KR20220003574A - Composition for forming a liquid crystal cured film and its use - Google Patents

Abstract

The subject of this invention is providing the composition for liquid crystal cured film formation for manufacturing a liquid crystal cured film with little film thickness nonuniformity. The present invention comprises at least one silicone or fluorine-based leveling agent, at least one acrylic leveling agent, and at least one polymerizable liquid crystal compound, wherein the total amount of the leveling agent is based on the total amount of the polymerizable liquid crystal compound. It provides a composition for liquid crystal cured film formation which is 3.0 weight% or less.

Description

Composition for forming a liquid crystal cured film and its use

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

The elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated, for example, in a device for displaying an image in a planar state (eg, an organic EL display device), to prevent light reflection from the electrodes constituting the device is being used for In this elliptically polarizing plate, a so-called λ/4 plate is used as the retardation plate.

As a retardation plate used for such an elliptically polarizing plate, it is preferable at the point which exhibits equivalent retardation performance in the wide wavelength range of visible light that exhibiting reverse wavelength dispersion property. As a retardation plate showing reverse wavelength dispersibility, a retardation plate made of a horizontally aligned liquid crystal cured film obtained by polymerization and curing in a state in which a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is oriented in the horizontal direction is known.

Moreover, by forming a vertically aligning liquid crystal cured film and combining the vertically oriented liquid crystal cured film with the said elliptically polarizing plate, when combined with an organic electroluminescent display device, it is known that the color change in all directions at the time of black display can be suppressed.

Japanese Laid-Open Patent Publication No. 2015-163935

However, a liquid crystal cured film such as a horizontally aligned cured film or a vertically aligned liquid crystal cured film generally forms a liquid crystal cured film by preparing a composition containing a polymerizable liquid crystal compound, then applying and curing the composition to a substrate or alignment film, etc. A liquid crystal cured film is a thin film of 5 micrometers or less generally, and it has become a problem that the product external appearance deteriorates greatly by film thickness nonuniformity. Moreover, when adding an additive to the composition containing a polymerizable liquid crystal compound, there existed a problem that the orientation of a polymerizable liquid crystal compound was deteriorated depending on an additive.

This invention was implemented in view of the said situation, It is providing the composition for manufacturing a liquid crystal cured film with little film-thickness nonuniformity.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, as a result of earnestly examining in order to solve the said subject. That is, this invention provides the following preferable aspects.

[1] at least one silicone-based or fluorine-based leveling agent, at least one acrylic-based leveling agent, and at least one polymerizable liquid crystal compound;

The composition for liquid crystal cured film formation whose total amount of a leveling agent is 3.0 mass % or less with respect to the total amount of a polymeric liquid crystal compound.

[2] The composition for forming a liquid crystal cured film according to [1], comprising at least one kind of a silicone-based leveling agent.

[3] The composition for forming a liquid crystal cured film according to any one of [1] or [2], further comprising 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 capable of forming 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 contains a polymerizable 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 aligned.

[7] The liquid crystal cured film according to [6], wherein the film thickness of the liquid crystal cured film is 0.3 µm or more and 5.0 µm or less.

[8] The liquid crystal cured film according to any one of [6] or [7], which is a horizontally aligned liquid crystal cured film cured in a state in which the polymerizable liquid crystal compound is oriented in a direction parallel to the plane.

[9] The liquid crystal cured film in any one of [6]-[8] which further satisfy|fills following formula (S1).

100 nm ≤ ReA (550) ≤ 180 nm … (S1)

(In formula (S1), ReA (550) represents an in-plane retardation value at a wavelength of 550 nm.)

[10] The liquid crystal cured film in any one of [6]-[9] which further satisfy|fills following formula (S2).

ReA (450)/ReA (550) < 1.0 … (S2)

(In formula (S2), ReA (450) represents an in-plane retardation value at a wavelength of 450 nm.)

[11] The horizontally aligned liquid crystal cured film according to any one of [6] to [10], wherein the liquid crystal cured film is a horizontally aligned liquid crystal cured film and exhibits a Bragg peak in X-ray diffraction measurement.

[12] The liquid crystal cured film according to any one of [6] or [7], which is a vertically aligned liquid crystal cured film cured in a state in which the polymerizable liquid crystal compound is oriented in a direction perpendicular to the plane.

[13] The liquid crystal cured film according to [12], which further satisfies the following formula (S3).

-150 nm ≤ RthC (550) ≤ -30 nm … (S3)

(In Formula (S3), RthC(550) shows the phase difference value of the thickness direction in wavelength 550nm of a liquid crystal cured film.)

[14] The liquid crystal cured film in any one of [12] or [13] which further satisfy|fills following formula (S4).

RthC(450)/RthC(550) ≤ 1.0 … (S4)

(in formula (S4), RthC(450) shows the retardation value of the thickness direction in wavelength 450nm of a liquid crystal cured film, RthC(550) shows the retardation value of the thickness direction in wavelength 550nm of a liquid crystal cured film .)

[15] An elliptically polarizing plate comprising a horizontal alignment retardation film and a polarizing film,

An elliptically polarizing plate wherein at least one of the horizontal alignment retardation film and the polarizing film is the liquid crystal cured film according to any one of [6] to [11].

[16] An elliptically polarizing plate comprising a horizontally aligned retardation film, a vertically aligned liquid crystal cured film, and a polarizing film,

An elliptically polarizing plate in which at least one of a horizontal alignment retardation film, a vertically aligned liquid crystal cured film, and a polarizing film is the liquid crystal cured film in any one of [6]-[14].

[17] The elliptically polarizing plate according to any one of [15] or [16], wherein an angle between the slow axis of the horizontal alignment retardation film and the absorption axis of the polarizing plate is 45 ± 5°.

[18] An organic EL display device comprising the elliptically polarizing plate according to any one of [15] to [17].

According to the present invention, two types of leveling agents (that is, silicone or fluorine-based leveling agent and acrylic leveling agent) are blended in the polymerizable liquid crystal composition in an amount of 3.0 mass% or less with respect to the total amount of the polymerizable liquid crystal compound in the total amount of the leveling agent. do. These two types of leveling agents differ in action in a liquid crystal composition. The silicone-based or fluorine-based leveling agent tends to segregate in the surface layer of the liquid crystal composition because of its low surface free energy, and by lowering the surface tension of the composition, it is effective in flattening the surface layer of the coating film, while the acrylic leveling agent is in the film of the liquid crystal composition There is an effect of homogenizing the local non-uniformity of the liquid physical properties, and by including the combination of both in a specific compounding amount, a liquid crystal cured film with little film thickness non-uniformity can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In addition, the scope of the present invention is not limited to the embodiments described herein, and various changes can be made in a range that does not impair the spirit of the present invention.

<Leveling agent>

In the present invention, as described above, at least one silicone-based or fluorine-based leveling agent and at least one acrylic-based leveling agent are polymerized in an amount of 3.0 mass% or less with respect to the total amount of the polymerizable liquid crystal compound in the total amount of the leveling agent. It is characterized in that it is blended into the liquid crystal composition.

As a silicone-type leveling agent, the leveling agent etc. which have polyorganosiloxane frame|skeleton are mentioned. A hydrocarbon group etc. are mentioned as a group couple|bonded with the silicon atom (silicon atom which forms a siloxane bond) in polyorganosiloxane. Especially, a C1-C10 alkyl group and an aryl group are preferable, More preferably, they are a methyl group and a phenyl group, More preferably, they are a methyl group. The number of groups couple|bonded with the said silicon atom may be one, and 2 or more types may be sufficient as them. Moreover, although the repetition number (polymerization degree) of a siloxane unit is although it does not specifically limit, 2-10000 are preferable, More preferably, it is 3-5000, More preferably, it is 5-1000.

A commercially available silicone leveling agent can be used, 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.) manufacture), TEGORad2300, TEGORad2200N, TEGORad2011 (manufactured by Degussa), a polyether chain having a radically polymerizable group such as a (meth)acryloyl group added thereto, BYK-UV3500, BYK-UV3505, BYK-3510, BYK- UV3530, BYK-UV3570, BYK-UV3575, BYK-UV3576 (above, manufactured by Big Chemie Japan), KP-422, KP-416, KP-418, KP-410, KP-411, KP-412, KP-413, KP-423, KP-414, KP-415, KP-420, KP-983 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) etc. are mentioned.

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

Although it does not specifically limit as said fluorine-type leveling agent, The leveling agent etc. which have a fluoro aliphatic hydrocarbon backbone are mentioned. The fluoroaliphatic hydrocarbon skeleton is not particularly limited, and for example, fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, and fluoroalkanes having 1 to 10 carbon atoms such as fluoropentane and fluorohexane. The fluoroaliphatic hydrocarbon skeleton is preferably a perfluoroaliphatic hydrocarbon skeleton in which at least some hydrogen atoms are substituted with fluorine atoms, but all hydrogen atoms are substituted with fluorine atoms.

Moreover, the said fluoroaliphatic hydrocarbon skeleton may form the polyfluoroalkylene ether skeleton which is a repeating unit via an ether bond. Although it does not specifically limit as a fluoroaliphatic hydrocarbon group as a repeating unit, For example, fluoro C1-4 alkylene groups, such as fluoromethylene, fluoroethylene, fluoropropylene, and fluoroisopropylene, are mentioned. The number of the said fluoroaliphatic hydrocarbon group may be one, and 2 or more types may be sufficient as it. Although the repetition number (polymerization degree) of a fluoroalkylene ether unit is not specifically limited, 10-10000 are preferable, More preferably, it is 30-5000, More preferably, it is 50-1000.

As an example of a fluorine-type leveling agent, a commercial item can be used, For example, "Megapac (registered trademark) R-08", copper "R-30", copper "R-90", copper "F-410", copper "F-411", East "F-443", East "F-445", East "F-470", East "F-471", East "F-477", East "F-479", East " F-482", East "F-483", East "F-281", East "F-253", East "F-251", East "F-114", East "F-510", East "F" -551”, “F-552”, “F-553”, “F-554”, “F-555”, “F-556”, “F-557”, “F-” 558", "F-559", "F-560", "F-561", "F-562", "F-563", "F-565", "F-568" ", East "F-569", East "F-570", East "F-572", East "F-574", East "F-575", East "F-576", East "R-40" , "R-41", "R-94", "RS-56", "RS-72-K", "RS-75", "RS-76-E", "RS" -76-NS", the same "RS-78", the same "RS-90", the same "DS-21" (DIC Co., Ltd.) ; "Suffron (registered trademark) S-381", "S-382", "S-383", "S-393", "SC-101", "SC-105", "KH-" 40" and "SA-100" (AGC Semi Chemical Co., Ltd.); "E1830", "E5844" (Daikin Fine Chemical Research Institute Co., Ltd.) ; "Ftop EF301", "Ftop EF303", "Ftop EF351" and "Ftop EF352" (Mitsubishi Material Electron Chemicals Co., Ltd.).

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

An acrylic leveling agent copolymerizes the monomer which has a (meth)acryloyl group, and is manufactured, for example. The acrylic leveling agent is a monomer having a (meth)acryloyl group, and a monomer having a hydrophilic group such as (meth)acrylate having a hydroxyl group and (meth)acrylate having an alkylene oxide represented by ethylene oxide and propylene oxide. It can be prepared by copolymerization.

A commercial item may be used for an 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" (by Big Chemie Japan Co., Ltd.) ) can be mentioned.

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

As mentioned above, in a liquid crystal cured film, since segregation in a film thickness direction does not occur easily, an acryl-type leveling agent tends to deteriorate the orientation of a liquid crystal cured film easily. As an acryl-type leveling agent, since there exists a tendency for the orientation of a polymeric liquid crystal compound not to be inhibited easily, so that molecular weight is small, the molecular weight (weight average molecular weight) of an acryl-type leveling agent becomes like this. Preferably it is 100-100000, More preferably, 500-50000 , More preferably, it is 500-10000, Especially preferably, it is 500-5000.

In the present invention, at least one silicone-based or fluorine-based leveling agent and at least one acrylic-based leveling agent are preferably blended in an amount of 3.0 wt% or less with respect to the total amount of the polymerizable liquid crystal compound in the total amount of the leveling agent. As described above, since the action of the silicone-based or fluorine-based leveling agent in the polymerizable liquid crystal composition is different from the action of the acrylic leveling agent in the polymerizable liquid crystal composition, it is preferable to mix both leveling agents. As a silicone type or fluorine type leveling agent, the direction of a silicone type leveling agent is preferable. When the total amount of a leveling agent exceeds 3.0 weight% with respect to the total amount of a polymeric liquid crystal composition, there exists a tendency for the orientation of a liquid crystal to deteriorate. The total amount of a leveling agent becomes like this. Preferably it is 0.001-3 mass %, More preferably, it is 0.01-2.5 mass %. When there is less leveling agent addition amount than the said range, there exists a tendency for the effect of leveling agent addition to not be exhibited well. The weight ratio of a silicone type or fluorine type leveling agent and an acrylic type leveling agent is 0.01-30 with a weight ratio of a silicone type or a fluorine type leveling agent/acrylic type leveling agent, More preferably, it is 0.05-10. Even if the quantity of any leveling agent increases, the balance of an action|action collapses, and a film thickness nonuniformity generate|occur|produces.

<Polymerizable liquid crystal composition>

Examples of the polymerizable liquid crystal compound include a polymerizable liquid crystal compound generally exhibiting forward wavelength dispersibility and a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion, and only either type of polymerizable liquid crystal compound may be used, or both. It is also possible to use a mixture of types of polymerizable liquid crystal compounds. When used for a vertically aligned liquid crystal cured film, when the vertically aligned liquid crystal cured film is applied to a display device, from the viewpoint of a large improvement effect of the directional reflection color at the time of black display, a polymerizable liquid crystal compound showing reverse wavelength dispersibility It is preferable to include In addition, when used for a horizontally aligned liquid crystal cured film, when the horizontally aligned liquid crystal cured film is applied to a display device, a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is included in that the front direction reflection color at the time of black display is improved. It is preferable to do

As a polymeric liquid crystal compound which shows reverse wavelength dispersion, it is preferable that it is a compound which has the characteristics of following (A)-(D).

(A) It is a compound which can form 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 on the direction [intersecting direction (b)] intersecting with respect to the major axis direction (a).

(D) The long axis of the polymerizable liquid crystal compound defined in the following formula (i) by setting the sum of π electrons in the major axis direction (a) to N(πa) and the molecular weight in the major axis direction to N(Aa) π electron density in direction (a):

D(πa) = N(πa)/N(Aa) (i)

A polymerizable liquid crystal compound defined by the following formula (ii) with N(πb) as the sum of π electrons present in the crossing direction (b) and N(Ab) as the sum of molecular weights present in the crossing direction (b) π electron density in the cross direction of (b):

D(πb) = N(πb)/N(Ab) (ii)

A, formula (iii)

0 ≤ [D(πa)/D(πb)] < 1 (iii)

[that is, the π electron density in the cross direction (b) is greater than the π electron density in the major axis direction (a)]. In addition, as described above, the polymerizable liquid crystal compound having pi electrons on the major axis and in the direction intersecting therewith has, for example, a T-shaped structure.

In the above characteristics (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, a rod-shaped major axis direction if it is a compound having a rod-like structure.

- The number of π electrons N(πa) present on the major axis direction (a) does not include π electrons lost by polymerization reaction.

· The number of π electrons in the long axis direction (a) N(πa) is the total number of π electrons on the long axis and π electrons conjugated thereto, for example, as a ring present in the long axis direction (a), The number of π electrons in the ring that satisfies Hickel's law is included.

- The number of π electrons N(πb) present in the crossing direction (b) does not include π electrons lost by polymerization reaction.

The polymerizable liquid crystal compound satisfying the above has a mesogenic structure in the major axis direction. A liquid crystal phase (nematic phase, smectic phase) is expressed by this mesogenic structure.

The polymerizable liquid crystal compound satisfying the above (A) to (D) can form a nematic phase or a smectic phase by applying it on a base material or an alignment film and heating it to a phase transition temperature or higher. In the nematic phase or smectic phase formed by aligning the polymerizable liquid crystal compound, the long axis directions of the polymerizable liquid crystal compound are usually oriented so as to be parallel to each other, and this long axis direction becomes the alignment direction of the nematic phase. When such a polymerizable liquid crystal compound is made into a film and polymerized in a nematic or smectic state, a polymer film made of a polymer polymerized in a state oriented in the long axis direction (a) can be formed. This polymer film absorbs ultraviolet rays by pi electrons on the major axis direction (a) and π electrons on the cross direction (b). Here, the absorption maximum wavelength of the ultraviolet ray absorbed by the π electrons on the crossing direction (b) is λbmax. ?bmax is usually 300 nm to 400 nm. The density of π electrons satisfies the above formula (iii), and since the π electron density in the intersecting direction (b) is larger than the π electron density in the major axis direction (a), linearly polarized light having a vibrational plane in the intersecting direction (b) A polymer film in which absorption of ultraviolet rays (wavelength is λbmax) is larger than absorption of linearly polarized ultraviolet rays (wavelength is λbmax) having a vibrational plane in the major axis direction (a). The ratio (ratio of absorbance in the intersecting direction (b) of linearly polarized ultraviolet light / 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 .

The polymerizable liquid crystal compound having the above characteristics generally exhibits reverse wavelength dispersion in many cases. Specifically, for example, the compound represented by a following formula (X) is mentioned. In addition, in this invention, the polymeric liquid crystal compound represented by following formula (X) may be called a polymeric liquid crystal compound which has a T-shaped structure.

In formula (X), Ar represents the divalent group which has an aromatic group which may have a substituent. The term "aromatic group" as used herein refers to the number of π electrons in the ring structure according to Hickel's law, which is [4n + 2], for example, an Ar group as exemplified by (Ar-1) to (Ar-23) described later; You may have two or more via a bivalent coupling group. Here, n represents an integer. When a ring structure is formed by including a hetero atom such as -N= or -S-, Hickel's rule is satisfied by including a pair of uncovalently bonded electrons on these hetero atoms, and the case includes aromaticity. It is preferable that at least 1 or more of a nitrogen atom, an oxygen atom, and a sulfur atom is contained in the aromatic group. The number of aromatic groups contained in the divalent group Ar may be one, and two or more may be sufficient as them. When there is one aromatic group, the divalent aromatic group which may have a substituent may be sufficient as the divalent group Ar. When two or more aromatic groups contained in the divalent group Ar are two or more, the two or more aromatic groups may be bonded to each other by a single bond or a divalent bonding group such as -CO-O- or -O-.

G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group 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 It may be substituted by the nitro group, and the carbon atom which comprises the bivalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted by the oxygen atom, a sulfur atom, or a nitrogen atom.

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

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

E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms. Moreover, the hydrogen atom contained in the alkanediyl group may be substituted by the halogen atom, and -CH ₂ - contained in the alkanediyl group is -O-, -S-, -SiH ₂ -, -C(=O )- may be substituted.

P ¹ and P ² each independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

G ¹ and G ² are each independently, preferably a 1,4-phenylenediyl group optionally 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, a halogen atom, and 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylenediyl group substituted with a methyl group, unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably an unsubstituted 1,4-phenylenediyl group, or unsubstituted 1,4-trans-cyclo It is a hexanediyl group.

In addition, ^{at least one of the plurality of G 1} and G ² 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 a divalent alicyclic hydrocarbon.} It is more preferable that it is a group.

L ¹ and L ² are each independently, 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 having 1 to 4 carbon atoms or a hydrogen atom. 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 - . Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent a single bond, -CH ₂ -, or -CH ₂ CH ₂ -. L ¹ and L ² are each independently, more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or OCO-.

B ¹ and B ² are each independently, 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 each independently, more preferably a single bond, -OR ^a10-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a12-1 -, or OCOR ^a14-1 - . Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 each independently represent a single bond, -CH ₂ -, or -CH ₂ CH ₂ -. B ¹ and B ² are each independently, more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO-, or OCOCH ₂ CH ₂ - .

From the viewpoint of expression of reverse wavelength dispersion, 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. If k = 2 and l = 2, it is preferable because it becomes a symmetric structure.

Examples ^{of the polymerizable group represented by P 1} or P ² include 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, an oxiranyl group. , and an oxetanyl group. Among these, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.

It is preferable that Ar has at least one selected from the aromatic hydrocarbon ring which may have a substituent, the aromatic heterocyclic ring which may have a substituent, and the electron withdrawing group. As said aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned, for example, A benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring , an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, and a phenanthroline ring. Especially, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazole ring. Moreover, when a nitrogen atom is contained in Ar, it is preferable that the said nitrogen atom has (pi) electron.

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, particularly preferably 16 More than that. Moreover, Preferably it is 30 or less, More preferably, it is 26 or less, More preferably, it is 24 or less.

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

In formulas (Ar-1) to (Ar-23), * represents a linking part, and Z ⁰ , Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and cya. No group, nitro group, C1-C12 alkylsulfinyl group, C1-C12 alkylsulfonyl group, carboxyl group, C1-C12 fluoroalkyl group, C1-C12 alkoxy group, C1-C12 alkylthio group , N-alkylamino group having 1 to 12 carbon atoms, N,N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 12 carbon atoms, or N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms indicates Moreover, Z ⁰ , Z ^{1 ,} and Z ² may contain a polymerizable group.

Q ¹ and Q ² each independently represent ^{-CR 2'} R ^3' -, -S-, -NH-, -NR ^2' -, -CO- or O-, R ^2' and R ^3' Each independently represents a hydrogen atom or a C1-C4 alkyl group.

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

Y ¹ , Y ² and Y ³ each independently represent an optionally substituted aromatic hydrocarbon group or an aromatic heterocyclic group.

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

Examples of the aromatic hydrocarbon group for Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups 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 and a naphthyl group preferable, and a phenyl group is more preferable. Examples of the aromatic heterocyclic group include a nitrogen atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group, and at least one hetero atom such as an oxygen atom and a sulfur atom having 4 to carbon atoms The aromatic heterocyclic group of 20 is mentioned, A furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

Y ¹ , Y ^{2 ,} and Y ³ may each independently represent an optionally substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring set. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring set.

Z ⁰ , Z ¹ and Z ² are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms, and Z ⁰ is a hydrogen atom , an alkyl group having 1 to 12 carbon atoms or a cyano group, and Z ¹ and Z ² are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group. Moreover, Z ⁰ , Z ^{1 ,} and Z ² may contain a polymerizable group.

Q ¹ and Q ² are preferably -NH-, -S-, -NR ^2' -, -O-, and R ^2' is preferably a hydrogen atom. Among these, -S-, -O-, and -NH- are especially preferable.

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

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

Moreover, as a polymeric liquid crystal compound which forms a liquid crystal cured film in this invention, you may use the compound (henceforth "polymerizable liquid crystal compound (Y)") containing a group represented, for example by a following formula (Y). . The polymerizable liquid crystal compound (Y) generally tends to exhibit positive wavelength dispersion. A polymerizable liquid crystal compound can be used individually or in combination of 2 or more types.

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 may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and the carbon number 1 to The hydrogen atom contained in the 6 alkyl group and the C1-C6 alkoxy group may be substituted by the fluorine atom.

B11 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CO-, - 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)-, -OC(=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)-O-, - OC(=O)-CH=CH- or a single bond.

E11 represents an alkanediyl group having 1 to 12 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and a hydrogen atom contained in the alkoxy group is substituted with a halogen atom, there may be In addition, -CH ₂ - constituting the alkanediyl group may be substituted with -O- or -CO-.]

It is preferable that carbon number of the aromatic hydrocarbon group and alicyclic hydrocarbon group of A11 is the range of 3-18, It is more preferable that it is the range of 5-12, It is especially preferable that it is 5 or 6. A11 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.

As E11, a linear C1-C12 alkanediyl group is preferable. _{-CH 2} - constituting the alkanediyl group may be substituted 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-diyl group C1-C12 linear alkanediyl groups, such as a diary; -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 especially.

B12 and B13 are each independently -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O) -O- is preferable, and -O- or -OC(=O)-O- is more preferable especially.

The polymerizable group represented by P11 is preferably a radical polymerizable group or a cation polymerizable group from the viewpoint of high polymerization reactivity, particularly photopolymerization reactivity, easy handling, and easy production of the liquid crystal compound itself. It is preferable that a sexual group is group represented by a following formula (P-11) - a formula (P-15).

[In formulas (P-11) to (P-15),

R ¹⁷ to R ²¹ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.]

As a specific example of the group represented by a formula (P-11) - a formula (P-15), group represented by a following formula (P-16) - a formula (P-20) is mentioned.

It is preferable that it is group represented by a formula (P-14) - a formula (P-20), and, as for P11, a vinyl group, p-stilbene group, an epoxy group, or oxetanyl group is more preferable.

It is more preferable that the group represented by P11-B11- is an acryloyloxy group or a methacryloyloxy group.

As a polymerizable liquid crystal compound (Y), the compound represented by a formula (I), a formula (II), a formula (III), a formula (IV), a formula (V), or a formula (VI) is mentioned.

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 meal,

A12 to A14 each independently have the same meaning as A11, B14 to B16 each independently have the same meaning as B12, B17 has the same meaning as B11, and E12 has the same meaning as 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, a sulfo group (-SO ₃ H), a carboxy group, an alkoxycarbonyl group having 1 to 10 carbon atoms or a halogen atom, and -CH ₂ - constituting the alkyl group and the alkoxy group may be substituted with -O-.)

Specific examples of the polymerizable liquid crystal compound (Y) include "3.8.6 network (completely crosslinked type)" and "6.5 .1 liquid crystal material b. A compound having a polymerizable group among the compounds described in "polymerizable nematic liquid crystal material", JP-A-2010-31223, JP-A-2010-270108 , JP-A 2011-6360 , and JP-A 2011- The polymerizable liquid crystal of No. 207765 is mentioned.

As a specific example of a polymeric liquid crystal compound (Y), following formula (I-1) - a formula (I-4), a formula (II-1) - a formula (II-4), a formula (III-1) - a formula (III-26), a compound represented by a formula (IV-1) to a formula (IV-26), a formula (V-1) to a formula (V-2), and a formula (VI-1) to a formula (VI-6) can be heard In addition, in the following formula, k1 and k2 respectively independently represent the integer of 2-12. These polymerizable liquid crystal compounds (Y) are preferable from the point of the easiness of the synthesis|combination or the easiness of acquisition.

By using the polymeric liquid crystal compound which shows smectic liquid crystallinity, it is preferable at the point which can form a horizontally aligned liquid crystal cured film with a high degree of orientation order, or a vertically aligned liquid crystal cured film. In the present invention, when a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity is used as the polymerizable liquid crystal compound for forming a liquid crystal cured film, from the viewpoint of realizing a higher degree of alignment order, the polymerizable liquid crystal compound is a high-order smect It is more preferable that it is a tick phase (higher-order smectic liquid crystal state). Here, the higher-order smectic phase refers to smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, and smectic phase. K phase and Smectic L phase are meant, and among these, Smectic B phase, Smectic F phase and Smectic I phase are more preferable. Although the liquid crystal may be a thermotropic liquid crystal or a lyotropic liquid crystal may be sufficient, a thermotropic liquid crystal is preferable at the point which precise|minute film thickness control is possible. Moreover, although a monomer may be sufficient as the polymeric liquid crystal compound which shows smectic liquid crystallinity, the oligomer which polymerizable group superposed|polymerized, or a polymer may be sufficient as it.

The polymerizable liquid crystal compound showing smectic liquid crystallinity is a liquid crystal compound having at least one polymerizable group, and is preferably a liquid crystal compound having two or more polymerizable groups from the viewpoint of improving the heat resistance of the liquid crystal cured film. Examples of the polymerizable group include a (meth)acryloyloxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an oxiranyl group, and an oxetanyl group. However, it is preferable to include a (meth)acryloyloxy group from the point which manufacture is easy especially, the point which the heat resistance of a liquid crystal cured film is easy to improve, and the point which it is easy to adjust the adhesiveness of a liquid crystal cured film and a base material.

Examples of the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity include a compound represented by the following formula (Z) (hereinafter sometimes 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 formula (Z), X ^1z and X ^2z represent, independently of each other, a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is , which may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, the divalent aromatic group or divalent alicyclic hydrocarbon group The constituting carbon atom may be substituted with an oxygen atom, 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 a divalent linking group.

nz is 1 to 3, and when nz is 2 or more, a plurality of X ^1z may be the same as or different from each other. X ^2z may be the same as or different from any or all of X ^1z. Moreover, when nz is 2 or more, some ^Y1z may mutually be same or different. As for nz from a liquid crystalline viewpoint, 2 or more are preferable.

U ^1z represents a hydrogen atom or a (meth)acryloyloxy group.

U ^2z represents a polymerizable group.

W ^1z and W ^2z are each independently a single bond or a divalent linking group.

V ^1z and V ^2z each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group is -O-, -CO-, -S - or NH- may be substituted.]

In the polymerizable liquid crystal compound (Z), X ^1z and X ^2z are each independently, preferably, a 1,4-phenylene group which may have a substituent, or cyclohexane-1,4- which may have a substituent. ^{a diyl} group, and 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, trans-cyclohexane-1; It is preferable that it is a 4-diyl group. Examples of the substituent optionally included in the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent include an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, and a butyl group; Halogen atoms, such as a no group and a chlorine atom, and a fluorine atom, are mentioned. Preferably, it is unsubstituted.

In addition, the polymerizable liquid crystal compound (Z) is, in formula (Z), formula (Z1):

-(X ^1z -Y ^1z -) _nz -X ^2z - (Z1)

^[Wherein , X 1z , Y ^1z , X ^2z and nz each represent the same meaning as above.]

The portion represented by [hereinafter referred to as partial structure (Z1)] is preferably an asymmetric structure from the viewpoint of easily expressing smectic liquid crystallinity.

Examples of the polymerizable liquid crystal compound (Z) in which the partial structure (Z1) is an asymmetric structure include a polymerizable liquid crystal compound (Z) in which nz is 1 and one X ^1z and one X ^2z are different from each other. . Further, a polymerizable liquid crystal compound (Z) in which nz is 2 and two Y ^1z have the same structure as each other, wherein two X ^1z have the same structure and one X ^2z has a different structure from these two X ^{1z )} , the X ^1z binding to W ^1z of the two X ^1z, is different from the structure of the other of X ^1z and X ^2z, there may be mentioned also X ^1z and X ^2z than the liquid crystal compound (Z) polymerizing the same structure each other, of the other . Further, a polymerizable liquid crystal compound (Z) in which nz is 3 and three Y ^1z has the same structure as each other ^{, wherein any one of the three X 1z} and one X ^2z has a different structure from all the other three can be mentioned. have.

Y ^1z is -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCOO-, single bond, -N=N-, -CR ^az =CR ^bz -, -C≡C-, -CR ^az =N- or CO-NR ^az - is preferred. R ^az and R ^bz each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ^1z is more preferably -CH ₂ CH ₂ -, -COO-, or a single bond, and when a plurality of Y ^1z is present, ^{Y 1z} bonded to ^{X 2z} is -CH ₂ CH ₂ - or CH ₂ It is more preferable that it is O-. When both X ^1z and X ^2z 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 mutually different bonding methods, are present, since they have an asymmetric structure, smectic liquid crystallinity tends to be easily expressed.

U ^2z is the above-mentioned polymeric group. U ^1z is a hydrogen atom or a polymerizable group. It is preferable that a polymeric group is a (meth)acryloyloxy group from the point which manufacture is easy, the point which the heat resistance of a liquid crystal cured film improves easily, and the point which it is easy to adjust the adhesiveness of a liquid crystal cured film and a base material. The polymerizable group may be in a superposed state or may be in an unpolymerized state, but is preferably in a non-polymerized state.

^{Examples of the} alkanediyl group represented by V 1z and V ^2z include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1, 5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl group and icosane-1,20-diyl group. 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 optionally included in the alkanediyl group include a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted, and more preferably an unsubstituted linear alkanediyl group.

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

The polymerizable liquid crystal compound (Z) preferably has an asymmetric molecular structure in its molecular structure, and specifically, more preferably a polymerizable liquid crystal compound having the partial structures (A-a) to (A-i) below. It is more preferable to have the partial structure of (A-a), (A-b), or (A-c) from a viewpoint of being easy to show higher-order smectic liquid crystallinity. In addition, in the following (A-a) - (A-i), * represents a bond (single bond).

As a polymeric liquid crystal compound (Z), the compound specifically, shown, for example by a formula (A-1) - a formula (A-25) is mentioned. When the polymerizable liquid crystal compound (Z) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans body.

Among these, formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7), formula (A-8) ), at least one selected from the group consisting of compounds represented by formulas (A-13), (A-14), (A-15), (A-16) and (A-17) is preferable. . As a polymerizable liquid crystal compound (Z), you may use individually by 1 type, and may use it in combination of 2 or more type.

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

It is preferable that the polymeric liquid crystal compound which forms a liquid crystal cured film is a polymeric liquid crystal compound which has a maximum absorption wavelength between wavelength 300-400 nm. When the polymerizable liquid crystal composition contains a photopolymerization initiator, there is a fear that 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 when exposed to ultraviolet light during storage, generation of reactive active species from the photopolymerization initiator and polymerization reaction and gelation of the polymerizable liquid crystal compound by the reactive species can effectively inhibit the progression of Therefore, it becomes advantageous in the point of long-term stability of a polymeric liquid crystal composition, and the orientation of the liquid crystal cured film obtained and the uniformity of a film thickness can be improved. In addition, the maximum absorption wavelength of a polymeric liquid crystal compound can be measured using the ultraviolet-visible spectrophotometer in a solvent. The solvent is a solvent capable of dissolving the 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 80 to 99 parts by mass, with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition, More preferably, it is 85-98 mass parts, More preferably, it is 90-95 mass parts. It is advantageous from a viewpoint of the orientation of the liquid crystal cured film obtained as content of a polymeric liquid crystal compound is in the said range. In addition, in this specification, the solid content of a polymeric liquid crystal composition means all the components except volatile components, such as an organic solvent, from a polymeric liquid crystal composition.

<Polymerizable liquid crystal composition>

The polymerizable liquid crystal composition used for formation of a liquid crystal cured film contains a polymerizable liquid crystal compound, the silicone type or fluorine type leveling agent, and an acryl type leveling agent. Moreover, additives, such as a solvent, a photoinitiator, a leveling agent, antioxidant, a photosensitizer, and a dichroic dye, may be included. These components may each use only 1 type, and may use them in combination of 2 or more type.

A polymerizable liquid crystal composition can be obtained by stirring the said component at predetermined temperature, etc.

Since the polymerizable liquid crystal composition for liquid crystal cured film formation is normally apply|coated to the base material etc. in the state melt|dissolved in the 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 inactive 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 propylene. alcohol solvents, such as glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents, such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; and amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used individually or in combination of 2 or more types. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferable.

To [ content of the solvent in a polymeric liquid crystal composition / 100 mass parts of polymeric liquid crystal composition ], Preferably it is 50-98 mass parts, More preferably, it is 70-95 mass parts. Therefore, as for solid content which occupies for 100 mass parts of polymeric liquid crystal compositions, 2-50 mass parts is preferable. When the solid content is 50 parts by mass or less, since the viscosity of the polymerizable liquid crystal composition is low, the thickness of the film becomes substantially uniform, and there is a tendency that unevenness is less likely to occur. The said solid content can consider the thickness of the liquid crystal cured film to manufacture, and can determine it suitably.

A polymerization initiator is a compound which produces|generates reactive active species by the contribution of heat|fever or light, and can initiate polymerization reaction, such as a polymerizable liquid crystal compound. Examples of the reactive active species include radicals or active species such as cations or anions. Among these, the photoinitiator which generate|occur|produces a radical by light irradiation from a viewpoint that reaction control is easy is preferable.

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. have. 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, manufactured by BASF Japan Co., Ltd.), Sakeol BZ, Sakeol Z, Sakeol BEE (above, manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 ( Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Corporation), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Optomer N-1919 Deca Accruz NCI-831, Adeca Accruz NCI-930 (above, manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above, manufactured by Nippon Siber Hegner) and TAZ-104 (manufactured by Sanwa Chemical) can be heard

A photoinitiator can fully utilize the energy emitted from a light source, and since it is excellent in productivity, it is preferable in it being 300 nm - 400 nm of maximum absorption wavelength, It is more preferable in it being 300 nm - 380 nm, Especially, α- An acetophenone-type polymerization initiator and an oxime-type photoinitiator are preferable.

Examples of the α-acetophenone polymerization initiator include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl). )-2-benzylbutan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, more preferably 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one can be heard As a commercial item of (alpha)-acetophenone compound, Irgacure 369, 379EG, 907 (above, BASF Japan Co., Ltd. make), Sikol BEE (made by Seiko Chemical Co., Ltd.), etc. are mentioned.

An oxime-type photoinitiator produces|generates radicals, such as a phenyl radical and a methyl radical, by irradiating light. Although polymerization of a polymerizable liquid crystal compound advances favorably by this radical, the oxime type photoinitiator which generate|occur|produces a methyl radical among them is preferable at the point with high initiation efficiency of a polymerization reaction. Moreover, it is preferable to use the photoinitiator which can utilize the ultraviolet-ray with a wavelength of 350 nm or more efficiently from a viewpoint of advancing a polymerization reaction more efficiently. As a photoinitiator which can utilize the ultraviolet-ray with a wavelength of 350 nm or more efficiently, the triazine compound and carbazole compound containing an oxime structure are preferable, and the carbazole compound containing an oxime ester structure from a viewpoint of a sensitivity is more preferable. Examples of the oxime-based photopolymerization initiator include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-) methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime); and the like. As a commercial item of an oxime ester type photoinitiator, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, BASF Japan Co., Ltd. make), Adeca Optomer N-1919, Adeka Accruz NCI-831 (above, manufactured by ADEKA Corporation) etc. are mentioned.

Content of a photoinitiator is 0.1-30 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 1-20 mass parts, More preferably, it is 1-15 mass parts. If it is in the said range, reaction of a polymeric group fully advances, and the orientation of a polymeric liquid crystal compound is hard to be disturbed.

By mix|blending antioxidant, the polymerization reaction of a polymeric liquid crystal compound can be controlled. The antioxidant may be a primary antioxidant selected from phenolic antioxidants, amine antioxidants, quinone antioxidants, and nitroso antioxidants, or may be secondary antioxidants selected from phosphorus antioxidants and sulfur antioxidants. In order to superpose|polymerize a polymeric liquid crystal compound without disturbing the orientation of a polymeric liquid crystal compound, content of antioxidant is 0.01-10 mass parts normally with respect to 100 mass parts of polymerizable liquid crystal compounds, Preferably it is 0.1- It is 5 mass parts, More preferably, it is 0.1-3 mass parts. Antioxidants can be used individually or in combination of 2 or more types.

Moreover, a photoinitiator can be made highly sensitive by using a photosensitizer. As a photosensitizer, For example, xanthone, such as a xanthone and a thioxanthone; anthracenes having a substituent such as anthracene and alkyl ether; phenothiazine; Rubrene may be mentioned. A photosensitizer can be used individually or in combination of 2 or more types. Content of a photosensitizer is 0.01-10 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-3 mass parts.

<dichroic dye>

The polymerizable liquid crystal composition of the present invention may contain a dichroic dye. Here, a dichroic dye means the dye which has the property from which the absorbance in the long-axis direction of a molecule|numerator differs from the absorbance in a short-axis direction. The dichroic dye which can be used in this invention will not restrict|limit, especially if it has the said property, A dye may be sufficient and a pigment may be sufficient as it. Moreover, you may use combining 2 or more types of dye or a pigment, respectively, and may use it combining dye and a pigment. When such a dichroic dye is included in a horizontally aligned liquid crystal cured film or a vertically aligned liquid crystal cured film, a dichroic dye may orientate together with a polymeric liquid crystal compound, and can express absorption anisotropy. In particular, when the degree of alignment order is high as represented by a smectic liquid crystal phase or the like, the absorption anisotropy derived from the dichroic dye to be contained tends to be remarkably improved.

As a dichroic dye, it is preferable to have a maximum absorption wavelength ((lambda _{)MAX) in the range of 300-700 nm.} As such a dichroic dye, an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, an anthraquinone dye, etc. are mentioned, for example.

Examples of the azo dye include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes and stilbenazo dyes, and bisazo dyes and trisazo dyes are preferable, for example, formula (I ) (hereinafter also referred to as “compound (I)”).

K ¹ (-N=NK ² ) _p -N=NK ³ (I)

[In formula (I), K ¹ and K ³ each independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. K ² represents a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic group which may have a substituent. p represents the integer of 1-4. when p is 2 or more integer, it may be a plurality of K ² may be the same or different from each other. -N=N- bonds may be substituted with -C=C-, -COO-, -NHCO-, -N=CH- bonds in 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, or benzoxazole. can be heard Examples of the divalent heterocyclic group include a group obtained by removing two hydrogen atoms from the heterocyclic compound.

Substituents optionally included in the phenyl group, naphthyl group and monovalent heterocyclic group for K ¹ and K ³ , and the p-phenylene group, naphthalene-1,4- ^{diyl group and divalent heterocyclic group for K 2 ,} A C1-C4 alkyl group; C1-C4 alkoxy groups, such as a methoxy group, an ethoxy group, and a butoxy group; a C1-C4 fluorinated alkyl group, such as a trifluoromethyl group; cyano group; nitro group; halogen atom; A substituted or unsubstituted amino group such as an amino group, a diethylamino group, or a pyrrolidino group (a substituted amino group is an amino group having one or two C1 to C6 alkyl groups, or two substituted alkyl groups having 2 to 8 carbon atoms bonded to each other refers to the amino group forming the alkanediyl group of . The unsubstituted amino group is -NH ₂ ) and the like.

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 each independently 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, a substituted or unsubstituted amino group (Definition of a substituted amino group and an unsubstituted amino group) represents the same as above), a chlorine atom or a trifluoromethyl group.

n1-n4 represent the integer of 0-3 mutually independently.

When n1 is 2 or more, a plurality of B ² may be the same as or different from each other,

When n2 is 2 or more, a plurality of B ⁶ may be the same as or different from each other,

When n3 is 2 or more, a plurality of B ⁹ may be the same as or different from each other,

When n4 is 2 or more, a plurality of B ¹⁴ may be the same as or different from each other.]

As said anthraquinone dye, the compound represented by Formula (I-9) is preferable.

[In formula (I-9),

R ¹ to R ⁸ each 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.]

As said oxazone dye, the compound represented by Formula (I-10) is preferable.

[In formula (I-8),

R ⁹ to R ¹⁵ each 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.]

As said acridine dye, the compound represented by Formula (I-11) is preferable.

[In formula (I-11),

R ¹⁶ to R ²³ each 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), (I-10) and (I-11), as ^{the C1-C6 alkyl group for R x} , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group etc. are mentioned, As a C6-C12 aryl group, a phenyl group, a toluyl group, a xylyl group, a naphthyl group, etc. are mentioned.

As said cyanine pigment|dye, the compound represented by Formula (I-12), and the compound represented by Formula (I-13) are preferable.

[In formula (I-12),

D ¹ and D ² each independently represent a group represented by any one of formulas (I-12a) to (I-12d).

n5 represents an integer of 1 to 3.]

[In formula (I-13),

D ³ and D ⁴ each independently represent a group represented by any one of formulas (I-13a) to (1-13h).

n6 represents an integer of 1 to 3.]

Among these dichroic dyes, it is preferable that a vertically aligned liquid crystal cured film contains at least 1 sort(s) of azo dye from an orientation viewpoint as a dichroic dye.

In this invention, the weight average molecular weights of a dichroic dye are 300-2000 normally, Preferably it is 400-1000.

The content of the dichroic dye in the polymerizable liquid crystal composition for forming the liquid crystal cured film can be appropriately determined depending on the kind of the dichroic dye to be used, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. , More preferably, it is 0.1-10 mass parts, More preferably, it is 0.1-5 mass parts. When content of a dichroic dye is in the said range, the orientation of a polymeric liquid crystal compound cannot be disturbed easily, and the liquid crystal cured film which has a high orientation order can be obtained.

<Vertical alignment liquid crystal cured film>

The vertically aligned liquid crystal cured film is a cured liquid crystal cured film in which the polymerizable liquid crystal composition is applied on a substrate or alignment film, and the polymerizable liquid crystal compound is oriented in a vertical direction with respect to the substrate or alignment film.

In this invention, as one aspect of a horizontally aligned liquid crystal cured film, it is preferable to satisfy|fill a following formula (S4).

RthC(450)/RthC(550) ≤ 1.0 … (S4)

[In Formula (S4), RthC(450) represents the retardation value of the thickness direction in wavelength 450nm of a liquid crystal cured film, RthC(550) represents the retardation value of the thickness direction in wavelength 550nm of a liquid crystal cured film )]

When a horizontally aligned liquid crystal cured film satisfy|fills Formula (S4), the said vertically aligned liquid crystal cured film shows so-called reverse wavelength dispersion property in which the retardation value of the thickness direction in a short wavelength becomes smaller than the retardation value of the thickness direction in a long wavelength. RthC(450)/RthC(550) becomes like this. Preferably it is 0.70 or more, More preferably, it is 0.78 or more, More preferably, it is 0.95 or less, More preferably, it is 0.92 or less.

The phase difference value of the said thickness direction can be adjusted with thickness dC of a vertically-aligned liquid crystal cured film. The retardation value in the thickness direction is

RthC (λ) = ((nxC (λ) + nyC (λ))/2 - nzC (λ)) × dC

Since it is determined by do.

Moreover, it is preferable that a vertical alignment liquid crystal cured film satisfy|fills following formula (S3).

-150 nm ≤ RthC (550) ≤ -30 nm … (S3)

[In Formula (S3), RthC(550) represents the retardation value of the thickness direction in wavelength 550nm of a liquid crystal cured film]

The more preferable range of thickness direction retardation RthC(550) of a vertically-aligned liquid crystal cured film is -110 nm<=RthC(550)<=-45 nm.

The vertical alignment liquid crystal cured film is, for example,

A step of forming a coating film of a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film;

drying the coating film to form a dry coating film; and

Step of irradiating an active energy ray to a dry coating film to form a vertically aligned liquid crystal cured film

It can be prepared by a method comprising

Formation of the coating film of a polymeric liquid crystal composition can be performed, for example by apply|coating the polymeric liquid crystal composition for vertical alignment liquid crystal cured film formation on a base material, an alignment film, or the horizontally aligned liquid crystal cured film mentioned later.

As a base material, although a glass base material, a film base material, etc. are mentioned, for example, From a viewpoint of workability, a resin film base material is preferable. As resin which comprises a film base material, For example, Polyolefin like polyethylene, a polypropylene, and a norbornene-type polymer; Cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid ester; polyacrylic acid ester; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; and plastics such as polyphenylene sulfide and polyphenylene oxide. Such a resin can be formed into a film by known means such as a solvent casting method and a melt extrusion method to be used as a substrate. The surface of the substrate may have a protective layer formed of an acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., and surface treatment such as silicone treatment, release treatment, corona treatment, plasma treatment, etc. may be performed.

A commercially available product may be used as the substrate. As a commercially available cellulose-ester base material, For example, a Fuji Photo Film Co., Ltd. cellulose-ester base material like Fujitac film; and Konica Minolta Opto Co., Ltd. cellulose ester base materials, such as "KC8UX2M", "KC8UY", and "KC4UY", etc. are mentioned. As commercially available cyclic olefin resin, For example, cyclic olefin resin by Ticona (Germany) like "Topas (trademark)"; Cyclic olefin resins manufactured by JSR Corporation such as “Aton (registered trademark)”; “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)” manufactured by Nippon Zeon Corporation such as Cyclic olefin resin; Cyclic olefin resin by Mitsui Chemicals, Inc. like "Apel" (trademark) is mentioned. A commercially available cyclic olefin-based resin substrate can also be used. As a commercially available cyclic olefin resin base material, Sekisui Chemical Industry Co., Ltd. product cyclic olefin resin base material like "Sucina (registered trademark)" and "SCA40 (registered trademark)"; Cyclic olefin resin base material by Optes Corporation like "Zeonoa Film (trademark)"; The cyclic olefin resin base material by JSR Corporation like "Aton Film (trademark)" is mentioned.

From the viewpoints of reduction in thickness of the laminate, ease of peeling of the base material, handling properties of the base material, and the like, the thickness of the base material is usually 5 to 300 µm, preferably 10 to 150 µm.

As a method of applying the polymerizable liquid crystal composition to a substrate, etc., a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an application method such as an applicator method, and a printing method such as a flexographic method are known. method can be found.

Then, a dry coating film is formed by removing a solvent by drying etc. As a drying method, the natural drying method, the ventilation drying method, heat drying, the reduced pressure drying method, etc. are mentioned. In this case, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent is removed from the coating film by drying, and the polymerizable liquid crystal compound can be orientated in a direction perpendicular to the plane of the coating film. The heating temperature of the coating film can be appropriately determined in consideration of the materials such as the polymerizable liquid crystal compound used and the substrate forming the coating film, but is a temperature higher than the liquid crystal phase transition temperature in order to phase transition the polymerizable liquid crystal compound to the liquid crystal layer state. something is needed In order to bring the polymerizable liquid crystal compound into a vertically aligned state while removing the solvent contained in the polymerizable liquid crystal composition, for example, the liquid crystal phase transition temperature (smectic phase transition temperature or It can be heated to a temperature higher than the nematic phase transition temperature).

In addition, the liquid crystal phase transition temperature can be measured using, for example, a polarization microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analysis apparatus (TG-DTA), etc. In addition, when using two or more types in combination as a polymerizable liquid crystal compound, the said phase transition temperature is polymerization obtained by mixing all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition in the same proportion as the composition in the polymerizable liquid crystal composition. It means the temperature measured by carrying out similarly to the case of using 1 type of polymerizable liquid crystal compound using the mixture of a liquid crystal compound. In addition, 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 as a single polymerizable liquid crystal compound.

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

Although removal of the solvent from a coating film may be performed simultaneously with the heating to the liquid crystal phase transition temperature or more of a polymeric liquid crystal compound, and may be performed separately, it is preferable to perform simultaneously from a viewpoint of productivity improvement. Prior to heating the polymerizable liquid crystal compound above the liquid crystal phase transition temperature, a preliminary drying step for appropriately removing the solvent in the coating film under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize You can prepare Examples of the drying method in this preliminary drying step include a natural drying method, a ventilation drying method, heat drying, and a reduced pressure drying method, and the drying temperature (heating temperature) in the drying step is determined by the polymerizable liquid crystal compound to be used. It can determine suitably according to the kind, the kind of solvent, its boiling point, its quantity, etc.

Next, the obtained dry coating film WHEREIN: A vertically aligned liquid crystal cured film is formed by superposing|polymerizing a polymeric liquid crystal compound, maintaining the vertical alignment state of a polymeric liquid crystal compound. Although a thermal polymerization method and a photopolymerization method are mentioned as a polymerization method, From a viewpoint of being easy to control a polymerization reaction, a photopolymerization method is preferable. In the photopolymerization, as light irradiated to the dry coating film, the type of the photoinitiator contained in the dry coating film, the type of the polymerizable liquid crystal compound (in particular, the type of the polymerizable group included in the polymerizable liquid crystal compound) and the amount thereof is appropriately selected according to Specific examples thereof include at least one light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays and γ-rays and active electron beams. Among them, ultraviolet light is preferable from the viewpoint of being easy to control the progress of the polymerization reaction and that one widely used in the art can be used as a photopolymerization device. It is preferable to select the kind of a polymeric liquid crystal compound and photoinitiator contained in a liquid crystal composition. Moreover, at the time of superposition|polymerization, superposition|polymerization temperature can also be controlled by irradiating with light, cooling a dry coating film with an appropriate cooling means. When a polymerizable liquid crystal compound is superposed|polymerized at lower temperature by employ|adoption of such a cooling means, even if a base material uses the thing with comparatively low heat resistance, a vertically aligned liquid crystal cured film can be formed suitably. Moreover, the polymerization reaction can also be accelerated|stimulated by making the polymerization temperature high in the range which does not generate|occur|produce the problem by the heat at the time of light irradiation (transformation by heat of a base material, etc.). At the time of photopolymerization, the patterned cured film can also be obtained by performing masking or image development.

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 excimer laser, a wavelength range of 380 An LED light source which emits light of -440 nm, a chemical lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, etc. are mentioned.

Ultraviolet irradiation intensity|strength is 10-3,000 mW/cm<2> normally. Ultraviolet irradiation intensity|strength, Preferably it is intensity|strength in the wavelength range effective for activation of a photoinitiator. The time period for irradiating light is usually from 0.1 second to 10 minutes, preferably from 0.1 second to 5 minutes, more preferably from 0.1 second to 3 minutes, still more preferably from 0.1 second to 1 minute. When irradiated once or multiple times with such ultraviolet irradiation intensity, the accumulated light quantity is 10-3,000 mJ/cm<2>, Preferably it is 50-2,000 mJ/cm<2>, More preferably, it is 100-1,000 mJ/cm<2>.

The thickness of a vertically-aligned liquid crystal cured film can be suitably selected according to the display apparatus applied, Preferably it is 0.2-3 micrometers, More preferably, it is 0.2-2 micrometers. When a vertical alignment liquid crystal cured film is positive wavelength dispersibility, 0.2-1 micrometer is more preferable, and in reverse wavelength dispersibility, 0.4-2 micrometers is still more preferable. Since light absorption in an oblique direction increases with respect to the same pigment|dye density|concentration compared with the case where a vertically-aligned liquid crystal cured film is normal wavelength dispersibility when a vertically-aligned liquid crystal cured film is reverse wavelength dispersibility, it is more preferable.

<Vertical alignment liquid crystal cured film containing dichroic dye>

As one aspect of the vertical alignment liquid crystal cured film in this invention, the vertically aligned liquid crystal cured film may contain the dichroic dye. In particular, in the case of a vertically aligned liquid crystal cured film containing a dichroic dye, the higher the alignment order of the liquid crystal, the higher the absorption selectivity derived from the dichroic dye. It is preferable to use a compound, and it is preferable to superpose|polymerize while maintaining the liquid-crystal state of a smectic phase, Preferably a higher-order smectic phase, and it is preferable to form the vertically-aligned liquid crystal cured film containing a dichroic dye.

The vertical alignment liquid crystal cured film containing the said dichroic dye satisfy|fills following formula (11) and (12).

0.001 ≤ AxC ≤ 0.3 (11)

AxC (z = 60)/AxC > 2 (12)

In Formulas (11) and (12), both AxC and AxC (z=60) represent the absorbance in the absorption maximum wavelength of wavelength 400-750 nm of a vertically-aligned liquid crystal cured film. In addition, AxC represents the absorbance of linearly polarized light vibrating in the x-axis direction, and AxC (z = 60) is a straight line vibrating in the x-axis direction when the vertically aligned liquid crystal cured film is rotated by 60 degrees with the y-axis as the rotation axis. It represents the absorbance of polarized light. In addition, the x-axis means the direction perpendicular|vertical to the x-axis in an arbitrary direction in the plane of a vertically-aligned liquid crystal cured film in a film plane, and a z-axis means the thickness direction of a vertically-aligned liquid crystal cured film. In addition, the absorbance in this specification shows the absorbance when all are measured in the state except the influence of the interfacial reflection at the time of measurement. As a method of eliminating the influence of interfacial reflection, for example, by using a spectrophotometer, the absorbance at a wavelength where absorption of the compound is negligible at a long wavelength such as 800 nm is set to 0, and absorption of the compound is present in that state. Methods, such as measuring the absorbance of the wavelength of the area|region to be used, are mentioned.

The AxC can be measured by injecting 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 within the plane of the vertically aligned liquid crystal cured film is 0.001 or more and 0.3 or less, and the smaller the value of AxC, the better the dichroic dye is perpendicular to the plane of the obtained liquid crystal cured film. It can be said to be oriented. When the value of AxC exceeds 0.3, since the coloration in the front direction of the vertically aligned liquid crystal cured film becomes strong, the front color when applied to a display device in combination with the horizontal alignment retardation film tends to fall, so that of AxC The value is preferably 0.1 or less, more preferably 0.05 or less. Moreover, the lower limit of the value of AxC is 0.001 or more normally, Preferably it is 0.003 or more, More preferably, it is 0.005 or more.

Said AxC (z=60) can be measured by injecting and measuring the same linear deflection as the linearly polarized light which measured Ax in the state which rotated the vertically-aligned liquid crystal cured film 60 degrees with the y-axis as a rotation axis. Here, the rotation of the film is performed by rotating the film in a state in which Ax is measured by 60° in the direction of incidence 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 becomes difficult to obtain good light absorption anisotropy. Therefore, the value of AxC (z = 60)/AxC is preferably 2.5 or more, more preferably is 3 or more. On the other hand, if the value of AxC (z = 60)/AxC is too large, the color changes greatly with only the four colors, and the difference between the front color and the four colors sometimes becomes large, so the value of AxC (z = 60)/AxC is , Preferably it is 50 or less, More preferably, it is 30 or less, More preferably, it is 20 or less. Further, AxC (z = 60) is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, and preferably 1.0 or less, more preferably 0.5 or less, still more preferably 0.3 or less.

In addition, although the absorbance of the linearly polarized light vibrating in the y-axis direction is represented by AyC, in the vertically-aligned liquid crystal cured film of this invention, AxC and AyC become substantially the same value normally. When AxC and AyC differ, it will have in-plane dichroism, and in this case, there exists a tendency for coloring with respect to the front color of this vertically-aligned liquid crystal cured film to become large.

When the vertical liquid crystal cured film satisfies the above formulas (11) and (12), it can be said that the vertical liquid crystal aligning film has excellent polarization performance (absorption anisotropy), thereby effectively transmitting light from the front direction, and also It is possible to effectively absorb light from the direction.

AxC and AxC (z=60) in the vertically aligned liquid crystal cured film containing the said dichroic dye are, for example, a polymeric liquid crystal compound which comprises a film thickness, the conditions of a manufacturing process, and a vertically aligned liquid crystal cured film, and a dichroism It can control by adjusting the kind, compounding quantity, etc. of a sex pigment|dye. 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 the desired optical properties It is possible to properly select according to

<Orientation film>

In one aspect of the present invention, the coating film of the polymerizable liquid crystal composition is formed on the alignment film. An alignment film has an orientation regulating force which liquid-crystal-aligns a polymeric liquid crystal compound in a desired direction. Among these, an alignment film having an orientation regulating force for aligning the polymerizable liquid crystal compound in the horizontal direction is sometimes called a horizontal alignment film, and an alignment film having an orientation regulating force for aligning the polymerizable liquid crystal compound in a vertical direction is sometimes called a vertical alignment film. The orientation regulating force can be arbitrarily adjusted according to the type of orientation film, surface state, rubbing conditions, etc., and when the orientation film is formed of a photo-alignable polymer, it can be arbitrarily adjusted by polarized light irradiation conditions or the like.

The alignment film preferably has solvent resistance that does not dissolve by application of the polymerizable liquid crystal composition or the like, and has heat resistance in heat treatment for removal of the solvent or orientation of the polymerizable liquid crystal compound described later. Examples of the alignment film include an alignment film containing an alignment polymer, a photo alignment film, a groove alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the alignment direction, and the like, from the viewpoint of precision and quality of alignment angle A photo-alignment film is preferable.

Examples of the orientation polymer include polyamide and gelatin having an amide bond in the molecule, polyimide having an imide bond in the molecule, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacryl which is a hydrolyzate thereof. amide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Especially, polyvinyl alcohol is preferable. An orientation polymer can be used individually or in combination of 2 or more types.

An alignment film containing an alignment polymer is usually prepared by applying a composition in which an alignment polymer is dissolved in a solvent (hereinafter, sometimes referred to as an “oriented polymer composition”) to a substrate to remove the solvent, or applying the alignment polymer composition to the substrate. It is obtained by apply|coating, removing a solvent, and rubbing (rubbing method). As a solvent, the thing similar to the solvent illustrated above as a solvent which can be used for a polymeric liquid crystal composition is mentioned.

The concentration of the orientation polymer in the orientation polymer composition may be in a range in which the orientation polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20%, more preferably about 0.1 to 10%, in terms of solid content with respect to the solution.

As the orientation polymer composition, a commercially available orientation 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).

As a method of apply|coating an orientation polymer composition to a base material, the thing similar to what was illustrated as a method of apply|coating a polymeric liquid crystal composition to a base material is mentioned.

As a method of removing the solvent contained in an orientation polymer composition, the natural drying method, the ventilation drying method, heat drying, the reduced pressure drying method, etc. are mentioned.

In order to provide an orientation regulating force to an orientation film, a rubbing process can be performed as needed (rubbing method). As a method of imparting an orientation regulating force by the rubbing method, a rubbing cloth wound and rotating a rubbing roll is coated with an oriented polymer composition to a substrate and annealed to make contact with a film of an oriented polymer formed on the surface of the substrate. . When performing a rubbing process, if masking is performed, a some area|region (pattern) from which an orientation direction differs can also be formed in an orientation film.

The photo-alignment film is usually prepared by applying a composition containing a polymer or a monomer having a photoreactive group and a solvent (hereinafter also referred to as "composition for photo-alignment film formation") to a substrate, and after removing the solvent, polarized light (preferably, polarized UV light) ) is obtained by irradiating The photo-alignment film is advantageous also in that the direction of an orientation regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to irradiate.

A photoreactive group means group which produces liquid-crystal orientation ability by light irradiation. Specific examples include groups that participate in photoreactions that are the origin of liquid crystal alignment ability, such as induction of molecular alignment or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photolysis reaction caused by light irradiation. Especially, group which participates in dimerization reaction or photocrosslinking reaction is preferable at the point excellent in orientation. As the photoreactive group, a group having an unsaturated bond, especially a double bond, is preferable, and a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N A group having at least one selected from the group consisting of a bond) and a carbon-oxygen double bond (C=O bond) is particularly preferred.

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a C=N bond include groups 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, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, or a halogenated alkyl group.

Among them, a photoreactive group involved in the photodimerization reaction is preferable, the amount of polarized light irradiation required for photoalignment is relatively small, and a photoalignment film excellent in thermal stability and temporal stability is easily obtained from the viewpoint of, cinnamoyl group and chalcone groups are preferred. As a polymer which has a photoreactive group, it is especially preferable that the terminal part of the said polymer side chain has a cinnamoyl group used as a cinnamic acid structure.

By applying the composition for forming a photo-alignment film on the substrate, the photo-alignment inducing layer can be formed on the substrate. Examples of the solvent contained in the composition include the same solvents as those exemplified above as solvents usable in the polymerizable liquid crystal composition, and may be appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group.

Although content of the polymer or monomer which has a photoreactive group in the composition for photo-alignment film formation can be suitably adjusted according to the kind of polymer or monomer, or the thickness of the target photo-alignment film, with respect to the mass of the composition for photo-alignment film formation, at least 0.2 mass % is preferable, and the range of 0.3-10 mass % is more preferable. In the range in which the characteristic of a photo-alignment film is not impaired remarkably, the composition for photo-alignment film formation may contain polymeric materials, such as polyvinyl alcohol and a polyimide, and a photosensitizer.

As a method of apply|coating the composition for photo-alignment film formation to a base material, the method similar to the method of apply|coating an orientation polymer composition to a base material is mentioned. As a method of removing a solvent from the apply|coated composition for photo-alignment film formation, a natural drying method, ventilation drying method, heat drying, the reduced pressure drying method etc. are mentioned, for example.

In order to irradiate the polarized light, from the composition for forming a photo-alignment film applied on the substrate, the solvent may be removed directly, and polarized UV may be irradiated, or polarized light may be irradiated from the substrate side, and the polarized light may be transmitted and irradiated. . Moreover, the said polarization|polarized-light is especially preferable if it is substantially parallel light. The wavelength of polarized light to be irradiated is preferably in a 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 of 250 to 400 nm is particularly preferable. Examples of the light source used for polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and ultraviolet light lasers such as KrF and ArF, high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps. is more preferable. Among these, a high-pressure mercury-vapor lamp, an ultra-high pressure mercury lamp, and a metal halide lamp are preferable because the light emission intensity of the ultraviolet-ray of wavelength 313nm is large. Polarized UV can be irradiated by irradiating the light from the said light source through a suitable polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as Glan Thompson or Glan Taylor, or a wire grid type polarizer can be used.

Moreover, when performing rubbing or polarization|polarized-light irradiation and masking, the some area|region (pattern) from which the direction of liquid-crystal orientation differs can also be formed.

A groove alignment film is a film|membrane which has an uneven|corrugated pattern or a plurality of grooves (grooves) in the film|membrane surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of straight grooves arranged at equal intervals, the liquid crystal molecules are aligned in a direction along the grooves.

As a method of obtaining a groove alignment film, a method of forming an uneven pattern by performing development and rinsing after exposure through an exposure mask having a pattern-shaped slit on the surface of the photosensitive polyimide film, a method of forming a concave-convex pattern on the surface A method of forming a layer of UV-curing resin before curing, transferring the formed resin layer to a substrate, and then curing, and pressing a roll-shaped disk having a plurality of grooves to a film of UV-curing resin formed on the substrate before curing The method of forming an unevenness|corrugation and hardening after that is mentioned.

Materials exhibiting an orientation regulating force for aligning the polymerizable liquid crystal compound in a direction perpendicular to the plane of the coating film include, in addition to the orientation polymers described above, fluorine-based polymers such as perfluoroalkyl and silane compounds, and polysiloxane compounds obtained by condensation reactions thereof. may be used.

When a silane compound is used as a material for forming the alignment film, from the viewpoint of easily lowering the surface tension and increasing the adhesion to the layer adjacent to the alignment film, a compound containing Si and C elements as constituent elements is preferable. , a 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 the ionic compound, etc. can be used. By using these silane compounds, the vertical alignment regulating force can be increased. These silane compounds may be used individually by 1 type, may be used in combination of 2 or more type, and may be used, mixing with other materials. When the silane compound is a nonionic silane compound, the silane compound having an alkyl group at the molecular terminal is preferable from the viewpoint of easily increasing the vertical alignment regulating force, and the silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable.

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

<Orientation promoter>

Another aspect of the vertically aligned liquid crystal cured film in the present invention WHEREIN: The coating film of a polymeric liquid crystal composition does not require an alignment film, and can be formed directly on a base material. Such an aspect WHEREIN: The polymeric liquid crystal composition for vertical alignment liquid crystal cured film formation contains an orientation promoter normally. In this invention, an orientation promoter means the material which accelerates|stimulates the liquid-crystal orientation of the polymeric liquid crystal compound in a desired direction. Examples of the alignment promoter for promoting the alignment of the polymerizable liquid crystal compound in the vertical direction include an ionic compound composed of a non-metal atom, a nonionic silane compound, and the like. The polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film preferably contains at least one of an ionic compound and a nonionic silane compound composed of a non-metal atom, and an ionic compound composed of a non-metal atom and a non-ionic silane compound. more preferably.

When the polymerizable liquid crystal composition for forming the vertically aligned liquid crystal cured film contains an ionic compound composed of non-metal atoms, in the dry coating film formed from the vertically aligned liquid crystal cured film forming composition on the substrate, the polymerizable liquid crystal by electrostatic interaction The vertical alignment regulating force with respect to a compound is expressed, and there exists a tendency for a polymeric liquid crystal compound to orientate in a direction perpendicular|vertical with respect to the base material surface in a dry coating film. Thereby, the state which the polymerizable liquid crystal compound vertically aligned can be maintained, and a liquid crystal cured film can be formed.

Examples of the ionic compound composed of a non-metal atom include an onium salt (more specifically, a quaternary ammonium salt in which the nitrogen atom has a positive charge, a tertiary sulfonium salt in which the phosphorus atom has a positive charge, and a quaternary in which the phosphorus atom has a positive charge. phosphonium salts); Among these onium salts, quaternary onium salts are preferable from the viewpoint of further improving the vertical alignment property of the polymerizable liquid crystal compound, and from the viewpoint of improving availability and mass productivity, quaternary phosphonium salts or quaternary Quaternary ammonium salt is more preferable. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or a polymer.

It is preferable that the molecular weights of an ionic compound are 100 or more and 10,000 or less. When molecular weight is in the said range, it will be easy to improve the vertical alignment property of a polymeric liquid crystal compound, ensuring the applicability|paintability of a polymeric composition. The molecular weight of the ionic compound is more preferably 5000 or less, still more preferably 3000 or less.

As a cation component of an ionic compound, an inorganic cation and organic cation are mentioned, for example. Especially, since the orientation defect of a polymeric liquid crystal compound is hard to raise|generate, an organic cation is preferable. Examples of the organic cation include imidazolium cation, pyridinium cation, ammonium cation, sulfonium cation, and phosphonium cation.

Ionic compounds generally have a counter anion. As an anion component used as the counter ion of the said cation component, an inorganic anion and organic anion are mentioned, for example. Especially, since the orientation defect of a polymeric liquid crystal compound does not raise|generate easily, an organic anion is preferable. In addition, a cation and an anion do not necessarily need to be a one-to-one correspondence.

As an anion component, the following are mentioned specifically, for example.

chloride anion [Cl ^- ],

bromide anion [Br ^- ],

iodide anion [I ^- ],

tetrachloroaluminate anion [AlCl ₄ ^- ],

heptachlorodialuminate anion [Al ₂ Cl ₇ ^- ],

tetrafluoroborate anion [BF ₄ ^- ],

hexafluorophosphate anion [PF ₆ ^- ],

perchlorate anion [ClO ₄ ^- ],

nitrate anion [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)methanide anion [(CF ₃ SO ₂ ) ₃ C ^- ],

hexafluoroacetate anion [AsF ₆ ^- ],

hexafluoroantimonate anion [SbF ₆ ^- ],

hexafluoroniobate anion [NbF ₆ ^- ],

hexafluorotantalate anion [TaF ₆ ^- ],

dimethylphosphinate anion [(CH ₃ ) ₂ POO ^- ],

(poly)hydrofluorofluoride anion [F(HF) _n ^- ] (for example, n represents an integer of 1 to 3);

dicyanamide anion [(CN) ₂ N ^- ],

thiocyanate [SCN ^- ],

perfluorobutanesulfonate 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 ⁻ ].

The specific example of an ionic compound can be suitably selected from the combination of the said cationic component and an anionic component. As a compound which is a combination of a specific cationic component and an anionic component, the following are mentioned.

(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.

(imidazolium 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 and the like.

(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;

tetrahexylammonium bis(fluorosulfonyl)imide;

trioctylmethylammonium bis(fluorosulfonyl)imide;

(2-hydroxyethyl) trimethylammonium bis (fluorosulfonyl) imide;

tetrabutylammonium bis(trifluoromethanesulfonyl)imide;

tetrahexylammonium bis(trifluoromethanesulfonyl)imide;

trioctylmethylammonium bis(trifluoromethanesulfonyl)imide;

(2-hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide;

tetrabutylammonium p-toluenesulfonate,

tetrahexylammonium p-toluenesulfonate,

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.

(phosphonium salt)

tributyl (2-methoxyethyl) phosphonium bis (trifluoromethanesulfonyl) imide;

tributylmethylphosphoniumbis(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]phosphoniumbis(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]phosphonium bis(trifluoromethanesulfonyl)imide.

These ionic compounds may be used individually, respectively, and may be used in combination of 2 or more type.

From the viewpoint of further improving the vertical alignment property of the polymerizable liquid crystal compound, the ionic compound preferably has an Si element and/or an F element in the molecular structure of the cation moiety. When an ionic compound has Si element and/or F element in the molecular structure of a cation site|part, it will become easy to segregate an ionic compound on the surface of a vertically-aligned liquid crystal cured film. Among them, the following ionic compounds (i) to (iii) and the like are preferable as the ionic compound in which all constituent elements are non-metal elements.

(ionic compound (i))

(ionic compound (ii))

(ionic compound (iii))

As a method of improving the vertical alignment property of a polymerizable liquid crystal compound, for example, a method of treating the surface of a substrate using a surfactant having an alkyl group having a long chain length is known (e.g., "Liquid Crystal Handbook" See Chapter 2, alignment and physical properties of liquid crystal (published by Maruzen Co., Ltd.). The method of improving the vertical alignment property of a liquid crystal compound by such a surfactant is applicable also to an ionic compound. That is, by treating the surface of the substrate using an ionic compound having an alkyl group having a long chain length to a certain extent, the vertical alignment property of the polymerizable liquid crystal compound can be effectively improved.

Specifically, it is preferable that the ionic compound satisfies the following formula (8).

5 < M < 16 (8)

In formula (8), M is represented by following formula (9).

M = (the number of covalent bonds from the positively charged atom to the molecular chain end of the substituent with the largest number of covalent bonds to the molecular chain end among the substituents directly bonded to the positively charged atom) ÷ (plus number of atoms with a charge) (9)

When the ionic compound satisfies the above (8), the vertical alignment property of the polymerizable liquid crystal compound can be effectively improved.

In addition, when two or more atoms having a positive charge exist in the molecule of the ionic compound, for a substituent having two or more atoms having a positive charge, counting from the atom having a positive charge considered as the starting point, the nearest Let the number of covalent bonds to other positively charged atoms be "the number of covalent bonds from the positively charged atom to the molecular chain end" described in the definition of M above. Moreover, when an ionic compound is an oligomer or polymer which has two or more repeating units, a structural unit is considered as one molecule, and said M is computed. When an atom having a positive charge is introduced into the ring structure, among the number of covalent bonds through the ring structure to the atom having a positive charge, or the number of covalent bonds to the end of the substituent bonded to the ring structure , where the number of covalent bonds is greater 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 aligned liquid crystal cured film contains an ionic compound, the content is usually preferably from 0.01 to 5 mass%, and from 0.05 to 4 mass% with respect to the solid content of the polymerizable liquid crystal composition. It is more preferable, and it is still more preferable that it is 0.1-3 mass %. When the content of the ionic compound is within the above range, the vertical alignment property of the polymerizable liquid crystal compound can be effectively promoted while maintaining the good applicability of the polymerizable liquid crystal composition.

When the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film includes a nonionic silane compound, the nonionic silane compound lowers the surface tension of the polymerizable liquid crystal composition, and is formed as a composition for forming a vertically aligned liquid crystal cured film on a substrate In the dry coating film, the nonionic silane compound is present on the surface opposite to the substrate of the dry coating film to increase the vertical alignment regulating force with respect to the polymerizable liquid crystal compound, and in the dry coating film, the polymerizable liquid crystal compound is directed perpendicular to the surface of the substrate tends to be oriented toward Thereby, the state which the polymerizable liquid crystal compound vertically aligned can be maintained, and a liquid crystal cured film can be formed.

A nonionic silane compound is a compound containing Si element as nonionic. 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, silsessiloxanes and alkoxysilanes (more specifically, A silane coupling agent etc.), the silane containing compound of the term of a leveling agent, etc. are mentioned.

The nonionic silane compound may be of a silicone monomer type or of a silicone oligomer (polymer) type. When the silicone oligomer is expressed in the form of (monomer) - (monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer , copolymers containing a mercaptopropyl group such as 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer and mercaptomethyltrie mercaptomethyl group-containing copolymers such as oxysilane-tetraethoxysilane copolymers; 3-Methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltrie oxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-methacryloyloxypropylmethyldie a copolymer containing a methacryloyloxypropyl group such as a toxysilane-tetraethoxysilane copolymer; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane- Tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyl Oxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer a copolymer containing an acryloyloxypropyl group such as a polymer; Vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer Polymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer and vinylmethyldiethoxysilane-tetraethoxy a copolymer containing a vinyl group such as a silane copolymer; 3-Aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3- Aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyl and copolymers containing an amino group such as a methyldiethoxysilane-tetramethoxysilane copolymer and a 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer. These nonionic silane compounds may be used individually by 1 type, or may be used in combination of 2 or more type. Especially, a silane coupling agent is preferable from a viewpoint of improving more adhesiveness with the adjacent layer.

The silane coupling agent is a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryl group, an amino group, an isocyanurate group, a ureide group, a mercapto group, an isocyanate group, a carboxy group, and a hydroxyl group from the group consisting of It is a compound containing the Si element which has the same functional group as at least 1 sort(s) selected and at least 1 alkoxysilyl group or silanol group. By appropriately selecting these functional groups, unique effects such as improvement of the mechanical strength of the vertically aligned liquid crystal cured film, surface modification of the vertically aligned liquid crystal cured film, and improvement of adhesion of the vertically aligned liquid crystal cured film and the adjacent layer (eg, substrate) It becomes possible to give From an adhesive viewpoint, it is preferable that a silane coupling agent is a silane coupling agent which has an alkoxysilyl group and another different reactive group (for example, the said functional group). Moreover, it is preferable that a silane coupling agent is a silane coupling agent which has 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 alignment property of the polymerizable liquid crystal compound tends to be improved more easily, and the vertical alignment promoting effect tends to be remarkably obtained. As a polar group, an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxy group, and a hydroxyl group are mentioned, for example. In addition, the polar group may have a substituent or a protecting group suitably in order to control the reactivity of a silane coupling agent.

Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene ) Propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxy Silane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy propyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.

In addition, commercially available silane coupling agents include, for example, KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM- 403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. such as KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007 can be heard

When the polymeric liquid crystal composition which forms a vertically aligned liquid crystal cured film contains a nonionic silane compound, it is preferable that the content is usually 0.01 mass % - 5 mass % with respect to solid content of a polymeric liquid crystal composition, and 0.05 mass % It is more preferable that they are -4 mass %, and it is still more preferable that they are 0.1 mass % - 3 mass %. When content of a nonionic silane compound is in the said range, the vertical alignment property of a polymeric liquid crystal compound can be promoted effectively, maintaining favorable applicability|paintability of a polymeric liquid crystal composition.

Since the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film contains both an ionic compound and a nonionic silane compound, in the dry coating film formed from the composition for vertically aligned liquid crystal cured film formation on a substrate, it is derived from an ionic compound The vertical alignment of the polymerizable liquid crystal compound is more facilitated by the electrostatic interaction and the surface tension lowering effect derived from the nonionic silane compound. Thereby, the polymeric liquid crystal compound can maintain the state which vertically aligned more accurately, and can form a liquid crystal cured film.

<Horizontal alignment liquid crystal cured film>

The horizontally aligned liquid crystal cured film in the present invention is a liquid crystal cured in a state in which the polymerizable liquid crystal composition described above is applied on a substrate or an alignment film, and the polymerizable liquid crystal compound in the polymerizable liquid crystal composition is oriented in the in-plane direction of the alignment film. A cured film is shown.

In this invention, as one aspect of a horizontally aligned liquid crystal cured film, it is preferable to satisfy|fill following formula (S2).

ReA (450)/ReA (550) < 1.00 (S2)

[In 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 (Formula (S2) Wherein, nxA (λ) represents the principal refractive index at a wavelength λ nm in the plane of the horizontal alignment retardation film, and nyA (λ) is the refractive index at a wavelength λ nm in a direction orthogonal to the direction of nxA in the same plane as nxA. , and dA represents the film thickness of the horizontal alignment retardation film)]

When a horizontal alignment liquid crystal cured film satisfy|fills Formula (S2), the said horizontal alignment liquid crystal cured film shows what is called reverse wavelength dispersion in which the in-plane retardation value in a short wavelength becomes smaller than the in-plane phase difference value in a long wavelength. The front reflection hue at the time of black display at the time of introduce|transducing such a horizontally aligned liquid crystal cured film into an organic electroluminescent display can be improved. Since the effect of improving the reflection color in the front direction can be further enhanced, ReA (450)/ReA (550) is preferably 0.70 or more, more preferably 0.78 or more, and more preferably 0.95 or less, more preferably In most cases, it is 0.92 or less.

The said in-plane retardation value can be adjusted with thickness dA of a horizontally aligned liquid crystal cured film. Since the in-plane retardation value is determined by the above formula ReA (λ) = (nxA (λ) - nyA (λ)) × dA, a desired in-plane retardation value (ReA (λ): horizontal alignment at a wavelength λ (nm)) In order to obtain the in-plane retardation value of a liquid crystal cured film), what is necessary is just to adjust a three-dimensional refractive index and film thickness dA.

Moreover, it is preferable that a horizontal alignment liquid crystal cured film satisfy|fills following formula (S1).

100 nm ≤ ReA (550) ≤ 180 nm (S1)

[In formula (S1), ReA (λ) has the same meaning as above]

When the in-plane retardation ReA (550) of the horizontally aligned liquid crystal cured film is within the range of the formula (S1), the effect of improving the front reflection hue at the time of black display when applied to an organic EL display device (effect of suppressing coloration) becomes remarkable . A more preferable range of the in-plane retardation value is 120 nm ≤ ReA ≤ 170 nm, and a further preferable range is 130 nm ≤ ReA (550) ≤ 150 nm.

In the field of a horizontally aligned liquid crystal cured film, a conventionally well-known polymeric liquid crystal compound can be used. Among them, a polymerizable liquid crystal compound showing so-called reverse wavelength dispersion is preferable, and as such a polymerizable liquid crystal compound, for example, a polymerizable liquid crystal compound represented by the formula (X) can be preferably used. A polymerizable liquid crystal compound can be used individually or in combination of 2 or more types.

Content of the polymeric liquid crystal compound in the polymeric liquid crystal composition used for formation of a horizontal alignment liquid crystal cured film is 70-99.5 mass parts with respect to 100 mass parts of solid content of a polymeric liquid crystal composition, Preferably it is 80-99. It is a mass part, More preferably, it is 85-98 mass parts, More preferably, it is 90-95 mass parts. It is advantageous from a viewpoint of the orientation of the liquid crystal cured film obtained as content of a polymeric liquid crystal compound is in the said range.

The polymerizable liquid crystal composition used for formation of a horizontally aligned liquid crystal cured film may further contain additives, such as a solvent, a photoinitiator, a leveling agent, antioxidant, and a photosensitizer, in addition to a polymeric liquid crystal compound. As these components, the thing similar to what was illustrated above as a component which can be used with a vertically-aligned liquid crystal cured film is mentioned, respectively, only 1 type may be used and may be used in combination of 2 or more type.

The polymerizable liquid crystal composition for horizontal alignment liquid crystal cured film formation can be obtained by stirring a polymerizable liquid crystal compound and components other than polymerizable liquid crystal compounds, such as a solvent and a photoinitiator, at predetermined temperature.

A horizontally aligned liquid crystal cured film is, for example,

A step of applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on a substrate or an alignment film to obtain a coating film;

drying the coating film to form a dry coating film; and

Process of irradiating an active energy ray to a dry coating film, and forming a horizontally aligned liquid crystal cured film

It can be prepared by a method comprising

Formation of the coating film of a polymeric liquid crystal composition can be performed by apply|coating the polymeric liquid crystal composition for horizontal alignment liquid crystal cured film formation on a base material, an alignment film, etc., for example. As a base material which can be used here, the thing similar to what was illustrated above as a base material which can be used for manufacture of a vertically aligned liquid crystal cured film can be used.

The alignment film can be appropriately selected from materials having a horizontal alignment regulating force that aligns 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 kind of orientation layer, surface state, rubbing conditions, etc., and when it is formed from a photo-alignment polymer, it is possible to adjust arbitrarily according to polarized light irradiation conditions, etc. As such a material, the orientation polymer etc. which were mentioned above as an orientation film which can be used for manufacture of a vertically aligned liquid crystal cured film are mentioned, for example. A horizontal alignment film can be obtained by apply|coating to a base material the composition containing such a material and a solvent, for example, the solvent illustrated in a vertically aligned liquid crystal cured film, and heating etc. to a coating film after solvent removal. As a horizontal alignment film, it is preferable to use a photo-alignment film from a quality viewpoint.

Then, a dry coating film is formed by removing a solvent by drying etc. As a drying method, the natural drying method, the ventilation drying method, heat drying, the reduced pressure drying method, etc. are mentioned. Heat drying is preferable in terms of productivity, and in that case, it is preferable that the heating temperature can remove a solvent and is more than the phase transition temperature of a polymerizable liquid crystal compound. As for the procedure and conditions in such a process, the thing similar to what can be employ|adopted with the manufacturing method of a vertically-aligned liquid crystal cured film is mentioned.

By irradiating an active energy ray (more specifically, ultraviolet rays, etc.) to the obtained dry coating film, and polymerizing the polymerizable liquid crystal compound while maintaining the state in which the polymerizable liquid crystal compound is oriented in the horizontal direction with respect to the plane of the coating film, horizontal alignment is performed. A liquid crystal cured film is formed. As a polymerization method, the method similar to the method employable with the manufacturing method of a vertically aligned liquid crystal cured film is mentioned.

<Horizontal alignment liquid crystal cured film containing a dichroic dye>

In this invention, the film|membrane which has a polarization function among the horizontally aligned liquid crystal cured film containing a dichroic dye may be called a polarizing film. In particular, in the case of a horizontally aligned liquid crystal cured film containing a dichroic dye, the higher the alignment order of the liquid crystal, the higher the absorption selectivity derived from the dichroic dye. It is preferable to use a compound, and it is preferable to form a polarizing film by polymerization while maintaining the liquid crystal state of the smectic phase, preferably of the higher-order smectic phase. A polarizing film obtained by polymerization of a polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase is accompanied by the action of the dichroic dye, a conventional host guest type polarizing film, that is, a polarizing film consisting of a liquid crystal state of a nematic phase; In comparison, there is an advantage that the polarization performance is high. Moreover, compared with the thing which apply|coated only the dichroic dye or the lyotropic liquid crystal, it also has the advantage of being excellent in intensity|strength.

As for the polarizing film with a high degree of orientation order, in X-ray diffraction measurement, the Bragg peak derived from a higher order structure like a hexatic phase and a crystal phase is obtained. 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, the polymerizable liquid crystal compound or its polymer is preferably oriented so that the polarizing film exhibits a Bragg peak in X-ray diffraction measurement, and light is absorbed It is more preferable that it is "horizontal alignment" in which molecules of a polymerizable liquid crystal compound orientate in the direction to In the present invention, a polarizing film having an in-plane periodic interval of molecular orientation of 3.0 to 6.0 angstroms is preferable. The high degree of alignment order showing the Bragg peak can be realized by controlling the type of the polymerizable liquid crystal compound to be used, the type and amount of antioxidant, the type and amount of the dichroic dye, and the like.

The thickness of a horizontally aligned liquid crystal cured film can be selected suitably, Preferably it is 0.1-5 micrometers, More preferably, it is 0.3-4 micrometers, More preferably, it is 0.4-3 micrometers.

<Elliptical Polarizer>

This invention includes the elliptically polarizing plate containing the liquid crystal cured film of this invention. The elliptically polarizing plate is a laminate including at least a retardation film and a polarizing film.

A polarizing film is a film having a polarizing function, and for example, the above-mentioned polarizing film, a stretched film to which a dye having absorption anisotropy is adsorbed, or a film to which a dye having absorption anisotropy is applied as a polarizer, etc. have. As a dye which has absorption anisotropy, a dichroic dye is mentioned, for example.

A film comprising, as a polarizer, a stretched film to which a dye having absorption anisotropy is adsorbed is usually used in a step of uniaxially stretching a polyvinyl alcohol-based resin film, by dyeing the polyvinyl alcohol-based resin film with a dichroic dye, the dichroic dye At least one surface of the polarizer manufactured through a process of adsorbing the polyvinyl alcohol-based resin film to which the dichroic dye is adsorbed, a process of treating the polyvinyl alcohol-based resin film with an aqueous solution of boric acid, and a process of washing with water after treatment with an aqueous boric acid solution, through an adhesive It is manufactured by sandwiching it with a transparent protective film.

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

The saponification degree of polyvinyl alcohol-type resin is about 85-100 mol% normally, Preferably it is 98 mol% or more. The polyvinyl alcohol-type resin may be modified|denatured, for example, polyvinyl formal and polyvinyl acetal modified|denatured with aldehydes can also be used. The polymerization degree of polyvinyl alcohol-type resin is about 1,000-10,000 normally, Preferably it is the range of 1,500-5,000.

What formed such a polyvinyl alcohol-type resin into a film is used as a raw film of a polarizing film. The method for forming a polyvinyl alcohol-type resin into a film is not specifically limited, A film can be formed by a well-known method. The film thickness of a polyvinyl alcohol-type raw film can be about 10-150 micrometers, for example.

Uniaxial stretching of a polyvinyl alcohol-type resin film can be performed before dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing|staining. When performing uniaxial stretching after dyeing|staining, this uniaxial stretching may be implemented before a boric-acid process, and may be implemented during a boric-acid process. Moreover, it is also possible to perform uniaxial stretching in these several steps. In uniaxial stretching, you may uniaxially stretch between the rolls from which circumferential speed differs, and you may stretch uniaxially using a hot roll. Moreover, uniaxial stretching may be dry extending|stretching extending|stretching in air|atmosphere, and wet extending|stretching which extends|stretches in the state which made the polyvinyl alcohol-type resin film swell using a solvent may be sufficient as it. The draw ratio is usually about 3 to 8 times.

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

As a dichroic dye, iodine and a dichroic organic dye are specifically used. Examples of the dichroic organic dye include a dichroic direct dye composed of a disazo compound such as C.I. DIRECT RED 39, and a dichroic direct dye composed of a compound such as trisazo and tetrakisazo. It is preferable that the polyvinyl alcohol-type resin film performs the immersion process with respect to water before a dyeing process.

When using an iodine as a dichroic dye, the method of dyeing by immersing a polyvinyl alcohol-type resin film in the aqueous solution containing an iodine and potassium iodide is usually employ|adopted. Content of the iodine in this aqueous solution is about 0.01-1 mass part normally per 100 mass parts of water. Moreover, content of potassium iodide is about 0.5-20 mass parts normally per 100 mass parts of water. The temperature of the aqueous solution used for dyeing|dyeing is about 20-40 degreeC normally. Moreover, the immersion time (dyeing time) with respect to this aqueous solution is about 20 to 1,800 second normally.

On the other hand, when using a dichroic organic dye as a dichroic dye, the method of dyeing by immersing a polyvinyl alcohol-type resin film in the aqueous solution containing a water-soluble dichroic dye is usually employ|adopted. Content of the dichroic organic dye in this aqueous solution is ^{about 1x10 -4} - 10 mass parts normally per 100 mass parts of water, Preferably it is 1x10 ^-3 - 1 mass part, More preferably 1 x 10 ^-3 to 1 x 10 ^-2 parts by mass. This aqueous solution may contain inorganic salts, such as sodium sulfate, as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is about 20-80 degreeC normally. Moreover, the immersion time (dyeing time) with respect to this aqueous solution is about 10 to 1,800 second normally.

The boric acid treatment after dyeing|dyeing with a dichroic dye can be performed by the method of immersing the dyed polyvinyl alcohol-type resin film in boric-acid aqueous solution normally. Content of the boric acid in this boric-acid aqueous solution is about 2-15 mass parts normally per 100 mass parts of water, Preferably it is 5-12 mass parts. When iodine is used as a dichroic dye, it is preferable that this aqueous boric acid solution contains potassium iodide, and content of potassium iodide in that case is about 0.1-15 mass parts normally per 100 mass parts of water, Preferably it is 5 -12 parts by mass. The immersion time with respect to boric-acid aqueous solution is about 60 to 1,200 second normally, Preferably it is 150 to 600 second, More preferably, it is 200 to 400 second. The temperature of a boric acid process is 50 degreeC or more normally, Preferably it is 50-85 degreeC, More preferably, it is 60-80 degreeC.

The polyvinyl alcohol-type resin film after a boric acid process is water washing process normally. The water washing process can be performed by the method of immersing the polyvinyl alcohol-type resin film by which the boric acid process was carried out, for example in water. The temperature of the water in a water washing process is about 5-40 degreeC normally. Moreover, immersion time is about 1-120 second normally.

A drying process is performed after water washing, and a polarizer is obtained. A drying process can be implemented using a hot-air dryer or a far-infrared heater, for example. The temperature of a drying process is about 30-100 degreeC normally, Preferably it is 50-80 degreeC. The time of a drying process is about 60 to 600 second normally, Preferably it is 120 to 600 second. By a drying process, the moisture content of a polarizer is reduced to a practical use grade. The moisture content is normally about 5-20 mass %, Preferably it is 8-15 mass %. When a moisture content is less than 5 mass %, the flexibility of a polarizer may be lost, and a polarizer may be damaged or fracture|rupture after the drying. Moreover, when a moisture content exceeds 20 mass %, the thermal stability of a polarizer may worsen.

In this way, the thickness of the polarizer obtained by performing uniaxial stretching, dyeing|staining by a dichroic dye, boric acid treatment, water washing, and drying to a polyvinyl alcohol-type resin film becomes like this. Preferably it is 5-40 micrometers.

As a film to which the dye which has absorption anisotropy was apply|coated, the film obtained by apply|coating the composition containing the dichroic dye which has liquid crystallinity, or the composition containing the dichroic dye and a polymeric liquid crystal, etc. are mentioned. The said film, Preferably, it has a protective film on the single side|surface or both surfaces. As the said protective film, the thing similar to the resin film previously illustrated as a base material which can be used for manufacture of a horizontally aligned liquid crystal cured film is mentioned.

A film coated with a dye having absorption anisotropy is preferably thin, but when it is too thin, the strength decreases and workability tends to be poor. The thickness of the said film is 20 micrometers or less normally, Preferably it is 5 micrometers or less, More preferably, it is 0.5-3 micrometers.

As a film which apply|coated the pigment|dye which has the said absorption anisotropy, the film of Unexamined-Japanese-Patent No. 2012-33249 etc. is mentioned specifically,.

A polarizing film is obtained by laminating|stacking a transparent protective film on the at least one surface of the polarizer obtained in this way through an adhesive agent. As a transparent protective film, the same transparent film as the resin film illustrated above as a base material which can be used for manufacture of a horizontally aligned liquid crystal cured film can be used preferably.

The elliptically polarizing plate of the present invention is constituted including the liquid crystal cured film of the present invention, for example, the elliptically polarizing plate of the present invention can be obtained by laminating the liquid crystal cured film of the present invention through a polarizing film or the like through an adhesive layer or the like.

In one embodiment of the present invention, when the laminate of the present invention and the polarizing film are laminated, the angle between the slow axis (optical axis) of the horizontal alignment retardation film constituting the laminate and the absorption axis of the polarizing film is 45 ± 5 It is preferable to laminate it so that it may become °.

The elliptically polarizing plate of this invention may have the structure with which the conventional general elliptically polarizing plate or a polarizing film and retardation film are equipped. In such a configuration, for example, an adhesive layer (sheet) for bonding the elliptically polarizing plate to a display element such as organic EL, the surface of the polarizing film or retardation film is used for the purpose of protecting it from scratches and contamination. A protection film etc. are mentioned.

The laminate and the elliptically polarizing plate of the present invention can be used for various display devices.

A display device is a device which has a display element, and contains a light emitting element or a light emitting device as a light emitting source. Examples of the display device 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 (eg, an electric field emission display device (FED) ), surface field emission display device (SED)), electronic paper (display device using electronic ink or electrophoresis element, plasma display device, projection display device (eg, grating light valve (GLV) display device, digital micromirror device) (DMD)) and a piezoelectric ceramic display, etc. Liquid crystal display devices include a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, a direct view liquid crystal display, and a projection liquid crystal display. Including any of etc. These display apparatus may be the display apparatus which displays a two-dimensional image, and the stereoscopic display apparatus which displays a three-dimensional image may be sufficient as these display apparatuses. In particular, the elliptically polarizing plate of this invention exhibits the effect remarkably. Since it is easy to be used, it can be preferably 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. In addition to the excellent front reflection color and all direction reflection color, the front color and all directions color in white display are also excellent, so that good image display characteristics can be expressed.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. In addition, unless otherwise indicated, "%" and "part" in an example mean mass % and mass part, respectively.

<Example 1>

[Preparation of liquid crystal compound]

Liquid crystal compound A was prepared according to the method described in Japanese Patent Application Laid-Open No. 2010-31223. Moreover, the liquid crystal compound B was manufactured according to the method of Unexamined-Japanese-Patent No. 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 the composition for forming a vertically aligned liquid crystal cured film]

The liquid crystal compound A and the liquid crystal compound B were mixed by mass ratio 90:10, and the mixture was obtained. With respect to 100 parts by mass of the obtained mixture, 0.10 parts by mass of a leveling agent "BYK-361N" (manufactured by BYK-Chemie), 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), Japanese Patent Application No. 2016-514802 2.0 parts by mass of the ionic compound A adjusted as a reference, 0.5 parts by mass of KBE-9103 manufactured by Shin-Etsu Chemical Industries, Ltd., 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl) as a photoinitiator ) 6 parts by mass of butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Co., Ltd.)) was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. By stirring at 80 degreeC for 1 hour, the composition for vertical alignment liquid crystal cured film formation was obtained.

Ionic compound A:

Moreover, as a result of measuring the molecular weight of acrylic leveling agent "BYK-361N" by GPC (The Tosoh Corporation make, HLC-8220GPC, solvent tetrahydrofuran, detector: RI), the number average molecular weight was 4800.

[Method for Producing a Vertically Aligned Liquid Crystal Cured Film]

Corona treatment is performed on a cycloolefin film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd., and a composition for forming a vertically aligned liquid crystal cured film is applied using a bar coater, heated at 120° C. for 60 seconds, followed by high pressure Using a mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.), ultraviolet rays are irradiated from the surface to which the composition for forming a horizontally aligned liquid crystal cured film is applied (in a nitrogen atmosphere, accumulated light quantity at a wavelength of 365 nm: 500 mJ/cm 2 ) to form a vertically aligned liquid crystal cured film. It was 1.2 micrometers when the film thickness of the obtained vertically-aligned liquid crystal cured film was measured with the ellipsometer (M-220 by Nippon Kogyo Co., Ltd.).

[Rth measurement of vertically aligned liquid crystal cured film]

In the case of using KOBRA-WPR manufactured by Oji Instruments Co., Ltd., the retardation of a film having anisotropic absorption to visible light cannot be measured. After preparing the composition for formation, using the composition to form vertically aligned liquid crystal curing in the same manner, and after confirming that there is no phase difference in the cycloolefin film, using "KOBRA-WPR" manufactured by Oji Measuring Co., Ltd., a sample for measuring optical properties The front retardation value (in-plane retardation value) of the vertically aligned liquid crystal cured film by changing the incident angle of the light, and the retardation value when tilted by 40° to the center of the fast axis were measured. The average refractive index in each wavelength was measured using the ellipsometer M-220 by the Nippon Spectroscopy Co., Ltd. product. In addition, the film thickness was measured using the Optical NanoGauge film thickness meter C12562-01 by the Hamamatsu Photonics Co., Ltd. product. 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 leading axis, average refractive index, and film thickness, Oji measurement equipment technical data (http: //www.oji-keisoku.co .jp/products/kobra/reference.html) to calculate the three-dimensional refractive index. From the obtained three-dimensional refractive index, the result of having calculated the optical characteristic of each vertically-aligned liquid crystal cured film according to the following formula is shown in Table 1.

RthC (λ) = ((nxC (λ) + nyC (λ))/2 - nzC (λ)) × dC

αthC = RthC (450)/RthC (550)

[Production of polarizing film]

A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of 99.9 mol% or more and a thickness of 75 μm was immersed in pure water at 30° C., and then in an aqueous solution having a weight ratio of iodine/potassium iodide/water of 0.02/2/100 at 30° C. It was immersed and dyed with iodine (iodine dyeing process). The polyvinyl alcohol film subjected to 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 give boric acid treatment (boric acid treatment step). After wash|cleaning the polyvinyl alcohol film which passed through the boric acid treatment process with 8 degreeC pure water, it dried at 65 degreeC, and the polarizer (27 micrometers in thickness after extending|stretching) in which the iodine adsorption-orientation is carried out to polyvinyl alcohol was obtained. At this time, it extended|stretched in the iodine dyeing process and the boric acid treatment process. The total draw ratio in this extending|stretching was 5.3 times. The obtained polarizer and the saponification-treated triacetyl cellulose film (KC4UYTAC 40 micrometers by Konica Minolta) were bonded together with the nip roll through the water-system adhesive agent. Maintaining the tension|tensile_strength of the obtained bonding material at 430 N/m, it was made to dry at 60 degreeC for 2 minute(s), and the polarizing film which has a triacetyl-cellulose film on one side as a protective film was obtained. In addition, the water-based adhesive is 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol (Kurarepoval KL318 manufactured by Kuraray), and a water-soluble polyamide epoxy resin (aqueous solution having a solid content concentration of 30% of Sumirez Resin 650 manufactured by Sumika Chemtex) It was prepared by adding 1.5 parts.

Confirmation of nonuniformity and evaluation of orientation were performed about the obtained polarizing film. The measurement was performed with a spectrophotometer (V7100, manufactured by Nippon Spectroscopy) using the polarizer surface of the polarizing plate obtained above as an incident surface. The obtained visibility corrected single transmittance was 42.1%, the visibility corrected polarization degree was 99.996%, the single color a was -1.1, and the single color b was 3.7.

[Confirmation of non-uniformity]

In a dark room, in the state which set the brightness|luminance of the backlight A4-500 by Tritec company to 4700 lux, it installed so that it might become cross nicol on the backlight, and 2 polarizing films manufactured by the said method. Next, the vertically oriented liquid crystal cured film prepared by the above method is installed between two polarizing films, and the vertically oriented liquid crystal cured film is rotated in a state that is inclined so that the angle formed with the backlight surface is 60°, and it is visually recognized from the polarizing film surface side. It was made so that the light leakage by the phase difference of a vertically-aligned liquid crystal cured film was largest at the time. The said state WHEREIN: The nonuniformity of the vertically-aligned liquid crystal cured film was confirmed on the following reference|standard.

(double-circle) : Nonuniformity is not recognized.

(circle): A slight nonuniformity is visually recognized.

(triangle|delta): Nonuniformity is visually recognized.

x: The nonuniformity is visually recognized strongly.

[Orientation evaluation]

First, the vertical alignment liquid crystal cured film was bonded to the glass of 5x5cmxth thickness 0.7mm through the Lintec pressure-sensitive adhesive (25 micrometers). About the obtained sample, using the polarizing microscope ("BX-51" by Olympus Corporation), it observed on the conditions of 200 times of magnification, and the number of orientation defects in 480 micrometers x 320 micrometers of visual fields was counted. Here, only the number of orientation defects resulting from the sample for measurement was counted, and the number of defects resulting from environmental foreign substances other than the sample was excluded and not counted. From the observation result with a polarizing microscope, the orientation of the vertically-aligned liquid crystal cured film was evaluated based on the following evaluation criteria. In addition, ○ and △ were judged to be excellent in orientation.

Evaluation standard :

○ (Very good): The number of orientation defects is 5 or less.

(triangle|delta) (good|favorableness): 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 it is not orientating at all.

<Examples 2 to 5>

As for the leveling agent to be added at the time of preparation of the composition for vertical alignment liquid crystal cured film formation, as Table 1, "BYK-361N" (acrylic-type leveling agent) by BYK-chemie company, copper "BYK-UV3500" (silicone-type leveling agent) ), manufactured by DIC Corporation "F-556" (fluorine-based leveling agent), and except having changed the addition amount, a vertically aligned liquid crystal cured film was prepared in the same manner as in Example 1, and the Rth measurement, non-uniformity and Orientation was confirmed. A result is shown in Table 1.

<Example 6>

[Preparation of a composition for forming a horizontal alignment film]

5 parts (weight average molecular weight: 30000) of the photo-alignment material of the following structure and 95 parts of cyclopentanone (solvent) were mixed as a component, The composition for horizontal alignment film formation was obtained by stirring the obtained mixture at 80 degreeC for 1 hour.

[Preparation of a composition for forming a horizontally aligned liquid crystal cured film]

The liquid crystal compound A and the liquid crystal compound B were mixed by mass ratio 90:10, and the mixture was obtained. With respect to 100 parts by mass of the obtained mixture, 0.1 parts by mass of a leveling agent "BYK-361N" (manufactured by BYK-Chemie), 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), and 2-dimethyl as a photoinitiator 6 parts by mass of amino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Co., Ltd.)) was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. The composition for horizontal alignment liquid crystal cured film formation was obtained by stirring at 80 degreeC for 1 hour.

Further, a 1 mg/50 ml tetrahydrofuran solution of the 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 measured using an ultraviolet-visible spectrophotometer (“UV- 2450"), the absorption spectrum was measured, and as a result of reading the wavelength used as the maximum absorption from the obtained absorption spectrum, the maximum absorption wavelength _λmax in the wavelength range of 300 to 400 nm was 350 nm.

[Method for producing a horizontally aligned liquid crystal cured film]

On a cycloolefin film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd., the composition for forming a horizontal alignment film was applied with a bar coater, dried at 80° C. for 1 minute, and polarized UV irradiation device (SPOT CURE SP-9; Ushio) Using the Electric Co., Ltd. product), polarization|polarized-light UV exposure was performed at the accumulated light quantity in wavelength 313nm:100mJ/cm<2>, and the horizontal alignment film was obtained. As a result of measuring the film thickness of the obtained horizontal alignment film with an ellipsometer, it was 200 nm.

Subsequently, the composition for forming a horizontally aligned liquid crystal cured film was applied on the horizontal alignment film using a bar coater, heated at 120° C. for 60 seconds, and then a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) A horizontally aligned liquid crystal cured film was formed by using and irradiating an ultraviolet-ray from the surface which apply|coated the composition for horizontal alignment liquid crystal cured film formation (in nitrogen atmosphere, wavelength 365nm: 500 mJ/cm<2>). After confirming that there is no phase difference in a COP film, Re (450) and Re (550) were measured using KOBRA-WPR by Oji Instruments Co., Ltd. A result is shown in Table 1.

[Confirmation of non-uniformity]

In a dark room, in the state which set the brightness|luminance of the backlight A4-500 by Tritec company to 4700 lux, it installed so that it might become cross nicol on the backlight, and 2 polarizing films manufactured by the said method. Then, a horizontally aligned liquid crystal cured film is installed between the two polarizing films so that the angle between the slow axis of the horizontally aligned liquid crystal cured film produced by the above method and the absorption axis of the polarizing film is 45°, and from the side opposite to the backlight It visually recognized and the following reference|standard confirmed the nonuniformity of a horizontally aligned liquid crystal cured film.

(double-circle) : Nonuniformity is not recognized.

(circle): A slight nonuniformity is visually recognized.

(triangle|delta): Nonuniformity is visually recognized.

x: The nonuniformity is visually recognized strongly.

[Orientation evaluation]

First, the horizontally aligned liquid crystal cured film was bonded together to the glass of 5x5cmxth thickness 0.7mm through the Lintec pressure-sensitive adhesive (25 micrometers). About the obtained sample, using the polarizing microscope ("BX-51" by Olympus Corporation), it observed on the conditions of 200 times of magnification, and the number of orientation defects in 480 micrometers x 320 micrometers of visual fields was counted. Here, only the number of orientation defects resulting from the sample for measurement was counted, and the number of defects resulting from environmental foreign substances other than the sample was excluded and not counted. From the observation result with a polarizing microscope, the orientation of the vertically-aligned liquid crystal cured film was evaluated based on the following evaluation criteria. In addition, ○ and △ were judged to be excellent in orientation.

Evaluation standard :

○ (Very good): The number of orientation defects is 5 or less.

(triangle|delta) (good|favorableness): 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 it is not orientating at all.

<Example 7>

[Preparation of a composition for forming a horizontal alignment film]

5 parts (weight average molecular weight: 30000) of the photo-alignment material of the following structure and 95 parts of cyclopentanone (solvent) were mixed as a component, The composition for horizontal alignment film formation was obtained by stirring the obtained mixture at 80 degreeC for 1 hour.

[Preparation of a horizontally aligned liquid crystal cured film composition]

The following component was mixed and the horizontal alignment liquid crystal cured film composition (composition for polarizing layer formation) was obtained by stirring at 80 degreeC for 1 hour. As a dichroic dye, the azo dye of the Example of Unexamined-Japanese-Patent No. 2013-101328 was used. The polymerizable liquid crystal compound represented by formulas (1-6) and (1-7) is described in lub et al., Recl. Trav. Chim. It was prepared according to the method described in Pays-Bas, 115, 321-328 (1996).

Polymeric liquid crystal compounds:

Dichroic dye 1: polyazo dye; compound (1-8) 2.5 copies

compound (1-5) 2.5 copies

compound (1-16) 2.5 copies

polymerization initiator;

2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by Chiba Specialty Chemicals) part 6

leveling agent;

「BYK-361N」 (manufactured by BYK-Chemie) 0.1 parts by mass (acrylic leveling agent)

"F-556" (manufactured by DIC) 0.25 parts by mass (fluorine-based leveling agent)

solvent; o-xylene 250 copies

[Production of horizontally aligned liquid crystal cured film]

The triacetyl cellulose film (KC4UY) manufactured by Konica Minolta Co., Ltd. was processed once under the conditions of an output of 0.3 kW and a processing speed of 3 m/min using a corona treatment apparatus (AGF-B10, manufactured by Kasuga Electric Corporation). On the corona-treated surface, a composition for forming a horizontal alignment film (composition for forming a polarizing layer) was applied with a bar coater, dried at 80° C. for 1 minute, and then polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) Using , polarized light UV exposure was performed at an axial angle of 90° with an accumulated light amount of 100 mJ/cm 2 . It was 150 nm when the film thickness of the obtained horizontal alignment layer was measured with an ellipsometer.

Then, after apply|coating the composition for horizontal alignment liquid crystal cured film formation (composition for polarizing layer formation) using a bar coater, a polymeric liquid crystal compound and a dichroic dye orientate by drying for 1 minute in the drying oven set to 120 degreeC A dry coating film was obtained. After naturally cooling this dry coating film to room temperature, using a high-pressure mercury lamp (Unicure VB-15201BY-A, Ushio Electric Co., Ltd. make) irradiates ultraviolet-ray (under nitrogen atmosphere, wavelength: 365 nm, integration in wavelength 365 nm) Light quantity: 1000 mJ/cm<2>), the polymerizable liquid crystal compound was superposed|polymerized, and the horizontally aligned liquid crystal cured film (polarizing film) was manufactured.

[Measurement of polarization degree and single transmittance]

The polarization degree of the obtained horizontally aligned liquid crystal cured film (polarizing film) and the single transmittance|permeability were measured as follows. The transmittance (T ¹ ) in the transmission axis direction and the transmittance (T ² ) in the absorption axis direction were measured by a double beam method using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) in which a folder with a polarizer was set. It measured in the wavelength range of 2 nm step 380-680 nm. Using the following formulas (p) and (q), the single transmittance and the polarization degree at each wavelength are calculated, and the visibility is corrected with a 2 degree field of view (C light source) of JIS Z 8701, and the visibility is corrected alone. When the transmittance|permeability (Ty) and visibility correction|amendment polarization degree (Py) were computed, the single transmittance|permeability is 42 % and the polarization degree is 97 %, and it confirmed that it was a value useful as a polarizing film.

^Single transmittance (%) = (T 1 + T ² )/2 (p)

Polarization degree (%) = {(T ¹ - T ² )/(T ¹ + T ² )} × 100 (q)

[Confirmation of non-uniformity]

In a dark room, in a state in which the luminance of the backlight A4-500 manufactured by Tritec was set to 4700 lux, one polarizing film prepared by the above method was installed on the backlight, and the absorption axis of the horizontally aligned liquid crystal cured film and the polarizing film A horizontally aligned liquid crystal cured film was installed so that the angle formed by the absorption axis of was set to 90 degrees (cross-Nicol state). The installed sample was visually recognized from the surface on the opposite side to a backlight, and the nonuniformity of the horizontal alignment liquid crystal cured film was confirmed on the following reference|standard.

(double-circle) : Nonuniformity is not recognized.

(circle): A slight nonuniformity is visually recognized.

(triangle|delta): Nonuniformity is visually recognized.

x: The nonuniformity is visually recognized strongly.

[Orientation evaluation]

First, the horizontally aligned liquid crystal cured film was bonded together to the glass of 5x5cmxth thickness 0.7mm through the Lintec pressure-sensitive adhesive (25 micrometers). About the obtained sample, using the polarizing microscope ("BX-51" by Olympus Corporation), it observed on the conditions of 200 times of magnification, and the number of orientation defects in 480 micrometers x 320 micrometers of visual fields was counted. Here, only the number of orientation defects resulting from the sample for measurement was counted, and the number of defects resulting from environmental foreign substances other than the sample was excluded and not counted. From the observation result with a polarizing microscope, the orientation of the vertically-aligned liquid crystal cured film was evaluated based on the following evaluation criteria. In addition, it was judged that (circle) and (triangle|delta) were excellent in orientation.

Evaluation standard :

○ (Very good): The number of orientation defects is 5 or less.

(triangle|delta) (good|favorableness): 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 it is not orientating at all.

<Example 8>

As shown below, except having changed the preparation method of the composition for vertical alignment liquid crystal cured film formation, it carried out similarly to Example 1, the vertical alignment liquid crystal cured film was manufactured, and nonuniformity and orientation were confirmed. A result is shown in Table 1. In addition, since a dichroic dye was included, the phase difference value measurement of the vertically-aligned liquid crystal cured film was not implemented. Moreover, when the absorbance of the vertically-aligned liquid crystal cured film was measured by the method as described below, it was (lambda)max=600nm, AxC=0.024, AxC(z=60)=0.175.

[Preparation of the polymerizable liquid crystal composition for forming a vertically aligned 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. To 100 parts by mass of the obtained mixture, 0.1 parts by mass of a leveling agent "BYK-361N" (manufactured by BYK-Chemie), 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC), JP 2013-101328 1.5 parts by mass of dichroic dye A described below, 2.0 parts by mass of ionic compound A (molecular weight: 645) adjusted with reference to Japanese Patent Application Publication No. 2016-514802, silane coupling agent "KBE-9103" (Shin-Etsu Chemical) 0.5 parts by mass (manufactured by Kogyo Co., Ltd.), 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one as a photopolymerization initiator (Irgacure (registered trademark) 369 by BASF Japan Co., Ltd.) (Irg369)") 6 parts by mass was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. By stirring this mixture at 80 degreeC for 1 hour, the polymeric liquid crystal composition for vertical alignment liquid crystal cured film formation was obtained.

Dichroic compound A:

[Measurement of absorbance of vertically aligned liquid crystal cured film]

The coated surface of the vertically aligned liquid crystal cured film produced by the above method was bonded to 4 × 4 cm × 0.7 mm thick glass via a 25 μm pressure-sensitive adhesive (manufactured by Lintec), and an ultraviolet and visible spectrophotometer (manufactured by Shimadzu Corporation) UV-2450"), the absorbance was measured, and the absorption maximum wavelength (λmax), AxC, and AxC (z=60) with a wavelength of 400 to 750 nm was calculated.

Incidentally, the x-axis is an arbitrary direction in the plane of the vertically aligned liquid crystal cured film, the y-axis is the direction perpendicular to the x-axis in the plane of the film, and the z-axis means the thickness direction of the vertically aligned liquid crystal cured film, AxC and AxC (z = 60 ) is the absorbance at the maximum absorption wavelength of 400 to 750 nm of the vertically aligned liquid crystal cured film, AxC represents the absorbance of linearly polarized light vibrating in the x-axis direction, AxC (z = 60) is y The absorbance of linearly polarized light vibrating in the x-axis direction when the film is rotated by 60 degrees with the axis as the rotation axis is shown.

In addition, 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. Also about AxC (z=60), after setting and tilting a sample similarly, after correcting so that the absorbance at 800 nm might become zero, AxC (z=60) was measured.

<Comparative Examples 1 to 4>

As for the leveling agent to be added at the time of preparation of the composition for vertical alignment liquid crystal cured film formation, as Table 1, "BYK-361N" by BYK-chemie company, "BYK-392", "F-556 by DIC company" ", except having changed the thing and addition amount, the vertical alignment liquid crystal cured film was manufactured similarly to Example 1, and the nonuniformity and orientation were confirmed. A result is shown in Table 1.

Moreover, as a result of measuring the molecular weight of acrylic leveling agent "BYK-392" by GPC (The Tosoh Corporation make, HLC-8220GPC, solvent tetrahydrofuran, detector: RI), the number average molecular weight was 13100.

In addition, Re in Table 1 shows either the in-plane retardation value of a horizontal alignment film, or the in-plane retardation value of a vertical alignment film.

According to this invention, nonuniformity can be improved, without impairing the orientation of a liquid crystal cured film by using a predetermined|prescribed leveling agent.

Claims (18)

At least one silicone-based or fluorine-based leveling agent, at least one acrylic-based leveling agent, and at least one polymerizable liquid crystal compound,
The composition for liquid crystal cured film formation whose total amount of a leveling agent is 3.0 mass % or less with respect to the total amount of a polymeric liquid crystal compound. The method of claim 1,
A composition for forming a liquid crystal cured film comprising at least one silicone-based leveling agent. 3. The method according to claim 1 or 2,
Furthermore, the composition for liquid crystal cured film formation containing a dichroic dye. 4. The method according to any one of claims 1 to 3,
The composition for forming a liquid crystal cured film, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound capable of forming a smectic phase. 5. The method according to any one of claims 1 to 4,
A composition for forming a liquid crystal cured film, wherein the polymerizable liquid crystal compound contains a polymerizable liquid crystal compound having a T-shaped structure. The liquid crystal cured film hardened|cured in the state which the polymeric liquid crystal compound contained in the composition for liquid crystal cured film formation in any one of Claims 1-5 orientated. 7. The method of claim 6,
The liquid crystal cured film whose film thickness of a liquid crystal cured film is 0.3 micrometer or more and 5.0 micrometers or less. 8. The method according to claim 6 or 7,
The liquid crystal cured film which is a horizontally aligned liquid crystal cured film hardened|cured in the state which a polymeric liquid crystal compound orientated in the parallel direction with respect to in-plane. 9. The method according to any one of claims 6 to 8,
Furthermore, the liquid crystal cured film which satisfy|fills following formula (S1).
100 nm ≤ ReA (550) ≤ 180 nm ... (S1)
(In formula (S1), ReA (550) represents an in-plane retardation value at a wavelength of 550 nm.) 10. The method according to any one of claims 6 to 9,
Furthermore, the liquid crystal cured film which satisfy|fills following formula (S2).
ReA (450)/ReA (550) < 1.0 … (S2)
(In formula (S2), ReA (450) represents an in-plane retardation value at a wavelength of 450 nm.) 11. The method according to any one of claims 6 to 10,
A liquid crystal cured film is a horizontally aligned liquid crystal cured film, Comprising: The horizontal alignment liquid crystal cured film which shows a Bragg peak in X-ray diffraction measurement. 8. The method according to claim 6 or 7,
A liquid crystal cured film, which is a vertically aligned liquid crystal cured film cured in a state in which the polymerizable liquid crystal compound is oriented in a direction perpendicular to the plane. 13. The method of claim 12,
Furthermore, the liquid crystal cured film which satisfy|fills following formula (S3).
-150 nm ≤ RthC (550) ≤ -30 nm ... (S3)
(In Formula (S3), RthC(550) shows the phase difference value of the thickness direction in wavelength 550nm of a liquid crystal cured film.) 14. The method according to claim 12 or 13,
Furthermore, the liquid crystal cured film which satisfy|fills following formula (S4).
RthC (450)/RthC (550) ≤ 1.0 … (S4)
(in formula (S4), RthC(450) shows the retardation value of the thickness direction in wavelength 450nm of a liquid crystal cured film, RthC(550) shows the retardation value of the thickness direction in wavelength 550nm of a liquid crystal cured film .] An elliptically polarizing plate comprising a horizontal alignment retardation film and a polarizing film,
The elliptically polarizing plate in which at least one of a horizontal orientation retardation film and a polarizing film is the liquid crystal cured film in any one of Claims 6-11. An elliptically polarizing plate comprising a horizontally aligned retardation film, a vertically aligned liquid crystal cured film, and a polarizing film,
The elliptically polarizing plate in which at least one of a horizontal alignment retardation film, a vertically aligned liquid crystal cured film, and a polarizing film is the liquid crystal cured film in any one of Claims 6-14. 17. The method according to claim 15 or 16,
An elliptically polarizing plate wherein an angle between the slow axis of the horizontal alignment retardation film and the absorption axis of the polarizing plate is 45±5°. An organic EL display device comprising the elliptically polarizing plate according to any one of claims 15 to 17.