaliphatic hydrocarbon skeleton. The fluoroaliphatic hydrocarbon skeleton is not particularly limited, and has, for example, the number of carbon atoms of fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, fluorohexane and the like. Examples thereof include 1 to 10 fluoroalkanes. The fluoroaliphatic hydrocarbon skeleton may be a perfluoroaliphatic hydrocarbon skeleton in which at least a part of hydrogen atoms are substituted with fluorine atoms, but all hydrogen atoms are substituted with fluorine atoms.

Further, the fluoroaliphatic hydrocarbon skeleton may form a polyfluoroalkylene ether skeleton which is a repeating unit via an ether bond. The fluoroaliphatic hydrocarbon group as the repeating unit is not particularly limited, and examples thereof include fluoroC1-4alkylene groups such as fluoromethylene, fluoroethylene, fluoropropylene, and fluoroisopropylene. The above-mentioned fluoroaliphatic hydrocarbon group may be only one kind or two or more kinds. The number of repetitions (degree of polymerization) of the fluoroalkylene ether unit is not particularly limited, but is preferably 10 to 10000, more preferably 30 to 5000, and further preferably 50 to 1000.

As an example of the fluorine-based leveling agent, a commercially available product can be used, for example, "Megafuck (registered trademark) R-08", "R-30", "R-90", "F-410". , "F-411", "F-443", "F-445", "F-470", "F-471", "F-477", "F-479" , "F-482", "F-483", "F-281", "F-253", "F-251", "F-114", "F-510", "F-551", "F-552", "F-553", "F-554", "F-555", "F-556", "F-557", same "F-558", "F-559", "F-560", "F-561", "F-562", "F-563", "F-565", "F-565" F-568 "," F-569 "," F-570 "," F-572 "," F-574 "," F-575 "," F-576 "," R " -40 "," R-41 "," R-94 "," RS-56 "," RS-72-K "," RS-75 "," RS-76-E ", "RS-76-NS", "RS-78", "RS-90", "DS-21" (DIC Co., Ltd.); "Surflon (registered trademark) S-381", "S" -382 "," S-383 "," S-393 "," SC-101 "," SC-105 "," KH-40 "and" SA-100 "(AGC Seimi Chemical Co., Ltd.) ); "E1830", "E5844" (Daikin Fine Chemical Laboratory Co., Ltd.); "Ftop EF301", "Ftop EF303", "Ftop EF351" and "Ftop EF352" (Mitsubishi Materials Electronics Chemical Co., Ltd.) ).

The content of the fluorine-based leveling agent in the polymerizable liquid crystal composition is preferably 0.001 part by mass to 2 parts by mass, and more preferably 0.01 part by mass to 100 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is 1.5 parts by mass, more preferably 0.1 parts by mass to 1.5 parts by mass.

The acrylic leveling agent is produced, for example, by copolymerizing a monomer having a (meth) acryloyl group. The acrylic leveling agent has a hydrophilic group such as a (meth) acrylate having a hydroxyl group and a (meth) acrylate having an alkylene oxide typified by ethylene oxide and propylene oxide as a monomer having a (meth) acryloyl group. It can be produced by copolymerizing a monomer.

Commercially available products may be used as the acrylic leveling agent, for example, "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", "BYK-356". "," BYK-358N "," BYK-361N "," BYK-380 "," BYK-381 "," BYK-392 "," BYK-394 "," BYK-3441 "(Big Chemie Japan Co., Ltd.) Company).

The content of the acrylic leveling agent in the polymerizable liquid crystal composition is preferably 0.001 part by mass to 3 parts by mass, and more preferably 0.01 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is ~ 2 parts by mass, more preferably 0.1 part by mass to 1.5 parts by mass.

As described above, the acrylic leveling agent tends to deteriorate the orientation of the cured liquid crystal film because segregation in the film thickness direction is unlikely to occur in the cured liquid crystal film. As an acrylic leveling agent, the smaller the molecular weight, the less likely it is to inhibit the orientation of the polymerizable liquid crystal compound. Therefore, the molecular weight (weight average molecular weight) of the acrylic leveling agent is preferably 100 to 100,000, more preferably 500 to 50,000. , More preferably 500 to 10000, and particularly preferably 500 to 5000.

In the present invention, at least one silicon-based or fluorine-based leveling agent and at least one acrylic-based leveling agent are used, and the total amount of the leveling agent is 3.0% by weight or less based on the total amount of the polymerizable liquid crystal compound. It is preferable to mix in an amount. As described above, since the action of the silicon-based or fluorine-based leveling agent in the polymerizable liquid crystal composition and the action of the acrylic-based leveling agent in the polymerizable liquid crystal composition are different, it is recommended to combine both leveling agents. preferable. As the silicon-based or fluorine-based leveling agent, a silicon-based leveling agent is preferable. When the total amount of the leveling agent exceeds 3.0% by weight with respect to the total amount of the polymerizable liquid crystal composition, the orientation of the liquid crystal tends to be deteriorated. The total amount of the leveling agent is preferably 0.001 to 3% by mass, more preferably 0.01 to 2.5% by mass. If the amount of the leveling agent added is smaller than the above range, the effect of adding the leveling agent tends to be difficult to be exhibited. The weight ratio of the silicon-based or fluorine-based leveling agent to the acrylic-based leveling agent is 0.01 to 30, more preferably 0.05 to 10 in terms of the weight ratio of the silicon-based or fluorine-based leveling agent / acrylic-based leveling agent. is there. Even if the amount of either leveling agent is increased, the balance of action is lost and uneven film thickness occurs.

<Polymerizable liquid crystal composition>
Examples of the polymerizable liquid crystal compound include a polymerizable liquid crystal compound exhibiting positive wavelength dispersibility and a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility, and only one of the polymerizable liquid crystal compounds can be used. However, both types of polymerizable liquid crystal compounds can be mixed and used. When used for a vertically oriented liquid crystal cured film, when the vertically oriented liquid crystal cured film is applied to a display device, it is polymerizable that exhibits inverse wavelength dispersibility from the viewpoint of having a large effect of improving the oblique reflection hue at the time of black display. It preferably contains a liquid crystal compound. Further, when used for a horizontally oriented liquid crystal cured film, when the horizontally oriented liquid crystal cured film is applied to a display device, a polymerizable liquid crystal exhibiting reverse wavelength dispersibility from the viewpoint of improving the frontal reflection hue at the time of black display. It preferably contains a compound.

The polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is preferably a compound having the following characteristics (A) to (D).
(A) A compound capable of forming a nematic phase or a smectic phase.
(B) The polymerizable liquid crystal compound has π electrons in the long axis direction (a).
(C) It has π electrons in the direction [intersection direction (b)] that intersects the major axis direction (a).
(D) A polymerizable liquid crystal compound defined by the following formula (i), where the total number of π electrons existing in the major axis direction (a) is N (πa) and the total molecular weight existing in the major axis direction is N (Aa). Π electron density in the major axis direction (a) of
D (πa) = N (πa) / N (Aa) (i)
The polymerizable liquid crystal compound defined by the following formula (ii), where the total number of π electrons existing in the crossing direction (b) is N (πb) and the total molecular weight existing in the crossing direction (b) is N (Ab). Π electron density in the crossing direction (b) of
D (πb) = N (πb) / N (Ab) (ii)
And, the formula (iii)
0 ≦ [D (πa) / D (πb)] <1 (iii)
[That is, the π-electron density in the crossing direction (b) is larger than the π-electron density in the major axis direction (a)]. Further, as described above, the polymerizable liquid crystal compound having π electrons on the major axis and in the intersecting direction with respect to the major axis has, for example, a T-shaped structure.

In the above features (A) to (D), the major axis direction (a) and the number of π electrons N are defined as follows.
The major axis direction (a) is, for example, the rod-shaped major axis direction of a compound having a rod-like structure.
The number of π electrons N (πa) existing in the long axis direction (a) does not include π electrons that disappear due to the polymerization reaction.
The number of π electrons N (πa) existing in the major axis direction (a) is the total number of π electrons on the major axis and π electrons conjugated thereto, for example, existing in the major axis direction (a). It contains the number of π electrons present in the ring that satisfies Hückel's law.
-The number of π electrons N (πb) existing in the crossing direction (b) does not include π electrons that disappear due to the polymerization reaction.
The polymerizable liquid crystal compound satisfying the above has a mesogen structure in the major axis direction. The liquid crystal phase (nematic phase, smectic phase) is expressed by this mesogen structure.

The polymerizable liquid crystal compound satisfying the above (A) to (D) can be applied on a substrate or an alignment film and heated to a phase transition temperature or higher to form a nematic phase or a smectic phase. In the nematic phase or smectic phase formed by orienting the polymerizable liquid crystal compound, the polymerizable liquid crystal compounds are usually oriented so that the major axis directions are parallel to each other, and this major axis direction is the orientation direction of the nematic phase. It becomes. When such a polymerizable liquid crystal compound is formed into a film and polymerized in a nematic phase or a smectic phase, a polymer film composed of a polymer oriented in the long axis direction (a) can be formed. .. This polymer film absorbs ultraviolet rays by π electrons in the long axis direction (a) and π electrons in the crossing direction (b). Here, the absorption maximum wavelength of ultraviolet rays absorbed by π electrons in the crossing direction (b) is defined as λbmax. λbmax is usually 300 nm to 400 nm. The density of π electrons satisfies the above equation (iii), and since the π electron density in the crossing direction (b) is larger than the π electron density in the major axis direction (a), the oscillating surface in the crossing direction (b). The absorption of linearly polarized ultraviolet rays (wavelength is λbmax) having a vibration plane in the long axis direction (a) is larger than the absorption of linearly polarized ultraviolet rays (wavelength is λbmax) having a vibration plane. The ratio (the ratio of the absorbance in the crossing direction (b) of the linearly polarized ultraviolet rays / the absorbance in the major axis direction (a)) is, for example, more than 1.0, preferably 1.2 or more, usually 30 or less, for example, 10 or less. Is.

In general, the polymerizable liquid crystal compound having the above characteristics often exhibits reverse wavelength dispersibility. Specifically, for example, a compound represented by the following formula (X) can be mentioned. In the present invention, the polymerizable liquid crystal compound represented by the following formula (X) may be referred to as a polymerizable liquid crystal compound having a T-shaped structure.

In formula (X), Ar represents a divalent group having an aromatic group which may have a substituent. The aromatic group referred to here refers to a group having a ring structure having [4n + 2] π electrons according to Hückel's law, and is exemplified by (Ar-1) to (Ar-23) described later, for example. Such Ar groups may have two or more such Ar groups via a divalent linking group. Here, n represents an integer. When a ring structure is formed by including heteroatoms such as −N = and −S−, the case where the Hückel's rule is satisfied including the non-covalent bond electron pair on these heteroatoms and the aromaticity is included is also included. It is preferable that the aromatic group contains at least one or more of a nitrogen atom, an oxygen atom and a sulfur atom. The divalent group Ar may contain one aromatic group or two or more aromatic groups. When there is one aromatic group, the divalent group Ar may be a divalent aromatic group which may have a substituent. When two or more aromatic groups are contained in the divalent group Ar, the two or more aromatic groups are single-bonded to each other or bonded to each other by a divalent bonding group such as -CO-O- or -O-. May be.
G ¹ and G ² independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, respectively. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and carbon. The carbon atoms constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with the alkoxy group, the cyano group or the nitro group of the number 1 to 4, and the carbon atom is an oxygen atom or a sulfur atom. Alternatively, it may be substituted with a nitrogen atom.
L ¹ , L ² , B ¹ and B ² are independently single-bonded or divalent linking groups, respectively.
k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ≦ k + l. Here, when 2 ≦ k + l, B ¹ and B ² , G ¹ and G ² may be the same as or different from each other.
Each of E ¹ and E ² independently represents an alkanediyl group having 1 to 17 carbon atoms, and an alkanediyl group having 4 to 12 carbon atoms is more preferable. Further, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH ₂ − contained in the alkanediyl group is -O-, -S-, -SiH _2- , -C. It may be replaced with (= O) −.
P ¹ and P ² independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.

G ¹ and G ² are each independently substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, preferably a 1,4-phenylenediyl group. , A 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group. , 4-phenylenediyl group, unsubstituted 1,4-phenylenediyl group, or unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably unsubstituted 1,4-phenylenediyl group, or no substituent. It is a substituted 1,4-trans-cyclohexanediyl group.
Further, at least one of a plurality of G ¹ and G ² present is preferably a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ or L ² is present. More preferably, it is a divalent alicyclic hydrocarbon group.

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

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

From the viewpoint of expressing reverse wavelength dispersibility, k and l are preferably in the range of 2 ≦ k + l ≦ 6, preferably k + l = 4, and more preferably k = 2 and l = 2. When k = 2 and l = 2, a symmetrical structure is obtained, which is preferable.

The polymerizable group represented by P ¹ or P ² includes an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, and an oxylanyl group. , And an oxetanyl group and the like. Of these, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.

Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring and the like, and a benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrrolin ring, an imidazole ring, and a pyrazole ring. , Thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, phenanthroline ring and the like. Among them, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazole group. When Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

In the formula (X), the total number N _π of π electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, and in particular. It is preferably 16 or more. Further, it is preferably 30 or less, more preferably 26 or less, and further preferably 24 or less.

Examples of the aromatic group represented by Ar include the following groups.

In formulas (Ar-1) to (Ar-23), * marks represent connecting parts, and Z ⁰ , Z ¹ and Z ² are independently hydrogen atoms, halogen atoms, and alkyl having 1 to 12 carbon atoms. Group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, Alkylthio group with 1 to 12 carbon atoms, N-alkylamino group with 1 to 12 carbon atoms, N, N-dialkylamino group with 2 to 12 carbon atoms, N-alkylsulfamoyl group with 1 to 12 carbon atoms or carbon Represents an N, N-dialkylsulfamoyl group of number 2-12. Further, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

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

J ¹ and J ² 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 independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.

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

Y ¹ , Y ² and Y ³ may be independently substituted polycyclic aromatic hydrocarbon groups or polycyclic aromatic heterocyclic groups, respectively. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

Z ⁰ , Z ¹ and Z ² are preferably hydrogen atoms, halogen atoms, alkyl groups having 1 to 12 carbon atoms, cyano groups, nitro groups, and alkoxy groups having 1 to 12 carbon atoms, respectively. ⁰ is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group, and Z ¹ and Z ² are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group. Further, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and ^{Q 2,} -NH -, - S -, - NR 2 '-, - O- are preferable, R ^2' is preferably a hydrogen atom. Of these, -S-, -O-, and -NH- are particularly preferable.

Among the formulas (Ar-1) to (Ar-23), the formulas (Ar-6) and (Ar-7) are preferable from the viewpoint of molecular stability.

In formulas (Ar-16) to (Ar-23), Y ¹ may form an aromatic heterocyclic group with the nitrogen atom to which it is attached and Z ⁰ . Examples of the aromatic heterocyclic group include those described above as the aromatic heterocycle that Ar may have. For example, a pyrrole ring, an imidazole ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and an indol. Examples thereof include a ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. This aromatic heterocyclic group may have a substituent. Further, Y ¹ may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted as described above, together with the nitrogen atom to which the Y ¹ is bonded and Z ⁰ . For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like can be mentioned.

Further, as the polymerizable liquid crystal compound forming the liquid crystal cured film in the present invention, for example, a compound containing a group represented by the following formula (Y) (hereinafter, also referred to as “polymerizable liquid crystal compound (Y)”) is used. May be good. The polymerizable liquid crystal compound (Y) generally tends to exhibit positive wavelength dispersibility. The polymerizable liquid crystal compound may be used alone or in combination of two or more.

P11-B11-E11-B12-A11-B13- (Y)
[In formula (Y), P11 represents a polymerizable group.
A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro. It may be substituted with a group, and the hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.
B11 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ^16- , -NR ^16- CO-, -CO-,- Represents CS- or single bond. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B12 and B13 are each _{independently, -C≡C -, - CH = CH} -, - CH 2 -CH 2 -, - O -, - S -, - C (= O) -, - C (= O ) -O-, -OC (= O)-, -O-C (= O) -O-, -CH = N-, -N = CH-, -N = N-, -C (= O) ) -NR ^16- , -NR ^16- C (= O)-, -OCH _2- , -OCF _2- , -CH ₂ O-, -CF ₂ O-, -CH = CH-C (= O)- Represents O-, -OC (= O) -CH = CH- or a single bond.
E11 represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group may be substituted. May be substituted with a halogen atom. Further, −CH ₂₋ constituting the alkanediyl group may be replaced with −O− or −CO−. ]

The carbon number of the aromatic hydrocarbon group and the alicyclic hydrocarbon group of A11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and particularly preferably in the range of 5 or 6. preferable. As A11, a cyclohexane-1,4-diyl group and a 1,4-phenylene group are preferable.

As E11, a linear alkanediyl group having 1 to 12 carbon atoms is preferable. -CH ₂₋ constituting the alkanediyl group may be replaced with −O−.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane. -1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group and dodecane-1,12- linear alkanediyl group having 1 to 12 carbon atoms such as diyl _{group; -CH 2 -CH 2 -O-CH} 2 -CH 2 -, - CH 2 -CH 2 -O-CH 2 -CH 2 -O- CH ₂ -CH ₂ - and _{-CH 2 -CH 2 -O-CH 2} -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 - and the like.
As B11, -O-, -S-, -CO-O-, and -O-CO- are preferable, and -CO-O- is more preferable.
As B12 and B13, -O-, -S-, -C (= O)-, -C (= O) -O-, -OC (= O)-, and -OC, respectively. (= O) -O- is preferable, and -O- or -OC (= O) -O- is more preferable.

［式（Ｐ−１１）〜（Ｐ−１５）中、
Ｒ^１７〜Ｒ^２１はそれぞれ独立に、炭素数１〜６のアルキル基または水素原子を表わす。］ As the polymerizable group represented by P11, a radically polymerizable group or a cationically polymerizable group is preferable in that it has high polymerization reactivity, particularly photopolymerization reactivity, and it is easy to handle and the liquid crystal compound itself is easy to produce. Therefore, the polymerizable group is preferably a group represented by the following formulas (P-11) to (P-15).

[In formulas (P-11) to (P-15),
R ^{17 to} R ²¹ independently represent an alkyl group or a hydrogen atom having 1 to 6 carbon atoms. ]

Specific examples of the groups represented by the formulas (P-11) to (P-15) include the groups represented by the following formulas (P-16) to (P-20).

P11 is preferably a group represented by the formulas (P-14) to (P-20), more preferably a vinyl group, a p-stilbene group, an epoxy group or an oxetanyl group.
It is more preferable that the group represented by P11-B11- is an acryloyloxy group or a metaacryloyloxy group.

Examples of the polymerizable liquid crystal compound (Y) include compounds represented by the formula (I), the formula (II), the formula (III), the formula (IV), the formula (V) or the formula (VI).
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12 (I)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11 (II)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12 (III)
P11-B11-E11-B12-A11-B13-A12-B14-A13-F11 (IV)
P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12 (V)
P11-B11-E11-B12-A11-B13-A12-F11 (VI)
(During the ceremony,
A12 to A14 are independently synonymous with A11, B14 to B16 are independently synonymous with B12, B17 is synonymous with B11, and E12 is synonymous with E11.
F11 is a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxy group, a methylol group, a formyl group, and a sulfo group. _(-SO 3 H), carboxyl group, an alkoxycarbonyl group or a halogen atom having 1 to 10 carbon atoms, -CH ₂ constituting the alkyl group and alkoxy group - is also have I replace the -O- Good. )

As a specific example of the polymerizable liquid crystal compound (Y), "3.8.6 network (completely crosslinked type)" of the liquid crystal handbook (edited by the liquid crystal handbook editorial committee, published by Maruzen Co., Ltd. on October 30, 2000). , "6.5.1 Liquid Crystal Material b. Polymerizable Nematic Liquid Crystal Material", a compound having a polymerizable group, JP-A-2010-31223, JP-A-2010-270108, JP-A. Examples thereof include polymerizable liquid crystals described in Japanese Patent Application Laid-Open No. 2011-6360 and Japanese Patent Application Laid-Open No. 2011-207765.

Specific examples of the polymerizable liquid crystal compound (Y) include the following formulas (I-1) to (I-4), formulas (II-1) to (II-4), and formulas (III-1) to formulas (III-1) to. (III-26), formulas (IV-1) to formulas (IV-26), formulas (V-1) to formulas (V-2) and formulas (VI-1) to formulas (VI-6). Examples include compounds. In the following formula, k1 and k2 independently represent integers of 2 to 12. These polymerizable liquid crystal compounds (Y) are preferable in terms of ease of synthesis or availability.

It is preferable to use a polymerizable liquid crystal compound exhibiting smectic liquid crystal property in that a horizontally oriented liquid crystal cured film or a vertically oriented liquid crystal cured film having a high degree of orientation order can be formed. When a polymerizable liquid crystal compound exhibiting smectic liquid crystal property is used as the polymerizable liquid crystal compound forming the liquid crystal cured film in the present invention, the polymerizable liquid crystal compound has a higher smectic phase from the viewpoint of achieving a higher degree of orientation order. (Higher-order smectic liquid crystal state) is more preferable. Here, the higher-order smectic phase includes smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase and smectic L phase. This means that among these, the smectic B phase, the smectic F phase and the smectic I phase are more preferable. The liquid crystal property may be a thermotropic liquid crystal or a liotropic liquid crystal, but the thermotropic liquid crystal is preferable in that precise film thickness control is possible. Further, the polymerizable liquid crystal compound exhibiting smectic liquid crystal property may be a monomer, but may be an oligomer or a polymer in which a polymerizable group is polymerized.

The polymerizable liquid crystal compound exhibiting smectic liquid crystal property is a liquid crystal compound having at least one polymerizable group, and may be a liquid crystal compound having two or more polymerizable groups from the viewpoint of improving the heat resistance of the liquid crystal cured film. preferable. Examples of the polymerizable group include (meth) acryloyloxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, oxylanyl group, oxetanyl group and the like. It is preferable to contain a (meth) acryloyloxy group because it is easy to use, the heat resistance of the cured liquid crystal film is easily improved, and the adhesion between the cured liquid crystal film and the base material is easily adjusted.

Examples of the polymerizable liquid crystal compound exhibiting smectic liquid crystal property include a compound represented by the following formula (Z) (hereinafter, may be referred to as “polymerizable liquid crystal compound (Z)”).
U ^1z −V ^1z −W ^1z − (X ^1z −Y ^1z −) _nz −X ^2z −W ^2z −V ^2z −U ^2z (Z)
[In the formula (Z), X ^1z and X ^2z independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or 2 The hydrogen atom contained in the valent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. It may be substituted with a group, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom or a sulfur atom or a nitrogen atom. However, at least one of X ^1z and X ^2z is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.
Y ^1z is a single bond or divalent linking group.
nz is 1 to 3, and when nz is 2 or more, a plurality of ^X1z may be the same as each other or may be different from each other. X ^2z may be the same as or different from any or all of the plurality of X ^1z . Further, when nz is 2 or more, a plurality of Y ^1z may be the same as each other or may be different from each other. From the viewpoint of liquid crystallinity, nz is preferably 2 or more.
U ^1z represents a hydrogen atom or a (meth) acryloyloxy group.
U ^2z represents a polymerizable group.
W ^1z and W ^2z are single-bonded or divalent linking groups independently of each other.
V ^1z and V ^2z represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent independently of each other, and −CH ₂₋ constituting the alkanediyl group is −O−, It may be replaced with −CO−, −S− or NH−. ]

In the polymerizable liquid crystal compound (Z), X ^1z and X ^2z are independent of each other and preferably have a 1,4-phenylene group which may have a substituent or a substituent. It is a good cyclohexane-1,4-diyl group, and at least one of X ^1z and X ^2z has a 1,4-phenylene group which may have a substituent, or a substituent. It is also a good cyclohexane-1,4-diyl group, preferably a trans-cyclohexane-1,4-diyl group. The substituents arbitrarily contained in the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent include a methyl group and an ethyl. Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a group and a butyl group, a cyano group and a halogen atom such as a chlorine atom and a fluorine atom. It is preferably unsubstituted.

Further, the polymerizable liquid crystal compound (Z) has the formula (Z1): in the formula (Z).
− (X ^1z −Y ^1z −) _nz −X ^2z − (Z1)
[In the formula, X ^1z , Y ^1z , X ^2z and nz have the same meanings as described above. ]
Part indicated by [hereinafter, referred to as a partial structure (Z1). ] Has an asymmetrical structure, which is preferable in that smectic liquid crystallinity is easily exhibited.
The partial structure (Z1) is asymmetrical structure polymerizable liquid crystal compound (Z), for example, nz is 1, and one X ^1z and X ^2z are different structures from each other polymerizable liquid crystal compound (Z) is Can be mentioned. Further, nz is 2, a two ^{Y 1z} compounds have the same structure each other, the two ^{X 1z} is same structure, one ^{X 2z} is different structure from these two ^{X 1z} the polymerizable liquid crystal compound (Z), ^{X 1z} that binds to ^{W 1z} of the two ^{X 1z} is, the other of ^{X 1z} and ^{X 2z} are different structures, the other of ^{X 1z} and ^{X 2z} mutually the same structure Also mentioned is the polymerizable liquid crystal compound (Z). Further, ^{polymerization} in which nz is 3 and three Y ^1z have the same structure as each other, and any one of the three X ^1z and one X ^{2z has} a structure different from all the other three. The sex liquid crystal compound (Z) can be mentioned.

Y ^1z _{is, -CH 2 CH 2 -, -} CH 2 O -, - CH 2 CH 2 O -, - COO -, - OCOO-, a single ^{bond, -N = N -, - CR} az = CR bz -, -C≡C-, -CR ^az = N- or CO-NR ^az -is preferable. R ^az and R ^bz independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ^1z _is, -CH ₂ CH 2 -, - more preferably COO- or a single bond, when a plurality of ^{Y 1z} is ^{present, Y 1z} that binds ^{X 2z} is, _-CH 2 CH ₂ - or CH It is more preferably ₂ O−. When X ^1z and X ^2z all have the same structure, it is preferable that two or more Y ^1z having different bonding methods exist. When a plurality of Y ^1z , which are different coupling methods from each other, are present, the structure is asymmetrical, so that smectic liquid crystallinity tends to be easily exhibited.

U ^2z is the above-mentioned polymerizable group. U ^1z is a hydrogen atom or a polymerizable group. The polymerizable group is a (meth) acryloyloxy group because it is easy to manufacture, the heat resistance of the cured liquid crystal film is easily improved, and the adhesion between the cured liquid crystal film and the substrate is easy to adjust. preferable. The polymerizable group may be in a polymerized state or a non-polymerized state, but is preferably in a non-polymerized state.

The alkanediyl groups represented by V ^1z and V ^2z include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-. 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decan-1,10-diyl group, tetradecane-1,14-diyl group Examples include groups and icosan-1,20-diyl groups. V ^1z and V ^2z are preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.

Examples of the substituent arbitrarily contained in the alkanediyl group include a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted and is an unsubstituted linear alkanediyl group. Is more preferable.

W ^1z and W ^2z are preferably single-bonded, -O-, -S-, -COO- or OCOO- independently of each other, and more preferably single-bonded or O-.

The polymerizable liquid crystal compound (Z) preferably has an asymmetric molecular structure in the molecular structure, and specifically, is a polymerizable liquid crystal compound having the following partial structures (Aa) to (Ai). More preferably. It is more preferable to have a partial structure of (A), (Ab) or (Ac) from the viewpoint of easily exhibiting higher-order smectic liquid crystal properties. In the following (Aa) to (Ai), * represents a bond (single bond).

Specific examples of the polymerizable liquid crystal compound (Z) include compounds represented by formulas (A-1) to (A-25). When the polymerizable liquid crystal compound (Z) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans form.

Among these, formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7), formula (A-). 8), formula (A-13), formula (A-14), formula (A-15), formula (A-16) and at least one selected from the group consisting of compounds represented by formula (A-17). Seeds are preferred. As the polymerizable liquid crystal compound (Z), one type may be used alone, or two or more types may be used in combination.

The polymerizable liquid crystal compound (Z) is described in, for example, Lub et al., Recl. Trav. Chim. It can be produced by a known method described in Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

The polymerizable liquid crystal compound forming the liquid crystal cured film is preferably a polymerizable liquid crystal compound having a maximum absorption wavelength between the wavelengths of 300 and 400 nm. When the polymerizable liquid crystal composition contains a photopolymerization initiator, the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage. However, if the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, even if ultraviolet light is exposed during storage, the reaction active species are generated from the photopolymerization initiator and the polymerizable liquid crystal compound by the reactive liquid compound is generated. The progress of polymerization reaction and gelation can be effectively suppressed. Therefore, it is advantageous in terms of long-term stability of the polymerizable liquid crystal composition, and the orientation and film thickness uniformity of the obtained liquid crystal cured film can be improved. The maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent capable of dissolving a polymerizable liquid crystal compound, and examples thereof include tetrahydrofuran and chloroform.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition forming the liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 70 to 99.5 parts by mass, based on 100 parts by mass of the solid content of the polymerizable liquid crystal composition. It is 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film. In the present specification, the solid content of the polymerizable liquid crystal composition means all the components of the polymerizable liquid crystal composition excluding volatile components such as organic solvents.

<Polymerizable liquid crystal composition>
The polymerizable liquid crystal composition used for forming the liquid crystal cured film contains a polymerizable liquid crystal compound, a silicon-based or fluorine-based leveling agent, and an acrylic-based leveling agent. Further, it may contain additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, a photosensitizer, and a dichroic dye. As each of these components, only one kind may be used, or two or more kinds may be used in combination.

The polymerizable liquid crystal composition can be obtained by stirring the above components at a predetermined temperature or the like.

Since the polymerizable liquid crystal composition for forming a liquid crystal cured film is usually applied to a substrate or the like in a state of being dissolved in a solvent, it is preferable to contain a solvent. As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable. Examples of the solvent include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and alcohols such as propylene glycol monomethyl ether. Solvents: Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone. Ketone solvent; aliphatic hydrocarbon solvent such as pentane, hexane and heptane; alicyclic hydrocarbon solvent such as ethylcyclohexane; aromatic hydrocarbon solvent such as toluene and xylene; nitrile solvent such as acetonitrile; tetrahydrofuran and dimethoxyethane and the like Ether solvent; chlorine-containing solvent such as chloroform and chlorobenzene; amide-based solvent such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, etc. Be done. These solvents can be used alone or in combination of two or more. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferable.

The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition is low, so that the thickness of the film becomes substantially uniform, and unevenness tends to be less likely to occur. The solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.

The polymerization initiator is a compound that can generate a reactive species by the contribution of heat or light and initiate a polymerization reaction such as a polymerizable liquid crystal compound. Examples of the reactive active species include active species such as radicals or cations or anions. Of these, a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint of easy reaction control.

Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, oxime compounds, triazine compounds, iodonium salts and sulfonium salts. Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, BASF Japan Co., Ltd.) (Made), Sakeol BZ, Sakeol Z, Sakeol BEE (manufactured by Seiko Kagaku Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), ADEKA PUTMER SP- 152, ADEKA OPTMER SP-170, ADEKA OPTMER N-1717, ADEKA OPTMER N-1919, ADEKA ARCULDS NCI-831, ADEKA ARCULDS NCI-930 (all manufactured by ADEKA Corporation), TAZ-A, TAZ -PP (above, manufactured by Nippon Sibel Hegner) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.) can be mentioned.

Since the photopolymerization initiator can fully utilize the energy emitted from the light source and is excellent in productivity, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and above all, the α-acetophenone type. A polymerization initiator and an oxime-based photopolymerization initiator are preferable.

Examples of the α-acetophenone-based polymerization initiator include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl. Examples thereof include butane-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butane-1-one, and more preferably 2-methyl-2-morpholino-. Included are 1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one. Examples of commercially available α-acetophenone compounds include Irgacure 369, 379EG, 907 (all manufactured by BASF Japan Ltd.) and Sequol BEE (manufactured by Seiko Kagaku Co., Ltd.).

Oxime-based photopolymerization initiators generate radicals such as phenyl radicals and methyl radicals when irradiated with light. The polymerization of the polymerizable liquid crystal compound proceeds preferably by this radical, and among them, the oxime-based photopolymerization initiator that generates a methyl radical is preferable in that the polymerization reaction initiation efficiency is high. Further, from the viewpoint of allowing the polymerization reaction to proceed more efficiently, it is preferable to use a photopolymerization initiator that can efficiently utilize ultraviolet rays having a wavelength of 350 nm or more. As the photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more, a triazine compound or a carbazole compound having an oxime structure is preferable, and a carbazole compound having an oxime ester structure is more preferable from the viewpoint of sensitivity. Oxime-based photopolymerization initiators include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned. Commercially available oxime ester-based photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Ltd.), ADEKA PUTMER N-1919, and ADEKA ARCULDS NCI-831. (The above is manufactured by ADEKA CORPORATION) and the like.

The content of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Is. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is not easily disturbed.

By blending an antioxidant, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. The antioxidant may be a primary antioxidant selected from phenol-based antioxidants, amine-based antioxidants, quinone-based antioxidants, and nitroso-based antioxidants, as well as phosphorus-based antioxidants and sulfur. It may be a secondary antioxidant selected from the system antioxidants. In order to polymerize the polymerizable liquid crystal compound without disturbing the orientation of the polymerizable liquid crystal compound, the content of the antioxidant is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass. Antioxidants can be used alone or in combination of two or more.

Further, by using a photosensitizer, the sensitivity of the photopolymerization initiator can be increased. Examples of the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes. The photosensitizer can be used alone or in combination of two or more. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.

<Dichroic pigment>
The polymerizable liquid crystal composition of the present invention may contain a dichroic dye. Here, the dichroic dye means a dye having a property that the absorbance in the major axis direction and the absorbance in the minor axis direction of the molecule are different. The dichroic dye that can be used in the present invention is not particularly limited as long as it has the above-mentioned properties, and may be a dye or a pigment. Further, two or more kinds of dyes or pigments may be used in combination, or dyes and pigments may be used in combination. When such a dichroic dye is contained in the horizontally oriented liquid crystal cured film or the vertically oriented liquid crystal cured film, the dichroic dye can be oriented together with the polymerizable liquid crystal compound and exhibit absorption anisotropy. In particular, when the degree of orientation order is high as represented by the smectic liquid crystal phase, the absorption anisotropy derived from the dichroic dye contained tends to be remarkably improved.

The dichroic dye preferably has a maximum absorption wavelength (λ _MAX ) in the range of 300 to 700 nm. Examples of such dichroic pigments include acridine pigments, oxazine pigments, cyanine pigments, naphthalene pigments, azo pigments and anthraquinone pigments.

Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, a stilbene azo dye, and the like, and a bisazo dye and a trisazo dye are preferable, and for example, a compound represented by the formula (I) (hereinafter, "compound"). (I) ”).
K ¹ (-N = N-K ² ) _p -N = N-K ³ (I)
[In formula (I), K ¹ and K ³ may independently have a phenyl group which may have a substituent, a naphthyl group which may have a substituent or a substituent. Represents a good monovalent heterocyclic group. K ² is a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocycle which may have a substituent. Represents a group. p represents an integer of 1 to 4. When p is an integer of 2 or more, the plurality of K ^2s may be the same or different from each other. The -N = N- bond may be replaced with the -C = C-, -COO-, -NHCO-, and -N = CH- bond within the range showing absorption in the visible region. ]

Examples of the monovalent heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole, and benzoxazole. Examples of the divalent heterocyclic group include a group obtained by removing two hydrogen atoms from the heterocyclic compound.

Phenyl group in K ¹ and K ^3, a naphthyl group and a monovalent heterocyclic group, and p- phenylene group in K ^2, as a naphthalene-1,4-diyl group and a divalent substituent heterocyclic group has optionally Is an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; an alkyl fluoride group having 1 to 4 carbon atoms such as a trifluoromethyl group; a cyano group; Nitro group; Halogen atom; Substituent or unsubstituted amino group such as amino group, diethylamino group, pyrrolidino group (Substituent amino group is an amino group having one or two alkyl groups having 1 to 6 carbon atoms, or two It means an amino group in which substituted alkyl groups are bonded to each other to form an alcandiyl group having 2 to 8 carbon atoms. The unsubstituted amino group is −NH ₂ ) and the like.

［式（Ｉ−１）〜（Ｉ−８）中、
Ｂ^１〜Ｂ^３０は、互いに独立して、水素原子、炭素数１〜６のアルキル基、炭素数１〜４のアルコキシ基、シアノ基、ニトロ基、置換または無置換のアミノ基（置換アミノ基および無置換アミノ基の定義は前記のとおり）、塩素原子またはトリフルオロメチル基を表わす。
ｎ１〜ｎ４は、互いに独立に０〜３の整数を表わす。
ｎ１が２以上である場合、複数のＢ^２は互いに同一でも異なっていてもよく、
ｎ２が２以上である場合、複数のＢ^６は互いに同一でも異なっていてもよく、
ｎ３が２以上である場合、複数のＢ^９は互いに同一でも異なっていてもよく、
ｎ４が２以上である場合、複数のＢ^１４は互いに同一でも異なっていてもよい。］ Among the compounds (I), compounds represented by any of the following formulas (I-1) to (I-6) are preferable.

[In formulas (I-1) to (I-8),
B ^{1 to} B ³⁰ are independent of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, and a substituted or unsubstituted amino group (substituted amino group). And the definition of an unsubstituted amino group is as described above), representing a chlorine atom or a trifluoromethyl group.
n1 to n4 represent integers 0 to 3 independently of each other.
When n1 is 2 or more, a plurality of B ^2s may be the same or different from each other.
If n2 is 2 or more, plural B ⁶ may be the same or different from each other,
If n3 is 2 or more, plural B ⁹ may be the same or different from each other,
When n4 is 2 or more, the plurality of B ^14s may be the same or different from each other. ]

［式（Ｉ−９）中、
Ｒ^１〜Ｒ^８は、互いに独立して、水素原子、−Ｒ^ｘ、−ＮＨ_２、−ＮＨＲ^ｘ、−ＮＲ^ｘ _２、−ＳＲ^ｘまたはハロゲン原子を表わす。
Ｒ^ｘは、炭素数１〜４のアルキル基または炭素数６〜１２のアリール基を表わす。］ As the anthraquinone dye, a compound represented by the formula (I-9) is preferable.

[In formula (I-9),
R ^{1 to} R ⁸ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

［式（Ｉ−８）中、
Ｒ^９〜Ｒ^１５は、互いに独立して、水素原子、−Ｒ^ｘ、−ＮＨ_２、−ＮＨＲ^ｘ、−ＮＲ^ｘ _２、−ＳＲ^ｘまたはハロゲン原子を表わす。
Ｒ^ｘは、炭素数１〜４のアルキル基または炭素数６〜１２のアリール基を表わす。］ As the oxazone dye, a compound represented by the formula (I-10) is preferable.

[In formula (I-8),
R ^{9 to} R ¹⁵ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

［式（Ｉ−１１）中、
Ｒ^１６〜Ｒ^２３は、互いに独立して、水素原子、−Ｒ^ｘ、−ＮＨ_２、−ＮＨＲ^ｘ、−ＮＲ^ｘ _２、−ＳＲ^ｘまたはハロゲン原子を表わす。
Ｒ^ｘは、炭素数１〜４のアルキル基または炭素数６〜１２のアリール基を表わす。］
式（Ｉ−９）、式（Ｉ−１０）および式（Ｉ−１１）において、Ｒ^ｘの炭素数１〜６のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基およびヘキシル基等が挙げられ、炭素数６〜１２のアリール基としては、フェニル基、トルイル基、キシリル基およびナフチル基等が挙げられる。 As the acridine dye, a compound represented by the formula (I-11) is preferable.

[In formula (I-11),
R ^{16 to} R ²³ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]
In formulas (I-9), formulas (I-10) and formulas (I-11), the alkyl groups having 1 to 6 carbon atoms of ^Rx include methyl group, ethyl group, propyl group, butyl group and pentyl group. And a hexyl group and the like, and examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xsilyl group and a naphthyl group.

［式（Ｉ−１２）中、
Ｄ^１およびＤ^２は、互いに独立に、式（Ｉ−１２ａ）〜式（Ｉ−１２ｄ）のいずれかで表される基を表わす。

ｎ５は１〜３の整数を表わす。］

［式（Ｉ−１３）中、
Ｄ^３およびＤ^４は、互いに独立に、式（Ｉ−１３ａ）〜式（１−１３ｈ）のいずれかで表される基を表わす。

ｎ６は１〜３の整数を表わす。］ As the cyanine dye, a compound represented by the formula (I-12) and a compound represented by the formula (I-13) are preferable.

[In formula (I-12),
D ¹ and D ² represent groups represented by any of the formulas (I-12a) to (I-12d) independently of each other.

n5 represents an integer of 1 to 3. ]

[In formula (I-13),
D ³ and D ⁴ represent groups represented by any of the formulas (I-13a) to (1-13h) independently of each other.

n6 represents an integer of 1 to 3. ]

Among these dichroic dyes, it is preferable that the vertically oriented liquid crystal cured film contains at least one azo dye as the dichroic dye from the viewpoint of orientation.
In the present invention, the weight average molecular weight of the dichroic dye is usually 300 to 2000, preferably 400 to 1000.

The content of the dichroic dye in the polymerizable liquid crystal composition forming the liquid crystal cured film can be appropriately determined depending on the type of the dichroic dye used and the like, but it is based on 100 parts by mass of the polymerizable liquid crystal compound. It is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass. When the content of the dichroic dye is within the above range, the orientation of the polymerizable liquid crystal compound is not easily disturbed, and a liquid crystal cured film having a high degree of orientation order can be obtained.

<Vertical alignment liquid crystal cured film>
The vertically oriented liquid crystal curing film is a liquid crystal curing in which the polymerizable liquid crystal composition is applied onto a base material or an alignment film and the polymerizable liquid crystal compound is cured in a state of being oriented perpendicular to the base material or the alignment film. It is a membrane.

In the present invention, it is preferable that the following formula (S4) is satisfied as the uniformness of the horizontally oriented liquid crystal cured film.
RthC (450) / RthC (550) ≤ 1.0 ... (S4)
[In the formula (S4), RthC (450) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 450 nm, and RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm)]

When the horizontally oriented liquid crystal cured film satisfies the formula (S4), the vertically oriented liquid crystal cured film has a so-called inverse value in which the phase difference value in the thickness direction at a short wavelength is smaller than the phase difference value in the thickness direction at a long wavelength. Shows wavelength dispersibility. RthC (450) / RthC (550) is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0.95 or less, more preferably 0.92 or less.

The retardation value in the thickness direction can be adjusted by the thickness dC of the vertically oriented liquid crystal cured film. The phase difference value in the thickness direction is
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2-nzC (λ)) × dC
Therefore, in order to obtain a desired thickness direction retardation value (RthC (λ): retardation value in the thickness direction of the vertically oriented liquid crystal cured film at a wavelength λ (nm)), a three-dimensional refractive index is used. The film thickness dC may be adjusted.

Further, it is preferable that the vertically oriented liquid crystal cured film satisfies the following formula (S3).
-150 ≤ RthC (550) ≤ -30 ... (S3)
[In the formula (S3), RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm]
A more preferable range of the thickness direction retardation RthC (550) of the vertically oriented liquid crystal cured film is −110 nm ≦ RthC (550) ≦ −45 nm.

The vertically oriented liquid crystal cured film is, for example,
A step of forming a coating film of a polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film,
A step of drying the coating film to form a dry coating film, and
It can be produced by a method including a step of irradiating a dry coating film with active energy rays to form a vertically oriented liquid crystal cured film.

The coating film of the polymerizable liquid crystal composition is formed, for example, by applying the polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film onto a substrate, an alignment film, or a horizontally oriented liquid crystal cured film described later. Can be done.
Examples of the base material include a glass base material and a film base material, and a resin film base material is preferable from the viewpoint of processability. Resins constituting the film substrate include, for example, polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohols; polyethylene terephthalates; polymethacrylic acid esters; polyacrylic acid esters; triacetylcellulose, Examples include diacetyl cellulose, and cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyphenylene sulfide and plastics such as polyphenylene oxide. Such a resin can be formed into a film by a known means such as a solvent casting method and a melt extrusion method to form a base material. The surface of the base material may have a protective layer formed of acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., and may be subjected to a mold release treatment such as silicone treatment, a corona treatment, etc. Surface treatment such as plasma treatment may be applied.

A commercially available product may be used as the base material. Commercially available cellulose ester base materials include, for example, cellulose ester base materials manufactured by Fuji Photo Film Co., Ltd. such as Fujitac Film; manufactured by Konica Minolta Opto Co., Ltd. such as "KC8UX2M", "KC8UY", and "KC4UY". Examples include the cellulose ester base material of. Commercially available cyclic olefin resins include, for example, cyclic olefin resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; cyclic olefins manufactured by JSR Corporation such as "Arton (registered trademark)". Resins; Cyclic olefin resins manufactured by Nippon Zeon Co., Ltd. such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; Mitsui such as "Apel" (registered trademark) Cyclic olefin resin manufactured by Chemical Co., Ltd. can be mentioned. A commercially available cyclic olefin resin base material can also be used. As commercially available cyclic olefin resin base materials, cyclic olefin resin base materials manufactured by Sekisui Chemical Industry Co., Ltd. such as "Scina (registered trademark)" and "SCA40 (registered trademark)"; "Zeonoa film (registered trademark)" A cyclic olefin resin base material manufactured by Optes Co., Ltd .; a cyclic olefin resin base material manufactured by JSR Corporation such as "Arton Film (registered trademark)" can be mentioned.

From the viewpoints of thinning the laminate, easy peeling of the base material, handleability of the base material, and the like, the thickness of the base material is usually 5 to 300 μm, preferably 10 to 150 μm.

Examples of the method for applying the polymerizable liquid crystal composition to a substrate or the like include a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method and other coating methods, and a flexography method and other printing methods. And the like.

Then, the solvent is removed by drying or the like to form a dry coating film. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method. At this time, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent can be dried and removed from the coating film, and the polymerizable liquid crystal compound can be oriented in the direction perpendicular to the plane of the coating film. The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material of the base material or the like forming the coating film, but the liquid crystal is used to make a phase transition of the polymerizable liquid crystal compound to the liquid crystal layer state. It is necessary that the temperature is equal to or higher than the phase transition temperature. In order to bring the polymerizable liquid crystal compound into a vertically oriented state while removing the solvent contained in the polymerizable liquid crystal composition, for example, the liquid crystal phase transition temperature (smetic phase transition) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. It can be heated to a temperature of about (temperature or nematic phase transition temperature) or higher.

The liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. When two or more kinds of polymerizable liquid crystal compounds are used in combination, the phase transition temperature is a polymerization in which all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition are mixed at the same ratio as the composition in the polymerizable liquid crystal composition. It means a temperature measured by using a mixture of sex liquid crystal compounds in the same manner as when one kind of polymerizable liquid crystal compound is used. It is generally known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition may be lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound alone.

The heating time can be appropriately determined depending on the heating temperature, the type of the polymerizable liquid crystal compound used, the type of the solvent, its boiling point and its amount, etc., but is usually 15 seconds to 10 minutes, preferably 0.5 to 0.5 minutes. 5 minutes.

The solvent may be removed from the coating film at the same time as heating the polymerizable liquid crystal compound to the liquid crystal phase transition temperature or higher, or separately, but it is preferable to remove the solvent at the same time from the viewpoint of improving productivity. Before heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, the solvent in the coating film is appropriately added under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize. A pre-drying step may be provided for removal. Examples of the drying method in the pre-drying step include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method, and the drying temperature (heating temperature) in the drying step is the type of polymerizable liquid crystal compound used and the solvent. It can be appropriately determined according to the type of the above, its boiling point, its amount and the like.

Next, in the obtained dry coating film, a vertically oriented liquid crystal cured film is formed by polymerizing the polymerizable liquid crystal compound while maintaining the vertically oriented state of the polymerizable liquid crystal compound. Examples of the polymerization method include a thermal polymerization method and a photopolymerization method, but the photopolymerization method is preferable from the viewpoint of easily controlling the polymerization reaction. In photopolymerization, the light irradiated to the dry coating film includes the type of photopolymerization initiator contained in the dry coating film and the type of polymerizable liquid crystal compound (particularly, the type of polymerizable group contained in the polymerizable liquid crystal compound). And appropriately selected according to the amount. Specific examples thereof include one or more types of light and active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays and γ-rays. Among them, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use a photopolymerization apparatus widely used in the art, so that photopolymerization can be performed by ultraviolet light. It is preferable to select the type of the polymerizable liquid crystal compound or the photopolymerization initiator contained in the polymerizable liquid crystal composition. Further, at the time of polymerization, the polymerization temperature can be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means. By adopting such a cooling means, if the polymerizable liquid crystal compound is polymerized at a lower temperature, a vertically oriented liquid crystal cured film can be appropriately formed even if a base material having a relatively low heat resistance is used. It is also possible to promote the polymerization reaction by raising the polymerization temperature within a range in which defects due to heat during light irradiation (deformation due to heat of the base material, etc.) do not occur. A patterned cured film can also be obtained by masking or developing during photopolymerization.

Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excima laser, and a wavelength range. Examples thereof include an LED light source that emits 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm ² . The ultraviolet irradiation intensity is preferably the intensity in the wavelength region effective for activating the photopolymerization initiator. The time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0.1 seconds to 1 minute. is there. When irradiated once or multiple times with such an ultraviolet irradiation intensity, the integrated light intensity is 10 to 3,000 mJ / cm ² , preferably 50 to 2,000 mJ / cm ² , and more preferably 100 to 1,000 mJ / cm. It is ² .

The thickness of the vertically oriented liquid crystal cured film can be appropriately selected depending on the display device to be applied, and is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm. When the vertically oriented liquid crystal cured film has a positive wavelength dispersibility, 0.2 to 1 μm is more preferable, and when the vertically oriented liquid crystal cured film has a reverse wavelength dispersibility, 0.4 to 2 μm is further preferable. When the vertically oriented liquid crystal cured film has a reverse wavelength dispersibility, the light absorption in the diagonal direction increases for the same dye concentration as compared with the case where the vertically oriented liquid crystal cured film has a positive wavelength dispersibility. preferable.

<Vertical alignment liquid crystal cured film containing dichroic dye>
As a uniform of the vertically oriented liquid crystal cured film in the present invention, the vertically oriented liquid crystal cured film may contain a dichroic dye. In particular, in the case of a vertically oriented liquid crystal cured film containing a dichroic dye, the higher the alignment order of the liquid crystal, the better the absorption selectivity derived from the dichroic dye. Therefore, the above-mentioned smectic phase, particularly the higher-order smectic phase, is used. It is preferable to use the polymerizable liquid crystal compound shown, and it is preferable to polymerize while maintaining the liquid crystal state of the smectic phase, preferably the higher-order smectic phase, to form a vertically oriented liquid crystal cured film containing a dichroic dye.

The vertically oriented liquid crystal cured film containing the dichroic dye satisfies the following formulas (11) and (12).
0.001 ≤ AxC ≤ 0.3 (11)
AxC (z = 60) / AxC> 2 (12)

In formulas (11) and (12), AxC and AxC (z = 60) both represent the absorbance of the vertically oriented liquid crystal cured film at the absorption maximum wavelength of 400 to 750 nm. Further, AxC represents the absorbance of linearly polarized light vibrating in the x-axis direction, and AxC (z = 60) is in the x-axis direction when the vertically oriented liquid crystal cured film is rotated by 60 ° with the y-axis as the rotation axis. Represents the absorbance of vibrating linearly polarized light. The x-axis means an arbitrary direction in the plane of the vertically oriented liquid crystal cured film, the y-axis means the direction perpendicular to the x-axis in the film surface, and the z-axis means the thickness direction of the vertically oriented liquid crystal cured film. In addition, the absorbance in the present specification indicates the absorbance when measured in a state excluding the influence of interfacial reflection at the time of measurement. As a method of removing the influence of interfacial reflection, for example, using a spectrophotometer, the absorbance at a wavelength where absorption of the compound can be ignored at a long wavelength such as 800 nm is set to 0, and in that state, the wavelength of the region where absorption of the compound exists is set to 0. Methods such as measuring the absorbance can be mentioned.

The AxC can be measured by incident linearly polarized light vibrating in the x-axis direction from the z-axis direction toward the film surface of the liquid crystal cured film. The above formula (11) means that the absorbance in the front direction in the plane of the vertically oriented liquid crystal cured film is 0.001 or more and 0.3 or less, and the smaller the value of AxC, the more the plane of the obtained liquid crystal cured film. It can be said that the dichroic dyes are accurately oriented in the vertical direction. When the AxC value exceeds 0.3, the vertically oriented liquid crystal cured film is strongly colored in the front direction, so that the front hue tends to be inferior when applied to a display device in combination with a horizontally oriented retardation film. Therefore, the value of AxC is preferably 0.1 or less, more preferably 0.05 or less. The lower limit of the value of AxC is usually 0.001 or more, preferably 0.003 or more, and more preferably 0.005 or more.

The AxC (z = 60) can be measured by injecting the same linear polarization as the linearly polarized light in which Ax is measured in a state where the vertically oriented liquid crystal cured film is rotated by 60 ° with the y-axis as the rotation axis. Here, the rotation of the film is performed by rotating the film in the state where Ax is measured by 60 ° in the incident direction of linearly polarized light with the y-axis as the rotation axis. If the value of AxC (z = 60) / AxC is 2 or less, it is difficult to obtain good light absorption anisotropy. Therefore, the value of AxC (z = 60) / AxC is preferably 2. It is 5 or more, more preferably 3 or more. On the other hand, if the value of AxC (z = 60) / AxC is too large, the hue changes significantly only in the orthorhombic hue, and the difference between the front hue and the orthorhombic hue may become large. Therefore, AxC (z = 60). ) / AxC value is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less. Further, AxC (z = 60) is preferably 0.01 or more, more preferably 0.03 or more, further preferably 0.05 or more, and preferably 1.0 or less, more preferably 0.5. Below, it is more preferably 0.3 or less.

The absorbance of linearly polarized light vibrating in the y-axis direction is expressed as AyC, but in the vertically oriented liquid crystal cured film described in the present invention, AxC and AyC are usually substantially equal values. When AxC and AyC are different, they have dichroism in the plane, and in this case, the front hue of the vertically oriented liquid crystal cured film tends to be heavily colored.

When the vertical liquid crystal cured film satisfies the above formulas (11) and (12), it can be said that the vertical liquid crystal alignment film has excellent polarization performance (absorption anisotropy), whereby light from the front direction is effectively emitted. It can transmit light and effectively absorb light from an oblique direction.

AxC and AxC (Z = 60) in the vertically oriented liquid crystal cured film containing the dichroic dye are, for example, the film thickness, the conditions of the manufacturing process, the polymerizable liquid crystal compound and the dichroic dye constituting the vertically oriented liquid crystal cured film. It can be controlled by adjusting the type and blending amount of the liquid crystal. In general, the value of AxC (z = 60) / AxC is about 2 to 10 when the polymerizable liquid crystal compound is a nematic liquid crystal and about 5 to 30 when the polymerizable liquid crystal compound is a smectic liquid crystal, and is adjusted to the desired optical characteristics. It can be selected as appropriate.

<Alignment film>
In one aspect of the present invention, the coating film of the polymerizable liquid crystal composition is formed on the alignment film. The alignment film has an orientation-regulating force that orients the polymerizable liquid crystal compound in a desired direction. Among these, an alignment film having an orientation regulating force for orienting a polymerizable liquid crystal compound in the horizontal direction may be referred to as a horizontal alignment film, and an alignment film having an orientation regulating force for orienting a polymerizable liquid crystal compound in the vertical direction may be referred to as a vertical alignment film. The orientation regulating force can be arbitrarily adjusted according to the type of alignment film, surface condition, rubbing conditions, etc., and when the alignment film is formed of a photoalignable polymer, it is arbitrarily adjusted according to the polarization irradiation conditions, etc. It is possible to do.

The alignment film preferably has solvent resistance that does not dissolve when the polymerizable liquid crystal composition is applied, and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound described later. Examples of the alignment film include an alignment film containing an orientation polymer, a photoalignment film, a grub alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the orientation direction, and the like, and the accuracy of the orientation angle and A photoalignment film is preferable from the viewpoint of quality.

Examples of the oriented polymer include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamic acid, which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and poly. Examples thereof include oxazol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Of these, polyvinyl alcohol is preferable. The oriented polymer can be used alone or in combination of two or more.

The alignment film containing the orientation polymer is usually obtained by applying a composition in which the orientation polymer is dissolved in a solvent (hereinafter, may be referred to as "orientation polymer composition") to a substrate to remove the solvent, or. It is obtained by applying an oriented polymer composition to a substrate, removing a solvent, and rubbing (rubbing method). Examples of the solvent include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition.

The concentration of the oriented polymer in the oriented polymer composition may be in the range where the oriented polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content with respect to the solution, and is 0. .1 to 10% is more preferable.

As the orientation polymer composition, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).

Examples of the method of applying the oriented polymer composition to the base material include the same methods as those exemplified as the method of applying the polymerizable liquid crystal composition to the base material.

Examples of the method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.

In order to impart an orientation regulating force to the alignment film, a rubbing treatment can be performed as needed (rubbing method). As a method of imparting orientation-regulating force by the rubbing method, a rubbing cloth is wrapped around a rotating rubbing roll, and an orientation polymer composition is applied to the substrate and annealed to form the surface of the substrate. A method of contacting a film of an oriented polymer can be mentioned. If masking is performed during the rubbing treatment, a plurality of regions (patterns) having different orientation directions can be formed on the alignment film.

The photoalignment film is usually formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as “composition for forming a photoalignment film”) to a substrate, removing the solvent, and then polarizing the photoalignment film. It is obtained by irradiating (preferably polarized UV). The photoalignment film is also advantageous in that the direction of the orientation regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that produces a liquid crystal alignment ability when irradiated with light. Specific examples thereof include groups involved in photoreactions that are the origin of liquid crystal orientation ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction generated by light irradiation. Of these, groups involved in the dimerization reaction or photocrosslinking reaction are preferable because they are excellent in orientation. As the photoreactive group, an unsaturated bond, particularly a group having a double bond is preferable, and a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), and a nitrogen-nitrogen bond are used. A group having at least one selected from the group consisting of a double bond (N = N bond) and a carbon-oxygen double bond (C = O bond) is particularly preferable.

Examples of the photoreactive group having a C = C bond include a vinyl group, a polyene group, a stilbene group, a stillbazol group, a stillvazolium group, a chalcone group, a cinnamoyl group and the like. Examples of the photoreactive group having a C = N bond include a group having a structure such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N = N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. Examples of the photoreactive group having a C = O bond include a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group and the like. These groups may have substituents such as an alkyl group, an alkoxy group, an allyl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group and an alkyl halide group.

Among them, a photoreactive group involved in a photodimerization reaction is preferable, and a photoalignment film having a relatively small amount of polarized light required for photoalignment and excellent thermal stability and stability over time can be easily obtained. A cinnamoyl group and a chalcone group are preferable. As the polymer having a photoreactive group, a polymer having a cinnamoyl group such that the terminal portion of the side chain of the polymer has a cinnamic acid structure is particularly preferable.

By applying the composition for forming a photoalignment film onto a base material, a photoalignment-inducing layer can be formed on the base material. Examples of the solvent contained in the composition include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition, and are appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group. can do.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the target photoalignment film, but the composition for forming a photoalignment film. It is preferably at least 0.2% by mass, more preferably 0.3 to 10% by mass, based on the mass of the above. The composition for forming a photoalignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer as long as the characteristics of the photoalignment film are not significantly impaired.

Examples of the method of applying the composition for forming a photoalignment film to the base material include the same method as the method of applying the orientation polymer composition to the base material. Examples of the method for removing the solvent from the applied composition for forming a photoalignment film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.

In order to irradiate polarized light, even in the form of directly irradiating polarized UV from the composition for forming a photoalignment film coated on the substrate, the polarized light is transmitted from the substrate side. It may be in the form of being irradiated. Further, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable. Examples of the light source used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halides. Lamps are more preferred. Among these, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm. Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizer. As such a polarizing element, a polarizing filter, a polarizing prism such as a Gran Thomson or a Granter, or a wire grid type polarizing element can be used.

If masking is performed during rubbing or polarized light irradiation, it is possible to form a plurality of regions (patterns) in which the directions of liquid crystal orientation are different.

A groove alignment film is a film having an uneven pattern or a plurality of grooves on the surface of the film. When the polymerizable liquid crystal compound is applied to a film having a plurality of linear grubs arranged at equal intervals, the liquid crystal molecules are oriented in the direction along the groove.

As a method of obtaining a grub alignment film, a method of forming an uneven pattern by performing exposure and rinsing treatment after exposure through an exposure mask having a pattern-shaped slit on the surface of the photosensitive polyimide film, and a plate having a groove on the surface. A method of forming a layer of UV-curable resin before curing on a shaped master, transferring the formed resin layer to a substrate and then curing, and a film of UV-curable resin before curing formed on the substrate. Examples thereof include a method in which a roll-shaped master having a plurality of grooves is pressed to form irregularities and then cured.

Examples of the material exhibiting the orientation-regulating force for orienting the polymerizable liquid crystal compound in the direction perpendicular to the plane of the coating film include fluoropolymers such as perfluoroalkyl and silane compounds, and their condensation reactions, in addition to the above-mentioned orientation polymers. You may use the polysiloxane compound obtained by the above.

When a silane compound is used as the material for forming the alignment film, the constituent elements include Si element and C element from the viewpoint that the surface tension can be easily lowered and the adhesion to the layer adjacent to the alignment film can be easily improved. The compound is preferable, and the silane compound can be preferably used. As the silane compound, a nonionic silane compound described later, a silane-containing ionic compound as exemplified in the section of ionic compound, and the like can be used, and by using these silane compounds, the vertical orientation regulating force can be used. Can be enhanced. These silane compounds may be used alone, in combination of two or more, or mixed with other materials. When the silane compound is a nonionic silane compound, a silane compound having an alkyl group at the molecular terminal is preferable, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable from the viewpoint of easily increasing the vertical orientation restricting force. ..

The thickness of the alignment film (alignment film containing an alignment polymer or photoalignment film) is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, more preferably 10 to 500 nm or less, and further preferably. Is in the range of 10 to 300 nm, particularly preferably 50 to 250 nm.

<Orientation accelerator>
In another aspect of the vertically oriented liquid crystal cured film in the present invention, the coating film of the polymerizable liquid crystal composition does not require an alignment film and can be formed directly on the substrate. In such an embodiment, the polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film usually contains an orientation accelerator. In the present invention, the orientation accelerator means a material that promotes the liquid crystal orientation of the polymerizable liquid crystal compound in a desired direction. Examples of the orientation promoter that promotes the vertical orientation of the polymerizable liquid crystal compound include an ionic compound composed of non-metal atoms and a non-ionic silane compound. The polymerizable liquid crystal composition forming the vertically oriented liquid crystal cured film preferably contains at least one of an ionic compound composed of non-metal atoms and a non-ionic silane compound, and an ionic compound composed of non-metal atoms and It is more preferable to contain both nonionic silane compounds.

When the polymerizable liquid crystal composition forming the vertically oriented liquid crystal cured film contains an ionic compound composed of non-metal atoms, in the dry coating film formed from the vertically oriented liquid crystal cured film forming composition on the substrate, the dry coating film is formed. The electrostatic interaction exerts a force to regulate the vertical orientation of the polymerizable liquid crystal compound, and the polymerizable liquid crystal compound tends to be oriented perpendicular to the surface of the substrate in the dry coating film. As a result, the liquid crystal cured film can be formed while maintaining the vertically oriented state of the polymerizable liquid crystal compound.

Examples of ionic compounds composed of non-metal atoms include onium salts (more specifically, quaternary ammonium salts in which nitrogen atoms have a positive charge, tertiary sulfonium salts, and phosphorus atoms have a positive charge. Quaternary phosphonium salt, etc.). Of these onium salts, a quaternary onium salt is preferable from the viewpoint of further improving the vertical orientation of the polymerizable liquid crystal compound, and a quaternary phosphonium salt or a quaternary from the viewpoint of improving availability and mass productivity. Ammonium salts are more preferred. The onium salt may have two or more quaternary onium salt moieties in the molecule, and may be an oligomer or a polymer.

The molecular weight of the ionic compound is preferably 100 or more and 10,000 or less. When the molecular weight is within the above range, it is easy to improve the vertical orientation of the polymerizable liquid crystal compound while ensuring the coatability of the polymerizable composition. The molecular weight of the ionic compound is more preferably 5000 or less, still more preferably 3000 or less.

Examples of the cation component of the ionic compound include an inorganic cation and an organic cation. Of these, organic cations are preferable because orientation defects of the polymerizable liquid crystal compound are unlikely to occur. Examples of the organic cation include imidazolium cation, pyridinium cation, ammonium cation, sulfonium cation, phosphonium cation and the like.

Ionic compounds generally have a counter anion. Examples of the anion component that becomes the counter ion of the cation component include an inorganic anion and an organic anion. Of these, organic anions are preferable because orientation defects of the polymerizable liquid crystal compound are unlikely to occur. It should be noted that the cation and the anion do not necessarily have to have a one-to-one correspondence.

Specific examples of the anion component include the following.
Chloride anion [Cl ^-],
Bromide anion [Br ^-],
Iodide anion [I ^-],
Tetrachloroaluminate anion [AlCl ₄ ^-],
Hepta-chloro-di-aluminate anion _[Al 2 Cl ₇ ^-],
Tetrafluoroborate anion [BF ₄ ^-],
Hexafluorophosphate anion [PF ₆ ^-],
Perchlorate anions [ClO ₄ ^-],
Nitrate anions [NO ₃ ^-],
Acetate anion _[CH 3 COO ^-],
Trifluoroacetate anion [CF ₃ COO ⁻ ],
Fluorosulfonate anion [FSO ₃ ^-],
Methanesulfonate anion _[CH 3 SO ₃ ^-],
Trifluoromethanesulfonate anion [CF ₃ SO ₃ ⁻ ],
p- toluenesulfonate anion _{[p-CH 3 C 6 H 4} SO 3 - ],
Bis (fluorosulfonyl) imide anion [(FSO ₂ ) ₂ N ⁻ ],
Bis (trifluoromethanesulfonyl) imide anion _{[(CF 3 SO 2) 2 N} - ],
Tris (trifluoromethanesulfonyl) meth acetonide anion _{[(CF 3 SO 2) 3 C} - ],
Hexafluoro Ah cell anion [AsF ₆ ^-],
Hexafluoroantimonate anion [SbF ₆ ^-],
Hexafluoro niobate anions [NbF ₆ ^-],
Hexafluoro tantalate anion [TaF ₆ ^-],
Dimethylphosphinate anion [(CH ₃ ) ₂ POO ⁻ ],
(Poly) Hydrofluoroolefin anion [F (HF) _n ⁻ ] (for example, n represents an integer of 1 to 3),
Dicyanamide anion _[(CN) 2 N ^-],
Thiocyanate anion [SCN ^-],
Perfluorobutane sulfonate anion _[C 4 _F 9 SO ₃ ^-],
Bis (pentafluoroethanesulfonyl) imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ⁻ ],
Perfluorobutanoate anion [C ₃ F ₇ COO ⁻ ], and (trifluoromethanesulfonyl) (trifluoromethanecarbonyl) imide anion [(CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ ].

Specific examples of the ionic compound can be appropriately selected from the combination of the above-mentioned cation component and anion component. Specific examples of the compound which is a combination of a cation component and an anion component include the following.

(Pyridinium salt)
N-hexylpyridinium hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-Methyl-4-hexylpyridinium hexafluorophosphate,
N-Butyl-4-methylpyridinium hexafluorophosphate,
N-octyl-4-methylpyridinium hexafluorophosphate,
N-hexylpyridinium bis (fluorosulfonyl) imide,
N-octylpyridinium bis (fluorosulfonyl) imide,
N-Methyl-4-hexylpyridinium bis (fluorosulfonyl) imide,
N-Butyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-octyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-hexylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octylpyridinium bis (trifluoromethanesulfonyl) imide,
N-Methyl-4-hexylpyridinium bis (trifluoromethanesulfonyl) imide,
N-Butyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,
N-hexylpyridinium p-toluenesulfonate,
N-octylpyridinium p-toluenesulfonate,
N-Methyl-4-hexylpyridinium p-toluenesulfonate,
N-Butyl-4-methylpyridinium p-toluenesulfonate, and N-octyl-4-methylpyridinium p-toluenesulfonate.

(Imidazole salt)
1-Ethyl-3-methylimidazolium hexafluorophosphate,
1-Ethyl-3-methylimidazolium bis (fluorosulfonyl) imide,
1-Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide,
1-Ethyl-3-methylimidazolium p-toluenesulfonate,
1-Butyl-3-methylimidazolium methanesulfonate, etc.

(Pyrrolidinium salt)
N-Butyl-N-Methylpyrrolidinium Hexafluorophosphate,
N-Butyl-N-Methylpyrrolidinium bis (fluorosulfonyl) imide,
N-Butyl-N-Methylpyrrolidinium bis (trifluoromethanesulfonyl) imide,
N-Butyl-N-methylpyrrolidinium p-toluenesulfonate and the like.

(Ammonium salt)
Tetrabutylammonium hexafluorophosphate,
Tetrabutylammonium bis (fluorosulfonyl) imide,
Tetrahexyl ammonium bis (fluorosulfonyl) imide,
Trioctylmethylammonium bis (fluorosulfonyl) imide,
(2-Hydroxyethyl) trimethylammonium bis (fluorosulfonyl) imide,
Tetrabutylammonium bis (trifluoromethanesulfonyl) imide,
Tetrahexyl ammonium bis (trifluoromethanesulfonyl) imide,
Trioctylmethylammonium bis (trifluoromethanesulfonyl) imide,
(2-Hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide,
Tetrabutylammonium p-toluenesulfonate,
Tetrahexyl ammonium p-toluene sulfonate,
Trioctylmethylammonium p-toluenesulfonate,
(2-Hydroxyethyl) trimethylammonium p-toluenesulfonate,
(2-Hydroxyethyl) trimethylammonium dimethylphosphinate 1- (3-trimethoxysilylpropyl) -1,1,1-tributylammonium bis (trifluoromethanesulfonyl) imide,
1- (3-Trimethoxysilylpropyl) -1,1,1-trimethylammonium bis (trifluoromethanesulfonyl) imide,
1- (3-Trimethoxysilylbutyl) -1,1,1-tributylammonium bis (trifluoromethanesulfonyl) imide,
1- (3-Trimethoxysilylbutyl) -1,1,1-trimethylammonium bis (trifluoromethanesulfonyl) imide,
N-{(3-Triethoxysilylpropyl) Carbamoyloxyethyl)} -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide, and N- [2- {3- (3-trimethoxysilylpropylamino) ) -1-Oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide.

(Phoenium salt)
Tributyl (2-methoxyethyl) phosphonium bis (trifluoromethanesulfonyl) imide,
Tributylmethylphosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1-[(trimethoxysilyl) methyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1- [2- (trimethoxysilyl) ethyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1- [3- (trimethoxysilyl) propyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1- [4- (trimethoxysilyl) butyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-Tributyl-1-[(trimethoxysilyl) methyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-Tributyl-1- [2- (trimethoxysilyl) ethyl] phosphonium bis (trifluoromethanesulfonyl) imide, and 1,1,1-tributyl-1- [3- (trimethoxysilyl) propyl] Phosphoniubis (trifluoromethanesulfonyl) imide.
Each of these ionic compounds may be used alone, or two or more thereof may be used in combination.

From the viewpoint of further improving the vertical orientation of the polymerizable liquid crystal compound, it is preferable that the ionic compound has a Si element and / or an F element in the molecular structure of the cationic moiety. When the ionic compound has a Si element and / or an F element in the molecular structure of the cation site, the ionic compound is likely to segregate on the surface of the vertically oriented liquid crystal cured film. Among them, the following ionic compounds (i) to (iii) are preferable as the ionic compounds in which all the constituent elements are non-metal elements.

（イオン性化合物（ｉｉ））

（イオン性化合物（ｉｉｉ））

(Ionic compound (i))

(Ionic compound (ii))

(Ionic compound (iii))

As a method for improving the vertical orientation of the polymerizable liquid crystal compound, for example, a method of treating the surface of the substrate with a surfactant having an alkyl group having a long chain length to some extent is known (for example, "Liquid Crystal Handbook"). See Chapter 2 Liquid Crystal Orientation and Physical Properties (published by Maruzen Co., Ltd.). The method of improving the vertical orientation of a liquid crystal compound by using such a surfactant can also be applied to an ionic compound. That is, the vertical orientation of the polymerizable liquid crystal compound can be effectively improved by treating the surface of the base material with an ionic compound having an alkyl group having a long chain length to some extent.

Specifically, it is preferable that the ionic compound satisfies the following formula (8).
5 <M <16 (8)
In the formula (8), M is represented by the following formula (9).
M = (Of the substituents directly bonded to the positively charged atom, the number of covalent bonds from the positively charged atom to the end of the molecular chain of the substituent having the largest number of covalent bonds to the end of the molecular chain ) ÷ (Number of atoms with a positive charge) (9)
When the ionic compound satisfies the above (8), the vertical orientation of the polymerizable liquid crystal compound can be effectively improved.

When there are two or more positively charged atoms in the molecule of the ionic compound, the substituents having two or more positively charged atoms are counted from the positively charged atoms considered as the base point. The number of covalent bonds to the closest atom having a positive charge is defined as "the number of covalent bonds from the atom having a positive charge to the end of the molecular chain" described in the definition of M above. When the ionic compound is an oligomer or polymer having two or more repeating units, the constituent unit is considered as one molecule and the above M is calculated. When a positively charged atom is incorporated into the ring structure, the number of covalent bonds to the positively charged atom via the ring structure, or to the end of the substituent bonded to the ring structure. Of the number of covalent bonds in the above, the one having the larger number of covalent bonds is defined as "the number of covalent bonds from an atom having a positive charge to the end of the molecular chain" described in the definition of M above.

When the polymerizable liquid crystal composition forming the vertically oriented liquid crystal cured film contains an ionic compound, the content thereof is usually 0.01 to 5% by mass with respect to the solid content of the polymerizable liquid crystal composition. It is preferably 0.05 to 4% by mass, more preferably 0.1 to 3% by mass. When the content of the ionic compound is within the above range, the vertical orientation of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coatability of the polymerizable liquid crystal composition.

When the polymerizable liquid crystal composition forming the vertically oriented liquid crystal cured film contains a nonionic silane compound, the nonionic silane compound lowers the surface tension of the polymerizable liquid crystal composition, and the vertically oriented liquid crystal cured film is placed on the substrate. In the dry coating film formed from the composition for formation, the nonionic silane compound is present on the surface of the dry coating film on the opposite side to the base material, which enhances the vertical orientation restricting force for the polymerizable liquid crystal compound and is dry-coated. In the film, the polymerizable liquid crystal compound tends to be oriented in the direction perpendicular to the surface of the substrate. As a result, the liquid crystal cured film can be formed while maintaining the vertically oriented state of the polymerizable liquid crystal compound.

The nonionic silane compound is a compound that is nonionic and contains a Si element. Nonionic silane compounds include, for example, silicon polymers such as polysilanes, silicone resins such as silicone oils and silicone resins, and organic-inorganic silane compounds such as silicone oligomers, silces siloxane and alkoxysilanes (more specifically). , Silane coupling agent, etc.), silane-containing compound described in the section of leveling agent, and the like.

The nonionic silane compound may be a silicone monomer type or a silicone oligomer (polymer) type. When the silicone oligomer is shown in the form of a (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercapto Propyl group-containing copolymers such as propyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetra Mercaptomethyl group-containing copolymers such as ethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer and mercaptomethyltriethoxysilane-tetraethoxysilane copolymer; 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3 − Methacloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane- Tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-methacryloxyylopropylmethyldiethoxysilane-tetraethoxysilane copolymer Copolymers containing methacryloyloxypropyl groups such as 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetramethoxy Silane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxy Acryloyloxypropyl group-containing copolymers such as propylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane -Tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxy Vinyl group-containing copolymers such as silane-tetramethoxysilane copolymer and vinylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane Copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetra Examples thereof include amino group-containing copolymers such as ethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer. One of these nonionic silane compounds may be used alone, or two or more thereof may be used in combination. Of these, a silane coupling agent is preferable from the viewpoint of further improving the adhesion with the adjacent layer.

The silane coupling agent is selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, an isocyanate group, a carboxy group, and a hydroxy group at the end. It is a compound containing a Si element having a functional group such as at least one thereof and at least one alkoxysilyl group or silanol group. By appropriately selecting these functional groups, the mechanical strength of the vertically oriented liquid crystal cured film can be improved, the surface of the vertically oriented liquid crystal cured film can be modified, and the vertically oriented liquid crystal cured film and an adjacent layer (for example, a base material) can be used. It is possible to impart a peculiar effect such as improvement of adhesion. From the viewpoint of adhesion, it is preferable that the silane coupling agent is a silane coupling agent having an alkoxysilyl group and another different reactive group (for example, the above-mentioned functional group). Further, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and a polar group. When the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical orientation of the polymerizable liquid crystal compound is more likely to be improved, and the vertical orientation promoting effect can be remarkably obtained. There is a tendency. Examples of the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxy group and a hydroxy group. The polar group may appropriately have a substituent or a protecting group in order to control the reactivity of the silane coupling agent.

Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-. (2-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltri Methoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethyl Examples include silane.

Examples of commercially available silane coupling agents include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, and 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 Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. such as -9103, KBM-573, KBM-575, KBM-9569, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007. Can be mentioned.

When the polymerizable liquid crystal composition forming the vertically oriented liquid crystal cured film contains a nonionic silane compound, the content thereof is usually 0.01% by mass to 5% by mass with respect to the solid content of the polymerizable liquid crystal composition. Is more preferable, 0.05% by mass to 4% by mass is more preferable, and 0.1% by mass to 3% by mass is further preferable. When the content of the nonionic silane compound is within the above range, the vertical orientation of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coatability of the polymerizable liquid crystal composition.

A dry coating formed from the composition for forming a vertically oriented liquid crystal cured film on a substrate by containing both an ionic compound and a nonionic silane compound in the polymerizable liquid crystal composition forming the vertically oriented liquid crystal cured film. In the film, the electrostatic interaction derived from the ionic compound and the surface tension lowering effect derived from the nonionic silane compound make it easier to promote the vertical orientation of the polymerizable liquid crystal compound. As a result, the liquid crystal cured film can be formed while maintaining the state in which the polymerizable liquid crystal compound is more accurately vertically oriented.

<Horizontal alignment liquid crystal cured film>
The horizontally oriented liquid crystal cured film in the present invention is a polymerized liquid crystal compound in which the above-mentioned polymerizable liquid crystal composition is coated on a base material or an oriented film, and the base sphere is in the plane of the oriented film. Shows a liquid crystal cured film cured in an oriented state.

In the present invention, it is preferable that the following formula (S2) is satisfied as the uniformness of the horizontally oriented liquid crystal cured film.
ReA (450) / ReA (550) <1.00 (S2)
[In the formula (S2), ReA (λ) represents the in-plane retardation value of the horizontally oriented retardation film at a wavelength of λ nm, and ReA (λ) = (nxA (λ) −nyA (λ)) × dA ( In the equation, nxA (λ) represents the main refractive index at the wavelength λ nm in the horizontal alignment retardation film plane, and nyA (λ) is the wavelength λ nm in the same plane as nxA and orthogonal to the direction of nxA. Represents the refractive index of, and dA indicates the thickness of the horizontally oriented retardation film)]

When the horizontally oriented liquid crystal cured film satisfies the formula (S2), the horizontally oriented liquid crystal cured film has a so-called inverse wavelength dispersion in which the in-plane retardation value at a short wavelength is smaller than the in-plane retardation value at a long wavelength. Show sex. When such a horizontally oriented liquid crystal cured film is incorporated into an organic EL display device, it is possible to improve the specular hue at the time of black display. The ReA (450) / ReA (550) is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0, because the effect of improving the reflected hue in the front direction can be further enhanced. It is 95 or less, more preferably 0.92 or less.

The in-plane retardation value can be adjusted by adjusting the thickness dA of the horizontally oriented liquid crystal cured film. Since the in-plane retardation value is determined by the above equation ReA (λ) = (nxA (λ) -nyA (λ)) × dA, the desired in-plane retardation value (ReA (λ): wavelength λ ( In order to obtain the in-plane retardation value of the horizontally oriented liquid crystal cured film at nm), the three-dimensional refractive index and the film thickness dA may be adjusted.

Further, it is preferable that the horizontally oriented liquid crystal cured film satisfies the following formula (S1).
100 nm ≤ ReA (550) ≤ 180 nm (S1)
[In equation (S1), ReA (λ) has the same meaning as above]
When the in-plane phase difference ReA (550) of the horizontally oriented liquid crystal cured film is within the range of the formula (S1), the effect of improving the specular hue at the time of black display when applied to an organic EL display device (suppressing coloring). The effect of causing) becomes remarkable. A more preferable range of the in-plane retardation value is 120 nm ≦ ReA ≦ 170 nm, and a more preferable range is 130 nm ≦ ReA (550) ≦ 150 nm.

Conventionally known polymerizable liquid crystal compounds can be used in the field of horizontally oriented liquid crystal cured films. Among them, a polymerizable liquid crystal compound exhibiting so-called reverse wavelength dispersibility is preferable, and as such a polymerizable liquid crystal compound, for example, a polymerizable liquid crystal compound represented by the above formula (X) can be preferably used. The polymerizable liquid crystal compound may be used alone or in combination of two or more.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition used for forming the horizontally oriented liquid crystal cured film is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. , It is preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film.

The polymerizable liquid crystal composition used for forming the horizontally oriented liquid crystal cured film further contains additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, and a photosensitizer in addition to the polymerizable liquid crystal compound. You may. Examples of these components include the same components as those exemplified above as components that can be used in the vertically oriented liquid crystal cured film, and each of these components may use only one type or a combination of two or more types. ..

The polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film can be obtained by stirring the polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as a solvent and a photopolymerization initiator at a predetermined temperature. ..

The horizontally oriented liquid crystal cured film is, for example,
A step of applying a polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film onto a base material or an oriented film to obtain a coating film.
A step of drying the coating film to form a dry coating film, and
It can be produced by a method including a step of irradiating a dry coating film with active energy rays to form a horizontally oriented liquid crystal cured film.

The coating film of the polymerizable liquid crystal composition can be formed, for example, by applying the polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film on a substrate or an alignment film. As the base material that can be used here, the same base material as those exemplified above can be used as the base material that can be used for producing the vertically oriented liquid crystal cured film.

The alignment film can be appropriately selected from materials having a horizontal orientation regulating force that orients the polymerizable liquid crystal compound in the horizontal direction with respect to the plane of the coating film. The orientation-regulating force can be arbitrarily adjusted according to the type of alignment layer, surface condition, rubbing conditions, etc., and when formed from a photo-alignable polymer, it can be arbitrarily adjusted according to polarization irradiation conditions, etc. It is possible. Examples of such a material include the above-mentioned oriented polymer as an oriented film that can be used for producing a vertically oriented liquid crystal cured film. The horizontally oriented film can be obtained by applying a composition containing such a material and a solvent, for example, the solvent exemplified in the vertically oriented liquid crystal cured film, to a substrate, removing the solvent, and then heating the coated film or the like. it can. As the horizontal alignment film, it is preferable to use a photoalignment film from the viewpoint of quality.

Then, the solvent is removed by drying or the like to form a dry coating film. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method. From the viewpoint of productivity, heat drying is preferable, and the heating temperature in that case is preferably equal to or higher than the phase transition temperature of the polymerizable liquid crystal compound while the solvent can be removed. Procedures and conditions in such a step include the same ones that can be adopted in the method for producing a vertically oriented liquid crystal cured film.

The obtained dry coating film is irradiated with active energy rays (more specifically, ultraviolet rays, etc.), and the polymerizable liquid crystal compound is maintained in a state of being oriented horizontally with respect to the plane of the coating film. By polymerizing, a horizontally oriented liquid crystal cured film is formed. Examples of the polymerization method include the same methods that can be adopted in the method for producing a vertically oriented liquid crystal cured film.

<Horizontal alignment liquid crystal cured film containing dichroic pigment>
In the present invention, among the horizontally oriented liquid crystal cured films containing a dichroic dye, a film having a polarizing function may be referred to as a polarizing film. In particular, in the case of a horizontally oriented liquid crystal cured film containing a dichroic dye, the higher the alignment order of the liquid crystal, the better the absorption selectivity derived from the dichroic dye. It is preferable to use the polymerizable liquid crystal compound shown above, and it is preferable to form a polarizing film by polymerizing while maintaining the liquid crystal state of the smectic phase, preferably the higher-order smectic phase. The polarizing film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase is obtained from the conventional host guest type polarizing film, that is, the liquid crystal state of the nematic phase due to the action of the dichroic dye. There is an advantage that the polarizing performance is high as compared with the polarizing film. Further, there is an advantage that the strength is excellent as compared with the one coated only with the dichroic dye or the lyotropic liquid crystal.

A polarizing film having a high degree of orientation order can obtain a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement. The Bragg peak means a peak derived from the plane periodic structure of molecular orientation. Therefore, in the polarizing film formed from the polymerizable liquid crystal composition of the present invention, it is preferable that the polymerizable liquid crystal compound or a polymer thereof is oriented so that the polarizing film shows a Bragg peak in X-ray diffraction measurement. It is more preferable that the molecules of the polymerizable liquid crystal compound are oriented in the direction of absorbing light in a "horizontal orientation". In the present invention, a polarizing film having a molecular orientation plane period interval of 3.0 to 6.0 Å is preferable. A high degree of orientation order such as showing the Bragg peak can be realized by controlling the type of the polymerizable liquid crystal compound used, the type and amount of the antioxidant, the type and amount of the dichroic dye, and the like.

The thickness of the horizontally oriented liquid crystal cured film can be appropriately selected, and is preferably 0.1 to 5 μm, more preferably 0.3 to 4 μm, and further preferably 0.4 to 3 μm.

<Elliptical polarizing plate>
The present invention includes an elliptical polarizing plate including the liquid crystal cured film of the present invention. The elliptical polarizing plate is a laminate including at least a retardation film and a polarizing film.

The polarizing film is a film having a polarizing function. For example, a film containing the above-mentioned polarizing film, a stretched film having a dye having absorption anisotropy adsorbed, or a film coated with a dye having absorption anisotropy as a polarizer. And so on. Examples of the dye having absorption anisotropy include a dichroic dye.

A film containing a stretched film having a dye having absorption anisotropy adsorbed as a polarizer is usually obtained by uniaxially stretching a polyvinyl alcohol-based resin film and dyeing the polyvinyl alcohol-based resin film with a bicolor dye. At least of the polarizer produced through a step of adsorbing a bicolor dye, a step of treating a polyvinyl alcohol-based resin film on which the bicolor dye is adsorbed with an aqueous boric acid solution, and a step of washing with water after treatment with the aqueous boric acid It is produced by sandwiching one surface with a transparent protective film via an adhesive.

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

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

A film formed of such a polyvinyl alcohol-based resin is used as a raw film for a polarizing film. The method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 μm.

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, at the same time as dyeing, or after dyeing. When the uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. It is also possible to perform uniaxial stretching at these multiple stages. In uniaxial stretching, rolls having different peripheral speeds may be uniaxially stretched, or thermal rolls may be used to uniaxially stretch the rolls. Further, the uniaxial stretching may be a dry stretching in which stretching is performed in the atmosphere, or a wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent. The draw ratio is usually about 3 to 8 times.

Dyeing of the polyvinyl alcohol-based resin film with a dichroic dye is performed, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

As the dichroic dye, specifically, iodine or a dichroic organic dye is used. Examples of the dichroic organic dye include C.I. I. Examples thereof include a dichroic direct dye composed of a disazo compound such as DIRECT RED 39, and a dichroic direct dye composed of a compound such as trisazo and tetrakisazo. The polyvinyl alcohol-based resin film is preferably immersed in water before the dyeing treatment.

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

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing is usually adopted. The content of the dichroic organic dye in this aqueous solution is usually about 1 × 10 ^-4 to 10 parts by mass, preferably 1 × 10 ^-3 to 1 part by mass, more preferably 1 × 10 ^-4 to 1 part by mass, per 100 parts by mass of water. Is 1 × 10 ^-3 to 1 × ^10-2 parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80 ° C. The immersion time (staining time) in this aqueous solution is usually about 10 to 1,800 seconds.

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

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

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

The thickness of the polarizer obtained by uniaxially stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying the polyvinyl alcohol-based resin film in this way is preferably 5 to 40 μm.

Examples of the film coated with the dye having absorption anisotropy include a composition containing a dichroic dye having liquid crystal properties, a film obtained by applying a composition containing a dichroic dye and a polymerizable liquid crystal, and the like. Can be mentioned. The film preferably has a protective film on one or both sides thereof. Examples of the protective film include the same resin films as those exemplified above as the base material that can be used for producing the horizontally oriented liquid crystal cured film.

The film coated with the dye having absorption anisotropy is preferably thin, but if it is too thin, the strength tends to decrease and the processability tends to be inferior. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

Specific examples of the film coated with the dye having absorption anisotropy include the films described in JP-A-2012-33249.

A polarizing film can be obtained by laminating a transparent protective film on at least one surface of the polarizing element thus obtained via an adhesive. As the transparent protective film, a transparent film similar to the resin film exemplified above can be preferably used as a base material that can be used for producing a horizontally oriented liquid crystal cured film.

The elliptical polarizing plate of the present invention is configured to include the liquid crystal cured film of the present invention. For example, the present invention is made by laminating the liquid crystal cured film of the present invention with a polarizing film or the like via an adhesive layer or the like. Elliptical polarizing plate can be obtained.

In one embodiment of the present invention, when the laminate of the present invention and the polarizing film are laminated, the slow axis (optical axis) of the horizontally oriented retardation film constituting the laminate and the absorption axis of the polarizing film It is preferable to stack the films so that the forming angle is 45 ± 5 °.

The elliptical polarizing plate of the present invention may have a configuration provided by a conventional general elliptical polarizing plate, or a polarizing film and a retardation film. Such a configuration is used for the purpose of protecting the surface of an adhesive layer (sheet) for bonding an elliptical polarizing plate to a display element such as an organic EL, a polarizing film or a retardation film from scratches and stains. Protective film and the like.

The laminate and elliptical polarizing plate of the present invention can be used in various display devices.
The display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. The display devices include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, an electric field emission display device (FED), and a surface electric field emission display device). (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection type display device (for example, grating light valve (GLV) display device, display device having a digital micromirror device (DMD)). ) And piezoelectric ceramic displays. The liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, a projection type liquid crystal display device, and the like. These display devices may be display devices that display two-dimensional images or three-dimensional display devices that display three-dimensional images. In particular, the elliptical polarizing plate of the present invention has an effect. Since it is remarkably easily exhibited, it can be suitably used for an organic electroluminescence (EL) display device, and the laminate of the present invention can be suitably used for a liquid crystal display device and a touch panel display device. These display devices can be used. It is excellent in frontal reflection hue and oblique reflection hue at the time of black display, and is also excellent at frontal hue and oblique hue at the time of white display, and can exhibit good image display characteristics.

Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, "%" and "part" in an example mean mass% and mass part, respectively, unless otherwise specified.

<Example 1>
[Preparation of liquid crystal compounds]
The liquid crystal compound A was produced according to the method described in JP-A-2010-31223. Further, the liquid crystal compound B was produced according to the method described in JP-A-2009-173893. The molecular structures of the liquid crystal compound A and the liquid crystal compound B are shown below, respectively.

(Liquid crystal compound A)

(Liquid crystal compound B)

[Preparation of composition for forming vertically oriented liquid crystal cured film]
Liquid crystal compound A and liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. 0.10 parts by mass of the leveling agent "BYK-361N" (manufactured by BYK-Chemie) and 0.25 parts by mass of the leveling agent "F-556" (manufactured by DIC) with respect to 100 parts by mass of the obtained mixture. 2.0 parts by mass of ionic compound A prepared with reference to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of KBE-9103 manufactured by Shin-Etsu Chemical Industry Co., Ltd., 2-dimethylamino as a photopolymerization initiator 6 parts by mass of -2-benzyl-1- (4-morpholinophenyl) butane-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. A composition for forming a vertically oriented liquid crystal cured film was obtained by stirring at 80 ° C. for 1 hour.

尚、アクリル系レベリング剤「ＢＹＫ−３６１Ｎ」をＧＰＣ（東ソー社製、ＨＬＣ−８２２０ＧＰＣ、溶媒テトラヒドロフラン、検出器：ＲＩ）にて分子量を測定したところ、数平均分子量は４８００であった。 Ionic compound A:

When the molecular weight of the acrylic leveling agent "BYK-361N" was measured by GPC (manufactured by Tosoh Corporation, HLC-8220GPC, solvent tetrahydrofuran, detector: RI), the number average molecular weight was 4800.

[Method for producing vertically oriented liquid crystal cured film]
Corona treatment is performed on a cycloolefin film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd., a composition for forming a vertically oriented liquid crystal cured film is applied using a bar coater, and the film is heated at 120 ° C. for 60 seconds. , High-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.) is used to irradiate ultraviolet rays from the surface coated with the composition for forming a horizontally oriented liquid crystal cured film (in a nitrogen atmosphere, integrated light intensity at a wavelength of 365 nm: By 500 mJ / cm ² ), a vertically oriented liquid crystal cured film was formed. The film thickness of the obtained vertically oriented liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation) and found to be 1.2 μm.

[Rth measurement of vertically oriented liquid crystal cured film]
When KOBRA-WPR manufactured by Oji Measuring Instruments Co., Ltd. is used, the phase difference of the film having anisotropic absorption in visible light cannot be measured. Therefore, two of the compositions for forming a vertically oriented liquid crystal cured film are used. After preparing a composition for forming a vertically oriented liquid crystal curing from which only the color dye A is removed, vertically oriented liquid crystal curing is similarly formed using the composition, and it is confirmed that there is no phase difference in the cycloolefin film. Using "KOBRA-WPR" manufactured by Oji Measurement Co., Ltd., the angle of incidence of light on the optical characteristic measurement sample is changed to change the front phase difference value (in-plane phase difference value) and phase advance of the vertically oriented liquid crystal cured film. The phase difference value when tilted by 40 ° to the center of the axis was measured. The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by JASCO Corporation. The film thickness was measured using an Optical NanoGauge film thickness meter C12562-01 manufactured by Hamamatsu Photonics Co., Ltd. From the above-mentioned front phase difference value (in-plane phase difference value), phase difference value when tilted by 40 ° to the center of the phase advance axis, average refractive index, and film thickness value, Oji measuring equipment technical data (http: //: The three-dimensional refractive index was calculated with reference to (www.oji-keisoku.co.jp/products/kobra/reference.html). Table 1 shows the results of calculating the optical characteristics of each of the vertically oriented liquid crystal cured films from the obtained three-dimensional refractive index according to the following formula.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2-nzC (λ)) × dC
αthC = RthC (450) / RthC (550)

[Manufacturing of polarizing film]
A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a saponification degree of 99.9 mol% or more and a thickness of 75 μm was immersed in pure water at 30 ° C., and then the weight ratio of iodine / potassium iodide / water was 0. It was immersed in an aqueous solution of 02/2/100 at 30 ° C. for iodine staining (iodine staining step). The polyvinyl alcohol film that had undergone the iodine dyeing step was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 12/5/100 at 56.5 ° C. to perform boric acid treatment (boric acid treatment step). ). The polyvinyl alcohol film that had undergone the boric acid treatment step was washed with pure water at 8 ° C. and then dried at 65 ° C. to obtain a polarizer (thickness 27 μm after stretching) in which iodine was adsorbed and oriented on the polyvinyl alcohol. .. At this time, stretching was performed in the iodine dyeing step and the boric acid treatment step. The total draw ratio in such stretching was 5.3 times. The obtained polarizer and a saponified triacetyl cellulose film (KC4UYTAC 40 μm manufactured by Konica Minolta) were bonded to each other with a nip roll via an aqueous adhesive. While maintaining the tension of the obtained laminate at 430 N / m, it was dried at 60 ° C. for 2 minutes to obtain a polarizing film having a triacetyl cellulose film as a protective film on one side. The water-based adhesive is 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol (Kuraray Poval KL318 manufactured by Kuraray), and a water-soluble polyamide epoxy resin (Aqueous solution of Sumire's resin 650 solid content concentration 30% manufactured by Sumika Chemtex). Prepared by adding 1.5 parts.

The obtained polarizing film was confirmed for unevenness and evaluated for orientation. The measurement was carried out with a spectrophotometer (V7100, manufactured by JASCO Corporation) using the polarizer surface of the polarizing plate obtained above as an incident surface. The obtained luminosity factor correction single transmittance was 42.1%, the luminosity factor correction polarization degree was 99.996%, the single hue a was −1.1, and the single hue b was 3.7.

[Confirmation of unevenness]
In a dark room, with the brightness of the Tritech backlight A4-500 set to 4700 lux, two polarizing films manufactured by the above method were installed on the backlight so as to form a cross Nicol. Subsequently, the vertically oriented liquid crystal cured film produced by the above method is placed between the two polarizing films, and the vertically oriented liquid crystal cured film is tilted so that the angle formed by the backlight surface is 60 °. When it was rotated and visually recognized from the surface side of the polarizing film, the light leakage due to the phase difference of the vertically oriented liquid crystal cured film was maximized. In the above state, unevenness of the vertically oriented liquid crystal cured film was confirmed based on the following criteria.
⊚: Unevenness is not visible.
〇: A little unevenness is visible.
Δ: Unevenness is visually recognized.
X: The unevenness is strongly visible.

[Orientation evaluation]
First, the vertically oriented liquid crystal cured film was bonded to a glass having a thickness of 5 × 5 cm × 0.7 mm via a pressure-sensitive adhesive (25 μm) manufactured by Lintec Corporation. The obtained sample was observed with a polarizing microscope (“BX-51” manufactured by Olympus Corporation) under the condition of a magnification of 200 times, and the number of orientation defects in a field of view of 480 μm × 320 μm was counted. Here, only the number of orientation defects caused by the measurement sample was counted, and the number of defects caused by environmental foreign substances other than the sample was excluded and not counted. From the observation results with a polarizing microscope, the orientation of the vertically oriented liquid crystal cured film was evaluated based on the following evaluation criteria. In addition, it was judged that 〇 and Δ had excellent orientation.
Evaluation criteria:
◯ (very good): The number of orientation defects is 5 or less.
Δ (good): The number of orientation defects is 6 or more and 20 or less.
X (bad): The number of orientation defects is 21 or more, or there is no orientation at all.

<Examples 2 to 5>
As shown in Table 1, the leveling agents to be added when preparing the composition for forming a vertically oriented liquid crystal cured film are "BYK-361N" (acrylic leveling agent) and "BYK-UV3500" (silicon type) manufactured by BYK-chemie. A vertically oriented liquid crystal cured film was produced in the same manner as in Example 1 except that the leveling agent), DIC's "F-556" (fluorine-based leveling agent) was changed, and the amount of addition was changed. The measurement of Rth, unevenness and orientation were confirmed. The results are shown in Table 1.

<Example 6>
[Preparation of composition for forming horizontal alignment film]
A horizontal alignment film is obtained by mixing 5 parts (weight average molecular weight: 30,000) of a photo-oriented material having the following structure and 95 parts of cyclopentanone (solvent) as components, and stirring the obtained mixture at 80 ° C. for 1 hour. A composition for forming was obtained.

[Preparation of composition for forming horizontally oriented liquid crystal cured film]
Liquid crystal compound A and liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.1 part by mass of the leveling agent "BYK-361N" (manufactured by BYK-Chemie) and 0.25 parts by mass of the leveling agent "F-556" (manufactured by DIC). With 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one as a photopolymerization initiator (“Irgacure® 369 (Irg369)” manufactured by BASF Japan Ltd.) Was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. A composition for forming a horizontally oriented liquid crystal cured film was obtained by stirring at 80 ° C. for 1 hour.

A 1 mg / 50 mL tetrahydrofuran solution of liquid crystal compound A was prepared, a measurement sample was placed in a measurement cell having an optical path length of 1 cm, and the measurement sample was an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation). When the absorption spectrum was measured and the wavelength at which the maximum absorption was obtained was read from the obtained absorption spectrum, the maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 350 nm.

[Method for producing horizontally oriented liquid crystal cured film]
A composition for forming a horizontally oriented film was coated on a cycloolefin film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd. with a bar coater, dried at 80 ° C. for 1 minute, and subjected to a polarized UV irradiation device (SPOT CURE SP-9). Polarized UV exposure was carried out at an integrated light amount of 100 mJ / cm ² at a wavelength of 313 nm using a Ushio Denki Co., Ltd. to obtain a horizontally aligned film. The film thickness of the obtained horizontal alignment film was measured with an ellipsometer and found to be 200 nm.

Subsequently, a composition for forming a horizontally oriented liquid crystal cured film is applied onto the horizontally aligned film using a bar coater, and after heating at 120 ° C. for 60 seconds, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.) ) Was irradiated from the surface coated with the composition for forming a horizontally oriented liquid crystal cured film (integrated light amount at a wavelength of 365 nm under a nitrogen atmosphere: 500 mJ / cm ² ) to form a horizontally oriented liquid crystal cured film. .. After confirming that there was no phase difference in the COP film, Re (450) and Re (550) were measured using KOBRA-WPR manufactured by Oji Measuring Instruments Co., Ltd. The results are shown in Table 1.

[Confirmation of unevenness]
In a dark room, with the brightness of the Tritech backlight A4-500 set to 4700 lux, two polarizing films manufactured by the above method were installed on the backlight so as to form a cross Nicol. Subsequently, a horizontally oriented liquid crystal cured film is placed between the two polarizing films so that the angle formed by the slow axis of the horizontally oriented liquid crystal cured film produced by the above method and the absorption axis of the polarizing film is 45 °. The film was installed and visually observed from the surface opposite to the backlight, and unevenness of the horizontally oriented liquid crystal cured film was confirmed according to the following criteria.
⊚: Unevenness is not visible.
〇: A little unevenness is visible.
Δ: Unevenness is visually recognized.
X: The unevenness is strongly visible.

[Orientation evaluation]
First, the horizontally oriented liquid crystal cured film was bonded to glass having a thickness of 5 × 5 cm × 0.7 mm via a pressure-sensitive adhesive (25 μm) manufactured by Lintec Corporation. The obtained sample was observed with a polarizing microscope (“BX-51” manufactured by Olympus Corporation) under the condition of a magnification of 200 times, and the number of orientation defects in a field of view of 480 μm × 320 μm was counted. Here, only the number of orientation defects caused by the measurement sample was counted, and the number of defects caused by environmental foreign substances other than the sample was excluded and not counted. From the observation results with a polarizing microscope, the orientation of the vertically oriented liquid crystal cured film was evaluated based on the following evaluation criteria. In addition, it was judged that 〇 and Δ had excellent orientation.
Evaluation criteria:
◯ (very good): The number of orientation defects is 5 or less.
Δ (good): The number of orientation defects is 6 or more and 20 or less.
X (bad): The number of orientation defects is 21 or more, or there is no orientation at all.

<Example 7>
[Preparation of composition for forming horizontal alignment film]
A horizontal alignment film is obtained by mixing 5 parts (weight average molecular weight: 30,000) of a photo-oriented material having the following structure and 95 parts of cyclopentanone (solvent) as components, and stirring the obtained mixture at 80 ° C. for 1 hour. A composition for forming was obtained.

[Preparation of horizontally oriented liquid crystal cured film composition]
The following components were mixed and stirred at 80 ° C. for 1 hour to obtain a horizontally oriented liquid crystal cured film composition (composition for forming a polarizing layer). As the dichroic dye, the azo dye described in Examples of JP2013-101328A was used. The polymerizable liquid crystal compounds represented by the formulas (1-6) and (1-7) are described in lube et al. , Recl. Trav. Chim. Manufactured according to the method described in Pays-Bas, 115, 321-328 (1996).

７５部

２５部
二色性色素１：ポリアゾ色素；化合物（１−８） ２．５部

化合物（１−５） ２．５部

化合物（１−１６） ２．５部

重合開始剤；
２−ジメチルアミノ−２−ベンジル−１−（４−モルホリノフェニル）ブタン−１−オン（イルガキュア３６９；チバスペシャルティケミカルズ社製） ６部
レベリング剤；
「ＢＹＫ−３６１Ｎ」（ＢＹＫ−Ｃｈｅｍｉｅ社製）０．１質量部（アクリル系レベリング剤）
「Ｆ−５５６」（ＤＩＣ社製）０．２５質量部（フッ素系レベリング剤）
溶剤；o-キシレン ２５０部 Polymerizable liquid crystal compound:

75 copies

25 parts dichroic dye 1: polyazo dye; compound (1-8) 2.5 parts

Compound (1-5) 2.5 parts

Compound (1-16) 2.5 parts

Polymerization initiator;
2-Dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals) 6-part leveling agent;
"BYK-361N" (manufactured by BYK-Chemie) 0.1 parts by mass (acrylic leveling agent)
"F-556" (manufactured by DIC Corporation) 0.25 parts by mass (fluorine-based leveling agent)
Solvent; 250 parts of o-xylene

[Manufacturing of horizontally oriented liquid crystal cured film]
A triacetyl cellulose film (KC4UY) manufactured by Konica Minolta Co., Ltd. was treated once using a corona treatment device (AGF-B10, manufactured by Kasuga Electric Works Ltd.) under the conditions of an output of 0.3 kW and a treatment speed of 3 m / min. A composition for forming a horizontal alignment film (composition for forming a polarizing layer) is applied to a corona-treated surface with a bar coater, dried at 80 ° C. for 1 minute, and a polarized UV irradiation device (SPOT CURE SP-7; Ushio Denki). Polarized UV exposure was carried out at an axial angle of 90 ° with an integrated light intensity of 100 mJ / cm ² using (manufactured by Co., Ltd.). The film thickness of the obtained horizontally oriented layer was measured with an ellipsometer and found to be 150 nm.
Subsequently, a composition for forming a horizontally oriented liquid crystal cured film (composition for forming a polarizing layer) is applied using a bar coater, and then dried in a drying oven set at 120 ° C. for 1 minute to obtain a polymerizable liquid crystal compound and dichroism. A dry coating film in which the color dye was oriented was obtained. After the dry coating film is naturally cooled to room temperature, it is irradiated with ultraviolet rays using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.) (in a nitrogen atmosphere, wavelength: 365 nm, integrated light amount at wavelength 365 nm: By polymerizing the polymerizable liquid crystal compound by 1000 mJ / cm ² ), a horizontally oriented liquid crystal cured film (polarizing film) was prepared.

[Measurement of polarization degree and single transmittance]
The degree of polarization and the single transmittance of the obtained horizontally oriented liquid crystal cured film (polarizing film) were measured as follows. The transmittance in the transmission axis direction (T ¹ ) and the transmittance in the absorption axis direction (T ² ) are doubled using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) with a folder with a polarizer set. It was measured by the beam method in a wavelength range of 2 nm step 380 to 680 nm. Using the following formulas (p) and (q), the single transmittance and the degree of polarization at each wavelength are calculated, and the visual sensitivity is corrected by the 2 degree field (C light source) of JIS Z 8701, and the single transmittance of the visual sensitivity correction is corrected. When the rate (Ty) and the luminosity-corrected polarization degree (Py) were calculated, it was confirmed that the single transmittance was 42% and the polarization degree was 97%, which were useful values as a polarizing film.
Elemental transmittance (%) = (T ¹ + T ² ) / 2 (p)
Polarization degree (%) = {(T ^1- T ² ) / (T ¹ + T ² )} x 100 (q)

[Confirmation of unevenness]
In a dark room, with the brightness of the Tritech backlight A4-500 set to 4700 lux, one polarizing film manufactured by the above method is placed on the backlight, and the horizontally oriented liquid crystal cured film is further absorbed. The horizontally oriented liquid crystal cured film was installed so that the angle formed by the axis and the absorption axis of the polarizing film was 90 ° (cross Nicol state). The installed sample was visually observed from the surface opposite to the backlight, and unevenness of the horizontally oriented liquid crystal cured film was confirmed according to the following criteria.
⊚: Unevenness is not visible.
〇: A little unevenness is visible.
Δ: Unevenness is visually recognized.
X: The unevenness is strongly visible.

[Orientation evaluation]
First, the horizontally oriented liquid crystal cured film was bonded to glass having a thickness of 5 × 5 cm × 0.7 mm via a pressure-sensitive adhesive (25 μm) manufactured by Lintec Corporation. The obtained sample was observed with a polarizing microscope (“BX-51” manufactured by Olympus Corporation) under the condition of a magnification of 200 times, and the number of orientation defects in a field of view of 480 μm × 320 μm was counted. Here, only the number of orientation defects caused by the measurement sample was counted, and the number of defects caused by environmental foreign substances other than the sample was excluded and not counted. From the observation results with a polarizing microscope, the orientation of the vertically oriented liquid crystal cured film was evaluated based on the following evaluation criteria. In addition, it was judged that 〇 and Δ had excellent orientation.
Evaluation criteria:
◯ (very good): The number of orientation defects is 5 or less.
Δ (good): The number of orientation defects is 6 or more and 20 or less.
X (bad): The number of orientation defects is 21 or more, or there is no orientation at all.

<Example 8>
A vertically oriented liquid crystal cured film was produced in the same manner as in Example 1 except that the method for preparing the vertically oriented liquid crystal cured film forming composition was changed as shown below, and unevenness and orientation were confirmed. The results are shown in Table 1. Since the dichroism was included, the phase difference value of the vertically oriented liquid crystal cured film was not measured. Further, when the absorbance of the vertically oriented liquid crystal cured film was determined by the method described below, it was λmax = 600 nm, AxC = 0.024, and AxC (z = 60) = 0.175.

[Preparation of polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film]
The liquid crystal compound (A) and the liquid crystal compound (B) were mixed at a mass ratio of 90:10 to obtain a mixture. 0.1 parts by mass of leveling agent "BYK-361N" (manufactured by BYK-Chemie), 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC), with respect to 100 parts by mass of the obtained mixture. Open 2013-101328, 1.5 parts by mass of the bicolor dye A shown below, 2.0 parts by mass of ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, silane cup. Ring agent "KBE-9103" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.5 parts by mass, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (BASF) as a photopolymerization initiator 6 parts by mass of "Irgacure (registered trademark) 369 (Irg369)") manufactured by Japan Co., Ltd. was added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film.

Dichro compound A:

[Measurement of absorbance of vertically oriented liquid crystal cured film]
The coated surface of the vertically oriented liquid crystal cured film produced by the above method is bonded to glass of 4 x 4 cm x 0.7 mm thickness via a 25 μm pressure-sensitive pressure-sensitive adhesive (manufactured by Lintec Corporation), and an ultraviolet visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation) was set and the absorbance was measured, and the maximum absorption wavelength (λmax) having a wavelength of 400 to 750 nm, AxC and AxC (z = 60) were calculated.
The x-axis means an arbitrary direction in the plane of the vertically oriented liquid crystal cured film, the y-axis means the direction perpendicular to the x-axis in the film surface, and the z-axis means the thickness direction of the vertically oriented liquid crystal cured film, and AxC and AxC. (Z = 60) is the absorbance of the vertically oriented liquid crystal cured film at the absorption maximum wavelength of 400 to 750 nm, and AxC represents the absorbance of linearly polarized light oscillating in the x-axis direction, and AxC (z = 60). 60) represents the absorbance of linearly polarized light that vibrates in the x-axis direction when the film is rotated by 60 ° with the y-axis as the rotation axis.

When measuring the absorbance, the sample was set in an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation), corrected so that the absorbance at 800 nm became zero, and then AxC was measured. For AxC (z = 60), the sample was set and tilted in the same manner, and after correction so that the absorbance at 800 nm became zero, AxC (z = 60) was measured.

<Comparative Examples 1 to 4>
As shown in Table 1, the leveling agents to be added when preparing the composition for forming a vertically oriented liquid crystal cured film are "BYK-361N" manufactured by BYK-chemie, "BYK-392" manufactured by BYK-chemie, and "F-556" manufactured by DIC. A vertically oriented liquid crystal cured film was produced in the same manner as in Example 1 except that the amount was changed to "" and the amount of addition was changed, and its unevenness and orientation were confirmed. The results are shown in Table 1.

When the molecular weight of the acrylic leveling agent "BYK-392" was measured by GPC (manufactured by Tosoh Corporation, HLC-8220GPC, solvent tetrahydrofuran, detector: RI), the number average molecular weight was 13100.

なお、表１におけるＲｅは、水平配向膜の面内位相差値又は垂直配向膜の面内位相差値のいずれかを表す。

In addition, Re in Table 1 represents either the in-plane retardation value of the horizontally oriented film or the in-plane retardation value of the vertically aligned film.

According to the present invention, unevenness can be improved by using a predetermined leveling agent without impairing the orientation of the liquid crystal cured film.

Claims (18)

It contains at least one silicon-based or fluorine-based leveling agent, at least one acrylic leveling agent, and at least one polymerizable liquid crystal compound.
A composition for forming a liquid crystal cured film in which the total amount of the leveling agent is 3.0% by mass or less with respect to the total amount of the polymerizable liquid crystal compound. The composition for forming a liquid crystal cured film according to claim 1, further comprising at least one silicon-based leveling agent, at least one acrylic leveling agent, and one or more polymerizable liquid crystal compounds. The composition for forming a liquid crystal cured film according to claim 1 or 2, further comprising a dichroic dye. The composition for forming a liquid crystal cured film according to any one of claims 1 to 3, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound exhibiting a smectic phase. The composition for forming a liquid crystal cured film according to any one of claims 1 to 4, wherein the polymerizable liquid crystal compound is a liquid crystal compound having a T-shaped structure. A liquid crystal cured film cured in a state in which the polymerizable liquid crystal compound contained in the composition for forming a liquid crystal cured film according to any one of claims 1 to 5 is oriented. The liquid crystal cured film according to claim 6, wherein the thickness of the liquid crystal cured film is 0.3 μm or more and 5.0 μm or less. The liquid crystal cured film according to any one of claims 6 or 7, wherein the polymerizable liquid crystal compound is a horizontally oriented liquid crystal cured film cured in a state of being oriented in a direction parallel to the in-plane. The liquid crystal cured film according to any one of claims 6 to 8, further satisfying the following formula (S1).
100 nm ≤ ReA (550) ≤ 180 nm ... (S1)
(In the equation, ReA (550) represents the in-plane retardation value at a wavelength of 550 nm.) The liquid crystal cured film according to any one of claims 6 to 9, further satisfying the following formula (S2).
ReA (450) / ReA (550) <1.0 ... (S2)
(In the equation, ReA (450) represents the in-plane retardation value at a wavelength of 450 nm.) The horizontally oriented liquid crystal cured film according to any one of claims 6 to 10, wherein the liquid crystal cured film is a horizontally oriented liquid crystal cured film and shows a Bragg peak in X-ray diffraction measurement. The liquid crystal cured film according to claim 6 or 7, wherein the polymerizable liquid crystal compound is a vertically oriented liquid crystal cured film cured in a state of being oriented in a direction perpendicular to the in-plane. The liquid crystal cured film according to claim 12, further satisfying the following relational expression (S3).
-150 ≤ RthC (550) ≤ -30 ... (S3)
[In the relational expression (S3), RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm]. The liquid crystal cured film according to any one of claims 12 and 13, further satisfying the following relational expression (S4).
RthC (450) / RthC (550) ≤ 1.0 ... (S4)
[In the relational expression (S4), RthC (450) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 450 nm, and RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm]. An elliptical polarizing plate including a horizontally oriented retardation film and a polarizing film.
An elliptical polarizing plate, wherein at least one of the horizontally oriented film or the polarizing film is the liquid crystal cured film according to any one of claims 6 to 11. An elliptical polarizing plate including a horizontally oriented retardation film, a vertically oriented liquid crystal cured film, and a polarizing film.
An elliptical polarizing plate, wherein at least one of a horizontally oriented film, a vertically oriented liquid crystal cured film, and a polarizing film is the liquid crystal cured film according to any one of claims 6 to 14. The elliptical polarizing plate according to claim 15, wherein the angle formed by the slow axis of the horizontally oriented retardation film and the absorption axis of the polarizing plate is 45 ± 5 °. An organic EL display device comprising the elliptical polarizing plate according to any one of claims 15 to 17.