JP2018120150A - Composition for anisotropic photoconversion material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To disclose a guest-host anisotropic photoconversion material that has a high dichroic ratio and prevents alignment defects from occurring in the case of deposition over a wide area, and disclose a polymerizable liquid crystal material that allows the preparation of such a material.SOLUTION: A composition for anisotropic photoconversion material is obtained by adding, to a host liquid crystal composition containing a compound represented by formula (1), a dichroic guest (where, A is a bivalent group derived from an aromatic ring, 1,4-cyclohexane, 1,3-dioxane, or 1,4-pyran, B is a single bond, -COO-, -CHCH-, -CH=CH-, -CH≡CH-, -OCH-, -CH=CHCOO-, or -CHCHCOO-, n is 5, 6, or 7, SP is a single bond or an organic group having 1-21 carbon atoms, PG is alkyl, alkoxyl, cyano, fluorine, or a polymerizable group).SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal composition and an anisotropic light conversion material prepared by applying a liquid crystal composition to a substrate.

As a material that absorbs light anisotropically, a uniaxially stretched polyvinyl alcohol (PVA) film impregnated with iodine is widely used, for example, as a polarizing plate of a liquid crystal display (LCD) element. On the other hand, this PVA film is generally used by being sandwiched between triacetyl cellulose (TAC) films in order to avoid moisture absorption and deterioration of optical performance due to heat and light. At this time, the thickness of the entire polarizing plate may be 100 μm or more including the adhesive layer. Therefore, as an approach for reducing the thickness of the polarizing plate and reducing the thickness of the entire LCD element, techniques described in Patent Document 1 and Non-Patent Document 1 have been studied.

  That is, Patent Document 1 and Non-Patent Document 1 disclose a polymerizable liquid crystal material containing a dichroic dye that exhibits a dichroic ratio of 15 or more. Specifically, as a polymerizable liquid crystal material, a composition having a smectic phase (other than smectic A or smectic C) having a large degree of orientation (order parameter) can be designed to obtain a film having a large dichroic ratio. Are disclosed.

  However, in the examples of Patent Document 1 and Patent Document 1, the film showing the dichroic ratio is manufactured by injecting a material between a pair of base materials in which an alignment film is installed above and below, and curing the material. Yes. According to such a manufacturing method, in order to apply the manufactured film to an element such as an actual LCD, the film must be peeled off from the base material. That is, the manufacturing process becomes complicated. On the other hand, when a film showing a dichroic ratio is formed on a substrate on which an alignment film is installed, that is, when there is an alignment control film only on one side, an alignment defect occurs and a sufficient dichroic ratio is not expressed. Met.

US Pat. No. 7,763,330

Chem. Mater., 20, 6076 (2008)

  The present invention discloses a guest-host anisotropic light conversion material having a high dichroic ratio and being less prone to orientation defects. In addition, a polymerizable liquid crystal material capable of producing such a material is disclosed.

  The present inventors use a specific liquid crystal composition as a host liquid crystal and a photo-alignment film as an alignment film in a guest-host anisotropic light conversion material using a guest having dichroism with a liquid crystal. The inventors have found that the anisotropic light conversion material having a high dichroic ratio can be obtained, and have completed the invention.

（式（１）中、Ａは、芳香環から由来する二価基、１，４−シクロヘキサン、１，３−ジオキサン、または１，４−ピランであり、Ｂは、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ≡ＣＨ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２ＣＯＯ−、または−ＯＣＯＣＨ_２ＣＨ_２−であり、ｎは、５、６、または７であり、ＳＰは、単結合または炭素数１から２１の二価の有機基であり、ＰＧは、アルキル、アルコキシル、シアノ、フッ素、または重合性基である。） The present invention includes items 1 to 6 and the like.
Item 1. A composition for an anisotropic light conversion material, in which a dichroic guest is added to a host liquid crystal composition containing a compound represented by the formula (1).

(In formula (1), A is a divalent group derived from an aromatic ring, 1,4-cyclohexane, 1,3-dioxane, or 1,4-pyran, and B is a single bond, —COO—, _{-OCO -, - CH 2 CH 2} -, - CH = CH -, - CH≡CH -, - OCH 2 -, - CH 2 O -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH ₂ COO—, or —OCOCH ₂ CH ₂ —, n is 5, 6, or 7, SP is a single bond or a divalent organic group having 1 to 21 carbon atoms, PG is alkyl , Alkoxyl, cyano, fluorine, or a polymerizable group.)

  Item 2. Item 6. The composition for anisotropic light conversion material according to Item 1, wherein 60% by weight or more of the host liquid crystal composition is a compound represented by Formula (1).

  Item 3. Item 3. The composition for an anisotropic light conversion material according to Item 1 or 2, wherein at least one of the two PGs is a polymerizable group in the compound represented by Formula (1).

  Item 4. An anisotropic light conversion material prepared using the composition according to Item 3.

  Item 5. An anisotropic light conversion material prepared by curing a nematic composition using the composition according to Item 3.

  Item 6. An anisotropic light conversion material prepared by curing a nematic composition on a photo-alignment film using the composition according to Item 3.

  By applying a specific liquid crystal composition containing a dichroic guest on the photo-alignment film, generation of defects in a large area can be suppressed, and an anisotropic light conversion material having a high dichroic ratio can be provided.

It is a polarization micrograph of anisotropic light conversion material LF-1 of the present invention. It is a polarizing microscope photograph of the conventional anisotropic light conversion material LF-ref2.

  In the present invention, “compound (X)” means a compound represented by the formula (X). Here, X in “compound (X)” is a character string, a number, a symbol, or the like.

  In the present invention, the “liquid crystal compound” is a generic term for (A) a compound having a liquid crystal phase as a pure substance and (B) a compound which is a component of a liquid crystal composition. The “host liquid crystal composition” is a composition comprising this liquid crystal compound.

In the present invention, the term “polymerizable group” means a functional group that, when contained in a compound, polymerizes by means of light, heat, catalyst, etc., and changes into a polymer having a larger molecular weight.
In the present invention, “monofunctional compound” means a compound having one polymerizable group, and “polyfunctional compound” means a compound having a plurality of polymerizable groups.
Further, in the present invention, the “X functional compound” is a compound having X polymerizable groups. Here, X in the “X functional compound” is an integer.

In the present invention, the “polymerizable liquid crystal compound” is a liquid crystal compound and a compound having a polymerizable group.
In the present invention, the “non-liquid crystalline polymerizable compound” is a polymerizable compound and is a compound having no liquid crystal phase alone.

  In the present invention, “polymerizable liquid crystal composition” means a composition containing a polymerizable compound and a liquid crystal compound, and a composition containing “polymerizable liquid crystal compound”.

In the present invention, “alignment” means that the major axes of liquid crystal molecules are aligned in a certain direction in an optically usable state.
In the present invention, the “tilt angle” is the angle of the liquid crystal alignment axis in the polar angle direction with respect to the substrate plane.
In the present invention, “homogeneous orientation” refers to a state in which the tilt angle is approximately 0 degrees and the film is uniaxially oriented in the azimuth direction with respect to the substrate plane.

In the present invention, “homeotropic alignment” means a state in which the tilt angle is approximately 90 degrees and the film is uniaxially aligned.
In the present invention, “tilt orientation” represents a state in which the tilt angle is oriented so as to increase according to the distance from the substrate surface.
In the present invention, “twist alignment” represents a state in which the alignment easy axis of the aligned liquid crystal molecules is twisted stepwise around the helical axis according to the distance from the substrate surface.

In the present invention, the “anisotropic light conversion material” refers to a light having a polymerizable liquid crystal compound as a host and a material that absorbs light and / or converts the wavelength of light added as a guest. Represents a material that changes the state of.
In the present invention, the “film thickness” represents the thickness of the anisotropic light conversion material.

≪Liquid crystal compound≫

式（１）中、
Ａは、芳香環から由来する二価基、１，４−シクロヘキサン、１，３−ジオキサン、または１，４−ピランである。
芳香環から由来する二価基は、１，４−フェニレン、フルオレン−２，７−ジイル、ナフタレン−２，６−ジイル、１，３−ピリミジン−２，５−ジイルなどであり、これらの二価基の水素は、フッ素、塩素、炭素数１から５のアルキル、アルコキシル、カルボニル、またはカルボキシルで置換されてもよい。
Ｂは、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ≡ＣＨ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２ＣＯＯ−、または−ＯＣＯＣＨ_２ＣＨ_２−である。
ｎは、５、６、または７であり、ｎ個のＡまたはｎ個のＢは、同一でも、異なっていてもよい。
ＳＰは、単結合または炭素数１から２１の二価の有機基である。
二価の有機基は、直鎖のアルキレンなどであり、これらの隣り合わない−ＣＨ_２は−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ≡ＣＨ−、またはこれらの組み合わせで置換されていてもよい。
ＰＧは、アルキル、アルコキシル、シアノ、フッ素、または重合性基である。
重合性基は、アクリロイル、メタクリロイル、ビニル、スチレン、マレイミド等のラジカル重合可能な基および、オキシラン、オキセタンなどのカチオンまたはアニオン重合可能な基である。 An anisotropic light conversion material having a high dichroic ratio can be created by using a host liquid crystal composition comprising a liquid crystal compound containing compound (1) and a composition containing a guest having dichroism as raw materials.

In formula (1),
A is a divalent group derived from an aromatic ring, 1,4-cyclohexane, 1,3-dioxane, or 1,4-pyran.
Divalent groups derived from aromatic rings are 1,4-phenylene, fluorene-2,7-diyl, naphthalene-2,6-diyl, 1,3-pyrimidine-2,5-diyl, and the like. The hydrogen of the valent group may be substituted with fluorine, chlorine, alkyl having 1 to 5 carbons, alkoxyl, carbonyl, or carboxyl.
B is a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH═CH—, —CH≡CH—, —OCH ₂ —, —CH ₂ O—, —CH═CHCOO—, _{-OCOCH = CH -, - CH 2} CH 2 COO-, or -OCOCH ₂ CH ₂ - is.
n is 5, 6 or 7, and n A or n B may be the same or different.
SP is a single bond or a divalent organic group having 1 to 21 carbon atoms.
The divalent organic group is linear alkylene or the like, and these non-adjacent —CH ₂ are —O—, —CO—, —COO—, —CH ₂ CH ₂ —, —CH═CH. It may be substituted with-, -CH≡CH-, or a combination thereof.
PG is an alkyl, alkoxyl, cyano, fluorine, or polymerizable group.
The polymerizable group is a radically polymerizable group such as acryloyl, methacryloyl, vinyl, styrene or maleimide, and a cation or anion polymerizable group such as oxirane or oxetane.

  The compound represented by the formula (1) is preferably a compound represented by the formula (1-1) to the formula (1-3) in order to develop the characteristics of the present invention.

In these formulas (1-1) to (1-3),
W ¹ is hydrogen, fluorine, chlorine, or an organic group having 1 to 5 carbon atoms. W ¹ is an alkyl having 1 to 5 carbon atoms, an alkoxycarbonyl having 1 to 4 carbon atoms, an aldehyde having 1 to 5 carbon atoms, or an alkylcarbonyl having 1 to 4 carbon atoms, which broadens the liquid crystal phase of the composition. In order to improve the compatibility with other liquid crystal compounds and increase the solubility in a solvent, it is more preferable.
W ² and W ³ are hydrogen, fluorine, or an organic group having 1 to 5 carbon atoms. W ² is alkyl having 1 to 5 carbon atoms, and W ³ is for hydrogen to expand the liquid crystal phase of the composition, improve the compatibility with other liquid crystal compounds, and increase the solubility in a solvent. More preferable.
W ⁴ is hydrogen, fluorine, or an organic group having 1 to 5 carbon atoms. W ⁴ is an alkyl having 1 to 5 carbon atoms, an alkoxycarbonyl having 1 to 4 carbon atoms, an aldehyde, or an alkylcarbonyl having 1 to 4 carbon atoms that expands the liquid crystal phase of the composition, It is more preferable because it improves the compatibility and increases the solubility in a solvent.

A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, or naphthalene-2,6-diyl, and in this 1,4-phenylene and naphthalene-2,6-diyl, Hydrogen may be replaced by fluorine, chlorine, or an organic group having 1 to 5 carbon atoms.

Z ¹ is independently a single _{bond, -CH 2 CH 2 -, -} COO -, - OCO -, - CH 2 O -, - OCH 2 -, - OCH 2 CH 2 O -, - CH = CHCOO-, _{-OCOCH = CH -, - CH 2} CH 2 COO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 OCO-, or -COOCH ₂ CH ₂ - is. Since at least one of Z ¹ is —CH ₂ CH ₂ COO— or —OCOCH ₂ CH ₂ — improves compatibility with other liquid crystal compounds and enhances solubility in a solvent. preferable.

m and n are independently integers from 0 to 7, and the sum of m and n is from 4 to 8.
Y ¹ is independently a single bond, —O—, —COO—, —OCO—, or —OCOO—, and Q ¹ is independently a single bond or alkylene having 1 to 20 carbons, In alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—. It is more preferable that Q ¹ is alkylene having 1 to 20 carbon atoms because the liquid crystal phase of the composition is expanded, compatibility with other liquid crystal compounds is improved, and solubility in a solvent is increased.

  PG is a polymerizable group. There is no particular limitation on the application of PG to the host liquid crystal of the present invention. For example, groups represented by formula (PG-1) to formula (PG-9) can be exemplified as specific examples. At this time, it is preferable that the group is a radically polymerizable group (PG-1) for the purpose of increasing the reactivity, increasing the solubility in a solvent, and preventing the dye from fading.

In formula (PG-1) to formula (PG-9), R ¹ is independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl.

  Among the compounds represented by formula (1-1) to formula (1-3), when an anisotropic light conversion material is used, the dichroic ratio is improved, the liquid crystal phase of the composition is expanded, and other liquid crystalline compounds In order to improve the compatibility of the compound and increase the solubility in a solvent, the formula (1-1-1) to the formula (1-1-48), (1-2-1) to the formula (1-2-17) And compounds represented by formulas (1-3-1) to (1-3-18) are particularly preferred examples.

Formula (1-1-1) to Formula (1-1-48), Formula (1-1-1) to Formula (1-2-17), and Formula (1-3-1) to Formula (1- 3-18)
Y ¹ is independently a single bond, —O—, —COO—, —OCO—, or —OCOO—.
Q ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, and in the alkylene, at least one —CH ₂ — may be replaced by —O—, —COO— or —OCO—.
PG is independently any polymerizable group represented by formula (PG-1) to formula (PG-9).

  These compounds represented by formula (1) are “Organic Syntheses” (John Wiley & Sons, Inc), “Organic Reactions” (Organic Reactions, John Wiley & Sons, Inc), “Comprehensive”. It can be synthesized by combining books such as “Organic Synthesis” (Comprehensive Organic Synthesis, Pergamon Press), “New Experimental Chemistry Course” (Maruzen), and methods known to those skilled in the art.

≪Liquid crystal composition≫
The host liquid crystal of the present invention is preferably two or more kinds of compositions in order to broaden the liquid crystal phase and increase the solubility in a solvent for the purpose of preventing crystal precipitation during film formation. At this time, in order to improve the dichroic ratio of the anisotropic light conversion film of the present invention, all the compounds used in the composition are represented by the formulas (1-1-1) to (1-1-48), ( The compound represented by 1-1-1) to formula (1-2-17) or formula (1-3-1) to formula (1-3-18) is preferable.

Further, the host liquid crystal of the present invention is not limited to (1-1-1) formula (1-1-48) and formula (1-1-1-) unless the characteristics such as the dichroic ratio of the anisotropic light conversion film of the present invention are deteriorated. A known liquid crystal compound other than the compounds represented by formula (1-2-17) and formula (1-3-1) to formula (1-3-18) may be included.
In this case, as examples of the liquid crystal compound, from the viewpoint of high liquid crystallinity, solubility in a solvent, and ease of production, the compounds (1M-1-1) to (1M-1-19), formula (1M-2) A bicyclic or tricyclic compound represented by formulas (-1) to (1M-2-31) or formulas (1M-3-1) to (1M-3-8) is preferable.

Formulas (1M-1-1) to (1M-1-19), Formulas (1M-2-1) to (1M-2-31), and Formulas (1M-3-1) to (1M-3-8) in), R ^M is independently hydrogen or methyl, a is an integer from 1 to 12 independently.

Formulas (1M-1-1) to (1M-1-19), Formulas (1M-2-1) to (1M-2-31), and Formulas (1M-3-1) to (1M-3-8) ), A polymerizable liquid crystal composition to which a monofunctional compound is added can easily control the liquid crystal temperature range, optical characteristics, and orientation. In particular, a polymerizable liquid crystal composition having an increased amount of a monofunctional compound can have a high tilt angle and can easily obtain homeotropic alignment.

  Formulas (1M-1-1) to (1M-1-19), Formulas (1M-2-1) to (1M-2-31), and Formulas (1M-3-1) to (1M-3-8) ), When a polyfunctional compound is used in the composition, the polymer has a three-dimensional structure. As a result, the mechanical strength and / or chemical resistance of the liquid crystal polymer can be improved.

  In order to prevent a decrease in the dichroic ratio of the anisotropic light conversion material of the present invention, to improve the compatibility with other liquid crystal compounds in the composition, and to increase the solubility in a solvent, the formula in the polymerizable liquid crystal composition (1M-1-1) to (1M-1-19), formulas (1M-2-1) to (1M-2-31), and formulas (1M-3-1) to (1M-3-8) Is preferably 40% by weight or less, and more preferably 20% by weight or less.

In order to give the anisotropic light conversion material of the present invention a substantially parallel anisotropy with respect to the substrate plane in a certain region, a method using an alignment film is generally used. There is no restriction | limiting in particular in such an alignment film, A well-known material can be used. At this time, in order to increase the dichroism of the anisotropic light conversion material, it is preferable to use a polyimide-based alignment film. In order to obtain an anisotropic light conversion material that imparts a larger dichroic ratio or has a different anisotropic direction depending on the region, it is preferable to use a photo-alignment film.
An alignment film can also be used to give the anisotropic light conversion material of the present invention anisotropy between substantially vertical and substantially horizontal to substantially vertical with respect to the substrate plane in a certain region.

  In order to obtain substantially perpendicular anisotropic light conversion, a known additive that induces vertical alignment of liquid crystal may be added to the composition. From the standpoint of vertical alignment and availability, suitable examples of such additives include compounds (α-1) to (α-3) having a bisphenol structure or a cardo structure.

式（α−１）から（α−３）において、Ｒ^αは独立して水素またはメチルであり、ｓは独立して０から４の整数である。

In formulas (α-1) to (α-3), R ^α is independently hydrogen or methyl, and s is independently an integer from 0 to 4.

  The content of the additive that induces vertical alignment is preferably 0.005 or more and 0.1 or less by weight with respect to the solid content of the composition in order to suppress the provision of vertical alignment and decrease in liquid crystallinity.

  The anisotropic light conversion material of the present invention contains a guest having dichroism. Such guests include dyes and pigments. In addition, these guests may be dispersed on a molecular scale in the liquid crystal composition, or may be dispersed as light-absorbing particles. The light absorption region of these guests can be appropriately selected depending on the use of the anisotropic light conversion material of the present invention. For example, when the material of the present invention is used as a polarizing plate for an LCD, it is preferable to select a guest having a broad absorption spectrum with respect to the visible light wavelength range of 380 to 700 nm.

  As a guest having absorption in such a wide wavelength range, one type of guest having absorption in a wide wavelength range may be used, or a plurality of types of guests having absorption in a narrow wavelength range may be used in combination. When the latter is selected, it is preferable to use a mixture of all the guests in a single host liquid crystal in order to prevent the manufacturing process of the anisotropic light absorption layer from becoming complicated. However, if necessary, an anisotropic conversion layer having absorption in a wide band may be obtained by mixing a plurality of guests with the host liquid crystal and laminating the obtained composition.

  In the anisotropic light conversion material of the present invention, in order to increase the dichroic ratio, it is preferable to select a dichroic dye as a guest having dichroism. As the dichroic dye at this time, an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, an anthraquinone dye, or the like can be used as a dichroic dye. Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, and a stilbene azo dye.

  In the anisotropic light conversion material of the present invention, a material that emits light having anisotropy can be obtained by adding a fluorescent or phosphorescent guest in addition to the light-absorbing guest.

  In order to increase the dichroism of the anisotropic light conversion material of the present invention, it is preferable to select a guest having a liquid crystal property. However, guests other than those having such characteristics can also be applied to the present invention. A dichroic guest can be applied to the present invention with or without polymerizability. However, when selecting a non-polymerizable guest, the concentration distribution of the guest in the material may change over time, and in order to prevent deterioration of the material properties due to this change, use of a dichroic guest having a polymerizable group Is preferred.

  In the anisotropic light conversion material of the present invention, the total amount of the dichroic guest can be arbitrarily selected within the range of 0.1 wt% to 50 wt% with respect to the total weight of the liquid crystal host. For example, when used for a polarizing plate of a display such as a normal LCD, in order to maintain a high dichroic ratio and sufficiently suppress the generation of unnecessary linearly polarized light, the total amount of dichroic guests is The range of 1% to 20% by weight is preferable, and the range of 1% to 10% by weight is more preferable.

  The anisotropic light conversion material of the present invention can be used by applying it on, for example, triacetyl cellulose or an acrylic film, and then attaching the film to an element such as an LCD or an organic EL. However, in order to reduce the thickness of the entire device, the anisotropic light conversion material of the present invention is preferably applied directly to the substrate of the device. In this case, the anisotropic light conversion material of the present invention may be installed on the outer side or the inner side of the substrate in accordance with the required characteristics.

≪Additives≫
The host liquid crystal composition used in the anisotropic light conversion material of the present invention may contain compounds other than those described above for the purpose of improving coating properties, storage stability, photoreactivity and the like.

For example, in order to improve the smoothness of the anisotropic light conversion material of the present invention, a surfactant is preferably added to the polymerizable liquid crystal composition. Surfactants include ionic surfactants and nonionic surfactants such as silicone, fluorine, vinyl, and hydrocarbon.
Addition of a nonionic surfactant to the composition further improves the smoothness of the liquid crystal polymer. The nonionic surfactant has an effect of suppressing tilt alignment on the air interface side of the liquid crystal polymer. Etc. are nonionic surfactants.
At this time, it is preferable to use a surfactant having a polymerizable group for the purpose of avoiding so-called bleed out. Further, from the viewpoint of reactivity with the polymerizable liquid crystal compound, it is more preferable to use a surfactant that is polymerized with ultraviolet rays.
In order to improve the coating property of the composition and obtain a uniformly oriented liquid crystal polymer, the amount of the surfactant in the composition is preferably 0.0001 to 0.1% by weight with respect to the total weight of the composition, More preferred is 0.0001 to 0.005% by weight.

  As ionic surfactants, titanate compounds, imidazolines, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and its esters, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate Amines, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropylbetaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamine, A fluoroalkyl sulfonate, a perfluoroalkyl carboxylate, etc. are mentioned.

  As will be described later, the anisotropic light conversion material of the present invention is obtained by directly applying a mixture of a host liquid crystal (polymerizable liquid crystal) represented by the general formula (1) and a dichroic dye on an alignment film, and exposing or heating it. Desired optical characteristics can be obtained by reacting a polymerizable group to form an immobilized film. Preferable examples of such a polymerization initiator include the following photo radical initiators.

  For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benz Phenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1- [ 4- (Methylthio) pheny ] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine mixture, Adekaoptomer N-1919, Adeka Cruz NCI-831, Adeka Cruz NCI-930, IRGACURE 127, IRGACURE 369, IRGACURE 379, IRGACURE 500, IRGACURE 754, IRGACURE 784, IRGACURE 754, IRGACURE 819, IRGACURE 907, IRGACURE 1300, IRGACURE 1700, IRGACURE 1800, IRGACURE 1850, IRGACURE 1870, IRGACURE 2959, IRGACURE OXE01, IRGACURE OXE02, DAROCURE 4265, DA Cure MBF, and the like Darocure TPO. Here, ADEKA, Irgacure and Darocur are registered trademarks.

  In the anisotropic light conversion material of the present invention, in order to develop a high dichroic ratio, the total content of the photo radical polymerization initiator in the polymerizable liquid crystal composition is 0. 0 by weight with respect to the solid content in the composition. 0001 to 0.20 is preferable, 0.001 to 0.15 is more preferable, and 0.01 to 0.15 is still more preferable.

  For the purpose of improving photoreactivity, a sensitizer may be added to the polymerizable liquid crystal composition together with the polymerization initiator. Examples of the sensitizer include isopropylthioxanthone, diethylthioxanthone, ethyl-4dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate and the like.

  In order to adjust the hardness of the anisotropic light conversion material of the present invention, there is a method of controlling the reaction rate of the liquid crystal polymer. For this purpose, a chain transfer agent may be added to the polymerizable liquid crystal composition. The reaction rate of the polymerizable liquid crystal composition decreases with an increase in the amount of the chain transfer agent. As such a chain transfer agent, a thiol derivative and a styrene dimer derivative are preferable.

In order to improve the storage stability of the polymerizable liquid crystal composition, a polymerization inhibitor may be added to the composition.
(1) 2,5-di (t-butyl) hydroxytoluene, hydroquinone, methylene blue, diphenylpicric acid hydrazide, phenothiazine, N, N-dimethyl-4-nitrosoaniline as a polymerization inhibitor And (2) o-hydroxybenzophenone which is a benzothiazine derivative, 2H-1,3-benzothiazine-2,4- (3H) dione, and the like. For the same purpose, a polymerization inhibitor may be added.
Examples of the polymerization inhibitor include (1) phenol-based antioxidant, (2) sulfur-based antioxidant, and (3) phosphoric acid-based antioxidant.

  In order to improve the weather resistance of the anisotropic light conversion material of the present invention, an ultraviolet absorber, a light stabilizer, and / or an antioxidant may be added to the polymerizable liquid crystal composition.

  The composition containing a polymerizable liquid crystal and a dichroic dye is preferably used after being dissolved in a solvent in order to facilitate coating.

  As components of the solvent, esters, amide compounds, alcohols, ethers, glycol monoalkyl ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, alicyclic hydrocarbons, Examples include ketones and acetate solvents.

  The amide compound is a compound having an amide group and serving as a solvent component. An acetate solvent refers to a compound having an acetate structure and serving as a solvent component.

  Examples of the ester include alkyl acetate, ethyl trifluoroacetate, alkyl propionate, alkyl butyrate, dialkyl malonate, alkyl glycolate, alkyl lactate, monoacetin, γ-butyrolactone, and γ-valerolactone.

  As used herein, “alkyl acetate” includes methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, and the like. As used herein, “alkyl propionate” includes methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate, butyl propionate, and the like. As used herein, “alkyl butyrate” includes methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, propyl butyrate and the like. As used herein, “dialkyl malonate” includes diethyl malonate and the like. As used herein, “alkyl glycolate” includes methyl glycolate, ethyl glycolate, and the like. As used herein, “alkyl lactate” includes methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate, ethyl hexyl lactate and the like.

  Examples of the amide compounds include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylacetamidodimethylacetal, N-methylcaprolactam, dimethylimidazolidinone and the like can be mentioned.

  Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, n-hexanol, n-heptanol, n -Octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-amyl alcohol, hexafluoro-2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, di Propylene glycol, tripropylene glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanedi Lumpur, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol, and the like methylcyclohexanol.

  As the ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane, THF and the like are preferable.

  As the glycol monoalkyl ether, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate , Triethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether acetate, diethylene glycol methyl ethyl ether, and the like.

As used herein, “ethylene glycol monoalkyl ether” includes ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and the like. As used herein, “diethylene glycol monoalkyl ether” includes diethylene glycol monoethyl ether and the like. As used herein, “propylene glycol monoalkyl ether” includes propylene glycol monobutyl ether and the like. As used herein, “dipropylene glycol monoalkyl ether” includes dipropylene glycol monomethyl ether and the like. As used herein, “ethylene glycol monoalkyl ether acetate” includes ethylene glycol monobutyl ether acetate and the like. As used herein, “diethylene glycol monoalkyl ether acetate” includes diethylene glycol monoethyl ether acetate and the like. As used herein, “propylene glycol monoalkyl ether acetate” includes propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and the like. As used herein, “dipropylene glycol monoalkyl ether acetate” includes dipropylene glycol monomethyl ether acetate.

Examples of the aromatic hydrocarbon include benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, tetralin and the like.

Examples of the halogenated aromatic hydrocarbon include chlorobenzene. Examples of the aliphatic hydrocarbon include hexane and heptane. Examples of halogenated aliphatic hydrocarbons include roloform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, and tetrachloroethylene. Examples of the alicyclic hydrocarbon include cyclohexane and decalin.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and methyl propyl ketone.

Examples of acetate solvents include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, 1-methoxy-2-propyl acetate and the like.

  The solvent in the polymerizable liquid crystal composition is preferably 30 to 96% by weight, more preferably 50 to 90% by weight, and still more preferably 60 to 80% by weight.

  The anisotropic light conversion material of the present invention may contain a compound having optical activity. This induces twist alignment of the liquid crystal polymer.

  Examples of the optically active compound include compounds having an asymmetric carbon, axial asymmetric compounds having a binaphthyl structure and a helicene structure, and surface asymmetric compounds having a cyclophane structure. From the viewpoint of fixing the twisted helical pitch, the compound having optical activity in this case is preferably a polymerizable compound.

≪Alignment film≫
In order to impart anisotropy to the anisotropic light conversion material of the present invention, an alignment film can be used. The alignment film has a role of defining the orientation of the host liquid crystal in the azimuth angle and / or polar angle direction with respect to the substrate plane. As such an alignment film, all known types of alignment films can be used. However, in order to increase the dichroic ratio of the anisotropic light conversion material of the present invention, it is preferable to use a photo-alignment film that can impart uniform alignment to the liquid crystal. Furthermore, for the same reason, it is more preferable to use a polyimide photo-alignment film.

Specific examples of such a photo-alignment film include Japanese Patent Publication No. 4620438, Japanese Patent Publication No. 4775796, Japanese Patent Publication No. 5034977, Japanese Patent Publication No. 5156894, Japanese Patent Publication No. 5487394, Japanese Patent Publication No. 5407394, Japanese Patent Publication No. 5671797, Japanese Patent Laid-Open No. 2012. -155311, JP2012-193167, WO2013-157463, JP2013-200511, JP2013-235130, WO2013-161569, JP2014-205659, JP2014-205819, JP2015-040950, JP2015. -212807, Japanese Patent Publication No. 4504665, WO2010-050523, WO2010-104082, WO2013-039168, WO2013-081067
The materials described in (1) are preferably used.

≪Base material≫
Examples of the material of the substrate of the element having the anisotropic light control layer of the present invention include glass, plastic, and metal. The glass or metal may be slit-like processed on the surface. The plastic may be subjected to a surface treatment such as a stretching treatment and a hydrophilic treatment and a hydrophobic treatment.

<< Preparation of Anisotropic Light Conversion Material >> The anisotropic light control material of the present invention is obtained, for example, in the following steps.

(I) Formation of Alignment Film An alignment film is formed on the substrate by the known method described above.
(II) Formation of anisotropic light conversion material layer (II-1) A solution of a composition for anisotropic light conversion material to be used as a host liquid crystal represented by formula (1) is applied on the alignment film prepared in (I). And dried to form a coating film.
(II-2) For the pretreatment for obtaining uniform alignment, the coating film formed in (II-1) is heated to a temperature at which the liquid crystal phase is exhibited, if necessary.
(II-3) The coating film is exposed to a temperature lower than the temperature at which the liquid crystal phase is exhibited.
(II-4) In order to further improve the adhesion with the alignment film, heating is performed as necessary to a temperature at which the performance of the anisotropic light conversion material can be allowed to be lowered.

  In the step (II-1), the coating method of the composition for anisotropic light conversion material is not limited, and various coating methods are used. At this time, from the viewpoint of the film thickness and its uniformity, the coating methods include spin coating method, micro gravure coating method, gravure coating method, wire bar coating method, dip coating method, spray coating method, meniscus coating method and die coating method. preferable.

  In each step (II), the heating and drying methods that can be used can be the same methods as described in step (I). Moreover, the exposure method in the process of (II-3) can also use the method similar to the description in process (I). However, non-polarized light is preferably used rather than linearly polarized light from the viewpoint of light utilization efficiency.

  In the step (II-3), there is no limitation on the temperature and time when the coating film is kept below the temperature at which the liquid crystal phase is exhibited. However, in order to increase the dichroic ratio, it is preferable to hold at a low temperature for a long time as long as the orientation of the composition is not impaired by precipitation of crystals or the like.

The invention is not limited to the published examples.
In the examples of the present invention, “room temperature” is 25 ° C.
In the examples of the present invention, the “glass substrate” is EagleXG manufactured by Corning.

In the examples of the present invention, “DMAP” is N, N-dimethyl-4-aminopyridine.
In the examples of the present invention, “DCC” is N, N′-dicyclohexylcarbodiimide.
In the examples of the present invention, “THF” is tetrahydrofuran.

In the examples of the present invention, “NMP” is 1-methyl-2-pyrrolidone.
In the examples of the present invention, “BC” is ethylene glycol monobutyl ether.
In the examples of the present invention, “GBL” is γ-butyrolactone.
In the examples of the present invention, “IPA” is 2-propanol.

<Determination of compound>
The synthesized compound was determined by ¹ H-NMR. At that time, the compound to be analyzed was dissolved in CDCl ₃ and the value of δ was expressed in units of ppm.

In the examples of the present invention, “standard polystyrene” is TSK standard polystyrene manufactured by Tosoh Corporation.
In an embodiment of the present invention, “GPC” is a system consisting of a Waters 2695 separation module and a Waters 2414 differential refractometer.
In the examples of the present invention, the “viscosity meter” is TV-22 manufactured by Toki Sangyo Co., Ltd.
In the embodiment of the present invention, the “step meter” is an alpha step IQ manufactured by KLA TENCOR.

In the embodiment of the present invention, the “light alignment light source device” is model number APL-L01212S1-ASN01 manufactured by USHIO INC.
In an embodiment of the present invention, the “ultra-high pressure mercury lamp” is a multilight-250 manufactured by USHIO INC. Having an output of 250 W.
In the examples of the present invention, the “ultraviolet / visible absorption spectrum measuring apparatus” is JASCO V-650 manufactured by JASCO Corporation.
In an embodiment of the present invention, the “differential scanning calorimeter” is a Diamond DSC manufactured by Perkin Elmer.

<Measurement of molecular weight of polyamic acid>
The weight average molecular weight was measured by GPC in comparison with standard polystyrene. The column was HSPgel RT MB-M manufactured by Waters.
A product obtained by dissolving the analyte in the phosphoric acid-DMF mixed solution so as to be 2% by weight was developed by GPC under conditions of a column temperature of 50 ° C. and a flow rate of 0.40 ml / min. The weight ratio of the phosphoric acid-DMF mixed solution was 0.6 / 100. The developing agent was the phosphoric acid-DMF mixed solution.

<Measurement of viscosity of polyamic acid>
The viscosity was measured with a viscometer at 25 ° C.

<Exposure conditions>
The exposure for forming the alignment film was performed with a light alignment light source device.
The exposure for preparing the liquid crystal polymer film was performed with an ultrahigh pressure mercury lamp.

<Film thickness measurement>
The film thickness of the alignment film was measured with an optical film thickness measurement system.
The film thickness of the liquid crystal polymer film having a glass substrate was measured by the following procedure.
(1) A liquid crystal polymer film is cut out from a glass substrate having a liquid crystal polymer film,
(2) Measure the level difference between the part having the liquid crystal polymer film and the part excluding the liquid crystal polymer film,
(3) The measured value was taken as the film thickness.
In the Example of this invention, the level | step difference of the part of a liquid crystal polymer film was measured with the level difference meter.

<Confirmation of alignment defects>
The presence or absence of alignment defects was determined by sandwiching a liquid crystal polymer film with a substrate between two polarizing plates arranged in crossed Nicols. The substrate was rotated in a horizontal plane, and the bright and dark state was visually confirmed. “There was no alignment defect” when there was no spot where light could be seen in the dark state and both the bright state and the dark state could be confirmed.

<Measurement of phase transition temperature>
Measurement was performed using a differential scanning calorimeter (DSC). The transition temperature was measured while increasing the temperature at a rate of 5 ° C./min.

<Measurement of dichroic ratio>
Using an ultraviolet / visible absorption spectrum measurement device, using linearly polarized light as a light source, and measuring the transmittance when the polarization axis of the linearly polarized light is perpendicular and parallel to the anisotropic axis of the material, the ratio of the former to the latter To obtain a measured dichroic ratio. The dichroic ratio was measured at 25 ° C. In order to eliminate the influence of film interference, the measured dichroic ratio at each absorption wavelength for every 1 nm was averaged to obtain the dichroic ratio.

<Polymerizable liquid crystal compound>
In the examples of the present invention, compound (1-1-3-1), compound (1-1-8-1), compound (1-1-9-1), compound (1-1-11-1) , Compound (1-1-17-1), Compound (1-1-18-1), Compound (1-1-19-1), Compound (1-1-35-1), and Compound (1- 2-1-1) is a polymerizable liquid crystal compound represented by the following formula.

  The compound (1M-2-7-1) obtained a commercially available compound. Compound (1M-1-19-1) and compound (1M-2-31-1) were synthesized according to Chem. Mater., 20, 6076 (2008).

Compound (1-1-3-1) was synthesized according to the following procedure.

<Synthesis of Compound (1-1-3-1)>
42.9 g of 4-acetoxybenzoic acid and 0.2 g of pyridine were added to 430 mL of toluene and stirred at 60 ° C. under a nitrogen atmosphere. Thereto, 34.0 g of thionyl chloride was added dropwise. After dropping, the mixture was stirred at 60 ° C. for 4 hours. Toluene was distilled off under reduced pressure. The obtained residue was added to 230 mL of toluene and stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise a toluene solution in which 20.0 g of methyl 2,5-dihydroxybenzoate, 200 mL of 33.7 g of triethylamine was dissolved. After dropping, the mixture was stirred at room temperature for 4 hours. Water was added to the stirred solution, and the organic layer was extracted. The organic layer was then washed with water and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, the residue was purified by column chromatography, and recrystallized with an eluent to obtain 42.9 g of compound (ex-1). Here, the packing material for column chromatography is silica gel. Here, the eluent is a mixture of toluene and ethyl acetate = 9/1 (volume ratio).

  42.9 g of compound ex-1 and 14 mL of 28 wt% aqueous ammonium solution were added to a mixed solution of 86 mL of THF and 43 mL of methanol and stirred at room temperature under a hydrogen atmosphere for 4 hours. Ethyl acetate and saturated brine were added to the reaction solution, and the organic layer was extracted. Next, the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and recrystallization was performed with a mixture of ethyl acetate and heptane = 10/1 (volume ratio) to obtain 24.2 g of compound (ex-2).

  Compound (ex-3) is Journal of Polymer Science, Part A; Polymer Chemistry, 2011.49 (3). 770-780. It was synthesized by the method described in 1.

  12.0 g of compound (ex-2), 18.0 g of compound (ex-3) and 1.5 g of DMAP were added to 180 mL of dichloromethane, and the mixture was stirred while cooling to 5 ° C. in an ice bath under a nitrogen atmosphere. did. Thereto was added dropwise a 26 mL dichloromethane solution in which 13.0 g DCC was dissolved. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was filtered off, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from methanol to obtain 22.7 g of the compound (1-1-3-1). Here, the packing material for column chromatography is silica gel. Here, the eluent is a mixture of toluene and ethyl acetate = 14/1 (volume ratio).

The transition temperature from the crystal phase of compound (1-1-3-1) to the nematic phase was 103 ° C. The transition temperature from the nematic phase of compound (1-1-3-1) to the isotropic liquid could not be confirmed at 250 ° C. or lower.
The ¹ H-NMR signal of the compound (1-1-3-1) was as follows: 8.31 (d, 2H), 8.28 (d, 2H), 8.17 (d, 4H) ), 7.96 (s, 1H), 7.51 (d, 1H), 7.40 (d, 4H), 7.33 (d, 1H), 6.99 (d, 4H), 6.41 (D, 2H), 6.16-6.08 (m, 2H), 5.83 (d, 2H), 4.19 (t, 4H), 4.05 (t, 4H), 3.78 ( s, 3H), 1.88-1.81 (m, 4H), 1.77-1.70 (m, 4H), 1.58-1.44 (m, 8H).

<Synthesis of Compound (1-1-8-1) and Compound (1-1-9-1)>
Compound (1-1-8-1) and compound (1-1-9-1), which are components of the polymerizable liquid crystal composition, were synthesized according to WO2015-147243 and JP2008-239567, respectively.

<Synthesis of Compound (1-1-11-1)>
Compound (1-1-11-1) was synthesized according to the following procedure.

Compound (ex-4) was synthesized by the method described in Example 5 of JP-A-2006-047813.
12.0 g of compound (ex-2), 19.3 g of compound (ex-4) and 1.5 g of DMAP were added to 180 mL of dichloromethane, and the mixture was stirred while being cooled to 5 ° C. with an ice bath under a nitrogen atmosphere. did. There, it was dripped at the 26 mL dichloromethane solution in which 13.0 g DCC was dissolved. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was filtered off, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from methanol to obtain 19.7 g of the compound (1-1-11-1). Here, the packing material for column chromatography is silica gel. Here, the eluent is a mixture of toluene and ethyl acetate = 14/1 (volume ratio).

The transition temperature from the crystal phase to the nematic phase of the compound (1-1-11-1) was 98 ° C. The transition temperature from the nematic phase to the isotropic liquid was 147 ° C.
The ¹ H-NMR signal of the compound (1-1-3-1) was as follows: 8.24 (d, 2H), 8.22 (d, 2H), 7.93 (s, 1H) ), 7.48 (d, 1H), 7.29 (d, 1H), 7.21-7.16 (m, 8H), 6.86 (d, 4H), 6.41 (d, 2H) 6.16-6.08 (m, 2H), 5.83 (d, 2H), 4.17 (t, 4H), 3.96 (t, 4H), 3.76 (s, 3H), 3.04 (s, 4H), 2.90 (t, 3H), 1.84-1.77 (m, 4H), 1.75-1.69 (m, 4H), 1.56-1. 42 (m, 8H).

<Synthesis of Compound (1-1-17-1)>
Compound (1-1-17-1) was synthesized according to the following procedure.

Compound (ex-5) was synthesized by the method described in Example 5 of JP-A-2006-047813.
50.0 g of compound (ex-5), 6.8 g of methylhydroquinone and 2.7 DMAP were added to 450 mL of dichloromethane and stirred while cooling under a nitrogen atmosphere. Thereto, 50 mL of a dichloromethane solution in which 24.3 g of DCC was dissolved was dropped. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was filtered off, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from methanol to obtain 47.5 g of the compound (1-1-17-1). Here, the packing material for column chromatography is silica gel, and the eluent is a toluene-ethyl acetate mixture = 9/1 (volume ratio).

The transition temperature from the crystalline phase of the compound (1-1-17-1) to the nematic phase was 114 ° C. The transition temperature from the nematic phase to the isotropic liquid of the compound (1-1-17-1) was 134 ° C.
The ¹ H-NMR signal of the compound (1-1-17-1) was as follows: 7.10 (d, 4H), 6.98-6.78 (m, 3H), 6.81 (D, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.80-4.72 (m, 2H), 4.17 (t, 4H), 3.93 (t, 4H), 2.89 (t, 4H), 2.61-2.48 (m, 6H), 2.21-2.11 (m, 7H), 2.09-2.01 (m, 4H), 1.83-1.63 (m, 12H), 1.55-1.37 (m, 12H).

<Synthesis of Compound (1-1-18-1)>
In the synthesis of compound (1-1-17-1), 2 ′, 5′-dihydroxyacetophenone was used in place of methylhydroquinone to synthesize compound (1-1-18-1).
The transition temperature from the crystal phase of the compound (1-1-18-1) to the nematic phase was 67 ° C. The transition temperature from the nematic phase to the isotropic liquid of the compound (1-1-18-1) was 104 ° C.
The ¹ H-NMR signal of the compound (1-1-18-1) was as follows: 7.48 (d, 1H), 7.25-7.22 (m, 1H), 7.10. (D, 4H), 7.07 (d, 1H), 6.82 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 ( d, 2H), 4.79-4.73 (m, 2H), 4.17 (t, 4H), 3.93 (t, 4H), 2.89 (t, 4H), 2.61-2 .51 (m, 9H), 2.24-2.15 (m, 4H), 2.09-2.04 (m, 4H), 1.82-1.66 (m, 12H), 1.55 -1.38 (m, 12H).

<Synthesis of Compound (1-1-19-1)>
In the synthesis of compound (1-1-17-1), compound (1-1-19-1) was synthesized using methyl 2,5-dihydroxybenzoate instead of methylhydroquinone.

The transition temperature from the crystal phase of the compound (1-1-19-1) to the nematic phase was 61 ° C. The transition temperature from the nematic phase to the isotropic liquid of the compound (1-1-19-1) was 100 ° C.
The ¹ H-NMR signal of the compound (1-1-19-1) was as follows: 7.70 (d, 1H), 7.28-7.24 (m, 1H), 7.11 (D, 4H), 7.06 (d, 1H), 6.82 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 ( d, 2H), 4.80-4.73 (m, 2H), 4.17 (t, 4H), 3.93 (t, 4H), 3.84 (s, 3H), 2.89 (t , 4H), 2.63-2.51 (m, 6H), 2.26-2.14 (m, 4H), 2.10-2.04 (m, 4H), 1.82-1.65. (M, 12H), 1.54-1.38 (m, 12H).

<Synthesis of Compound (1-1-35-1)>
Compound (1-1-35-1) was synthesized according to the following procedure.

Compound (ex-6) was obtained from ACS. Medicinal. Chemistry. Letters., 2011. 1 (7). 345-349. It was synthesized by the method described in 1.
68.1 g of compound (ex-6), 21.8 g of methyl 2,5-dihydroxybenzoate and 6.5 g of DMAP were added to 560 mL of dichloromethane, and cooled to 5 ° C. in an ice bath under a nitrogen atmosphere. Stir. There, it was dripped at the 120 mL dichloromethane solution in which 57.6 g DCC was dissolved. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was filtered off, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from methanol to obtain 74.5 g of the compound (ex-7). Here, the packing material for column chromatography is silica gel. Here, the eluent is a mixture of toluene and ethyl acetate v / v = 20/1.

  74.5 g of the compound (ex-7) and 3.7 g of palladium carbon were added to 745 mL of THF, and the mixture was stirred at room temperature for 24 hours under a hydrogen atmosphere. Insoluble matter was filtered off, THF was distilled off under reduced pressure, and the residue was dried under reduced pressure to obtain 53.0 g of compound (ex-8).

  12.9 g of compound (ex-3), 10.0 g of compound (ex-8) and 1.1 g of DMAP are added to 110 mL of dichloromethane, and the mixture is stirred while being cooled to 5 ° C. with an ice bath under a nitrogen atmosphere. did. There, it was dripped at the 20 mL dichloromethane solution in which 9.6g DCC was dissolved. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was filtered off, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from methanol to obtain 8.8 g of the compound (1-1-35-1). Here, the packing material for column chromatography is silica gel. Here, the eluent is a mixture of toluene and ethyl acetate = 9/1 (volume ratio).

The transition temperature from the crystal phase of compound (1-1-35-1) to the nematic phase was 83 ° C. The transition temperature from the nematic phase to the isotropic liquid of the compound (1-1-35-1) was polymerized at around 140 ° C. and could not be confirmed.
The ¹ H-NMR signal of the compound (1-1-35-1) was as follows: 8.14 (d, 4H), 7.71 (s, 1H), 7.33 (d, 2H) ), 7.31 (d, 2H), 7.23 (d, 1H), 7.18-7.14 (m, 4H), 7.04 (d, 1H), 6.97 (d, 4H) , 6.41 (d, 2H), 6.16-6.08 (m, 2H), 5.83 (d, 2H), 4.19 (t, 4H), 4.05 (t, 4H), 3.82 (s, 3H), 3.14-3.07 (m, 4H), 2.97 (t, 2H), 2.91 (t, 2H), 1.88-1.81 (m, 4H), 1.77-1.69 (m, 4H), 1.58-1.44 (m, 8H).

<Synthesis of Compound (1-2-1-1)>
Compound (1-2-1-1) was synthesized by the following procedure.

  5.0 g of compound (ex-6), 2.0 g of 2,7-dihydroxy-9-methylfluorene and 0.5 g of DMAP were added to 50 mL of dichloromethane and stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise a 10 mL dichloromethane solution in which 4.2 g of DCC was dissolved. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was filtered off, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from methanol to obtain 5.6 g of compound (ex-9). Here, the packing material for column chromatography is silica gel. Here, the eluent is toluene-ethyl acetate mixture = 14/1 (volume ratio).

  5.6 g of compound (ex-9) and 0.3 g of palladium carbon were added to 56 mL of THF, and the mixture was stirred at room temperature for 24 hours under a hydrogen atmosphere. Insoluble matter was filtered off, THF was distilled off under reduced pressure, and dried under reduced pressure to obtain 3.8 g of compound (ex-10).

  3.8 g of compound (ex-10), 4.5 g of compound (ex-3) and 0.4 g of DMAP were added to 40 mL of dichloromethane and stirred while cooling under a nitrogen atmosphere. Thereto, 7 mL of a dichloromethane solution in which 3.3 g of DCC was dissolved was dropped. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was filtered off, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from methanol to obtain 5.6 g of compound (1-2-1-1). Here, the packing material for column chromatography is silica gel. Here, the eluent is toluene-ethyl acetate mixture = 14/1 (volume ratio).

The transition temperature from the crystal phase of compound (1-2-1-1) to the nematic phase was 111 ° C. The transition temperature from the nematic phase to the isotropic liquid could not be confirmed below 250 ° C.
The ¹ H-NMR signal of the compound (1-2-1-1) was as follows: 8.15 (d, 4H), 7.67 (d, 2H), 7.34 (d, 4H) ), 7.17 (d, 6H), 7.01 (d, 2H), 6.97 (d, 4H), 6.41 (d, 2H), 6.16-6.08 (m, 2H) , 5.83 (d, 2H), 4.18 (t, 4H), 4.05 (t, 4H), 3.96-3.90 (m, 2H), 3.12 (t, 4H), 2.93 (t, 4H), 1.88-1.81 (m, 4H), 1.77-1.70 (m, 4H), 1.58-1.44 (m, 11H).

<Dichroic dye>
In Examples of the present invention, “G-205” is an azo dye manufactured by Hayashibara Co., Ltd., and was used as a guest having dichroism.
In Examples of the present invention, “G-241” is an azo dye manufactured by Hayashibara Co., Ltd., and was used as a guest having dichroism.
In the examples of the present invention, “LSB-278” is an anthraquinone dye manufactured by Hayashibara Co., Ltd. and used as a guest having dichroism.

<Photopolymerization initiator, surfactant>
In the examples of the present invention, “Irg-907”, “Irg-184”, and “Irg-TPO” are Irgacure ™ 907, Irgacure ™ 184, manufactured by BASF Japan, respectively. Irgacure ™ TPO.
In the examples of the present invention, “NCI-930” is Adeka Cruz ™ NCI-930 manufactured by ADEKA Corporation.
In the examples of the present invention, “FTX-218” is Footage ™ FTX-218 manufactured by Neos Co., Ltd.
In the example of the present invention, “TEGOFlow 370” is TEGOFlow (trademark) 370 manufactured by Evonik Japan.

In the examples of the present invention, the following materials were used as the alignment film of the composition for anisotropic light conversion material.

In the compound (DA-5), “Boc” means —CO—C (CH ₃ ) ₃ which is a functional group.
Compound (DA-1), compound (DA-2), and compound (DA-4) purchased from Wako Pure Chemical Industries, Ltd. were used. The compound (DA-3) and the compound (DA-5) were synthesized according to Japanese Patent Publication Nos. 5643985 and WO2013 / 039168, respectively.

In the examples of the present invention, compound (AA-1) to compound (AA-3) and compound (AE-1) are compounds represented by the following formulae.

Compound (AA-2) and compound (AA-3) purchased from Tokyo Chemical Industry Co., Ltd. were used. Compound (AA-1) was synthesized according to Japanese Patent Publication No. 5407394. Compound (AE-1) was synthesized according to WO2013 / 039168.

<Preparation of photo-alignment agent>
In the same manner as described in JP 2010-197999 A (Synthesis Example 4), a diamine (DA-1) 1 was added to a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet. 0.0292 g and 17.4 ml of dehydrated NMP were added and dissolved under stirring in a nitrogen stream. Next, 1.9708 g of acid dianhydride (AA-1) and 10 ml of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. BC20.8ml was added to this reaction solution, and this solution was stirred at 75 degreeC for 8 hours, and the polyamic acid solution (PA-1) was obtained. The polymer solid content concentration of PA-1 is 6% by weight. In addition, since 1.0292 g of compound (DA-1) and 1.9708 g of compound (AA-1) are equimolar amounts, 1.0292 g of compound (DA-1) and 1.9708 g of compound (AA-1) The molar fraction is 0.5 and 0.5, respectively.

  Among the preparation procedures of the polyamic acid solution (PA-1), by changing the name of the diamine and its mole fraction and the name of the acid dianhydride and its mole fraction to those described in Table 1, the polyamic acid solution (PA -2) and a polyamic acid solution (PA-3) were obtained. Their polymer solids concentration is 6% by weight. Table 1 shows the viscosity of the polyamic acid solution and the weight average molecular weight of the polyamic acid. Hereinafter, the polyamic acid solution (PA-1) to the polyamic acid solution (PA-3) are collectively referred to as a polyamic acid solution.

<Preparation of polyamic acid ester solution (PAE-1)>
In the same manner as in Synthesis Example 7 and Synthesis Example 8 described in International Publication No. 2013/039168, 2.80 g of Compound (DA-4) and 1.45 g of Compound (DA-5 were added to a 100 ml four-necked flask. ), 6.18 g of pyridine, and 110 ml of NMP. To this mixture was slowly added 9.89 g of compound (AE-1) on an ice bath, and the mixture was stirred overnight at room temperature. Thereafter, 0.38 g of acryloyl chloride was added and reacted at room temperature for 5 hours. Thereafter, the obtained solution was added to 1.2 L of pure water, and the precipitated white precipitate was filtered, washed with 1.2 L of IPA three times, and finally dried under vacuum. The obtained solid was 9.5 g (yield 77%). The solid had a weight average molecular weight of 32,000.
To 1.00 g of the solid, 19.0 g of GBL was added and stirred at room temperature for 30 minutes to dissolve. To this solution was added 0.35 g N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl L-histidine, and 5.0 g BC to give an approximately 5.6 wt% solution. And named as polyamic acid ester solution (PAE-1).

<Preparation of polyacrylic acid ester / itaconic acid ester solution (J)>
In the same manner as described in Example 9 of JP2012-087286, a polymer represented by the formula (J) was synthesized, and a solution prepared by the method was used as a polyacrylate ester / itaconate ester solution (J). I named it.

式（Ｊ）においてｘは０．１であり、重量平均分子量Ｍｗは５３，７００であった。

In the formula (J), x was 0.1 and the weight average molecular weight Mw was 53,700.

[Example 1]
<Formation of alignment film>
PA-1 and PA-2 were weighed out to 3.0 g and 7.0 g, respectively, and NMP 5.0 g was added. About 4% by weight of this solution was spin-coated on a glass substrate at a rotational speed of 2000 rpm, and the solvent was evaporated on a hot plate at 80 ° C. for 1 minute to prepare a coating film. This coating film was irradiated with linearly polarized light having a wavelength of 365 nm from a direction of 90 degrees with respect to the coating surface so that the exposure amount to the coating film was ² J / cm ² . Thereafter, it was baked in an oven at 220 ° C. for 10 minutes to obtain a photo-alignment film having a film thickness of about 100 nm, and was named photo-alignment film (AF-1).

  In the preparation process of the photo-alignment film (AF-1), instead of weighing 3.0 g and 7.0 g of PA-1 and PA-2, respectively, 3.0 g and 7. A photoalignment film having a thickness of about 100 nm was obtained by weighing out 0 g, and was named photoalignment film (AF-1).

A solution of about 4% by weight prepared by adding 5.0 g of NMP to PAE-1 was spin-coated on a glass substrate at a rotational speed of 2500 rpm, and the solvent was evaporated on a hot plate at 80 ° C. for 1 minute, and then 220 ° C. Was baked in an oven for 10 minutes to prepare a coating film. This coating film was irradiated with linearly polarized light having a wavelength of 254 nm from a direction of 90 degrees with respect to the coating surface so that the exposure amount to the coating film was 1 J / cm ² . Then, after immersing in an ethyl lactate solution at room temperature for 3 minutes, rinsing with IPA for 1 minute and drying in an oven at 80 ° C. for 10 minutes to obtain a photo-alignment film having a film thickness of about 100 nm. ).

Further, 1 part by weight of the polymer represented by the formula (J) is dissolved in 19 parts by weight of cyclopentanone and filtered through a filter having a pore size of 0.2 μm to obtain a photo-alignment agent. -J). This photo-alignment agent (PA-J) was spin-coated on glass at a rotation speed of 1800 rpm to prepare a coating film. Thereafter, the solvent is removed from the coating film on a hot plate at 100 ° C. so that the exposure amount to the coating film is 200 mJ / cm ² from the direction of 90 ° to the coating surface. Irradiated with linearly polarized ultraviolet light having a wavelength of around 313 nm, a photo-alignment film having a film thickness of about 100 nm was obtained, and named photo-alignment film (AF-J).

<Preparation of composition for anisotropic light conversion material>
[Example 2]
Compound (1-1-19-1) and compound (1-1-3-1) were weighed 0.3570 g and 0.1530 g, respectively, and dissolved in 2.49 g of cyclohexanone. To this solution, 0.0102 g of G-205, 0.0051 g of Irg-184, and FTX-218 were added and dissolved, and the composition was named (LC-1). The composition (LC-1) contains 17% by weight of the total amount of the compound (1).

  In the same manner, a composition as a raw material for an anisotropic light conversion material containing 17% by weight of a polymerizable liquid crystal component shown in Table 2 was prepared. The numerical values in brackets in Table 2 are relative weights when the total weight of compound (1) is 100.

<Production of anisotropic light conversion material>
[Example 3]
The anisotropic light conversion material was prepared by the following procedure. On the photo-alignment film (AF-1), the composition (LC-1) was applied by spin coating at a rotation speed of 1000 rpm. Each photo-alignment film (AF-1) was placed on a hot plate at 80 ° C. for 3 minutes, and then placed at room temperature for 3 minutes. The composition (LC-1) exhibited a nematic phase at 80 ° C. Thereafter, the composition (LC-1) was irradiated with ultraviolet rays in a nitrogen stream at room temperature to polymerize the composition (LC-1) and named the anisotropic light conversion material (LF-1). However, the illuminance of ultraviolet rays for the composition (LC-1) was 30 mW / cm ² (measured at 365 nm), and the exposure amount of ultraviolet rays for the composition (LC-1) was 1 J / cm ² .

  In preparation of the anisotropic light conversion material (LF-1), an anisotropic light conversion material was prepared using the composition shown in Table 3 instead of the composition (LC-1), and the anisotropic light conversion shown in Table 3 was made. Named the material. Table 3 shows the measurement results of the film thickness and dichroic ratio of the anisotropic light conversion material prepared.

また、異方性光変換材料（ＬＦ−９）の偏光顕微鏡写真を図１に示す。 Table 3. Anisotropic light conversion material evaluation results

In addition, FIG. 1 shows a polarizing microscope photograph of the anisotropic light conversion material (LF-9).

In the production of the anisotropic light conversion material (LF-9), an anisotropic light conversion material is prepared using linearly polarized light in the same direction as the treatment of the alignment film instead of the ultraviolet ray, and the anisotropic light conversion material (LF-9 ′) Named. Linearly polarized light could place a wire grid polarizer between the UV light source and the composition. The illuminance of linearly polarized light with respect to the composition (LC-9) was 10 mW / cm ² (measured at 365 nm), and the exposure amount of ultraviolet rays to the composition (LC-9) was 1 J / cm ² . Table 4 shows the measurement results of the film thickness and dichroic ratio of the anisotropic light conversion material (LF-9 ′).

Table 4. Anisotropic light conversion material evaluation result HH

  In the production of the anisotropic light conversion material (LF-9), an anisotropic light conversion material was prepared using the photo alignment film shown in Table 5 instead of the photo alignment film (AF-1). Named as isotropic light conversion material. Table 5 shows the measurement results of the film thickness and dichroic ratio of the above-mentioned photo-anisotropic light conversion material.

Table 5. Anisotropic light conversion material evaluation results

[Comparative Example 1]
In the production of the anisotropic light conversion material (LF-1), instead of the composition (LC-1), the composition (LC-ref1) is used to prepare the anisotropic light conversion material, and the anisotropic light conversion material (LF-) ref1). Table 6 shows the measurement results of the film thickness and dichroic ratio of this anisotropic light conversion material (LF-ref1).

Table 6. Anisotropic light conversion material evaluation results

[Comparative Example 2]
On the photo-alignment film (AF-1), the composition (LC-ref2) was applied by spin coating (rotation speed: 1000 rpm). The resulting film was placed on a 120 ° C. hot plate for 1 minute, placed on a 70 ° C. hot plate for 3 minutes, and then allowed to stand at room temperature for 3 minutes. Thereafter, the composition (LC-ref2) was irradiated with ultraviolet rays in a nitrogen stream at room temperature to polymerize the composition (LC-ref2) and named the anisotropic light conversion material (LF-ref2). However, the irradiation conditions of the ultraviolet rays were the same as the preparation conditions of the anisotropic light conversion material (LF-1).
Table 7 shows the measurement results of the film thickness and dichroic ratio of the anisotropic light conversion material (LF-ref2).

Table 7. Anisotropic light conversion material evaluation results

  A polarization micrograph of the anisotropic light conversion material (LF-ref2) is shown in FIG. In observation with a polarizing microscope under crossed Nicols, there is a region that does not become bright when the LF-ref 2 is rotated, so this region is considered to be vertically aligned.

[Comparative Example 3]
The composition (LF-ref2) was put in an aluminum container for DSC measurement, heated at 80 ° C. for 30 minutes to evaporate the solvent, and a sample was prepared. This sample was measured by DSC, and a peak was observed at 69 ° C. Therefore, this sample is a smectic B phase from room temperature to 69 ° C.

  From Example 3 and the comparative example, it can be seen that the anisotropic light conversion material of the present invention can be formed without alignment defects and has a high dichroic ratio.

  Since the anisotropic light conversion material of the present invention can be applied and formed without alignment defects and exhibits high dichroic ratio characteristics, it can be widely used in place of conventional polarizing plates.

Claims (6)

A composition for an anisotropic light conversion material, in which a dichroic guest is added to a host liquid crystal composition containing a compound represented by the formula (1).

(In formula (1), A is a divalent group derived from an aromatic ring, 1,4-cyclohexane, 1,3-dioxane, or 1,4-pyran, and B is a single bond, —COO—, _{-OCO -, - CH 2 CH 2} -, - CH = CH -, - CH≡CH -, - OCH 2 -, - CH 2 O -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH ₂ COO-, or -OCOCH ₂ CH _2- , n is 5, 6, or 7, SP is a single bond or an organic group having 1 to 21 carbon atoms, PG is alkyl, alkoxyl, Cyano, fluorine, or polymerizable group.)   The composition for anisotropic light conversion materials according to claim 1, wherein 60% by weight or more of the host liquid crystal composition is a compound represented by the formula (1).   The composition for anisotropic light conversion materials according to claim 1 or 2, wherein in the compound represented by the formula (1), at least one of the two PGs is a polymerizable group.   An anisotropic light conversion material produced using the composition according to claim 3.   An anisotropic light conversion material prepared by curing a nematic composition using the composition according to claim 3.   An anisotropic light conversion material prepared by curing a nematic composition on a photo-alignment film using the composition according to claim 3.

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